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This content will become publicly available on November 20, 2018

Title: Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption

The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. Here, we took the view that generating transition metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Using density functional theory, we find that the formation energy of desired Ni 4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal phosphorus. Here we synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics by employing in situ soft X-ray absorption (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni 4+ under low overpotential conditions. NiCoFeP catalyst outperforms IrO 2 and retains its performance following 100 hours of operation. We showcase NiCoFeP in a membrane-free CO 2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm -2, reducing CO 2 into CO and oxidizing H 2O to O 2 with a 64% electricity-to-chemical-fuel efficiency.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo ;  [3] ;  [4] ; ORCiD logo [4] ;  [5] ;  [4] ;  [4] ;  [4] ;  [6] ;  [6] ;  [7] ; ORCiD logo [8] ;  [7] ;  [3] ;  [9] ; ORCiD logo [4]
  1. Univ. of Toronto, ON (Canada). Dept. of Electrical and Computer Engineering; Tianjin Univ. (China). Inst. of New-Energy Materials and School of Materials Science and Engineering
  2. Univ. of Toronto, ON (Canada). Dept. of Electrical and Computer Engineering; Fudan Univ., Shanghai (China). State Key Lab. of Molecular Engineering of Polymers, Dept. of Macromolecular Science and Lab. of Advanced Materials
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
  4. Univ. of Toronto, ON (Canada). Dept. of Electrical and Computer Engineering
  5. Tianjin Univ. (China). Inst. of New-Energy Materials and School of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  6. Canadian Light Sources, Inc., Saskatoon, SK (Canada)
  7. Fudan Univ., Shanghai (China). State Key Lab. of Molecular Engineering of Polymers, Dept. of Macromolecular Science and Lab. of Advanced Materials
  8. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  9. Tianjin Univ. (China). Inst. of New-Energy Materials and School of Materials Science and Engineering
Publication Date:
Report Number(s):
BNL-203448-2018-JAAM
Journal ID: ISSN 1755-4330
Grant/Contract Number:
SC0012704; AC02-05CH11231; 20140625004; 2014CB931703; 16JC1400702; 14ZR14110200; 21503079; 201406745001
Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 10; Journal Issue: 2; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Ontario Research Fund; Natural Sciences and Engineering Research Council of Canada (NSERC); Canadian Inst. for Advanced Research (CIFAR); China Scholarship Council (CSC); National Basic Research Program of China; Shanghai Science and Technology Committee (STCSM); National Natural Science Foundation of China (NNSFC); Univ. of Toronto (Canada); Canadian Light Sources, Inc., Saskatoon, SK (Canada); Beijing Synchrotron Radiation Facility; Southern Ontario Smart Computing Innovation Platform (SOSCIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; in situ soft X-ray absorption; electrocatalysis; energy; fluorescence spectroscopy
OSTI Identifier:
1431449