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Title: Universal molecular-confined synthesis of interconnected porous metal oxides-N-C frameworks for electrocatalytic water splitting

Abstract

The rational synthesis of high performance electrocatalysts at low cost for water splitting (hydrogen and oxygen evolution reaction, HER and OER) is highly desirable but remains a key challenge. Herein, we report a versatile molecular-confining route to construct strongly coupled metal oxides-N-C frameworks with interconnected configuration. By simply chelating various transition metal ions with ethylenediaminetetraacetic acid disodium salt (EDTA) in agarose hydrogel and subsequent carbonization, the high specific surface area porous N-C frameworks with strongly coupled metal oxides (e.g., manganese, iron, cobalt, nickel and their mixed oxides) can be prepared as advanced nonprecious water splitting electrocatalysts. For instance, the resulting Co3O4-N-C frameworks with the high surface area of 153 m2 g-1, and the moderate nitrogen content of 1.23%, require an overpotential of 324 mV to afford a current density of 10 mA cm-2 in 0.1 M KOH for OER, superior to commercial RuO2 catalysts. Density functional theory (DFT) calculations reveal that the strong coupling between N-C and Co3O4 tunes the local electronic structure of Co for high-valence active sites and assures optimal adsorption energies of OER intermediates. Moreover, Co2P-N-C electrocatalysts derived from Co3O4-N-C also exhibit excellent HER performance under 1.0 M KOH with a low overpotential of 139 mV tomore » reach 10 mA cm-2, a small Tafel slope of 45 mV dec-1 and impressive stability, underscoring the versatility of our synthetic strategy.« less

Authors:
 [1];  [2];  [1];  [2];  [3]
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  1. University of Science and Technology of China, Hefei (China)
  2. University of California, Riverside, CA (United States)
  3. Utah State University, Logan, UT (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Utah State University; National Science Foundation (NSF); University of California, Riverside
OSTI Identifier:
1543574
Alternate Identifier(s):
OSTI ID: 1496460
Grant/Contract Number:  
AC02-05CH11231; CHE-1653978; AC02–05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 48; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; water splitting; porous frameworks; electrocatalysis; nonprecious; theory modeling

Citation Formats

You, Bo, Zhang, Yadong, Yin, Peiqun, Jiang, De-en, and Sun, Yujie. Universal molecular-confined synthesis of interconnected porous metal oxides-N-C frameworks for electrocatalytic water splitting. United States: N. p., 2018. Web. doi:10.1016/j.nanoen.2018.04.009.
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You, Bo, Zhang, Yadong, Yin, Peiqun, Jiang, De-en, & Sun, Yujie. Universal molecular-confined synthesis of interconnected porous metal oxides-N-C frameworks for electrocatalytic water splitting. United States. https://doi.org/10.1016/j.nanoen.2018.04.009
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You, Bo, Zhang, Yadong, Yin, Peiqun, Jiang, De-en, and Sun, Yujie. Wed . "Universal molecular-confined synthesis of interconnected porous metal oxides-N-C frameworks for electrocatalytic water splitting". United States. https://doi.org/10.1016/j.nanoen.2018.04.009. https://www.osti.gov/servlets/purl/1543574.
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@article{osti_1543574,
title = {Universal molecular-confined synthesis of interconnected porous metal oxides-N-C frameworks for electrocatalytic water splitting},
author = {You, Bo and Zhang, Yadong and Yin, Peiqun and Jiang, De-en and Sun, Yujie},
abstractNote = {The rational synthesis of high performance electrocatalysts at low cost for water splitting (hydrogen and oxygen evolution reaction, HER and OER) is highly desirable but remains a key challenge. Herein, we report a versatile molecular-confining route to construct strongly coupled metal oxides-N-C frameworks with interconnected configuration. By simply chelating various transition metal ions with ethylenediaminetetraacetic acid disodium salt (EDTA) in agarose hydrogel and subsequent carbonization, the high specific surface area porous N-C frameworks with strongly coupled metal oxides (e.g., manganese, iron, cobalt, nickel and their mixed oxides) can be prepared as advanced nonprecious water splitting electrocatalysts. For instance, the resulting Co3O4-N-C frameworks with the high surface area of 153 m2 g-1, and the moderate nitrogen content of 1.23%, require an overpotential of 324 mV to afford a current density of 10 mA cm-2 in 0.1 M KOH for OER, superior to commercial RuO2 catalysts. Density functional theory (DFT) calculations reveal that the strong coupling between N-C and Co3O4 tunes the local electronic structure of Co for high-valence active sites and assures optimal adsorption energies of OER intermediates. Moreover, Co2P-N-C electrocatalysts derived from Co3O4-N-C also exhibit excellent HER performance under 1.0 M KOH with a low overpotential of 139 mV to reach 10 mA cm-2, a small Tafel slope of 45 mV dec-1 and impressive stability, underscoring the versatility of our synthetic strategy.},
doi = {10.1016/j.nanoen.2018.04.009},
journal = {Nano Energy},
number = C,
volume = 48,
place = {United States},
year = {Wed Apr 04 00:00:00 EDT 2018},
month = {Wed Apr 04 00:00:00 EDT 2018}
}
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https://doi.org/10.1016/j.nanoen.2018.04.009
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