Ann L Greenaway, Sijia Ke, Theodore Culman, Kevin R Talley, John S Mangum, Karen N Heinselman, Ryan S Kingsbury, Rebecca W Smaha, Melissa K Gish, Elisa M Miller, Kristin A Persson, John M Gregoire, Sage R Bauers, Jeffrey B Neaton, Adele C Tamboli, Andriy Zakutayev
Author Information
Ann L Greenaway: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Sijia Ke: Materials and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Theodore Culman: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States.
Kevin R Talley: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
John S Mangum: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Karen N Heinselman: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Ryan S Kingsbury: Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Rebecca W Smaha: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Melissa K Gish: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Elisa M Miller: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Kristin A Persson: Department of Materials Science and Engineering, University of California Berkeley, Berkeley, California 94720, United States. ORCID
John M Gregoire: Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California 91125, United States. ORCID
Sage R Bauers: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Jeffrey B Neaton: Materials and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Adele C Tamboli: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States.
Andriy Zakutayev: Materials Chemical and Computational Science Directorate, National Renewable Energy Laboratory, Golden, Colorado 80401, United States. ORCID
Photoelectrochemical fuel generation is a promising route to sustainable liquid fuels produced from water and captured carbon dioxide with sunlight as the energy input. Development of these technologies requires photoelectrode materials that are both photocatalytically active and operationally stable in harsh oxidative and/or reductive electrochemical environments. Such photocatalysts can be discovered based on co-design principles, wherein design for stability is based on the propensity for the photocatalyst to self-passivate under operating conditions and design for photoactivity is based on the ability to integrate the photocatalyst with established semiconductor substrates. Here, we report on the synthesis and characterization of Zinc Titanium Nitride (ZnTiN) that follows these design rules by having a wurtzite-derived crystal structure and showing self-passivating surface oxides created by electrochemical polarization. The sputtered ZnTiN thin films have optical absorption onsets below 2 eV and n-type electrical conduction of 3 S/cm. The band gap of this material is reduced from the 3.36 eV theoretical value by cation-site disorder, and the impact of cation antisites on the band structure of ZnTiN is explored using density functional theory. Under electrochemical polarization, the ZnTiN surfaces have TiO- or ZnO-like character, consistent with Materials Project Pourbaix calculations predicting the formation of stable solid phases under near-neutral pH. These results show that ZnTiN is a promising candidate for photoelectrochemical liquid fuel generation and demonstrate a new materials design approach to other photoelectrodes with self-passivating native operational surface chemistry.
