Thermochemical Water Splitting Cycle
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Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production
University of Central Florida STARS UCF Patents Technology Transfer 4-8-2014 Solar metal sulfate-ammonia based thermochemical water splitting cycle for hydrogen production. Cunping Huang University of Central Florida Nazim Muradov University of Central Florida Ali Raissi University of Central Florida Find similar works at: https://stars.library.ucf.edu/patents University of Central Florida Libraries http://library.ucf.edu This Patent is brought to you for free and open access by the Technology Transfer at STARS. It has been accepted for inclusion in UCF Patents by an authorized administrator of STARS. For more information, please contact [email protected]. Recommended Citation Huang, Cunping; Muradov, Nazim; and Raissi, Ali, "Solar metal sulfate-ammonia based thermochemical water splitting cycle for hydrogen production." (2014). UCF Patents. 525. https://stars.library.ucf.edu/patents/525 I lllll llllllll Ill lllll lllll lllll lllll lllll 111111111111111111111111111111111 US008691068B 1 c12) United States Patent (10) Patent No.: US 8,691,068 Bl Huang et al. (45) Date of Patent: *Apr. 8, 2014 (54) SOLAR METAL SULFATE-AMMONIA BASED 3,882,222 A * 5/1975 Deschamps et al. .......... 423/575 THERMOCHEMICAL WATER SPLITTING (Continued) CYCLE FOR HYDROGEN PRODUCTION (75) Inventors: Cunping Huang, Cocoa, FL (US); Ali FOREIGN PATENT DOCUMENTS T-Raissi, Melbourne, FL (US); Nazim GB 1486140 * 9/1977 Muradov, Melbourne, FL (US) OTHER PUBLICATIONS (73) Assignee: University of Central Florida Research Foundation, Inc., Orlando, FL (US) Licht, Solar Water Splitting to Generate Hydrogen Fuel: Photothermal Electrochemical Analysis, Journal of Physical Chem ( *) Notice: Subject to any disclaimer, the term ofthis istry B, 2003, vol. 107, pp. -
Photoelectrochemical Water Splitting: a Road from Stable Metal Oxides to Protected Thin Film Solar Cells
Journal of Materials Chemistry A View Article Online REVIEW View Journal | View Issue Photoelectrochemical water splitting: a road from stable metal oxides to protected thin film solar cells Cite this: J. Mater. Chem. A, 2020, 8, 10625 Carles Ros, *a Teresa Andreu ab and Joan R. Morante ab Photoelectrochemical (PEC) water splitting has attracted great attention during past decades thanks to the possibility to reduce the production costs of hydrogen or other solar fuels, by doing so in a single step and powered by the largest source of renewable energy: the sun. Despite significant efforts to date, the productivities of stable semiconductor materials in contact with the electrolyte are limited, pushing a growing scientific community towards more complex photoelectrode structures. During the last decade, several groups have focused on the strategy of incorporating state of the art photovoltaic absorber materials (such as silicon, III–V compounds and chalcogenide-based thin films). The stability of these devices in harsh acidic or alkaline electrolytes has become a key issue, pushing transparent, conductive and protective layer research. The present review offers a detailed analysis of PEC devices from metal oxide electrodes forming a semiconductor–liquid junction to protected and catalyst- Received 9th March 2020 decorated third generation solar cells adapted into photoelectrodes. It consists of a complete overview Accepted 7th May 2020 of PEC systems, from nanoscale design to full device scheme, with a special focus on disruptive DOI: 10.1039/d0ta02755c advances enhancing efficiency and stability. Fundamental concepts, fabrication techniques and cell rsc.li/materials-a schemes are also discussed, and perspectives and challenges for future research are pointed out. -
Hydrogen Production by Direct Contact Pyrolysis
HYDROGEN CYCLE EMPLOYING Thermochemical Considerations for the UT-3 Cycle CALCIUM-BROMINE AND ELECTROLYSIS The significant aspects of the thermodynamic operation of the Richard D. Doctor,1 Christopher L. Marshall,2 UT-3 cycle can be discussed with reasonable assurance. The and David C. Wade3 developers of the UT-3 process have observed that in this series of 4 reactions, the “…hydrolysis of CaBr2 is the slowest reaction.” 1Energy Systems Division 2Chemical Technology Division [1] Water splitting with HBr formation (730ºC; solid-gas; 3 Reactor Analysis and Engineering Division UGT = +50.34 kcal/gm-mole): Argonne National Laboratory 9700 South Cass Ave. CaBr2 + H2O JCaO + 2HBr [Eqn. 1] Argonne, IL 60439 Hence, there is the greatest uncertainty about the practicality of this Introduction cycle because of this reaction. The Secure Transportable Autonomous Reactor (STAR) project is [2] Oxygen formation occurs in an exothermic reaction (550ºC; part of the U.S. Department of Energy’s (DOE’s) Nuclear Energy solid-gas; UGT = -18.56 kcal/gm-mole): Research Initiative (NERI) to develop Generation IV nuclear reactors that will supply high-temperature heat at over 800ºC. The CaO + Br2 JCaBr2 + 0.5O2 [Eqn. 2] NERI project goal is to develop an economical, proliferation- In reviewing this system of reactions, there is a difficulty inherent resistant, sustainable, nuclear-based energy supply system based on in the first and second stages [Eqns. 1 and 2]. This difficulty is a modular-sized fast reactor that is passively safe and cooled with linked to the significant physical change in dimensions as the heavy liquid metal. STAR consists of: calcium cycles between bromide and oxide. -
Low-Temperature, Manganese Oxide-Based, Thermochemical Water Splitting Cycle
Low-temperature, manganese oxide-based, thermochemical water splitting cycle Bingjun Xu, Yashodhan Bhawe, and Mark E. Davis1 Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 Contributed by Mark E. Davis, April 17, 2012 (sent for review April 5, 2012) Thermochemical cycles that split water into stoichiometric amounts advantage of both the low-temperature multistep and high-tem- of hydrogen and oxygen below 1,000 °C, and do not involve toxic perature two-step cycles. Here, we show that more than two or corrosive intermediates, are highly desirable because they can reactions will be necessary to perform themochemical water split- convert heat into chemical energy in the form of hydrogen. We ting below 1,000 °C, and then introduce a new thermochemical report a manganese-based thermochemical cycle with a highest water splitting cycle that involves non-corrosive solids that can operating temperature of 850 °C that is completely recyclable and operate with a maximum temperature of 850 °C. does not involve toxic or corrosive components. The thermochemi- cal cycle utilizes redox reactions of Mn(II)/Mn(III) oxides. The shut- Results and Discussion tling of Naþ into and out of the manganese oxides in the hydrogen Thermodynamic Analysis of Two-Step Thermochemical Cycles Shows and oxygen evolution steps, respectively, provides the key thermo- Temperatures Above 1,000 °C will be Necessary. Consider a thermo- dynamic driving forces and allows for the cycle to be closed at tem- chemical cycle with the following two steps: (i) oxidation of a peratures below 1,000 °C. The production of hydrogen and oxygen metal or metal oxide, referred to as Red, by water to its oxidized is fully reproducible for at least five cycles. -
Solar Thermochemical Hydrogen Production Research (STCH)
SANDIA REPORT SAND2011-3622 Unlimited Release Printed May 2011 Solar Thermochemical Hydrogen Production Research (STCH) Thermochemical Cycle Selection and Investment Priority Robert Perret Prepared by Sandia National Laboratories Albuquerque, New Mexico 87185 and Livermore, California 94550 Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. Approved for public release; further dissemination unlimited. Issued by Sandia National Laboratories, operated for the United States Department of Energy by Sandia Corporation. NOTICE: This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government, nor any agency thereof, nor any of their employees, nor any of their contractors, subcontractors, or their employees, make any warranty, express or implied, or assume any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represent that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government, any agency thereof, or any of their contractors or subcontractors. The views and opinions expressed herein do not necessarily state or reflect those of the United States Government, any agency thereof, or any of their contractors. Printed in the United States of America. This report has been reproduced directly from the best available copy. -
Artificial Photosynthesis Challenges: Water Splitting at Nanostructured Interfaces
Artificial Photosynthesis Challenges: Water Splitting at Nanostructured Interfaces Marcella Bonchio a ITM-CNR, University of Padova, Department of Chemical Sciences, via Marzolo 1, Padova I- 35131, Italy [email protected] Solar-powered water oxidation can be exploited for hydrogen generation by direct photocatalytic water splitting. A recent breakthrough in the field of artificial photosynthesis is the discovery of innovative oxygen evolving catalysts taken from the pool of the nano-sized, water soluble, molecular metal oxides, the so-called polyoxometalates (POMs). These catalysts provide a unique mimicry of the oxygen evolving centre in photosynthetic II enzyme (PSII), sharing a common functional-motif, i.e., a redox-active tetranuclear {M4(m-O)4} core, and effecting H2O oxidation to IV O2 with unprecedented efficiency. In this scenario, the tetra-ruthenium based POM [Ru 4(m- 10- OH)2(m-O)4(H2O)4(g-SiW10O36)2] , Ru4(SiW10)2, displays fast kinetics, exceptionally light-driven performance and electrocatalytic activity powered by carbon nanotubes.1-2 Research in the field of artificial photosynthesis for the conversion of water to fuel has recently come to the awakening turning-point that a key issue is the design of efficient catalytic routines that can operate with energy and rates commensurate with the solar flux at ground level. A factual solution to this need implies the mastering of the electron transfer distance, junctions and potential gradients at the molecular level and within a nano-structured environment. Our vision points to a careful choice/design of the nano-structured support, and to a precise positioning of the catalytic domain on such templates, by tailored synthetic protocols. -
Appendix a Rate of Entropy Production and Kinetic Implications
Appendix A Rate of Entropy Production and Kinetic Implications According to the second law of thermodynamics, the entropy of an isolated system can never decrease on a macroscopic scale; it must remain constant when equilib- rium is achieved or increase due to spontaneous processes within the system. The ramifications of entropy production constitute the subject of irreversible thermody- namics. A number of interesting kinetic relations, which are beyond the domain of classical thermodynamics, can be derived by considering the rate of entropy pro- duction in an isolated system. The rate and mechanism of evolution of a system is often of major or of even greater interest in many problems than its equilibrium state, especially in the study of natural processes. The purpose of this Appendix is to develop some of the kinetic relations relating to chemical reaction, diffusion and heat conduction from consideration of the entropy production due to spontaneous processes in an isolated system. A.1 Rate of Entropy Production: Conjugate Flux and Force in Irreversible Processes In order to formally treat an irreversible process within the framework of thermo- dynamics, it is important to identify the force that is conjugate to the observed flux. To this end, let us start with the question: what is the force that drives heat flux by conduction (or heat diffusion) along a temperature gradient? The intuitive answer is: temperature gradient. But the answer is not entirely correct. To find out the exact force that drives diffusive heat flux, let us consider an isolated composite system that is divided into two subsystems, I and II, by a rigid diathermal wall, the subsystems being maintained at different but uniform temperatures of TI and TII, respectively. -
Metal Oxides Applied to Thermochemical Water-Splitting for Hydrogen Production Using Concentrated Solar Energy
chemengineering Review Metal Oxides Applied to Thermochemical Water-Splitting for Hydrogen Production Using Concentrated Solar Energy Stéphane Abanades Processes, Materials, and Solar Energy Laboratory, PROMES-CNRS, 7 Rue du Four Solaire, 66120 Font Romeu, France; [email protected]; Tel.: +33-0468307730 Received: 17 May 2019; Accepted: 2 July 2019; Published: 4 July 2019 Abstract: Solar thermochemical processes have the potential to efficiently convert high-temperature solar heat into storable and transportable chemical fuels such as hydrogen. In such processes, the thermal energy required for the endothermic reaction is supplied by concentrated solar energy and the hydrogen production routes differ as a function of the feedstock resource. While hydrogen production should still rely on carbonaceous feedstocks in a transition period, thermochemical water-splitting using metal oxide redox reactions is considered to date as one of the most attractive methods in the long-term to produce renewable H2 for direct use in fuel cells or further conversion to synthetic liquid hydrocarbon fuels. The two-step redox cycles generally consist of the endothermic solar thermal reduction of a metal oxide releasing oxygen with concentrated solar energy used as the high-temperature heat source for providing reaction enthalpy; and the exothermic oxidation of the reduced oxide with H2O to generate H2. This approach requires the development of redox-active and thermally-stable oxide materials able to split water with both high fuel productivities and chemical conversion rates. The main relevant two-step metal oxide systems are commonly based on volatile (ZnO/Zn, SnO2/SnO) and non-volatile redox pairs (Fe3O4/FeO, ferrites, CeO2/CeO2 δ, perovskites). -
1 Progress in Thermochemical Water Splitting with the Cu-Cl Cycle For
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Memorial University Research Repository Progress in Thermochemical Water Splitting with the Cu-Cl Cycle for Hydrogen Production G. F. Naterer1*, S. Suppiah2, M. A. Rosen3, K. Gabriel4, I. Dincer5, O. Jianu6, Z. Wang7, E. B. Easton8, B. M. Ikeda9, G. Rizvi10, I. Pioro11, K. Pope12, J. Mostaghimi13, S. Lvov14 1, 12 Memorial University of Newfoundland, St. John’s, Newfoundland, Canada 2 Canadian Nuclear Laboratories, Chalk River, Ontario, Canada 3-6, 8-11 University of Ontario Institute of Technology (UOIT), Oshawa, Ontario, Canada 7 Xiamen University, Xiamen City, Fujian Province, China 13 University of Toronto, Toronto, Ontario, Canada 14 Pennsylvania State University, University Park, Pennsylvania, U.S. Abstract This paper presents recent advances by an international team of five countries – Canada, U.S., China, Slovenia and Romania – on the development and scale-up of the copper chlorine (Cu-Cl) cycle for thermochemical hydrogen production using nuclear or solar energy. Electrochemical cell analysis and membrane characterization for the CuCl/HCl electrolysis process are presented. Constituent solubility in the ternary CuCl/HCl/H2O system and XRD measurements are reported in regards to the CuCl2 crystallization process. Materials corrosion in high temperature copper chloride salts and performance of coatings of reactor surface alloys are examined. Finally, system integration is examined, with respect to scale-up of unit operations, cascaded heat pumps for heat upgrading, and linkage of heat exchangers with solar and nuclear plants. 1* Corresponding Author: Professor and Dean, Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. -
Hydrogen Production by Photoprocesses
SERifTP• -230:3418 UC Category: 241 DE88001198 Hydrogen Production by Photoprocesses Stanley R. Bull October 1988 Prepared for the International Renewable Energy Conference Honolulu, Hawaii September 19-23, 1988 Prepared under Task No. 1 050.2300 Solar Energy Research Institute A Division of Midwest Research Institute 1617 Cole Boulevard Golden, Colorado 80401-3393 Prepared for the U.S. Department of Energy Contract No. DE-AC02-83CH1 0093 NOTICE This report was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, com pleteness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily con stitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or any agency thereof. Printed in the United States of America Available from: National Technical Information Service U.S. Department of Commerce 5285 Port Royal Road Springfield, VA 22161 Price: Microfiche A01 Printed Copy A02 Codes are used for pricing all publications. The code is determined by the number of pages in the publication. Information pertaining to the pricing codes can be found in the current issue of the following publications which are generally available in most libraries: Energy Research Abstracts (ERA); Govern ment ReportsAnnouncements and Index ( GRA and I); Scientific and Technical Abstract Reports(STAR); and publication NTIS-PR-360 available from NTIS at the above address. -
H2O(G)⇔ H2 + 1 2 Because of the Small Equilibrium Constant of This
HYDROGEN PRODUCTION BY HIGH-TEMPERATURE WATER SPLITTING USING MIXED OXYGEN ION-ELECTRON CONDUCTING MEMBRANES T. H. Lee, S. Wang, S. E. Dorris, and U. Balachandran Energy Technology Division Argonne National Laboratory Argonne, IL 60439, USA ABSTRACT Hydrogen production from water splitting at high temperatures has been studied with novel mixed oxygen ion-electron conducting cermet membranes. Hydrogen production rates were investigated as a function of temperature, water partial pressure, membrane thickness, and oxygen chemical potential gradient across the membranes. The hydrogen production rate increased with both increasing moisture concentration and oxygen chemical potential gradient across the membranes. A maximum hydrogen production rate of 4.4 cm3/min-cm2 (STP) was obtained with a 0.10-mm-thick membrane at 900°C in a gas containing 50 vol.% water vapor in the sweep side. Hydrogen production rate also increased with decreasing membrane thickness, but surface kinetics play an important role as membrane thickness decreases. INTRODUCTION Water dissociates into oxygen and hydrogen at high temperatures, and the dissociation increases with increasing temperature: ⇔ + 1 H2O(g ) H2 O2 . 2 Because of the small equilibrium constant of this reaction, the concentrations of generated hydrogen and oxygen are very low even at relatively high temperatures, i.e., 0.1 and 0.042% for hydrogen and oxygen, respectively, at 1600°C (1). However, significant amounts of hydrogen or oxygen could be generated at moderate temperatures if the equilibrium were shifted toward dissociation by removing either oxygen or hydrogen using a mixed-conducting membrane. While hydrogen can also be produced by high-temperature steam electrolysis, the use of mixed-conducting membranes offers the advantage of requiring no electric power or electrical circuitry. -
Thermochemical Energy Storage by Water-Splitting Via Redox Reaction of Alkali Metals
Available online at www.sciencedirect.com ScienceDirect Energy Procedia 49 ( 2014 ) 927 – 934 SolarPACES 2013 Thermochemical energy storage by water-splitting via redox reaction of alkali metals H. Miyaokaa,*, T. Ichikawab, Y. Kojimab aInstitute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8530, Japan bInstitute for Advanced Materials Research, Hiroshima University1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8530, Japan Abstract The reaction cycles for water-splitting based on redox reactions of alkali metals are composed of four reactions, which are hydrogen generation by solid-liquid reaction, metal separation by thermolysis, oxygen generation by hydrolysis, and phase transition of the metal. Although all the cycles theoretically require more than 1000 qC in thermodynamic equilibrium condition, the reaction temperature are reduced to below 800 qCn− by no equilibrium techniques using phase transition of metal vapor. In this work, thermodynamic analyses are performed by using the parameters such as operating temperature and partial pressures of the products obtained by the experiments to determine that the alkali metal redox cycles are potential hydrogen production technique as thermochemical energy storage. © 2013 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (©http://creativecommons.org/licenses/by-nc-nd/3.0/ 2013 The Authors. Published by Elsevier Ltd.). Selection and and peer peer review review by by the the scientific scientific conference conference committee committee of SolarPACES of SolarPACES 2013 under 2013 responsibility under responsibility of PSE AG. of PSE AG. Final manuscript published as received without editorial corrections.