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Understanding Water Splitting on Model Mixed Metal Oxide Photocatalysts


EMSL Project ID
48287

Abstract

There is a need for new fundamental insights into photocatalytic water splitting particularly how to design catalyst systems that extend the catalytic and photocatalytic functionalities of simple materials (like TiO2) through the use of co-catalysts, dopants (to increase photoabsorptivity), promoters (to increase chemical activity) and tandem systems. RuO2 has been widely used as a co-catalysis supported on TiO2 to promote both water photoreduction and photooxidation. However, the fundamental science of how RuO2 functions as a cocatalyst in these water splitting reactions is not well-understood. It is generally believed that RuO2 does not promote optical absorption or extend the absorptivity of the photocatalyst into previously inaccessible spectral regions, but instead that RuO2 as co-catalyst promotes thermal reactions that do not readily occur on the photocatalyst itself. Nevertheless, the role of RuO2 as a co-catalyst in charge separation and trapping has not been well explored. We propose examining the thermal and photochemical properties of RuO2, as a co-catalyst with TiO2, for water splitting (to H2 and/or O2), as well as the importance or RuO2 as a co-catalyst in H2 (and O2) utilization reactions. In particular, we will explore the photochemistry on supported RiO2 clusters grown on TiO3(110) and extend such studies to model high surface area nanoporous RuO2, TiO2 and mixed RuO2-TiO2 systems. We will employ a variety of state-of-the-art surface science approaches (e.g., STM, TPD, vibrational spectroscopies, electron spectroscopies, etc.) to examine the mechanisms, energetics and surface site dependences for water splitting. The role of RuO2 as a photocatalyst and co-photocatalyst will also be explored using the probe reactions (e.g., O2 photodesorption and photodissociation, trimethyl acetate photodecomposition and methyl radical evolving processes). This research effort will provide deeper insight into not only chemistry and photochemistry of water splitting but also into relationships between catalysts and co-catalysts.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2014-10-01
End Date
2016-09-30
Status
Closed

Team

Principal Investigator

Michael Henderson
Institution
Pacific Northwest National Laboratory

Co-Investigator(s)

Gregory Herman
Institution
Oregon State University

Team Members

Manh Thuong Nguyen
Institution
Pacific Northwest National Laboratory

Congqiao Xu
Institution
Tsinghua University

Martin McBriarty
Institution
Pacific Northwest National Laboratory

Malsoon Lee
Institution
Pacific Northwest National Laboratory

Yanggang Wang
Institution
Pacific Northwest National Laboratory

Zongtang Fang
Institution
Idaho National Laboratory

Roger Rousseau
Institution
Pacific Northwest National Laboratory

James McKinley
Institution
Pacific Northwest National Laboratory

Nathaniel Deskins
Institution
Worcester Polytechnic Institute

Igor Lyubinetsky
Institution
Pacific Northwest National Laboratory

Vassiliki-Alexandra Glezakou
Institution
Pacific Northwest National Laboratory

Gregory Kimmel
Institution
Pacific Northwest National Laboratory

Janos Szanyi
Institution
Pacific Northwest National Laboratory

Zdenek Dohnalek
Institution
Pacific Northwest National Laboratory

David Dixon
Institution
University of Alabama

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