气候变化领域集成服务门户(CCPortal): Mutually-dependent kinetics and energetics of photocatalyst/co-catalyst/two-redox liquid junctions

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DOI	10.1039/c9ee02910a
	Mutually-dependent kinetics and energetics of photocatalyst/co-catalyst/two-redox liquid junctions
	Pan Z.; Yanagi R.; Wang Q.; Shen X.; Zhu Q.; Xue Y.; Röhr J.A.; Hisatomi T.; Domen K.; Hu S.
发表日期	2020
ISSN	17545692
起始页码	162
结束页码	173
卷号	13 期号:1
英文摘要	Water-splitting by photocatalyst particles has attracted much attention recently for its potential to produce renewable H2 at scale. However, the correlation between the energetics at photocatalyst/co-catalyst/water interfaces and their interfacial charge-transfer kinetics is still elusive, especially when the energetics are expected to vary spatially along the liquid-junction interface. First, we derived a kinetic model for photocatalyst particles in contact with two-redox potentials, H+/H2 and O2/H2O, i.e., a semiconductor/two-redox liquid junction. We adopted the principle of detailed balance proven for one-redox liquid junctions and extended this principle to a locally out-of-equilibrium electrolyte containing multiple redox potentials, the condition typical for photocatalysts. To validate the model, we established a characterization framework to simulate photocatalyst operation by using photoelectrodes. The open-circuit conditions mimicked operating photocatalyst surfaces; and the (quasi-) Fermi levels, probed by ohmic back contacts, indicated charge-separation efficiency. Quantitative data fitting further validated the two-redox kinetic model. These characterizations correlated local energetics with multi-electron charge-transfer kinetics, which exhibit tuneable branching ratios controlled by H2-and-O2 gas-mixture compositions and co-catalyst selectivity. Unlike the conventional photoelectrode/electrolyte interfaces, SrTiO3 model particles decorated with Pt co-catalysts were found to bear liquid-junction interfaces of spatially varying energetics with designated reductive and oxidative sites. It is shown that, uniquely for photocatalysts, the local kinetic-controlled energetics vary spatially across photocatalyst/co-catalyst/water interfaces of individual particles, and affect charge-separation efficiency sensitively. The mutually dependent behaviour between local kinetics and spatially varying energetics were confirmed for two practical photocatalytic systems, Al-doped SrTiO3 and Ta3N5. This study exemplified and elucidated the design principles for developing efficient photocatalysts. © 2020 The Royal Society of Chemistry.
英文关键词	Aluminum compounds; Catalyst selectivity; Charge transfer; Efficiency; Electrolytes; Kinetic parameters; Kinetic theory; Liquids; Nitrogen compounds; Phase interfaces; Redox reactions; Strontium titanates; Tantalum compounds; Titanium compounds; Charge separations; Individual particles; Interfacial charge transfer; Kinetic controlled; Mixture compositions; Open circuit conditions; Out of equilibrium; Photocatalytic systems; Semiconductor junctions; catalyst; energetics; energy efficiency; liquid; photodegradation; reaction kinetics; redox conditions
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/189754
作者单位	Department of Chemical and Environmental Engineering, Yale University, New Haven, CT 06520, United States; Energy Sciences Institute, Yale University 810 West Campus Drive, West Haven, CT 06516, United States; Department of Chemical System Engineering, School of Engineering, University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo, 113-8656, Japan; National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China; Research Initiative for Supra-Materials, Shinshu University, 4-17-1 Wakasato Nagano-shi, Nagano, 380-8553, Japan; Office of University Professor, University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo, 113-8656, Japan
推荐引用方式 GB/T 7714	Pan Z.,Yanagi R.,Wang Q.,et al. Mutually-dependent kinetics and energetics of photocatalyst/co-catalyst/two-redox liquid junctions[J],2020,13(1).
APA	Pan Z..,Yanagi R..,Wang Q..,Shen X..,Zhu Q..,...&Hu S..(2020).Mutually-dependent kinetics and energetics of photocatalyst/co-catalyst/two-redox liquid junctions.Energy & Environmental Science,13(1).
MLA	Pan Z.,et al."Mutually-dependent kinetics and energetics of photocatalyst/co-catalyst/two-redox liquid junctions".Energy & Environmental Science 13.1(2020).