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Title: Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water

Abstract

The development of low-cost hybrid water splitting-biosynthetic systems that mimic natural photosynthesis to achieve solar-to-chemical conversion is of great promise for future energy demands. However, it is often limited by the kinetically sluggish hydrogen evolution reaction (HER) on the surface of nonprecious transition metal catalysts in neutral media. It is thus highly desirable to rationally tailor the reaction interface to boost the neutral HER catalytic kinetics. Herein, we report a general surface nitrogen modification of diverse transition metals (e.g., iron, cobalt, nickel, copper, and nickel-cobalt alloy), accomplished by a facile low-temperature ammonium carbonate treatment, for significantly improved hydrogen generation from neutral water. Various physicochemical characterization techniques including synchrotron X-ray absorption spectroscopy (XAS) and theory modeling demonstrate that the surface nitrogen modification does not change the chemical composition of the underlying transition metals. Notably, the resulting nitrogen-modified nickel framework (N-Ni) exhibits an extremely low overpotential of 64 mV at 10 mA cm -2, which is, to our knowledge, the best among those nonprecious electrocatalysts reported for hydrogen evolution at pH 7. Our combined experimental results and density functional theory (DFT) calculations reveal that the surface electron-rich nitrogen simultaneously facilitates the initial adsorption of water via the electron-deficient H atom and themore » subsequent dissociation of the electron-rich HO-H bond via H transfer to N on the nickel surface, beneficial to the overall hydrogen evolution process.« less

Authors:
ORCiD logo [1];  [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, United States
  2. Department of Chemistry, University of California, Riverside, California 92521, United States
  3. Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465415
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 35; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

You, Bo, Liu, Xuan, Hu, Guoxiang, Gul, Sheraz, Yano, Junko, Jiang, De-en, and Sun, Yujie. Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water. United States: N. p., 2017. Web. doi:10.1021/jacs.7b06434.
You, Bo, Liu, Xuan, Hu, Guoxiang, Gul, Sheraz, Yano, Junko, Jiang, De-en, & Sun, Yujie. Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water. United States. doi:10.1021/jacs.7b06434.
You, Bo, Liu, Xuan, Hu, Guoxiang, Gul, Sheraz, Yano, Junko, Jiang, De-en, and Sun, Yujie. Tue . "Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water". United States. doi:10.1021/jacs.7b06434.
@article{osti_1465415,
title = {Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water},
author = {You, Bo and Liu, Xuan and Hu, Guoxiang and Gul, Sheraz and Yano, Junko and Jiang, De-en and Sun, Yujie},
abstractNote = {The development of low-cost hybrid water splitting-biosynthetic systems that mimic natural photosynthesis to achieve solar-to-chemical conversion is of great promise for future energy demands. However, it is often limited by the kinetically sluggish hydrogen evolution reaction (HER) on the surface of nonprecious transition metal catalysts in neutral media. It is thus highly desirable to rationally tailor the reaction interface to boost the neutral HER catalytic kinetics. Herein, we report a general surface nitrogen modification of diverse transition metals (e.g., iron, cobalt, nickel, copper, and nickel-cobalt alloy), accomplished by a facile low-temperature ammonium carbonate treatment, for significantly improved hydrogen generation from neutral water. Various physicochemical characterization techniques including synchrotron X-ray absorption spectroscopy (XAS) and theory modeling demonstrate that the surface nitrogen modification does not change the chemical composition of the underlying transition metals. Notably, the resulting nitrogen-modified nickel framework (N-Ni) exhibits an extremely low overpotential of 64 mV at 10 mA cm-2, which is, to our knowledge, the best among those nonprecious electrocatalysts reported for hydrogen evolution at pH 7. Our combined experimental results and density functional theory (DFT) calculations reveal that the surface electron-rich nitrogen simultaneously facilitates the initial adsorption of water via the electron-deficient H atom and the subsequent dissociation of the electron-rich HO-H bond via H transfer to N on the nickel surface, beneficial to the overall hydrogen evolution process.},
doi = {10.1021/jacs.7b06434},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 35,
volume = 139,
place = {United States},
year = {2017},
month = {8}
}