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Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications

Greenaway, Ann L. and Ke, Sijia and Culman, Theodore and Talley, Kevin R. and Mangum, John S. and Heinselman, Karen N. and Kingsbury, Ryan S. and Smaha, Rebecca W. and Gish, Melissa K. and Miller, Elisa M. and Persson, Kristin A. and Gregoire, John M. and Bauers, Sage R. and Neaton, Jeffrey B. and Tamboli, Adele C. and Zakutayev, Andriy (2022) Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications. Journal of the American Chemical Society, 144 (30). pp. 13673-13687. ISSN 0002-7863. PMCID PMC9354241. doi:10.1021/jacs.2c04241.

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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 (ZnTiN₂) that follows these design rules by having a wurtzite-derived crystal structure and showing self-passivating surface oxides created by electrochemical polarization. The sputtered ZnTiN₂ 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 ZnTiN₂ is explored using density functional theory. Under electrochemical polarization, the ZnTiN₂ surfaces have TiO₂- 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 ZnTiN₂ 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.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper CentralArticle
Greenaway, Ann L.0000-0001-6681-9965
Talley, Kevin R.0000-0003-4575-4140
Mangum, John S.0000-0002-5926-7565
Heinselman, Karen N.0000-0003-0287-3019
Smaha, Rebecca W.0000-0002-8349-2615
Gish, Melissa K.0000-0002-9886-3626
Miller, Elisa M.0000-0002-7648-5433
Persson, Kristin A.0000-0003-2495-5509
Gregoire, John M.0000-0002-2863-5265
Bauers, Sage R.0000-0002-6505-5016
Neaton, Jeffrey B.0000-0001-7585-6135
Tamboli, Adele C.0000-0003-2839-9634
Zakutayev, Andriy0000-0002-3054-5525
Alternate Title:Co-design of zinc titanium nitride semiconductor towards durable photoelectrochemical applications
Additional Information:© 2022 The Authors. Published by American Chemical Society. Attribution 4.0 International (CC BY 4.0). Received 22 April 2022. Published online 20 July 2022. This work was performed in part at the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. This material is primarily based upon work performed by the Liquid Sunlight Alliance, a DOE Energy Innovation Hub, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0021266. T.C. acknowledges support from DOE Office of Science, Office of Workforce Development for Teachers and Scientists under the Science Undergraduate Laboratory Internship program (optical and electrical characterization). R.W.S. acknowledges support from the Director’s Fellowship within NREL’s Laboratory Directed Research and Development program (oriented material growth). The development and analysis of the hybrid Pourbaix diagrams was supported by the Materials Project, which is funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05-CH11231: Materials Project program KC23MP. Maintenance and development of the NRELMatDB is currently supported by the US Department of Energy, Office of Science, Basic Energy Sciences under contract DE-AC36-08GO28308 to NREL, as part of an Energy Frontier Research Center. The authors acknowledge the support of Dennice Roberts and David Moore in the preparation of this manuscript. The views expressed in this article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. The authors declare no competing financial interest.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC36-08GO28308
Department of Energy (DOE)DE-SC0021266
National Renewable Energy LaboratoryUNSPECIFIED
Department of Energy (DOE)DE-AC02-05-CH11231
Subject Keywords:Cations, Electrical conductivity, Materials, Oxides, Thin films
Issue or Number:30
PubMed Central ID:PMC9354241
Record Number:CaltechAUTHORS:20220414-25692000
Persistent URL:
Official Citation:Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications. 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, and Andriy Zakutayev. Journal of the American Chemical Society 2022 144 (30), 13673-13687; DOI: 10.1021/jacs.2c04241
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114293
Deposited By: George Porter
Deposited On:19 Apr 2022 20:35
Last Modified:17 Aug 2022 16:39

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