Proceedings of the Solar Photo Thirty-Fourth Chemistry DOE Solar Photochemistry Research Conference Catalysis acceptors active site H2S S Mo H2 2S S antennae The Westin Annapolis, Annapolis, Maryland, June 3-6, 2012 Sponsored by: Chemical Sciences, Geosciences, and Biosciences Division U.S. Department of Energy Cover Graphics The cover figures are taken from the abstracts of this meeting. The symbol for catalysis (upper right corner) is a 147-atom Au nanoparticle decorated with Pt (Crooks et al., p. 88). In the middle section, from the left, the first figure is a representation of detection of single sulfur atoms at the edge of industry style MoS2 crystals (Kisielowski et al., p. 187). The second figure shows how 13C-labeled single wall carbon nanotubes modify vibrational energies (Blackburn et al., p. 116). The figure on the right is an idealized heterometallic modular system for water oxidation (Verani et al., p. 53). The bottom figure shows the structure of a new family redox shuttle for dye-sensitized solar cells (Hupp, p. 143). Program and Abstracts 34th Solar Photochemistry Program Research Meeting The Westin Annapolis Annapolis, Maryland June 3–6, 2012 Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences Office of Science U.S. Department of Energy This document was produced under contract number DE-AC05-06OR23100 between the U.S. Department of Energy and Oak Ridge Associated Universities. The research grants and contracts described in this document are supported by the U.S. DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division. Foreword The 34th Department of Energy Solar Photochemistry Research Meeting, sponsored by the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, is being held June 3–6, 2010, at the Westin Annapolis Hotel in Annapolis, Maryland. These proceedings include the meeting agenda, abstracts of the formal presentations and posters of the conference, and an address list for the participants. This Conference is composed of the grantees who do research in solar photochemical energy conversion with the support of the Chemical Sciences, Geosciences, and Biosciences Division. It will feature presentations on photocatalysis, spectroscopy at nanoparticles, dye sensitized solids, novel molecular structures and charge transfer in organic molecular systems. These Program Meetings provide a unique environment for the initiation of collaborations between researchers as well as exchanges of new concepts and ideas. This synergistic element of research within the program is one of its major strengths and promotes the excellence in research that has sustained this program over the years. The program is pleased to have Professor Richard Schrock of the Massachusetts Institute of Technology as a special guest lecturer for this conference. He will give a presentation on the history and challenges of the reduction of dinitrogen to ammonia and will illustrate this lecture with a discussion of his own research on this topic. The mechanistic complexity of this reaction will be familiar to many in the Solar Photochemistry Program who have concerned themselves over the past years with the reduction of water and CO2 to produce fuels. Perhaps it is the case that a means for a photoinduced reduction of dinitrogen to ammonia could be found that would not require the hydrogen gas that is essential for the commercial Haber-Bosch process. The Solar Photochemistry Research Conference will also have as its guests this year a number of researchers from the Catalysis Program, which is a sibling program in the Chemical Sciences, Geosciences, and Biosciences Division. They will be providing the attendees of this meeting with lectures and posters on their approaches to the study of catalysis at surfaces, which is a research area of recent focus in the Solar Photochemistry Program. I would like to express my appreciation to Dr. Amy Ryan of the Pacific Northwest National Laboratory, to Diane Marceau of the Division of Chemical Sciences and to Tim Ledford and Connie Lansdon of the Oak Ridge Institute for Science and Education for their assistance with the preparation of this volume and the coordination of the logistics of this meeting. I must also thank all of the researchers whose dedication to scientific inquiry and enduring interest in research on solar energy transduction have enabled these advances in solar photoconversion and made this meeting possible. Mark T. Spitler Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences i Solar Photochemistry Research Conference Overview Time Sunday, June 3 Monday, June 4 Tuesday, June 5 Wednesday, June 6 Time 7:00 AM 7:00 AM 7:15 AM BREAKFAST 7:15 AM 7:30 AM 7:00 - 8:00 7:30 AM BREAKFAST BREAKFAST 7:45 AM 7:45 AM 7:30 - 8:15 7:30 - 8:15 8:00 AM 8:00 AM 8:15 AM GUEST SPEAKER Introduction 8:15 AM Opening Remarks 8:30 AM 8:30 AM 8:45 AM Session VIII 8:45 AM 9:00 AM Session II Session V 9:00 AM 9:15 AM Surface Structure 9:15 AM 9:30 AM Sensitized Complex Catalysis and Analysis 9:30 AM 9:45 AM Semiconductors I 9:45 AM 10:00 AM BREAK BREAK BREAK 10:00 AM 10:15 AM 10:00 - 10:30 10:00 - 10:30 10:00 - 10:30 10:15 AM 10:30 AM 10:30 AM 10:45 AM Session III Session IX 10:45 AM 11:00 AM Session VI 11:00 AM 11:15 AM Sensitized Catalysis at Surfaces 11:15 AM 11:30 AM Semiconductors II Photochemical I 11:30 AM 11:45 AM Water Splitting 11:45 AM 12:00 PM 12:00 PM 12:15 PM LUNCH 12:15 PM 12:30 PM 12:00 - 1:00 LUNCH 12:30 PM 12:45 PM LUNCH 12:00 - 1:30 12:45 PM 1:00 PM 12:30 - 1:30 1:00 PM 1:15 PM 1:15 PM 1:30 PM 1:30 PM 1:45 PM Free time Session X 1:45 PM 2:00 PM 1:00 - 5:00 2:00 PM 2:15 PM Free time Catalysis at Surfaces 2:15 PM 2:30 PM 1:30 - 4:15 II 2:30 PM 2:45 PM 2:45 PM 3:00 PM BREAK 3:00 PM 3:15 PM 3:00 - 3:30 3:15 PM 3:30 PM 3:30 PM 3:45 PM Registration 3:45 PM 4:00 PM 3:00 - 6:00 Session XI 4:00 PM 4:15 PM 4:15 PM 4:30 PM Catalysis at Surfaces 4:30 PM 4:45 PM III 4:45 PM 5:00 PM Session VII 5:00 PM 5:15 PM Session IV 5:15 PM 5:30 PM No-Host Reception Systems for Electron Transfer 5:30 PM 5:45 PM 5:30 - 6:30 Photoconversion 5:45 PM 6:00 PM at the bar DINNER BREAK 6:00 PM Free time 6:15 PM (on your own) 6:15 PM SOCIAL HOUR 6:30 PM 5:30 - 7:30 6:30 PM 6:15 - 7:00 6:45 PM DINNER 6:45 PM 7:00 PM DINNER 6:30 - 7:30 7:00 PM 7:15 PM 6:30 - 7:45 DINNER 7:15 PM 7:30 PM 7:00 - 8:00 7:30 PM 7:45 PM Welcome 7:45 PM 8:00 PM POSTERS POSTERS 8:00 PM 8:15 PM Session I odd numbers (1-59) POSTERS Catalysis at Surfaces 8:15 PM 8:30 PM Photocatalysis even numbers (2-60) (C1 - C18) 8:30 PM 8:45 PM 8:45 PM 9:00 PM 7:30 - 9:30 9:00 PM 9:15 PM Reception Continues 7:30 - 10:00 8:00 - 9:45 9:15 PM 9:30 PM 9:00 - 10:00 9:30 PM 9:45 PM at the bar Program Manager's Closing Remarks 9:45 PM & Announcements 10:00 PM Comments 10:00 PM ii Table of Contents iii iv TABLE OF CONTENTS Foreword ......................................................................................................................................... i Overview ........................................................................................................................................ ii Abstracts .........................................................................................................................................v Program ..................................................................................................................................... xvii Oral Presentations Session I – Photocatalysis ..............................................................................................................1 Nanostructured Photocatalytic Water Splitting Systems Y. Zhao, E.A. Hernandez-Pagan, N. M. Vargas-Barbosa, J. R. Swierk, S. A. Lee, W. J. Youngblood, N. McCool, L. Blasdel, and Thomas E. Mallouk The Pennsylvania State University Jackson D. Megiatto, Jr., Ana L. Moore, Thomas A. Moore, and Devens Gust Arizona State University ..................................................................................................................3 Effect of Composition and Structure on the Performance of Photocatalytic Materials C. Buddie Mullins and Allen J. Bard, The University of Texas at Austin ...................................6 Session II – Sensitized Semiconductors I .....................................................................................9 Molecular Design of Zinc Oxide Nanoparticle-Dye Dyads and Triads Wayne L. Gladfelter, David A. Blank, and Kent R. Mann; The University of Minnesota ......11 Tuning the Ultrafast Excited-State Dynamics of First-Row Transition-Metal–Based Chromophores A. M. Brown, L. L. Jamula, and James K. McCusker; Michigan State University ....................14 Session III – Sensitized Semiconductors II ................................................................................17 Surface Chemistry for Photoelectrochemical Charge Transfer at Metal Oxide Interfaces Robert J. Hamers, University of Wisconsin-Madison.................................................................19 Quantum Dot Sensitization of Single Crystal Semiconductors Justin B. Sambur1, Dae Jin Choi1, Shannon Riha2, Thomas Novet3, and B. A. Parkinson1 1University of Wyoming, 2Colorado State University, 3Voxtel Inc...............................................22 v Single-Particle Current Blinking in Semiconductor Quantum Dots Klara Maturova and Jao van de Lagemaat, National Renewable Energy Laboratory ................25 Session IV – Systems for Photoconversion