Feeding and Powering the World 2019: the Next Generation Feeding and Powering the World 2019

Feeding and Powering the World 2019: The Next Generation Feeding and Powering the World 2019

Oxford, Mississippi July 15 & 16, 2019 Feeding and Powering the World 2019: The Next Generation

In this collaborative research program funded by the National Science Foundation under grant number OIA-1539035, the expertise of ten research groups has been combined to address critical, multi-disciplinary challenges in the Water-Energy-Food Nexus: the production of hydrogen, the reduction of carbon dioxide to useable fuel, and the reduction of nitrogen to synthetic fertilizer. Currently, nearly all hydrogen is synthesized from non-renewable carbon sources and carbon dioxide is treated as an abundant waste. Additionally, the Haber-Bosch process for using this hydrogen to reduce nitrogen is energy intensive, which demands further fossil fuel consumption. This program has a long-range approach (1) to establish technologies to extract hydrogen efficiently and economically from water using sunlight; (2) to establish technologies that use electron/proton pairs to directly reduce carbon dioxide to usable fuels at voltages obtainable by DSC devices; (3) to establish technologies that will fix nitrogen at lower temperatures and pressures, and ultimately (4) to link these technologies with high-voltage solar cells to use electron/proton pairs derived from catalytic water splitting to directly produce molecular hydrogen fuel, reduce carbon dioxide to produce fuels and nitrogen in one cell to produce ammonia - a key component of synthetic fertilizer. State-of-the-art photoelectrochemical (PEC) cells rely on water soluble, high-toxicity lead-based materials to produce hydrogen from water and operate at 12.3% efficiency with a tandem double-layer solar cell. Goals here include: (1) the design and demonstration of practical, low- toxicity organic materials as single-layer solar cell components in PEC devices, and (2) the demonstration of a hydrogen production efficiency nearing 15% - a commercially viable number with low-cost materials. These materials would be a dramatic step forward in the PEC field for hydrogen production. Additionally, viable carbon reduction catalysts and a low pressure, reduced-temperature process for nitrogen reduction are highly desirable technologies. The iterative evaluation of carbon dioxide and molecular nitrogen reduction catalysts is proposed through a research loop including: (1) synthesis of potential catalysts, (2) photophysical analysis, (3) electrochemical analysis, and (4) computational analysis to suggest future catalyst targets. This process will allow for a rapid evaluation of catalyst designs for high reduction activity. Ideally, these processes will be linked to facilitate the formal reduction of carbon dioxide and nitrogen with water and sunlight as inputs. The reduction of carbon dioxide and molecular nitrogen with hydrogen are critical processes to fuel and food production. Dramatic improvements in PEC hydrogen-producing cell efficiencies with viable, non-toxic materials, as well as the low-pressure, low-temperature reduction of molecular nitrogen are desirable for practical, sustainable fertilizer synthesis. The importance of efforts improving the route to synthetic fertilizer should not be understated. As such, a key aspect to sustainable funding is public awareness and involvement of the community through outreach. The critical goal of heightening public awareness through science cafes and public service announcements directed at the K-12, community college, and university levels as well as at the general public is also a key priority. The goal of this conference is to bring together in one location all of the faculty, students, and all other participants of this program to report achievements, develop new relationships and collaborations, teach each other new skills, and make plans for future funding opportunities.

Feeding and Powering the World 2019: The Next Generation

Jackson Avenue Center Auditorium A, 1111 West Jackson Avenue, Oxford, MS 38655

Monday July 15

8:00 am - 9:30 am : Breakfast on Your Own 9:30 am - 10:00 am : Pick up Name Tags and Programs and Hang up Posters 10:00 am : Welcome 10:05 am - Noon : Graduate Student Talks Dalton Burks, Papish, Alabama Hammad Cheema, Delcamp, Ole Miss Sriloy Dey, Hollis, MSU Liping Guo, Yan, Alabama Noon - 1:00 pm : Lunch and Networking 1:00 pm - 2:30 pm : Graduate Student Presentations Christine Curiac, Delcamp, Ole Miss Sanjit Das, Papish, Alabama Leigh Anna Hunt, Hammer, Ole Miss 2:30 pm : Break 2:45 pm - 4:15 pm : Graduate Student Presentations Robert W. Lamb, Webster, MSU Xiao Li, Pan, Alabama Sayontani Sinha Roy, Jurss, Ole Miss 4:15 pm : Group Picture 4:30 pm - 5:15 pm : Poster Presentations 5:30 pm - 8:00 pm : Dinner, Collaboration, and Networking on Your Own

Tuesday July 16 7:00 am - 9:00 am : Breakfast on Your Own 9:00 am - noon : Student Networking (On Your Own) 9:00 am - noon : Senior Personnel & Seed Grant Recipients Meeting (Auditorium A)

Feeding and Powering the World 2019: The Next Generation

Senior Faculty at the 2015 SouthEastern Regional Meeting of the American Chemical Society (SERMACS 2015) in Memphis, Tennessee in November, 2015

Senior Faculty at the 255th National Meeting of the American Chemical Society in New Orleans, LA, March 2018

Feeding and Powering the World 2019: The Next Generation

Dr. Jared Delcamp Dr. Keith Hollis University of Mississippi Mississippi State University Senior Personnel Senior Personnel

Dr. Nathan Hammer Dr. Shanlin Pan University of Mississippi University of Alabama Senior Personnel, PI Senior Personnel

Feeding and Powering the World 2019: The Next Generation

Dr. Russ Schmehl Dr. Charles Edwin Webster Tulane University Mississippi State University Senior Personnel Senior Personnel

Feeding and Powering the World 2019: The Next Generation

Dr. James Donahue Dr. Jonah Jurss Tulane University University of Mississippi Seed Grant Recipient, Year 2 & 3 Seed Grant Recipient, Years 1 - 4

Dr. Feng Yan Dr. Elizabeth Papish University of Alabama University of Alabama Seed Grant Recipient, Year 4 Seed Grant Recipient, Years 1 - 4 Feeding and Powering the World 2019: The Next Generation

Feeding and Powering the World 2019: The Next Generation

Mechanistic Studies of Ruthenium CNC-Pincer Complexes for Carbon Dioxide Reduction Catalysis

Dalton B. Burks,1 Robert W. Lamb,2 Sanjit Das,1 Chance M. Boudreaux,1 Charles Edwin Webster,2 Elizabeth T. Papish1*

1Department of Chemistry & Biochemistry, The University of Alabama, Tuscaloosa, AL 2Department of Chemistry, Mississippi State University, Mississippi State, MS

The reduction of carbon dioxide to useful products, especially fuel sources, has the potential to help alleviate the world’s energy problem. The Papish group has recently developed catalysts for photocatalytic carbon dioxide reduction based on CNC-pincers composed of N-heterocyclic carbenes and pyridinol rings. Several ruthenium complexes of this ligand scaffold act as self- sensitized photocatalysts for the reduction of CO2 to CO, which eliminates the need for an additional photosensitizer. These catalysts all have different turnover numbers (TON) and turnover frequencies (TOF) for this reaction, with the highest TON of any of the catalysts being 33,000 at low catalyst concentration. The differences in the catalytic activity of these catalysts is of interest to help determine how to design improved catalysts, and mechanistic studies can help elucidate reasons for the differences observed in catalytic activities. Initially, the catalyst s were reduced by a chemical reductant and then were exposed to CO2. UV/vis and IR spectroscopies were used to monitor how the spectra changed upon reduction and upon the subsequent exposure to CO2. In situ IR spectra measured with a ReactIR instrument were used to monitor changes when CO2 and 13 CO2 was exposed to the reduced catalyst; from these experiments, a peak for a C=O stretch of a -1 -1 13 bound formate was observed at 1652 cm and 1596 cm when CO2 or CO2 was used, respectively. ReactIR experiments were also performed with CO and 13CO to try to observe a Ru- CO species formed in situ; however, these experiments were unsuccessful due to the low solubility of CO in acetonitrile. Computational studies were also used to help determine possible reaction pathways for carbon dioxide conversion to carbon monoxide. From these studies, it was determined that CO l oss from a Ru-CO species is the rate-limiting step during catalysis.

Feeding and Powering the World 2019: The Next Generation

Engineering of Sequential-Series Multijunction Dye- Sensitized Solar Cells for Greater than 10% Efficiency and 2.0 V Output

Hammad Cheema and Jared H. Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, University, MS 38677

Sequential series multijunction dye-sensitized solar cells (SSM-DSCs) are mechanically stacked single illuminated area DSC devices wired in series to harness photovoltage for novel applications such as powering solar fuels, charging batteries etc. SSM-DSCs are strategically designed to optimally utilize the potential energy of photons in different parts of the spectrum. In this study, strategies to minimize photon reflection losses from glass and glass-air interface and photon management are combined. With a judicious choice of the sensitizer, TiO2 film thickness, solution processable “CYTOP” antireflection coating and immersion oil SSM-DSCs with power conversion efficiency >10% and 2.3 V photovoltage were achieved. Importantly, the SSM-DSC efficiency was substantially higher than any single device in the stack. Furthermore, without external bias this SSM-DSC configuration shows an impressive overall solar-to-fuel conversion efficiency of 6% when powering IrO2 and Au2O3 electrocatalysts for CO2 and H2O to CO and H2 conversion in aqueous solution. Concept of photon management in SSM-DSCs, device engineering, and role of CYTOP will be covered in the talk.

Feeding and Powering the World 2019: The Next Generation

Organic Dyes and Transition Metal Complexes for Ultrahigh Voltage Solar Cells and Probing Inverted Marcus Region Kinetics at Interfaces

Christine Curiac, Roberta R. Rodrigues, Adithya Peddapuram, and Jared Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

The progress towards designing potent photoinduced oxidants at TiO2/dye interfaces will be discussed. These oxidants are critical to a number of applicaitons including solar cells generating the highest possible photovoltages from visible sunlight. An organic dye (CC3) has reach the practicle oxidant strength limit for a visible sunlight absorbing photoinduced oxidant for the first time in literature. When paired with an appropriate redox shuttle, this dye is capable of generating >2.0 V solar cells from early photons for the first time. The quest to find a suitable redox shuttle will be discussed including current approaches to a Ni(III)bipyridyl derivative accessed through the use of K2NiF6. Importantly, having reached the oxidant strength limit, we are uniquely positioned for the first time to probe the Inverted Marcus Region kinetics at interfaces with a maxium possible free energy from visible light which has been a topic of interest for >30 years with regard to TiO2 with current photoinduced systems sitting only in the Normal Marcus Region due to the lack of a strong photoinduced oxidant and the large reorgization of Ti(IV) to Ti(III) limiting the overpotential beyond the reorganization energy required for TiO2.

Feeding and Powering the World 2019: The Next Generation

Ruthenium CNC-pincer Complexes as Photocatalysts for Carbon Dioxide Reduction under Visible Light

Sanjit Das1, Chance M. Boudreaux1, Fengrui Qu1, Hunter Shirley2, Roberta R. Rodrigues2, Phillip E. Burrow2, Jared H. Delcamp2, Elizabeth T. Papish1*

1Department of Chemistry and Biochemistry, University of Alabama, Tuscaloosa, Alabama 35401 2Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

Ruthenium CNC-pincer complexes presented here are photocatalysts for carbon dioxide reduction under visible light. The strong influence of a remote methoxy group on the pyridine ring at a specific position is evident. The influence of other groups and methoxy group at a different position are tested and compared for structure-function relationship. Pincers with extended conjugation are employed for self-sensitized photocatalysis and the introduction of 2,2’-bipyridine along with the pincer with phenyl wing-tip leads to rapid photocatalysis in absence of an external photosensitizer. Surface attachment of self-sensitized photocatalyst improves the turnover number (TON) dramatically.

Feeding and Powering the World 2019: The Next Generation

Toward Nitrogen Fixation with Lower Valent Titanium Pincer Complexes

Sriloy Dey and T. Keith Hollis*

Department of Chemistry and Center for Computational Sciences, Mississippi State University, Mississippi State, Mississippi 39762

The dramatic expansion of the earth’s population can be directly corelated with the Haber-Bosch process for nitrogen fixation becoming widely available after World War II. The ready availability of artificial fertilizer derived thereof feeds the world. Recently artificial nitrogen fixation surpassed the natural process. The H-B process is extremely energy and green-house gas intensive due to its high-temperature and H2 demands. Many low valent Ti(II) complex of N2 are known. We report herein a preliminary investigation of the low-valent chemistry of Ti with the CCC-NHC ligand architecture. These CCC-NHC pincer Ti(IV) complex are readily reduced with KC8 or Mg powder. Preliminary results indicate very different reactivity patterns with alkynes and phosphines obtain. Successful reduction to CCC-NHC Ti(II) was confirmed by re-oxidation with PhICl2.

Feeding and Powering the World 2019: The Next Generation

Scalable Core-shell MoS2/Sb2Se3 Nanorod Array Photocathodes for Enhanced Photoelectrochemical Water Splitting

Liping Guo1, Pravin S. Shinde2, Yanxiao Ma2, Lin Li1, Shanlin Pan2, and Feng Yan1,3*

1Department of Metallurgical and Materials Engineering, The University of Alabama, Tuscaloosa, Alabama, 35487 2Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama, 35487 3Alabama Water Institute, The University of Alabama, Tuscaloosa, Alabama, 35487

Photoelectrochemical (PEC) hydrogen generation is a promising technique to harvest solar energy to address the concerns over the energy crisis. Antimony selenide (Sb2Se3) with van der Waals bonded quasi-one-dimensional (1D) nanoribbons, for instance, (Sb4Se6)n, have attracted great interest as a light absorber. By tuning its anisotropic growth behavior, it is possible to achieve Sb2Se3 films with nanostructured morphology that can improve the light absorption and photogenerated charge carrier separation, eventually boosting the PEC water splitting performance. In this work, we synthesized high-quality Sb2Se3 films with nanorod (NR) array surface morphology by a low-cost, high-yield and scalable close-spaced sublimation method. By sputtering a non-precious and scaleable crystalline molybdenum sulfide (MoS2) film as a cocatalyst and a prote ctive layer on Sb2Se3 NR arrays, the fabricated core-shell structured −2 MoS2/Sb2Se3 NR PEC devices can achieve a photocurrent density as high as −10 mAcm at 0 VRHE in a buffered near-neutral solution (pH 6.5) under a standard simulated AM 1.5 solar illumination. This work demonstrates scalable manufacturing of nanostructured MoS2/Sb2Se3 NR array thin film photocathode electrodes for the efficient PEC water splitting to generate solar fuel.

Feeding and Powering the World 2019: The Next Generation

Determination of Dye Regeneration Efficiency in Dye Sensitized Solar Cells

Leigh Anna Hunt, Ali Baumann, Jared Delcamp, Nathan Hammer*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

Regeneration of the sensitizing dye in dye-sensitized solar cells (DSCs) is frequently studied using transient absorption spectroscopy. The regeneration process is critical to DSC operation and must occur rapidly in order to avoid charge recombination between the oxidized dye molecule and the injected electrons. The overall efficiency of regeneration can be estimated from fitting TA decays of cells employing either a redox-active electrolyte solution or a redox-inactive electrolyte solution. In this study, nanosecond transient absorption spectroscopy was used to study the regeneration kinetics of a novel series of dyes.

Feeding and Powering the World 2019: The Next Generation

Building Better Catalysts from Systematic Experimental and Computational Studies

Robert W. Lamb,1 Dalton B. Burks,2 Sanjit Das,2 Roberta R. Rodrigues,3 Fengrui Qu,2 Chance M. Boudreaux,2 Jared H. Delcamp,3 Elizabeth T. Papish,2 and Charles Edwin Webster1*

1Department of Chemistry, Mississippi State University, Mississippi State, Mississippi 39762 2Department of Chemistry and Biochemistry, University of Alabama, Shelby Hall, Tuscaloosa, Alabama 35487 3Department of Chemistry and Biochemistry, University of Mississippi, Coulter Hall, University, Mississippi 38677

The efficient production of useful Cn chemicals and fuels under ambient conditions from CO2 reduction requires the development of robust and active catalysts that can utilize sunlight to drive this thermodynamically disfavored process. Papish, Delcamp, and Webster have recently published a series of CNC-Ru complexes capable of reducing CO2, one of which acts as a self-sensitized photocatalyst achieving 33,000 TON. However, even this number is still far short of industrial applicability. To further improve design, we must understand how these structurally similar complexes are different at a mechanistic level. This talk will focus on our recent efforts to develop plausible catalytic mechanisms from combined computational and experimental studies.

Feeding and Powering the World 2019: The Next Generation

Electrocatalytic Oxygen Evolution Reaction at NH2-MIL-125 Derived Carbon- and Nitrogen-Modified Titanium Oxides Nanostructures

Xiao Li and Shanlin Pan*

Department of Chemistry and Biochemistry, The University of Alabama, 35487

Hydrogen production through the wind and solar-powered water splitting is expected to be a sustainable system with a high energy utilization efficiency. Developing high-performance catalytic materials for the bottleneck half reaction, oxygen evolution reaction (OER), is one of the keys to success. Herein, a new NanoCONT anode material for OER was developed by modifying the surface of conventional TiO2 electrode with NH2-MIL-125 (a Ti-based metal-organic frameworks (MOFs)) derived structure using a three-step approach. A high-temperature pyrolysis of NH2-MIL-125 under N2 atmosphere was utilized to fabricate a highly porous NanoCONT material being composed of C and N modified TiOx (Ti, TiO2, Ti3O, and Ti6O) on Ti plate with a double-layer nanorods/nanoparticle islands nanostructure. The enhanced electrocatalytic activity of NanoCONT for OER could be attributed to the abundant active sites from Ti3O and Ti6O crystals, a large surface area exposing more active sites to promote efficient mass transfer, and the improved electrical conductivity by C and N matrix. Surface interrogation mode of scanning electrochemical microscopy (SI-SECM) was adopted to quantitatively investigate the generated reactive surface species (RSSs) on NanoCONT indicating an increased surface coverage of RSSs under a higher substrate potential.

Feeding and Powering the World 2019: The Next Generation

Electrocatalytic and Photocatalytic CO2 Reduction with Substituted Rhenium Polypyridyl Complexes

Sayontani Sinha Roy, Eva Amatya, Kallol Talukdar, Shakeiya Davis, Jared H. Delcamp, and Jonah W. Jurss*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

The consumption of fossil fuels has increased exponentially since the Industrial Revolution, which has caused CO2 emissions to skyrocket. This greenhouse gas is primarily responsible for climate change and ocean acidification. Concerns over depleting fossil fuel reserves and mounting greenhouse gas emissions have motivated efforts to harness energy from renewable sources. Using sunlight or renewable electricity to generate chemical fuels is a promising solution to address these concerns while storing energy in a convenient form. Carbon dioxide (CO2) is a cheap and abundant feedstock for the generation of fuels, fuel precursors, and commodity chemicals. The main challenge in reducing carbon dioxide lies in designing more efficient catalysts that are long-lived, selective, and operate near the thermodynamic potential for the desired reaction. Anthracene- functionalized mononuclear and dinuclear rhenium complexes have been reported previously by our group for electrocatalytic and photocatalytic CO2 reduction to carbon monoxide (CO). Further modifications have been made to the published systems to develop next-generation photocatalysts that can more effectively utilize the long-lived anthracene triplet excited states that are accessible in these complexes. In addition, multiple strategies have been employed in the literature to reduce the overpotential for electrochemical CO2 reduction; the integration of different functional groups into the secondary coordination sphere is one of them. In this context, we report the synthesis, characterization, and electrochemical properties of new rhenium-based catalysts containing pendant functionality for CO2 reduction. Incorporation of the second-sphere functional group is shown to be effective in improving the catalytic activity relative to the unfunctionalized parent complex.

Feeding and Powering the World 2019: The Next Generation

New Co(I)-Pincer Complexes for Photocatalyzed CO2 Reduction

Chance M. Boudreaux1, Hunter Shirley2, Fengrui Qu1, Jared H. Delcamp2, and Elizabeth T. Papish1*

1Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35401 2Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

The para-substituted pincers have shown great promise of enhanced activity and selectivity in several catalytic reactions, particularly photocatalytic CO2 reduction. The Papish group has synthesized a wide variety of CNC derivatives and have obtain useful structure to function relationships leading to unique results. Current research has bloomed and now efforts are being made to expand to new metals, particularly more earth abundant metals. Through these efforts, a new cobalt CNC pincer complex has been produced and characterized. The complex was tested for activity in photocatalytic CO2 reduction and produced 15 TON of CO over 24 h. This reactivity is promising for cobalt and more complexes are currently being investigated to obtain the same structure to function relationship that ignited the ruthenium project.

Feeding and Powering the World 2019: The Next Generation

Hydrogen Evolution by Molybdenum Chalcogenide Clusters: Catalysis as Function of Chalcogen Composition

Kyra Brakefield, Gayathri Ragunathan, Patricia R. Fontenot, Russell H. Schemehl, and James P. Donahue*

Department of Chemistry, Tulane University, 6400 Freret Street, New Orleans, Louisiana 70118

i Photolysis of [Mo3(μ3-S)(μ2-S2)3(S2CNR2)3]I (R = Me, Et; Bu, CH2C6H5) in a mixed aqueous- 2+ polar organic medium with [Ru(bipy)3] as photosensitizer leads to H2 evolution. Maximum i activity (300 turnovers, 3 h) is found with R = Bu in 1:9 H2O:MeCN; Monitoring of the photolysis + mixture by mass spectrometry suggests transformation of [Mo3(μ3-S)(μ2-S2)3(S2CNR2)3] to + 0 [Mo3(μ3-S)(μ2-S)3(S2CNR2)3] via extrusion of S on a timescale of minutes without accumulation + + of the intermediate [Mo3S6(S2CN Et2)3] or [Mo3S5(S2CNEt2)3] species. Deliberate preparation of + 1– [Mo3S4(S2CNEt2)3] and treatment with Et2NCS2 yields [Mo3S4(S2CNEt2)4], where the fourth dithiocarbamate ligand bridges one edge of the Mo3 triangle. Subsequent photolysis of 4 leads to + H2 evolution but at ~25% the level observed for [Mo3S7(S2CNEt2)3] . Early time monitoring of the photolyses shows that [Mo3S4(S2CNEt2)4] evolves H2 immediately and at constant rate, while + [Mo3S7(S2CNEt2)3] shows a distinctive incubation prior to a more rapid H2 evolution rate. This observation implies the operation of catalysts of different identity in the two cases. Photolysis i + solutions of [Mo3S7(S2CN Bu2)3] left undisturbed over 24 h deposit the asymmetric Mo6 cluster i 2 1 1 i i [( Bu2NCS2)3(μ2-S2)2(μ3-S)Mo3](μ3-S)(μ3-η ,η S′,η SÊº-S2)[Mo3(μ2-S)3(μ3-S)(S2CN Bu2)2(μ2-S2CN Bu2)] in crystalline form, suggesting that such species are the probable H2-evolving catalysts in + photolyses beginning with [Mo3S7(S2CNR2)3] . When used as solvent, N,N-dimethylformamide (DMF) suppresses H2-evolution but to a greater degree for [Mo3S4(S2CNEt2)4] than for + [Mo3S7(S2CNEt2)3] . Recrystallization of [Mo3S4(S2CNEt2)4] from DMF affords 1 [Mo3S4(S2CNR2)4(η ,κO-DMF)], implying that inhibition by DMF arises from competition for a Mo coordination site that is requisite for H2 evolution. Computational assessment of + + – [Mo3S4(S2CNEt2)3] following addition of 2H and 2e suggests a Mo(H)–μ2(SH) intermediate as the lowest energy species for H2 elimination. This insight sugge sts a broader study of + – [Mo3E7(E2CNR2)3] I (E = S or Se; R = alkyl) for the effect of chalcogen, especially bridging chalcogenide, on H2-evolving activity levels. Routes to such complexes are outlined.

Feeding and Powering the World 2019: The Next Generation

Electrodeposition of Methylammonium Lead Iodide Perovskites

Megan Bruneau, Jeetika Yadav, Yanxiao Ma and Shanlin Pan*

Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, AL 35487

Methylammonium lead iodide (MAPbI3) perovskites play key roles in efficient solar cells. MAPbI3 can be produced by chemical conversion of lead dioxide films that have been electrodeposited onto a substrate to form a film. The purpose of this research is to find the optimum conditions for perovskite formation, which appears as a dark coating, as this material has been found to increase conversion efficiency as a light harvester. Similar to the conditions executed by the Switzer group, PbO2 is electrodeposited from a solution of 0.1 M Pb(NO3)2 and 5.0 M NaOH in deionized water. The film is then immersed in 0.1 M CH3NH3I in a 2-propanol solution to form the MAPbI3. This is conducted at varied voltages on ITO (indium tin oxide) glass as well as TiO2 nanowires produced on FTO (fluorine doped tin oxide) glass in order to study the optimum variables for maximizing light harvesting. Charge separation and transport as well as stability. The PbO2 and MAPbI3 films are characterized using SEM and XRD techniques. Researching the most favorable formation conditions can provide insight into the properties and benefits of use in photovoltaic cell applications.

Feeding and Powering the World 2019: The Next Generation

Synthesis of [Fe(PT)]2+ and [Fe(MPT)]2+ for Dye Sensitized Solar Cells

Courtney L. Dale1, Chance M. Boudreaux1, Jared H. Delcamp2, and Elizabeth T. Papish1*

1Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35487 2Department of Chemistry, University of Mississippi, Oxford, Mississippi 38677

Dye sensitized solar cells (DSSCs) are used as a renewable energy source by converting light energy into electrical energy. Light, a ubiquitous energy source, is used to excite electrons in the dye and then the electrons are injected into the titanium dioxide. Electrons then flow through a circuit to perform work and then the redox shuttle completes the circuit by returning the electrons to the dye. Redox shuttles should be stable in both redox states in order to be an efficient redox shuttle. In this project, 1,4,7-Tris(2-pyridylmethyl)-1,4,7-triazacyclononane (PT) and 1,4,7[(6- methyl-2-pyridyl)methyl]-1,4,7-triazacyclononane (MPT) ligands are used to stabilize iron(II/III) complexes and are investigated for enhanced efficiency in DSSCs. In current DSSCs, the redox shuttle is not efficient enough, nor is the current solar cell cost effective enough to be put into wide use. This project is meant to look into more efficient and cost effective DSSCs that can deliver greater voltages. Currently, research is being conducted to synthesize the ligands and the metal complexes thereof. After synthesis and characterization, these redox shuttles will be tested by the Delcamp group in a DSSC device.

Feeding and Powering the World 2019: The Next Generation

Naphthobisthiadiazole-based Organic Dyes for Near-Infrared Absorption in Dye-Sensitized Solar Cells

Andrew Daniel, Alexandra Baumann, Jared Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

In an effort to increase the overall efficiency of dye-sensitized solar cells (DSCs), there is an interest to synthesize dyes capable of absorbing into the near-infrared region (NIR). One method that is being utilized in order to achieve this goal is extending the overall conjugation of the system through modification of the individual components of a typical D-π-A (donor-π bridge-acceptor) structure. With their characteristic low-energy LUMOs, the π-bridge benzothiadiazole (BTD) has become a widely used building block in the DSC community. Computational modeling has suggested that by extending the conjugation of a dye’s π-bridge from a BTD to a napthobisthiadiazole (NTz), the absorption spectra should also extend closer to the desired NIR region. For these studies, we are evaluating napthobisthiodiazoles as a potential π-bridge for D-π-A systems in DSC devices, with the future directions of this project including: 1 ) addition of more electron dense donors or more electron deficient acceptors to further develop the red shift in the absorption spectra 2) develop dyes of this series for co-sensitization studies.

Feeding and Powering the World 2019: The Next Generation

Near Infrared Light-Absorbing Metal-Free Dyes for High Photocurrent Dye-Sensitized Solar Cell Devices

Ndaleh D. N. David, Hammad Cheema, and Jared H. Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

In this work, we designed and synthesized four new NIR absorbing metal-free organic molecules (ND1, ND2, ND3 and ND4) for use in dye-sensitized solar cell devices with high photocurrents. These dyes are designed with the record-breaking performance of AP25 in mind (25 mA/cm2 from a metal-free dye for the first time). Seeking to improve on the overall device performance of AP25 by tuning the dye energy levels, several donor groups are examined including a bulky triarylamine, carbazole, indoline, and phenothiazine for comparison to the triarylamine donor group used with AP25. The four new dyes (ND1, ND2, ND3, ND4) all absorb into the NIR spectral region until energies as low as 800 nm. Among the dyes ND3 has the highest excited-state oxidation potential (-0.80V) implying that it can inject electron to TiO2 more effectively than ND1 with -0.69V or ND2 with -0.71V. This raised energy is an improvement over the prior AP25 dye which may lead to improved power conversion efficiencies.

Feeding and Powering the World 2019: The Next Generation

Synthesis, Characterization and Luminescent Properties of Zirconium Metal Based CCC-NHC Pincer Ligand

Sriloy Dey and T. Keith Hollis*

Department of Chemistry, Mississippi State University, Mississippi State, MS 39762

Luminescent complexes based on precious metals such as platinum or iridium are well known for the applications in organic light emitting diodes (OLEDs). But earth abundant metal complexes featuring luminescence properties are very limited, yet are highly desired due their lower cost. Bu i i Bu Previously reported [( C C C )Zr(Cl)2(NMe2)] complex was reacted with TMSCl to obtain the Bu i i Bu Bu i i Bu [( C C C )Zr(Cl)3] complex. The solid-state crystal packing of [( C C C )Zr(Cl)3] was found to Bu i i Bu be slipped stacked, but [( C C C )Zr(Cl)2(NMe2)] complex as brick layer stacked. Photophysical characterization was conducted in the solid and the liquid state. In the solid and in the solution states Bu i i Bu Bu i i Bu [( C C C )Zr(Cl)3] gave a white light emission, whereas [( C C C )Zr(Cl)2(NMe2)] showed no Bu i i Bu emission. Computed TDDFT shows that emission of [( C C C )Zr(Cl)3] is due to ligand to metal and ligand to ligand transitions. DFT shows delocalized HOMO and LUMO in a dimer exciplex Bu i i Bu that results in excimer emission. The concentration dependence of [( C C C )Zr(Cl)3] was consistent with an exciplex.

Feeding and Powering the World 2019: The Next Generation

Characterizing the Fluxional Behavior in (TMCOT)M(CO)3 and (COT)Cr(CO)3 Complexes with Computational Approaches

Nathan C. Frey, Eric Van Dornshuld, Fatemeh Aghabozorgi, and Charles Edwin Webster*

Department of Chemistry, Mississippi State University, Mississippi State, MS 39762

Fluxionality in molecules plays a significant role in influencing enantioselectivity during asymmetric catalysis. Density functional theory computations were used to investigate the fluxional mechanisms of 1,3,5,7-tetramethylcyclooctatetraene chromium, molybdenum, and tungsten tricarbonyl [(TMCOT)M(CO)3 (M= Cr, Mo, and W)] and cyclooctatetraene chromium tricarbonyl [(COT)Cr(CO)3]. All geometries were fully characterized with PBEPBE and B3LYP methods. Transition states have been identified in the fluxional mechanisms of both (TMCOT)M(CO)3 and (COT)Cr(CO)3, which were compared to experimental data. Experimental data was also compared to computed GIAO-B3LYP 1H-NMR chemical shifts for the (TMCOT)M(CO)3 (M = Cr and Mo) complexes at three different temperature regimes (the low- temperature limit, low temperature, and high-temperature limit for each respective complex).

Feeding and Powering the World 2019: The Next Generation

Examining the Electronic Properties of Twisted Pyrene Compounds

Nathan C. Frey1, Robert W. Lamb1, Eric Van Dornshuld1, Kelsie E. Krantz2, Wenlong Yang2, Paul Miller2, Diane A. Dickie2, Robert J. Gilliard, Jr.2, Charles Edwin Webster1

1Department of Chemistry, Mississippi State University, Mississippi State, MS 39762 2Department of Chemistry, University of Virginia, Charlottesville, VA 22904

Polycyclic Aromatic Hydrocarbons (PAHs) are arenes that typically deviate from planarity, thereby forming bowl-shaped and/or twisted structures. In this computational study, the electronic properties of five pyrene-containing PAHs have been studied. Three of these compounds contain two diazaborolidines and two compounds contain two N-heterocyclic germylenes (NHGes)—one of which contains an NHC coordinated to each germanium and one contains two coordinatively unsaturated germaniums. The geometric differences and fluorescent properties will be compared and discussed. Nucleus-independent chemical shift (NICS) values were computed at the center of mass of each five or six-membered ring [NICS(0)] using the B3LYP/BS1 level of theory (BS1 is defined as the 6-311+G** basis sets for C, H, N, F, and B and 6-31G* basis set for Ge). Molecular orbitals were analyzed for each compound. Time-dependent DFT (TD-DFT) computations were also performed to produce the simulated UV-Vis spectrum for each compound

Feeding and Powering the World 2019: The Next Generation

Fluorescence Lifetime Studies of Donor-π Bridge-Acceptor (D-π-A) Dyes for use in Dye-Sensitized Solar Cells

Leigh Anna Hunt, Roberta Rodrigues, Jared Delcamp, Nathan Hammer*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

Dye-sensitized solar cells (DSCs) are a low cost and promising alternative to standard photovoltaic cells, but sensitizing dyes must have broad absorption spectra and high electron injection efficiency. The functionality of DSCs is reliant on the light-induced charge transfer processes and the kinetics of such processes largely determine the performance of the device. The fundamental charge separation step in DSCs constitutes electron injection from the excited state into the conduction band of TiO2. In order to study the efficiency of this electron injection process, fluorescence lifetime studies both in solution and on TiO2 films were conducted in order to yield insights into understanding the performance of these novel dyes in DSC devices.

Feeding and Powering the World 2019: The Next Generation

A Simplification in the Cathodic Portion of Photoelectrochemical Cells to Maximize Their Efficiency

Qing Li, Hunter P. Shirley, and Jared Delcamp*

Department of Chemistry & Biochemistry, University of Mississippi, Oxford, Mississippi 38677

The solar powered conversion of CO2 into energy sources through photocatalytic reactions has shown to be a possible renewable energy source.1-4 These processes often feature multiple metal complexes that exhibit both photosensitizing and catalytic properties that when coupled with water as a reducing agent, are able to provide fuel or fuel precursors by powering CO2 reduction. Current PEC systems involve multiple electron transfers because of the need for multiple components on the cathodic and anodic sites. Furthermore, these systems require that all electron transfers occur at the same rate in order to work efficiently in non-biased systems. However, the electrode processes can be simplified by switching to catalysts that are able to self-sensitize which would eliminate some of these electron transfers. Another approach to increase the efficacy of these photoelectrochemical cells is to maximize catalytic yields. Because previous studies have shown that catalysts being anchored onto TiO2 by methylene-bridged phosphonic acids exhibit increased turnover numbers, this idea is currently being studied on a ruthenium-centered photocatalyst that has already shown exceptional TONs. Future studies include using the catalyst in PEC systems under various conditions.

1. Shirley, H.; Su, X.; Sanjanwala, H.; Talukdar, K.; Jurss, J. W.; Delcamp, J. H. "Durable Solar Powered Molecular Catalyst Systems for CO2 to CH4 Conversion" J. Am. Chem. Soc. 2019,141, 6617. 2. Das, S.; Rodrigues, R. R.; Boudreaux, C. M.; Qu, F.; Reinheimer, E.; Delcamp, J. H.; Papish, E. T. "Highly Acitve Ruthenium CNC Pincer Photocatalysts for Visible Light Driven Carbon Dioxide Reduction" Inorg. Chem. 2019, 58, 8012. 3. Rodrigues, R. R.; Boudreaux, C. M.; Papish, E. T.; Delcamp, J. H. "Photocatalytic Reduction of CO2 to CO and Formate: Do Reaction Conditions or Ruthenium Catalysts Control Product Selectivity?" ACS Appl. Energy Mater. 2019, 2, 37. 4. Boudreaux, C. M.; Liyanage, N. P.; Shirley, H.; Siek, S.; Gerlach, D. L.; Qu, F.; Delcamp, J. H.; Papish, E. T. "Ruthenium(II) complexes of pyridinol and N-heterocyclic carbene derived pincers as robust photocatalysts for selective carbon dioxide reduction" Chem. Commun. 2017, 53, 11217.

Feeding and Powering the World 2019: The Next Generation

High-Throughput Screening and Surface Interrogation Studies of Au-Modified Hematite Photoanodes with Scanning Electrochemical Microscopy for Solar Water Splitting

Yanxiao Ma, Pravin Shinde and Shanlin Pan*

Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487

Au-incorporated hematite photoanode was screened for photoelectrochemical water oxidation by scanning electrochemical microscope (SECM) technique with a scanning probe of optical fiber for visible light irradiation of the photoanode substrate. Au-incorporated hematite exhibited an enhancement in photocurrent for up to 3% of Au and the performance drop was observed with 4- 10% of Au. Subsequently, pristine and Au-incorporated hematite thin film photoanodes were fabricated by spin coating method with optimal precursor concentrations of Au and Fe(NO3)3 to confirm the results of SECM. The photoelectrochemical (PEC) response confirms that 3% Au is optimum for efficient water oxidation from Au-hematite photoanode. The pristine and Au-hematite materials were also characterized by scanning electron microscopy (SEM) and X -ray photoelectron spectroscopy (XPS) techniques. Au was found to exist in the form of embedded nanoparticles in the incorporated hematite nanostructures. Mott-Schottky analysis of the bulk samples confirms an improvement in charge carrier density for Au-doped hematite. Additionally, there was little plasmonic enhancement as evidenced by UV-vis spectroscopy, with a minimal contribution towards photoactivity. Surface generation tip collection mode of SECM was performed to quantify the generation of oxygen. Oxygen reduction current increases with the increase of photocurrent and reached at 4.75 nA for 3% Au-hematite sample. Thus, the enhanced water splitting performance by Au is attributed to enhancing the electronic conductivity of hematite film.

Feeding and Powering the World 2019: The Next Generation

Nanocolloid SnO2 Buffered Sb2Se3 Thin Film Photocathodes for Highly Efficient Photoelectrochemical Water Splitting

John McDonough1, Liping Guo2, Yanxiao Ma3, Lin Li2, Shanlin Pan3*, and Feng Yan1,4*

1Department of Mechanical Engineering, The University of Alabama, Tuscaloosa, Alabama, 35487 2Department of Metallurgical and Materials Engineering, The University of Alabama, Tuscaloosa, Alabama, 35487, USA 3Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama, 35487, USA 4Alabama Water Institute, The University of Alabama, Tuscaloosa, Alabama, 35487, USA

Solar hydrogen generation through photoelectrochemical (PEC) water splitting is a promising technique to convert solar energy to chemical energy. Antimony selenide (Sb2Se3) with quasi-one- dimensional (Q1D) ribbons, e.g., (Sb4Se6)n, has been investigated intensely. It is a challenge to achieve the well-oriented ribbons vertically to the transparent conducting oxides coated substrate due to its low-symmetry crystalline structure. In addition, it is also difficult to achieve high photocurrent for the pristine Sb2Se3 films due to the high resistivity of the as-deposited Sb2Se3 films by close space sublimation. Here, we employ a nanocolloid SnO2 as a buffer layer and electron transport layer to assist the ribbons alignment and enhance the photogenerated carrier extraction in the Sb2Se3 films. By tuning the SnO2 thickness and surface roughness, it is demonstrated that highly efficient bare Sb2Se3 thin films with a photocurrent density as high as −2 −7.5 mAcm at 0 VRHE in a buffered near-neutral solution (pH 7.0) under a standard simulated AM 1.5 solar illumination. This work demonstrates that SnO2 buffered Sb2Se3 films could be more efficient for PEC water splitting to generate solar fuel.

Feeding and Powering the World 2019: The Next Generation

Deposition of Semiconductors onto A Nanoelectrode of Electrochemically Etched, Sharp Tungsten Wires Insulated With Polymer

Michael Murphy, Yanxiao Ma, Jeetika Yadav, and Shanlin Pan*

Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, AL 35487

In this project, the goal is to fabricate nanoparticles (NPs) at the tip of an electrochemically etched tungsten wire. NPs, such as CdS or perovskite, are deposited onto the tip of the W wire for observations as materials act differently at the NP scale. It is difficult to develop a reproducible method of a properly insulated and electrodeposited tip. So far, the methods for insulating the wires, as mentioned in Electrochemica Acta 269 (2018) 291-298, had to be adjusted. Previously, the coating was drastically over-insulating the wires, consequently the tips of the wire were not being exposed after annealing them. By ensuring an initial current of < 1e-5 A, proper insulation of the wires in a three electrode system (counter Pt, reference Ag/AgCl) can occur. When depositing a NP onto the wires such as CdS, proper deposition time and voltage is still being tested. However, a time of around .5 seconds appears to be the best with voltage around -.8 V (vs. Ag/AgCL).

Feeding and Powering the World 2019: The Next Generation

Pyridine-Based Donor Dyes for Association to Coordinatively Unsaturated Redox Shuttles to Promote Fast Electron Transfers in Dye-Sensitized Solar Cells

Dinesh Nugegoda, Jonah Jurss, and Jared Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

Harnessing the power of the sun using dye-sensitized solar cells (DSCs) is a possible answer address energy challenge. Increasing the rate of electron transfers within DSC devices is critical to minimize thermal losses within these cells and to ensure productive electron transfers. In this regard, to increase the rate of electron transfers from the redox shuttle to the dye a strategy of coordinating to the redox shuttle through a pyridine-based donor dye is considered. In this study, dye DN1 is synthesized and tested in DSC devices with cobalt based redox shuttles both coordinatively saturated and unsaturated. Future studies are planned with transient absorption spectroscopy to identify the different electron transfer rates from the two shuttles to oxidized DN1.

Feeding and Powering the World 2019: The Next Generation

Assessing the performance of DFT energetics on small oxygen/sulfur containing compounds

Laura Olive, Eric Van Dornshuld, and Charles Edwin Webster*

Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA

The structures and energetics of the skewed anticlinal geometries of X–O–O–Y, X–O–S–Y, and X–S–S–Y (where X,Y = H or Me), as well as the corresponding trigonal pyramidal isomers including X–O(O)–Y, X–S(O)–Y, X–O(S)–Y, and X–S(S)–Y were analyzed with computational approaches. Geometries were fully characterized with post-SCF ab initio and 22 density functional methods in conjunction with 12 different correlation consistent basis sets of double-, triple-, and quadruple-zeta quality. In general, the skewed anticlinal isomers are lower in energy than their trigonal pyramidal counterparts. However, two isomer pairs show qualitative relative electronic energy inconsistencies and exhibit significant basis set dependence.

Feeding and Powering the World 2019: The Next Generation

Copper-Based Redox Shuttles Supported by Preorganized Tetradentate Ligands for Dye-Sensitized Solar Cells

Roberta R. Rodrigues, Joseph M. Lee, Jonah W. Jurss*, and Jared H. Delcamp*

Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677

Two novel copper redox shuttles, [Cu(2)]2/1+ and [Cu(3)]2/1+, were synthesized, characterized, and incorporated into DSC devices. These redox shuttles systems exploit biphenyl as an unyielding structural unit where its substituted phenyl groups are not coplanar, allowing the appended donors to bind at a single metal center and prevent the favored square planar geometry of Cu(II). Donors are bonded to the 2,2’ positions of the biphenyl backbone to provide a rigid framework which provides a pseudo tetrahedral geometry and a strong chelate effect. [Cu(2)]2/1+ and [Cu(3)]2/1 are a rare example of Cu redox shuttles that operate in DSC devices via diffusion. DSC devices were analyzed via J-V curve, IPCE, EIS, electron lifetime, and charge extraction measurements. 2/1+ 3/2+ Interestingly, [Cu(2)] was found to give JSC v alues comparable to the benchmark [Co(bpy)3] and higher than [Cu-ARM] 2+/1+. [Cu(2)]2/1+ high current was offset with a lower than usual FF th which could be attributed to an interaction of TiO2 CB to the 5 open coordination site of these redox shuttles. This was probed experimentally by the introduction 1H,1H,2H,2H- perfluorooctyltrimethoxysilane (PFTS) as a fluorine self-assembled monolayer (FSAM) treatment. FSAM treatment acts as an effective TiO2 surface insulating layer to reduce interactions of redox 2/1+ shuttles with the TiO2 surface. Devices of [Cu(2)] treated with FSAM displayed a substantial increase in FF offset by a reduced Jsc. Evidence of high current with a diffusion-based [Cu(2)]2/1+ in DSC devices warrants further exploration with this ligand architectur e designed to fully protect the copper center. Given the tetracoordinate ligand design, protection of the Cu center could lead to an exceptionally stable Cu redox shuttles for DSC devices which have already show promising JSC values from the generation 1 materials.

Feeding and Powering the World 2019: The Next Generation

Dehydrogenation of Alcohols using an Iridium-Based Catalyst

Emily D. Shrewsbury, Wenzhi Yao, and Elizabeth T. Papish*

Department of Chemistry and Biochemistry, University of Alabama, Tuscaloosa, Alabama 35401

Dehydrogenation of an alcohol can lead to hydrogen and an aldehyde in a disproportionation reaction. This reaction results in the acceptorless oxidation of an alcohol (alongside the reduction of protons) and is a green chemistry pathway that can be catalyzed by [Cp*Ir(6,6’-dihydroxy-2,2’- bipyridine)H2O](OTf)2, [Cp*Ir(dhbp)H2O](OTf)2. However, this reaction may not be selective but may also lead to formation of a carboxylic acid. The purpose of this research is to study the catalytic efficiency and selectivity of [Cp*Ir(dhbp)H2O](OTf)2because it was reported to show high catalytic dehydrogenation activity and high water solubility. We are currently replicating the reaction conditions featured by the Fujita group (JACS 2012) and we are studying the factors leading to the production of benzaldehyde and benzoic acid from benzyl alcohol, in lieu of the limited mechanistic details. These factors are being currently probed by varying the pH range from 4-10, to see if product ratio results differ. By conducting this research, a deeper knowledge of the catalytic cycle at a variety of pH levels is being studied to better build upon and refine the current mode of action of the Ir(dhbp) complex in the catalytic cycle. This work intends to move towards the most efficient system while producing very little waste and promoting a safer green chemistry environment.

Feeding and Powering the World 2019: The Next Generation

Improving fac-Re(CO)3 catalysts by strategic second sphere modifications for selective and efficient CO2 reduction

Kallol Talukdar, Sayontani Sinha Roy, Eva Amatya, and Jonah W. Jurss*

Department of Chemistry and Biochemistry, University of Mississippi, University, MS 38677

Carbon dioxide (CO2) serves as a crucial atmospheric component that plays a fundamental role in regulating earth’s temperature. However, excess atmospheric CO2 concentrations produced by human activity pose a tremendous threat to the environment and to public health. Thus arises the demand for an alternative to fossil fuels in order to reduce anthropogenic CO2 emissions. In this context, electrocatalytic reduction of CO2 to fuels and value-added commodities is a clean energy alternative to meet our long-term energy demands. fac-Re(bpy)(CO)3X-type complexes are well known for their selective catalysis and have been extensively studied for the last few decades. Progressive improvements have been made to the parent catalyst through both first- and second- coordination sphere modifications such as altering the basicity of the donors and adding different functional groups to the ligand framework. Here, we present the synthesis, characterization, and electrochemical CO2 reduction activity of a novel series of fac-Re(CO)3 catalysts having second- sphere functional groups at variable predefined distances from the metal center. In general, all of the synthesized catalysts show significantly faster catalysis than the parent (unsubstituted) catalyst. Importantly, a structure-activity relationship has been established with the catalyst series, which will guide future catalyst development.

Feeding and Powering the World 2019: The Next Generation

Optical properties of CH3NH3PbI3 perovskite films

Jeetika Yadav and Shanlin Pan*

Department of Chemistry & Biochemistry, The University of Alabama, Tuscaloosa, AL, 35487

Metal halide perovskites have gained immense interest due to their rapid increase in solar cell efficiency over a short span of time. Due to unique combination of optoelectronic properties these materials are suitable for applications in lasing and lighting. We have studied the fluorescence properties of CH3NH3PbI3 films. The stability of films under 405nm laser was investigated with and without the polymers such as Poly (methyl methacrylate) (PMMA) and Polyethylene oxide (PEO). A dull green fluorescence at 512nm was observed with an intense red fluorescence at 745nm. The red fluorescence is ascribed to perovskite film and the green fluorescence is believed to originate from PbI2. Optical images of the films show fluorescence heterogeneity and both red and the green fluorescence were observed. The s hift in the fluorescence wavelength was studies as a function of molar variation of PbI2: MAI. SEM images show a fiber like morphology. The fluorescence evolution was also studied as a function of temperature by heating ITO substrate with a 10V DC voltage. A light emitting electrochemical cell was fabricated based on CH3NH3PbI3 as the emissive layer in PEO and LiCF3SO3 polymer blend. This study will have applications in the lighting industry.

Feeding and Powering the World 2019: The Next Generation

Dr. Katie Echols Mississippi State University Outreach Coordinator

Outreach activities take place throughout the year at different locations within Mississippi, Alabama, and Louisiana. Outreach is directed at K-12, community college, and university levels, in addition to local community outreach in the form of science cafés and public service announcements. Outreach activities are coordinated by Ms. Katie Echols.

Women in STEM Seminars:

This program raises student awareness of various STEM careers and the women who are successful in those fields. Women who are positive role models in STEM careers to speak at various institutions such as PUIs, HBCUs, and secondary schools. Each speaker discusses the path to her STEM career, what girls today can do to be successful in STEM fields, and opportunities available for students interested in getting involved in STEM. Three or Four seminars are conducted each year.

November 10, 2015: East Mississippi Community College (Speaker: Megan Holmes) November 19, 2015: Itawamba Community College (Speaker: Lindsey Brown) January 20, 2016: Tougaloo College (Speaker: Denise Cornelius) February 27, 2017: Northwest MS Community College (Speaker: Dr. Syndey Murphy) March 24, 2017: Columbus High School, Columbus, MS (Speaker: Ashli Brown) March 30, 2017: Baton Rouge Community College (Speaker: Dr. Anne Robinson) November 2, 2017: Columbus High School (Speaker: Dr. Brittney Oliver) April 10, 2018: Itawamba Community College, Fulton, MS (Speaker: Dr. Leslie Burger) September 21, 2018: Bishop State Community College, Mobile, AL (Speaker: Dr. Janet Donaldson) September 27, 2018: Itawamba Community College, Fulton, MS (Speaker: Dr. Deb Mlsna) November 14, 2018: Itawamba Community College, Fulton, MS (Speaker: Dr. Nikki Reinemann)

Feeding and Powering the World 2019: The Next Generation

Science Cafés: Science Cafés increase knowledge of material science research and provide opportunities for public engagement and discussion of important research topics. Science cafés are lively events that take place in informal settings like a coffee house. They are open to everyone and include a conversation with a researcher on a particular topic. Scientists discuss current research directly related to the water-energy-food nexus and the role chemistry can play in solving the problem. At least four café’s are held each year, targeting college students and adults with one café a year specifically for high school students. We work with teachers at the local high schools to promote and encourage the student’s attendance. Participants are asked to complete short surveys so data can be collected on the participants’ increased knowledge on the topic.

January 21, 2016: 929 Café, Starkville, MS (Speaker: Todd French) January 27, 2016: High Point Café, Oxford, MS (Speaker: Jared Delcamp) April 14, 2016: Nehemiah's, Tuscaloosa, AL (Speaker: David A. Dixon) April 26, 2016: Tulane University Lavin Bernick Center (Speaker: Russ Schmehl) November 2, 2016: Tulane University Lavin Bernick Center (Drs. Doug Chrisey and Tom Sherry) November 3, 2016: Starbucks Coffee, Tuscaloosa, AL (Speaker: Dr. Elizabeth Papish) November 29, 2016: High Point Café, Oxford, MS (Speaker: Gregory Tschumper) April 18, 2017: Starkville Coffee, Starkville, MS (Speaker: Keith Hollis) March 5, 2018: Starbucks Coffee, Starkville, MS (Speaker: Dr. Jared Delcamp) March 20, 2018: Fair Grinds Coffeehouse, New Orleans, LA (Speaker: Dr. Keith Hollis) April 18, 2018: Uptown Coffee, Oxford, MS (Speaker: Dr. Davita Watkins) March 19, 2019: Uptown Coffee, Oxford, MS (Speaker: Dr. Nikki Reinemann) March 20, 2019: Amite, LA (Speakers: Latasha Franklin, Kimberly Madison, and Takia Smith) March 20, 2019: Mandeville, LA (Speakers: Latasha Franklin, Kimberly Madison, and Takia Smith)

Feeding and Powering the World 2019: The Next Generation

.Middle and High School Science Teacher Summer Workshops:

These annual workshops increase teachers’ teaching efficacy and knowledge of content related to material science and the water-energy-nexus theme. They last two weeks each summer and include 15 teachers. The location of the workshop will change annually in order to target different geographical areas. Workshops were held at Mississippi State University in 2016, in New Orleans in 2017, and in Alabama in 2018. A workshop will be held in the Mississippi Delta in 2019. Pictures from previous workshops are below.

Feeding and Powering the World 2019: The Next Generation

Research Experience for Undergraduates (REU) and College Teacher Program: Undergraduate students, college teachers, and high school teachers are supported each summer to perform research in the laboratories of senior personnel. Applications are accepted on the program website. Shown below are participants from Years 1-4 in the summer program.

Feeding and Powering the World 2019: The Next Generation

Clean Energy Harvesting:

Training and education activities closely integrated with the concept of clean energy harvesting and conversion are underway at the University of Alabama. The goal is to help improve clean energy and nanotechnology program for underrepresented minority K- 12 school teachers and students in Alabama’s rural Black Belt Counties and undergraduate students by providing them with hands-on research projects and classroom education modules. The following high school students were supported by the program during Years 1-4: Kryana Brown, Alissa Nicole, and Mackenzie Rymond (Paul W. Bryant High School), Robert Rainwater and Jace Strickland (Brookwood High School), Jada Bibb (Autaugaville High School), and Kayla Hawthorne (Central High School).

Feeding and Powering the World 2019: The Next Generation

2019

X. Su, K. M. McCardle,L. Chen, J. A. Panetier, and J. W. Jurss, “Robust and Selective Cobalt Catalysts Bearing Redox-Active Bipyridyl-NHC Frameworks for Electrochemical CO2 Reduction in Aqueous Solutions,” ACS Catalysis (2019). DOI: 10.1021/acscatal.9b00708

K. Talukdar, A. Issa and J. W. Jurss, “Synthesis of a Redox-Active NNP-type Pincer Ligand and its Application to Electrocatalytic CO2 Reduction with First-Row Transition Metal Complexes,” Frontiers in Chemistry, 7, 330 (2019). DOI: 10.3389/fchem.2019.00330

N. Kaneza, P. Shinde, Y. Ma, and S. Pan, “Photoelectrochemical Study of Carbon-Modified p-type Cu2O Nanoneedles and n-type TiO2−x Nanorods for Z-scheme Solar Water Splitting in Tandem Cell Configuration,” RSC Advances, 9, 13576-13585 (2019). DOI: 10.1039/C8RA09403A

S. Spring, P. S. Shinde, P. R. Fontenot, J. P. Donahue and S. Pan, “Self-Assembled Monolayers of Molybdenum Sulfide Clusters on Au Electrode as Hydrogen Evolution Catalyst for Solar Water Splitting,” Inorganics, 7, 79 (2019). DOI: 10.3390/inorganics7060079

S. Das, R. R. Rodrigues, R. W. Lamb, F. Qu, E. Reinheimer, C. M. Boudreaux, C. E. Webster, J. H. Delcamp, and E. T. Papish, “Highly Active Ruthenium CNC Pincer Photocatalysts for Visible Light Driven Carbon Dioxide Reduction,” Inorganic Chemistry, 58, 8012-8020 (2019). DOI: 10.1021/acs.inorgchem.9b00791

A. E. Steen, S. T. Nguyen, T. L. Ellington, S. Balasubramaniam, I. Chandrasiri, J. H. Delcamp, G. S. Tschumper, N. I. Hammer, and D. L. Watkins, “Characterization of Furan- and Thiophene-containing Bispyridyl Oligomers via Spectroscopic, Electrochemical, and TD-DFT Methods,” Journal of Physical Chemistry C, 123, 15176-15185 (2019). DOI: 10.1021/acs.jpcc.9b01510

H. Cheema, P. Brogdon, E. K. Loya, L. E. McNamara, C. A. Carpenter, N. I. Hammer, S. Mathew, C. Risko, and J. H. Delcamp, “A NIR Absorbing Indolizine-Porphyrin Push-Pull Dye for Dye-Sensitized Solar Cells,” ACS Applied Materials & Interfaces (2019). DOI: 10.1021/acsami.8b21414

H. Shirley, X. Su, H. Sanjanwala, K. Talukdar, J. W. Jurss, and J. H. Delcamp, “Durable Solar-Powered Systems with Ni-Catalysts for Conversion of CO2 or CO to CH4,” Journal of the American Chemical Society (2019). DOI: 10.1021/jacs.9b00937

R. M. Rajapakse, N. H. Attanayake, D. Karunathilaka, A. E. Steen, N. I. Hammer, D. R. Strongin, and D. L. Watkins, “Advances in Electro-copolymerization of NIR Emitting and Electronically Conducting Block Copolymers,” Journal of Materials Chemistry C, 7, 3168-3172 (2019). DOI:

S. Autry, J. N. Gayton, W. Meador, S. Parkin, G. Hill, N. I. Hammer, and J. H. Delcamp, “Indolizine-Cyanine Dyes: Near Infrared Emissive Cyanine Dyes with Increased Stokes Shifts,” Journal of Organic Chemistry, 84, 687-697 (2019). DOI: 10.1021/acs.joc.8b02521

Feeding and Powering the World 2019: The Next Generation

K. Martinez, J. Stash, K. R. Benson, J. J. Paul, and R. H. Schmehl, “Direct Observation of Sequential Electron and Proton Transfer in Excited-State ET/PT Reactions,” Journal of Physical Chemistry C, 123, 2728–2735 (2019). DOI: 10.1021/acs.jpcc.8b09268

P. Wang, G. Liang, C. L. Boyd, C. E. Webster, and X. Zhao, “Catalytic H2 Evolution by a Mononuclear Cobalt Complex with a Macrocyclic Pentadentate Ligand,” European Journal of Inorganic Chemistry, 2019, 2134- 2139 (2019). DOI: 10.1002/ejic.201801418

Y. O. Wong, L. A. Freeman, A. D. Agakidou, D. A. Dickie, C. E. Webster, and R. J. Gilliard, Jr., “Two Carbenes versus One in Magnesium Chemistry: Synthesis of Terminal Dihalide, Dialkyl, and Grignard Reagents,” Organometallics, 38, 688–696 (2019). DOI: 10.1021/acs.organomet.8b00866

H. Cheema and J. H. Delcamp, “The Role of Antireflective Coating CYTOP, Immersion Oil, and Sensitizer Selection in Fabricating a 2.3 V, 10% Power Conversion Efficiency SSM‐DSC Device,” Advanced Enery Materials, 9, 1900162 (2019). DOI: 10.1002/aenm.201900162

N. P. Liyanage, W. Yang, S. Guertin, S. Sinha Roy, C. A. Carpenter, R. E. Adams, R. H. Schmehl, J. H. Delcamp, and J. W. Jurss, “Photochemical CO2 reduction with mononuclear and dinuclear rhenium catalysts bearing a pendant anthracene chromophore ,” Chemical Communications, 5, 993-996 (2019). DOI: 10.1039/C8CC09155B

R. R. Rodrigues, C. M. Boudreaux, E. T. Papish, and J. H. Delcamp, “Photocatalytic Reduction of CO2 to CO and Formate: Do Reaction Conditions or Ruthenium Catalysts Control Product Selectivity?,” ACS Applied Energy Materials, 2, 37-46 (2019). DOI: 10.1021/acsaem.8b01560

Y. Wusimanjiang, J. Yadav, V. Arau, A. E. Steen, N. I. Hammer, and S. Pan, “Blue Electrogenerated Chemiluminescence from Halide Perovskite Nanocrystals,” Journal of Analysis and Testing (2019). DOI: 10.1007/s41664-018-0082-4

2018

D. A. Clayton, K. S. Brooks, and S. Pan, “A Single Molecule Surface-Enhanced Raman Spectroscopic Study of Regioregular Poly (3-Hexylthiophene-2, 5-Diyl) on Nanostructured Silver Substrate,” Frontiers in Science, Technology, Engineering, and Mathematics, 2, 92-104 (2018).

L. Chen, H. A. Dulaney, B. O. Wilkins, S. Farmer, Y. Zhang, F. R. Fronczek, and J. W. Jurss, “High-spin enforcement in first-row metal complexes of a constrained polyaromatic ligand: synthesis, structure, and properties,” New Journal of Chemistry, 42, 18667-18677 (2018). DOI: 10.1039/C8NJ02072H

Y. Ma, A. L. Highsmith, and S. Pan, “Dark Field Scattering Spectroelectrochemistry of Single Au Nanoparticles at Transparent Planar and Micro-Sized Electrodes,” ECS Transactions, 85, 1155-1162 (2018). DOI: 10.1149/08513.1155ecst

A. Yengantiwar, P. S. Shinde, S. Pan, and A. Gupta, “Delafossite CuFeO2 Photocathodes Grown by Direct Liquid Injection Chemical Vapor Deposition for Efficient Photoelectrochemical Water Reduction,” Journal of the Electrochemical Society, 165, H831-H837 (2018). DOI: 10.1149/2.0471813jes

Feeding and Powering the World 2019: The Next Generation

W. Yang, S. Sinha Roy, W. C. Pitts, R. L. Nelson, F. R. Fronczek, and J. W. Jurss, “Electrocatalytic CO2 Reduction with Cis and Trans Conformers of a Rigid Dinuclear Rhenium Complex: Comparing the Monometallic and Cooperative Bimetallic Pathways,” Inorganic Chemistry, 57, 9564–9575 (2018). DOI: 10.1021/acs.inorgchem.8b01775

Y. Ma, A. L. Highsmith, C. M. Hill, and S. Pan, “Dark-Field Scattering Spectroelectrochemistry Analysis of Hydrazine Oxidation at Au Nanoparticle-Modified Transparent Electrodes,” Journal of Physical Chemistry C, 122, 18603–18614 (2018). DOI: 10.1021/acs.jpcc.8b05112

M. Rambukwella, N. A. Sakthivel, J. H. Delcamp, Luca Sementa, A. Fortunelli, and A. Dass, “Ligand Structure Determines Nanoparticles' Atomic Structure, Metal-Ligand Interface and Properties,”Frontiers in Chemistry, 6, 330 (2018). DOI: 10.3389/fchem.2018.00330

F. Qu, K. Martinez, A. M. Arcidiacono, S. Park, M. Zeller, R. H. Schmehl, J. J. Paul, Y. Kim, and E. T. Papish, “Sterically Demanding Methoxy and Methyl Groups in Ruthenium Complexes Lead to Enhanced Quantum Yields for Blue Light Triggered Photodissociation,” Dalton Transactions, 47, 15685-91563 (2018). DOI: 10.1039/c8dt03295e

S. Autry, J. N. Gayton, R. C. Fortenberry, N. I. Hammer, and J. H. Delcamp, “Counter Anion Effect on the Photophysical Properties of Emissive Indolizine-Cyanine Dyes in Solution and Solid State,” Molecules, 23, 3051 (2018). DOI: 10.3390/molecules23123051

S. J. Cassidy, I. Brettell-Adams, L. E. McNamara, M. F. Smith, M. Bautista, H. Cao, M. Vasiliu, D. L. Gerlach, F. Qu, N. I. Hammer, D. A. Dixon, and P. A. Rupar, “Boranes with Ultra High Stokes Shifts Fluorescence,” Organometallics, 37, 3732–3741 (2018). DOI: 10.1021/acs.organomet.8b00460

S. N. Johnson, C. R. Hutchison, C. Williams, C. L. Hussey, G. S. Tschumper and N. I. Hammer, “Intermolecular interactions and vibrational perturbations within 1-ethyl-3-methlimidazolium thiocyanate / water mixtures,” Journal of Physical Chemistry C, 22, 27673–27680 (2018). (Featured on Cover) DOI: 10.1021/acs.jpcc.8b07114

A. Peddapuram, H. Cheema, L. E. McNamara, Y. Zhang, N. I. Hammer, and J. H. Delcamp, “Quinoxaline- based Dual Donor, Dual Acceptor Organic Dyes for Dye-Sensitized Solar Cells,” Applied Sciences, 8, 1421 (2018). DOI: 10.3390/app8091421

G. K. Kosgei, D. Breen, R. W. Lamb, M. Y. Livshits, L. A. Crandall, C. J. Ziegler, C. E. Webster, and J. J. Rack, “Controlling Photoisomerization Reactivity Through Single Functional Group Substitutions in Ruthenium Phosphine Sulfoxide Complexes,” Journal of the American Chemical Society, 140, 9819–9822 (2018). DOI: 10.1021/jacs.8b05957

P. Wang, G. Liang, M. R. Reddy, M. Long, K. Driskill, C. Lyons, B. Donnadieu, J. C. Bollinger, C. E. Webster, and X. Zhao, “Electronic and Steric Tuning of Catalytic H2 Evolution by Cobalt Complexes with Pentadentate Polypyridyl-Amine Ligands,” Journal of the American Chemical Society, 140, 9219–9229 (2018). DOI: 10.1021/jacs.8b05108

Feeding and Powering the World 2019: The Next Generation

H. H. C. Lakmal, J. X. Xu, X. Xu, B. Ahmed, C. Fong, D. J. Szalda, K. Ramig, A. Sygula, C. E. Webster, D. Zhang, and X. Cui, “Synthesis of C-unsubstituted 1,2-Diazetidines and their Ring-opening Reactions via Selective N-N Bond Cleavage,” Journal of Organic Chemistry, 83, 9497-9503 (2018). DOI: 10.1021/acs.joc.8b01223

J. A. Denny, R. W. Lamb, S. W. Reilly, B. Donnadieu, C. E. Webster, and T. K. Hollis, “Investigation of Metallation/Transmetallation Reactions to Synthesize a Series of CCC-NHC Co Pincer Complexes and Their X-ray Structures,” Polyhedron, 151, 568-574 (2018). DOI: 10.1016/j.poly.2018.05.040

G. Liang, T. K. Hollis, and C. E. Webster, “Computational Analysis of the Intramolecular Oxidative Amination of an Alkene Catalyzed by the Extreme π-loading N-Heterocyclic Carbene Pincer Tantalum(V) Bis(imido) Complex,” Organometallics, 37, 1671-1681 (2018). DOI: 10.1021/acs.organomet.8b00097

A. Baumann, H. Cheema, A. Sabuj, L. E. McNamara, A. Peddapuram, Y. Zhang, S. T. Nguyen, D. L. Watkins, N. I. Hammer, N. Rai and J. H. Delcamp, “Iodine Binding with Thiophene and Furan Based Dyes for DSCs,” Physical Chemistry Chemical Physics, 20, 17859-17870. DOI: 10.1039/C8CP03065K

P. S. Shinde, X. Peng, J. Wang, Y. Ma, L. McNamara, N. I. Hammer, A. Gupta, S. Pan, “Rapid Screening of Photoanode Materials using SPECM Technique and Formation of Z-scheme Solar Water Splitting System by Coupling p- and n-type Heterojunction Photoelectrodes,” ACS Applied Energy Materials, 1, 2283–2294 (2018). DOI: 10.1021/acsaem.8b00381

P. S. Shinde, P. Fontenot, J. P. Donahue, J. L. Waters, P. Kung, L. E. McNamara, N. I. Hammer, A. Gupta, and S. Pan, “Synthesis and Thin Film Coating of MoS2 from [Mo3S7(S2CNEt2)3]I for Enhanced Photoelectrochemical Performance and Stability of Cu2O Photocathode Toward Efficient Solar Water Splitting,” Journal of Materials Chemistry A, 6, 9569-9582 (2018). DOI: 10.1039/C8TA01771A

A. O. Weldeab, A. Steen, D. J. Starkenburg, J. S. D. Williams, J. Xue, N. I. Hammer, R. K. Castellano, and D. L. Watkins, “Tuning the Structural and Spectroscopic Properties of Donor-Acceptor-Donor Oligomers via Mutual X-Bonding, H-Bonding, and π-π Interactions,” Journal of Materials Chemistry C, 6, 11992-12000 (2018). DOI: 10.1039/C8TC00074C

S. Nguyen, T. Ellington, K. E. Allen, J. Gorden, A. Rheingold, G. S. Tschumper, N. I. Hammer, and D. L. Watkins, “Systematic Experimental and Computational Studies of Substitution and Hybridization in Solid- State Halogen Bonded Assemblies,” ACS Crystal Growth and Design, 18 3244-3254 (2018). DOI: 10.1021/acs.cgd.8b00398.

R. Rodrigues, H. Cheema, and J. H. Delcamp, “A High‐Voltage Molecular‐Engineered Organic Sensitizer– Iron Redox Shuttle Pair: 1.4 V DSSC and 3.3 V SSM‐DSSC Devices,” Angewandte Chemie International International Edition, 57, 5472-5476 (2018). DOI: 10.1002/anie.201712894

Y. Zhang, H. Cheema, L. McNamara, L. A. Hunt, N. I. Hammer, J. H. Delcamp, “Ullazine Donor-Pi bridge- Acceptor Organic Dyes for DSCs,” Chemistry – A European Journal, 24, 5936 (2018). DOI: 10.1002/chem.201800030

A. J. Huckaba, H. Shirley, R. W. Lamb, S. Guertin, S. Autry, H. Cheema, K. Talukdar, T. Jones, J. W. Jurss, A. Dass, N. I. Hammer, R. H. Schmehl, C. E. Webster, J. H. Delcamp, “A Mononuclear Tungsten Photocatalyst for H2 Production,” ACS Catalysis, 8, 4838 (2018). DOI: 10.1021/acscatal.7b04242

Feeding and Powering the World 2019: The Next Generation

R. E. Adams, T. A.Grusenmeyer, A. L. Griffith, and R. H. Schmehl,“ Transition metal hydride complexes as mechanistic models for proton reduction catalysis,” Coordination Chemistry Reviews, 362, 44 (2018). DOI: 10.1016/j.ccr.2018.02.014

Y. Wusimanjiang, Y. Ma, M. Lee, and S. Pan, “ Single gold nanoparticle electrode for electrogenerated chemiluminescence and dark field scattering spectroelectrochemistry,” Electrochimica Acta, 269, 291 (2018). DOI: 10.1016/j.electacta.2018.02.154

D. Burks, M. Vasiliu, D. Dixon, and E. Papish, “Thermodynamic Acidity Studies of 6,6'-dihydroxybipyridine: A Combined Experimental and Computational Approach,” The Journal of Physical Chemistry A, 122, 2221- 2231 (2018). DOI: 10.1021/acs.jpca.7b11441

C. A. Carpenter, P. Brogdon, L .E. McNamara, G. S. Tschumper, N. I. Hammer, and J. H. Delcamp, “A Robust Pyridyl-NHC Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen,” Inorganics, 6, 22 (2018). DOI: 10.3390/inorganics6010022

D. B. Burks, S. Davis, R. W. Lamb, X. Liu, R. R. Rodrigues, N. P. Liyanage, Y. Sun, C. E. Webster, J. H. Delcamp, and E. T. Papish, “Nickel(ii) pincer complexes demonstrate that the remote substituent controls catalytic carbon dioxide reduction,” Chemical Communications, 54, 3819-3822 (2018). DOI: 10.1039/c7cc09507d

T. R. Helgert, C. E. Webster, T. K. Hollis, H. U. Valle, P. Hillesheim, A. G. Oliver, “Free Methylidyne? CCC- NHC Tantalum Bis(imido) Reactivity: Protonation, Rearrangement to a Mixed Unsymmetrical CCC-N- Heterocyclic Carbene/N-Heterocyclic Dicarbene (CCC-NHC-NHDC) Pincer Tantalum Bis(imido) Complex,” Inorganica Chimica Acta, 469, 164 (2018). DOI: 10.1016/j.ica.2017.08.050

G. Liang and C. E. Webster, “The missing agostomer in the fluxionality of cyclohexenylmanganese tricarbonyl,” Journal of Organometallic Chemistry, 864, 128-135 (2018). DOI: 10.1016/j.jorganchem.2018.02.039

X. Su, K. M. McCardle, J. A. Panetier, and J. W. Jurss, “Electrocatalytic CO2 reduction with nickel complexes supported by tunable bipyridyl-N-heterocyclic carbene donors: understanding redox-active macrocycles,” Chemical Communications, 54, 3351-3354 (2018). DOI: 10.1039/c8cc00266e

2017

K. M. Dreux, L. E. McNamara, J. T. Kelly, A. M. Wright, N. I. Hammer, and G. S. Tschumper, “Probing dative and dihydrogen bonding in ammonia borane with electronic structure computations and Raman under nitrogen spectroscopy,” Journal of Physical Chemistry A, 121, 5884 (2017). (Featured on Cover) DOI: 10.1021/acs.jpca.7b03509

A. Obanda, K. Martinez, R. H. Schmehl, J. T. Mague, I. V. Rubtsov, S. N. MacMillan, K. M. Lancaster, S. 2+ 2+ Sproules, and J. P. Donahue, “Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni , Pd , Pt2+) To Afford New Heteroleptic Dithiolene Complexes,” Inorganic Chemistry, 56, 10257 (2017). DOI: 10.1021/acs.inorgchem.7b00971

Feeding and Powering the World 2019: The Next Generation

P. Fontenot, B. Wang, Y. Chen, J. P. Donahue, “Crystal Structure of Tetraisobutylthiuram Disulfide,” Acta Crystallographic Section E: Crystallographic Communications, 73, 1764 (2017). DOI: 10.1107/S2056989017015158

C. M. Boudreaux, N. P. Liyanage, H. Shirley, S. Siek, D. L. Gerlach, F. Qu, J. H. Delcamp, E. T. Papish, “Ruthenium(II) complexes of pyridinol and N-heterocyclic carbene derived pincers as robust catalysts for selective carbon dioxide reduction,” Chemical Communications, 53, 11217 (2017). DOI: 10.1039/c7cc05706g

Jue Wang and Shanlin Pan, “Electrodeposition of vertically standing Ag nanoplates and nanowires on transparent conductive electrode using porous anodic aluminum oxide membrane,” Nanotechnology, 28, 425601 (2017). DOI: 10.1088/1361-6528/aa8614

H. Cheema, R. R. Rodrigues, and J. H. Delcamp, “Sequential Series Multijunction Dye-Sensitized Solar Cells (SSM-DSCs): 4.7 Volts from a Single Illuminated Area,” Energy & Environmental Science, 10, 1764 (2017). DOI: 10.1039/C7EE01526G

A. Peddapuram, H. Cheema, R. E. Adams, R. H. Schmehl, and J. H. Delcamp, “A Stable Panchromatic Green Dual Acceptor, Dual Donor Organic Dye for Dye-Sensitized Solar Cells,” Journal of Physical Chemistry C, 121, 8770 (2017). DOI: 10.1021/acs.jpcc.7b01621

S. Pan, “Surface Enhanced Visible Light Photocurrent and Switching Behavior of Metal Oxide Semiconductor Electrodes Modified with Plasmonic Nanoparticles,” ECS Transactions, 77, 1559-1569. DOI: 10.1149/07711.1559ecst

E. Dyer, J. Hitt, Z. Shan, and S. Pan, “High Surface Area OER or HER Catalysts on Ni Foam Framework for Efficient Water Electrolysis,” ECS Transactions, 77, 61-70 (2017). DOI: 10.1149/07709.0061ecst

H. Cheema, A. Peddapuram, R. E. Adams, L. McNamara, L. Hunt, N. Le, D. L. Watkins, N. I. Hammer, R. H. Schmehl, and J. H. Delcamp, “Molecular Engineering of NIR Absorbing Thienopyrazine Double Donor Double Acceptor Organic Dyes for DSCs,” The Journal of Organic Chemistry (2017). DOI: 10.1021/acs.joc.7b01750

G. Liang and C. E. Webster, “Phosphoramidate hydrolysis catalyzed by human histidine triad nucleotide binding protein 1 (hHint1): a cluster-model DFT computational study,” Organic & Biomolecular Chemistry, 15, 8661 (2017). DOI: 10.1039/c7ob02098h

G. Liang, N. J. DeYonker, X. Zhao, and C. E. Webster, “Prediction of the Reduction Potential in Transition- Metal Containing Complexes: How Expensive? For What Accuracy?,” Journal of Computational Chemistry, 38, 2430 (2017). DOI: 10.1002/jcc.24894

W. J. Dressick, J. R. Deschamps, R. H. Schmehl, K. P. Martinez, S. A. Trammell, E. Goldberg, and D. A. Knight, “A luminescent 2,2′-bipyridyl tricarbonyl rhenium(I) complex containing a non-bridging dicyanamide ligand,” Inorganic Chemistry Communications, 83, 55 (2017). DOI: 10.1016/j.inoche.2017.06.010

Feeding and Powering the World 2019: The Next Generation

L. E. McNamara, T. A. Rill, A. J. Huckaba, V. Ganeshraj, J. Gayton, R. A. Nelson, E. A. Sharpe, A. Dass, N. I. Hammer and J. H. Delcamp, “Indolizine-Squaraines: NIR Fluorescent Materials with Molecular Engineered Stokes Shifts,” Chemistry - A European Journal, 23, 12494 (2017). DOI: 10.1002/chem.201702209

D. L. Gerlach, S. Siek, D. B. Burks, J. M. Tesh, C. R. Thompson, R. M. Vasquez, N. J. White, M. Zeller, D. B. Grotjahn, and E. T. Papish, “Ruthenium (II) and Iridium (III) Complexes of N-Heterocyclic Carbene and Pyridinol Derived Bidentate Chelates: Synthesis, Characterization, and Reactivity,” Inorganica Chimica Acta, 466, 442 (2017). DOI: 10.1016/j.ica.2017.06.063

F. Qu, S. Park, K. Martinez, J. L. Gray, F. Shazna Thowfeik, J. A. Lundeen, A. E. Kuhn, D. J. Charboneau, D. L. Gerlach, M. M. Lockart, J. A. Law, K. L. Jernigan, N. Chambers, M. Zeller, N. A. Piro, W. S. Kassel, R. H. Schmehl, J. J. Paul, E. J. Merino, Y. Kim, and E. T. Papish, “Ruthenium Complexes are pH-Activated Metallo Prodrugs (pHAMPs) with Light Triggered Selective Toxicity Towards Cancer Cells,” Inorganic Chemistry, 56, 7519–7532 (2017). DOI: 10.1021/acs.inorgchem.7b01065

K. A. N. Sachinthani, N. Kaneza, R. Kaudal, E. Manna, A. Eastman Margaret, B. Sedai, S. Pan, J. Shinar, R. Shinar, and L. Nelson Toby, “Synthesis, characterization, and electrogenerated chemiluminescence of deep blue emitting eumelanin‐inspired poly(indoylenearylene)s for polymer light emitting diodes,” Journal of Polymer Science Part A: Polymer Chemistry, 56, 125-131 (2017). DOI: 10.1002/pola.28881

C. J. Saint-Louis, R. N. Shavnore, C. D. C. McClinton, J. A. Wilson, L. L. Magill, B. M. Brown, R. W. Lamb, C. E. Webster, A. K. Schrock, and M. T. Huggins, “Synthesis, computational, and spectroscopic analysis of tunable highly fluorescent BN-1,2-azaborine derivatives containing the N-BOH moiety,” 15, 10172 (2017). DOI: 10.1039/c7ob02415k

J. D. Cope, J. A. Denny, R. W. Lamb, L. E. McNamara, N. I. Hammer, C. E. Webster, and T. K. Hollis, “Synthesis, Characterization, Photophysics and a Ligand Rearrangement of CCC-NHC Pincer Nickel Complexes: Colors, Polymorphs Emission and Raman Spectra,” Journal of Organometallic Chemistry, 845, 258–265 (2017). DOI: 10.1016/j.jorganchem.2017.05.046

Y. Zhang, S. A. Autry, L. E. McNamara, S. T. Nguyen, N. Le, P. Brogdon, D. L. Watkins, N. I. Hammer, and J. H. Delcamp“Near-Infrared Fluorescent Thienothiadiazole Dyes with Large Stokes Shifts and High Photostability,” Journal of Organic Chemistry, 82, 5597–5606 (2017). DOI: 10.1021/acs.joc.7b00422

J. D. Cope, N. P. Liyanage, P. J. Kelley, J. A. Denny, E. J. Valente, C. E. Webster, J. H. Delcamp, T. K. Hollis, “Electrocatalytic Reduction of CO2 with CCC-NHC Pincer Nickel Complexes,” Chemical Communications, 53, 9442-9445 (2017). DOI: 10.1039/C6CC06537F

H. K. Box, T. O. Howell, W. E. Kennon, G. A. Burk, H. U. Valle, T. K. Hollis, “An efficient route to unsymmetrical bis(azolium) salts: CCC-NHC pincer ligand complex precursors,” Tetrahedron, 73, 2191- 2195 (2017). DOI: 10.1016/j.tet.2017.02.020

S. Siek, D. B. Burks, D. L. Gerlach, G. Liang, J. M. Tesh, C. R. Thompson, F. Qu, J. E. Shankwitz, R. M. Vasquez, N. Chambers, G, J. Szulczewski, D. B. Grotjahn, C. E. Webster, and E. T. Papish, “Iridium and Ruthenium Complexes of NHC and Pyridinol Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal,” Organometallics, 36, 1091-1106 (2017). DOI: 10.1021/acs.organomet.6b00806

Feeding and Powering the World 2019: The Next Generation

A. Panikar, Z. Shan, S. Pan, and A. Gupta, “Photocatalytic Water Oxidation at Bismuth Vanadate Thin Film Electrodes Grown by Direct Liquid Injection Chemical Vapor Deposition Method International Journal of Hydrogen Energy,” International Journal of Hydrogen Energy, 121, 5914–5924 (2017). DOI: 10.1016/j.ijhydene.2016.12.113

A. Yengantiwar, S. Palanivel, A. Panikar, Y. Ma, S. Pan, and A. Gupta, “Direct Liquid Injection Chemical Vapor Deposition of Molybdenum Doped Bismuth Vanadate Photoelectrodes for Efficient Solar Water Splitting,” Journal of Physical Chemistry C, (2017). DOI: 10.1021/acs.jpcc.6b12710

S. Siek, N. A. Dixon, and E. T. Papish, “Electrochemical Reduction of Ttz Copper(II) Complexes in the Presence and Absence of Protons: Processes Relevant to Enzymatic Nitrite Reduction. (TtzR,R’ = tris(3-R, 5- R’-1, 2, 4-triazolyl)borate),” Inorganica Chimica Acta, 459, 80 (2017). DOI: 10.1016/j.ica.2017.01.021

H. Cheema and J. H. Delcamp, “Harnessing Photovoltage: Effects of Film Thickness, TiO2 Nanoparticle Size, MgO and Surface Capping with DSCs,” ACS Applied Materials and Interfaces,” 9, 3050–3059 (2017). DOI: 10.1021/acsami.6b11456

Kevin M. Williams, Morgan Gruner, Julia Gensheimer, Alexandra Wright, Morgan Blair, Shane A. Autry, and Nathan I. Hammer, “Partial displacement of a triamine ligand from a platinum(II) complex after reaction with N-acetylmethionine,” Inorganica Chimica Acta, 458, 163-170 (2017). DOI: 10.1016/j.ica.2017.01.010

J. L. Gray, D. L. Gerlach, and E. T. Papish, “Crystal structure of [(1,4,7,10-tetraazacyclododecane)copper(II)] perchlorate,” Acta Crystallographica Section E: Crystallographic Communications, E73, 31-34 (2017). DOI: 10.1107/S2056989016019563

Jessica K. White, Russell H. Schmehl, and Claudia Turro, “An Overview Of Photosubstitution Reactions Of Ru(II) Imine Complexes And Their Application In Photobiology And Photodynamic Therapy,” Inorganica Chimica Acta, 454, 7-20 (2017). DOI: 10.1016/j.ica.2016.06.007

J. Wang, J. Waters, P. Kung, S. Kim, J. T. Kelly, L. E. McNamara, N. I. Hammer, A. Gupta, and S. Pan, “A Facile Electrochemical Reduction Method for Improving Photocatalytic Performance of α-Fe2O3 Photoanode for Solar Water Splitting,” ACS Applied Materials and Interfaces, 9, 381-390 (2017). DOI: 10.1021/acsami.6b11057

J. Wang, A. Gupta, and S. Pan, ”A Facile Template-free Electrodeposition Method for Vertically Standing Nanorods on Conductive Substrates and Their Applications for Photoelectrochemical Catalysis,” International Journal of Hydrogen Energy, 42, 8462-8474 (2017). DOI: 10.1016/j.ijhydene.2016.10.072

2016

R. L. Letterman, N. J. DeYonker, T. J. Burkey, and C. E. Webster, “Calibrating Reaction Enthalpies: the Use of Density Functional Theory and the Correlation Consistent Composite Approach in the Design of Photochromic Materials,” Journal of Physical Chemistry A (2016). DOI: 10.1021/acs.jpca.6b09278

Feeding and Powering the World 2019: The Next Generation

C. J. Saint-Louis, L. L. Magill, J. A. Wilson, A. R. Schroeder, S. E. Harrell, N. S. Jackson, J. A. Trindell, S. Kim, A. R. Fisch, L. Munro, V. J. Catalano, C. E. Webster, P. P. Vaughan, K. S. Molek, A. K. Schrock, and M. T. Huggins, “The Synthesis and Characterization of Highly Fluorescent Polycyclic Azaborine Chromophores,” Journal of Organic Chemistry, 81, 10955-10963 (2016). DOI: 10.1021/acs.joc.6b01998

A. J. Huckaba, A. Yella, L. E. McNamara, A. E. Steen, J. S. Murphy, C. A. Carpenter, G. D. Puneky, N. I. Hammer, M. K. Nazeeruddin, M. Grätzel, and J. H. Delcamp, “Molecular Design Principles of Near-Infrared Absorbing and Emitting Indolizine Dyes,” Chemistry - A European Journal, 22, 15536-15542 (2016). DOI: 10.1002/chem.201603165

R. Adams and R. Schmehl, “Micellar Effects on Photoinduced Electron Transfer in Aqueous Solutions 2+ Revisited: Dramatic Enhancement of Cage Escape Yields in Surfactant Ru(II) Diimine Complex/[Ru(NH3)6] Systems,” Langmuir, 32, 8598-8607 (2016). DOI: 10.1021/acs.langmuir.6b02193

T. R. Helgert, X. Zhang, H. K. Box, J. A. Denny, H. U. Valle, A. G. E10029, G. Akurathi, C. E. Webster, and T. K. Hollis, “Extreme Pi-Loading as a Design Element for Accessing Imido Ligand Reactivity. A CCC-NHC Pincer Tantalum Bis(imido) Complex: Synthesis, Characterization, and Catalytic Oxidative Amination of Alkenes,” Organometallics, 35, 3452-3460 (2016). DOI: 10.1021/acs.organomet.6b00216

N. P. Liyanage, H. A. Dulaney, A. J. Huckaba, J. W. Jurss, and J. H. Delcamp, “Electrocatalytic Reduction of CO2 to CO With Re-Pyridyl- NHCs: Proton Source Influence on Rates and Product Selectivities,” Inorganic Chemistry, 55, 6085-6094 (2016). DOI: 10.1021/acs.inorgchem.6b00626

K. Bhattacharya, Q. Tejani, and S. Pan, “Construction and Characterization of p-type heterojunction CuO|CuBi2O4 photocathode electrode for photoelectrochemical reduction of water as sustainable source of energy,” Joshua, The Journal of Science and Health at The University of Alabama, 13, 17-21 (2016).

J. Hitt, D. Trotman, and S. Pan, “Synthesis of α-FeOOH and CoPi Thin Films for use as Catalysts in Electrochemical Water Oxidation and Efficiency Comparison to Known Effective Catalysts,” Joshua, The Journal of Science and Health at The University of Alabama, 13, 12-16 (2016).

P. Brogdon, L. E. McNamara, A. Peddapuram, N. I. Hammer, and J. H. Delcamp, ”Toward Tightly Bound Carboxylic Acid-Based Organic Dyes for DSCs: Relative TiO2 Binding Strengths of Benzoic Acid, Cyanoacrylic Acid, and Conjugated Double Carboxylic Acid Anchoring Dyes,” Synthetic Metals, 222, 66-75 (2016). DOI: 10.1016/j.synthmet.2016.03.031

N. Kaneza, J. Zhang, A. Panikar, Z. Shan, A. Gupta, H. Liu, M. Vasiliu, S. H. Polansky, D. A. Dixon, R. E. Adams, R. H. Schmehl, and S. Pan, “Electrochemical and Spectroscopy Studies of BODIPY-Thiophene- Triphenylamine Based Dyes for Dye-Sensitized Solar Cells,” Journal of Physical Chemistry C, 120, 9068- 9080. DOI: 10.1021/acs.jpcc.6b01611

W. D. Clark, K. N. Leigh, C. E. Webster, and T. K. Hollis, “Experimental and Computational Studies of the Mechanisms of Hydroamination/Cyclisation of Unactivated α,ω-Amino-alkenes with CCC-NHC Pincer Zr Complexes,” Australian Journal of Chemistry, 69, 573-582 (2016). DOI: 10.1071/CH15779

Feeding and Powering the World 2019: The Next Generation

H. U. Valle, G. Akurathi, J. Cho, W. D. Clark, A. Chakraborty, and T. K. Hollis, “CCC-NHC Pincer Zr Diamido Complexes: Synthesis, Characterisation, and Catalytic Activity in Hydroamination/Cyclisation of Unactivated Amino-Alkenes, -Alkynes, and Allenes,” Australian Journal of Chemistry, 69, 565-572 (2016). DOI: 10.1071/CH15795

S. W. Reilly, C. E. Webster, T. K. Hollis, and H. U. Valle, “Transmetallation from CCC-NHC Pincer Zr Complexes in the Synthesis of Air-Stable CCC-NHC Pincer Co (III) Complexes and Initial Hydroboration Trials,” Dalton Transactions, 45, 2823-2828 (2016). DOI: 10.1039/C5DT04752H

A. J. Huckaba, E. A. Sharpe, and J. H. Delcamp, “Photocatalytic Reduction of CO2 with Re-Pyridyl-NHCs,” Inorganic Chemistry, 55, 682-690 (2016). DOI: 10.1021/acs.inorgchem.5b02015

L. E. McNamara, N. Liyanage, A. Peddapuram, J. S. Murphy, J. H. Delcamp, and N. I. Hammer, “Donor- Acceptor-Donor Thienopyrazines via Pd-Catalyzed C-H Activation as NIR Fluorescent Materials,” Journal of Organic Chemistry, 81, 32-42 (2016). DOI: 10.1021/acs.joc.5b01958

2015

S. Pan, J. Liu, and C. M. Hill, “Observation of Local Redox Events at Individual Au Nanoparticles Using Electrogenerated Chemiluminescence Microscopy,” Journal of Physical Chemistry C, 119, 27095–27103 (2015). DOI: 10.1021/acs.jpcc.5b06829

Feeding and Powering the World 2019: The Next Generation

Name Role E-Mail Address School Mentor Enock Amoateng Grad [email protected] MSU Hollis Shane Autry Grad [email protected] OleMiss Hammer Meghna Bajaj UG [email protected] MSU Hollis Chance Boudreaux Grad [email protected] Alabama Papish Kyra Brakefield UG [email protected] Tulane Donahue Kice Brown UG [email protected] MSU Hollis Megan Bruneau UG [email protected] Alabama Pan Dalton Burks Grad [email protected] Alabama Papish Hammad Cheema PD [email protected] OleMiss Delcamp

Christine Curiac Grad [email protected] OleMiss Delcamp Courtney Dale UG [email protected] Alabama Papish Andrew Daniel UG [email protected] OleMiss Delcamp Sanjit Das Grad [email protected] Alabama Papish Ndaleh David Grad [email protected] OleMiss Delcamp Kelli Dawkins HS [email protected] MSU Hollis

Sriloy Dey PD [email protected] MSU Hollis Austin Dorris Grad [email protected] OleMiss Hammer Ryley Fallon HS [email protected] OleMiss Jurss Matthew Figgins UG [email protected] MSUOleMiss Webster Nathan Frey UG [email protected] MSU Webster Alison Fullilove UG [email protected] OleMiss Hammer Liping Guo Grad [email protected] Alabama Yan April Hardin Grad [email protected] OleMiss Hammer Leigh Anna Hunt Grad [email protected] OleMiss Hammer Trip Johnson UG [email protected] OleMiss Hammer Nicholas Kruse UG [email protected] OleMiss Hammer Cornell Jones UG [email protected] OleMiss Hammer Robert Lamb Grad [email protected] MSU Webster Chase Lance UG [email protected] OleMiss Jurss Nghia Le Grad [email protected] MSU Webster Qing Li UG [email protected] OleMiss Delcamp Xiao Li Grad [email protected] Alabama Pan Yanxiao Ma Grad [email protected] Alabama Pan John McDonough UG [email protected] Alabama Yan William Meador UG [email protected] OleMiss Delcamp Michael Murphy UG [email protected] Alabama Pan

Feeding and Powering the World 2019: The Next Generation

Skylar Nash UG [email protected] OleMiss Jurss Khue Nguyen UG [email protected] OleMiss Delcamp Dinesh Nugegoda Grad [email protected] OleMiss Delcamp Laura Olive UG [email protected] MSU Webster Kyle Pauly UG [email protected] OleMiss Hammer Trey Pittman UG [email protected] MSU Hollis Roberta Rodrigues Grad [email protected] OleMiss Delcamp Sayontani Roy Grad [email protected] OleMiss Jurss Sha Sahil Grad [email protected] OleMiss Jurss Emily Shrewsbury UG [email protected] Alabama Papish Kalee Sigworth UG [email protected] OleMiss Hammer Libby Sleeper UG [email protected] OleMiss Jurss Jacob Smith UG [email protected] MSU Webster Kallol Talukdar Grad [email protected] OleMiss Jurss Cameron Trussell UG [email protected] OleMiss Jurss Zane Turner Grad [email protected] OleMiss Jurss Genevieve Verville UG [email protected] OleMiss Hammer Ashley Williams Grad [email protected] OleMiss Hammer Uriel Witrago HS [email protected] OleMiss Jurss Jeetika Yadav Grad [email protected] Alabama Pan Wenzhi Yao Grad [email protected] Alabama Papish