气候变化领域集成服务门户(CCPortal): Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides

CCPortal

DOI	10.1039/c7ee02052j
	Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides
	Hong W.T.; Stoerzinger K.A.; Lee Y.-L.; Giordano L.; Grimaud A.; Johnson A.M.; Hwang J.; Crumlin E.J.; Yang W.; Shao-Horn Y.
发表日期	2017
ISSN	17545692
起始页码	2190
结束页码	2200
卷号	10 期号:10
英文摘要	Numerous studies have reported electronic activity descriptors of oxygen evolution reaction (OER) for oxide catalysts under a single reaction mechanism. However, recent works have revealed that a single mechanism is not at play across oxide chemistries. These works underscore a need to deeply investigate the electronic structure details of active oxide catalysts and how they align with the OER potential, which is critical to understanding the interfacial charge-transfer kinetics that dictate catalytic mechanisms. In this work, we use soft X-ray emission and absorption spectroscopy of perovskites to analyze the partial density of states on an absolute energy scale, from which energetic barriers for electron transfer and surface deprotonation were estimated and correlated with OER activity. Through this lens, we identify that decreasing the solid-state charge-transfer energy of perovskites can change the mechanisms of the OER from electron-transfer-limited to proton-electron-coupled, to proton-transfer-limited reactions. This concept is supported by the analysis of potential energy surfaces for sequential and concerted proton-electron transfer pathways using a Marcus model. Our work highlights the importance of understanding the physical origin of experimental OER activity trends with electronic descriptors and the need to promote surface deprotonation from oxides to discover new catalysts with enhanced activity. © The Royal Society of Chemistry.
英文关键词	Absorption spectroscopy; Catalysts; Charge transfer; Electron transitions; Electronic structure; Electrons; Perovskite; Potential energy; Quantum chemistry; Solid state reactions; Catalytic mechanisms; Charge transfer energy; Electron transfer pathways; Electronic activity; Interfacial charge transfer; Oxygen evolution reaction; Partial density of state; Soft x-ray emissions; Catalyst activity; catalysis; catalyst; chemical analysis; density; electric field; electron; oxygen; perovskite; potential energy; reaction kinetics
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/190406
作者单位	Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, United States; Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA 02139, United States; Dipartimento di Scienza Dei Materiali, Università di Milano-Bicocca, Milano, Italy; Department of Mechanical Engineering, University of St. Thomas, St. Paul, MN 55105, United States; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, United States; Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, United States; Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, United States; National Energy Technology Laboratory, Pittsburgh, PA 15236, United States; Chimie du Solide et de l'Energie, FRE 3677, Collège de France, Paris Cedex 05, 75231, France; Réseau sur le Stockage Electrochimique de l'Energie (RS2E), FR CNRS 3459, Amiens Cedex, 8003...
推荐引用方式 GB/T 7714	Hong W.T.,Stoerzinger K.A.,Lee Y.-L.,et al. Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides[J],2017,10(10).
APA	Hong W.T..,Stoerzinger K.A..,Lee Y.-L..,Giordano L..,Grimaud A..,...&Shao-Horn Y..(2017).Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides.Energy & Environmental Science,10(10).
MLA	Hong W.T.,et al."Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides".Energy & Environmental Science 10.10(2017).