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Title: Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation

Abstract

As one of the most remarkable oxygen evolution reaction (OER) electrocatalysts, metal chalcogenides have been intensively reported during the past few decades because of their high OER activities. It has been reported that electron-chemical conversion of metal chalcogenides into oxides/hydroxides would take place after the OER. However, the transition mechanism of such unstable structures, as well as the real active sites and catalytic activity during the OER for these electrocatalysts, has not been understood yet; therefore a direct observation for the electrocatalytic water oxidation process, especially at nano or even angstrom scale, is urgently needed. In this work, by employing advanced Cs-corrected transmission electron microscopy (TEM), a step by step oxidational evolution of amorphous electrocatalyst CoSx into crystallized CoOOH in the OER has been in situ captured: irreversible conversion of CoSx to crystallized CoOOH is initiated on the surface of the electrocatalysts with a morphology change via Co(OH)2 intermediate during the OER measurement, where CoOOH is confirmed as the real active species. Besides, this transition process has also been confirmed by multiple applications of X-ray photoelectron spectroscopy (XPS), in situ Fourier-transform infrared spectroscopy (FTIR), and other ex situ technologies. Moreover, on the basis of this discovery, a high-efficiency electrocatalyst ofmore » a nitrogen-doped graphene foam (NGF) coated by CoSx has been explored through a thorough structure transformation of CoOOH. In conclusion, we believe this in situ and in-depth observation of structural evolution in the OER measurement can provide insights into the fundamental understanding of the mechanism for the OER catalysts, thus enabling the more rational design of low-cost and high-efficient electrocatalysts for water splitting.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [4]; ORCiD logo [5];  [6]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Wuhan University of Technology (China)
  2. Beijing University of Technology (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Dalian University of Technology (China)
  5. Dalian University of Technology (China); KTH Royal Institute of Technology, Stockholm (Sweden)
  6. Guangzhou University (China)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1493412
Grant/Contract Number:  
AC02-76SF00515; WUT: 2017 IVA 092; 2015CFA001; 51772234; 11704015; 21433007; 21573170; 51320105001; 2017-ZD-4
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 12; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cobalt chalcogenide; in situ TEM; structural evolution; water oxidation; XPS

Citation Formats

Fan, Ke, Zou, Haiyuan, Lu, Yue, Chen, Hong, Li, Fusheng, Liu, Jinxuan, Sun, Licheng, Tong, Lianpeng, Toney, Michael F., Sui, Manling, and Yu, Jiaguo. Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b06312.
Fan, Ke, Zou, Haiyuan, Lu, Yue, Chen, Hong, Li, Fusheng, Liu, Jinxuan, Sun, Licheng, Tong, Lianpeng, Toney, Michael F., Sui, Manling, & Yu, Jiaguo. Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation. United States. https://doi.org/10.1021/acsnano.8b06312
Fan, Ke, Zou, Haiyuan, Lu, Yue, Chen, Hong, Li, Fusheng, Liu, Jinxuan, Sun, Licheng, Tong, Lianpeng, Toney, Michael F., Sui, Manling, and Yu, Jiaguo. Mon . "Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation". United States. https://doi.org/10.1021/acsnano.8b06312. https://www.osti.gov/servlets/purl/1493412.
@article{osti_1493412,
title = {Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation},
author = {Fan, Ke and Zou, Haiyuan and Lu, Yue and Chen, Hong and Li, Fusheng and Liu, Jinxuan and Sun, Licheng and Tong, Lianpeng and Toney, Michael F. and Sui, Manling and Yu, Jiaguo},
abstractNote = {As one of the most remarkable oxygen evolution reaction (OER) electrocatalysts, metal chalcogenides have been intensively reported during the past few decades because of their high OER activities. It has been reported that electron-chemical conversion of metal chalcogenides into oxides/hydroxides would take place after the OER. However, the transition mechanism of such unstable structures, as well as the real active sites and catalytic activity during the OER for these electrocatalysts, has not been understood yet; therefore a direct observation for the electrocatalytic water oxidation process, especially at nano or even angstrom scale, is urgently needed. In this work, by employing advanced Cs-corrected transmission electron microscopy (TEM), a step by step oxidational evolution of amorphous electrocatalyst CoSx into crystallized CoOOH in the OER has been in situ captured: irreversible conversion of CoSx to crystallized CoOOH is initiated on the surface of the electrocatalysts with a morphology change via Co(OH)2 intermediate during the OER measurement, where CoOOH is confirmed as the real active species. Besides, this transition process has also been confirmed by multiple applications of X-ray photoelectron spectroscopy (XPS), in situ Fourier-transform infrared spectroscopy (FTIR), and other ex situ technologies. Moreover, on the basis of this discovery, a high-efficiency electrocatalyst of a nitrogen-doped graphene foam (NGF) coated by CoSx has been explored through a thorough structure transformation of CoOOH. In conclusion, we believe this in situ and in-depth observation of structural evolution in the OER measurement can provide insights into the fundamental understanding of the mechanism for the OER catalysts, thus enabling the more rational design of low-cost and high-efficient electrocatalysts for water splitting.},
doi = {10.1021/acsnano.8b06312},
journal = {ACS Nano},
number = 12,
volume = 12,
place = {United States},
year = {Mon Dec 03 00:00:00 EST 2018},
month = {Mon Dec 03 00:00:00 EST 2018}
}

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