首页|Coordination environments build up and tune a superior synergistic"genome"toward novel trifunctional(TM-NxO4-x)@g-C16N3-H3:High-throughput inspection of ultra-high activity for water splitting and oxygen reduction reactions
Coordination environments build up and tune a superior synergistic"genome"toward novel trifunctional(TM-NxO4-x)@g-C16N3-H3:High-throughput inspection of ultra-high activity for water splitting and oxygen reduction reactions
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Emerging as a prominent area of focus in energy conversion and storage technologies,the development of highly active metal-based single-atom catalysts(SACs)holds great significance in searching alternatives to replace precious metals toward the efficient,stable,and low-cost hydrogen evolution reaction(HER),as well as the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR).Combining the tremendous tunability of ligand and coordination environment with rich metal-based electrocatalysts can create breakthrough opportunities for achieving both high stability and activity.Herein,we propose a novel and stable holey graphene-like carbon nitride monolayer g-C16N5(N4@g-C16N3)stoichiometries interestingly behaving as a natural substrate for constructing SACs((TM-N4)@g-C16N3),whose evenly distributed holes map rich and uniform nitrogen coordination positions with electron-rich lone pairs for anchoring transition metal(TM)atoms.Then,we employed density functional theory(DFT)calculations to systematically investigate the electrocatalytic activity of(TM-N4)@g-C16N3 toward HER/OER/ORR,meanwhile considering the synergistic modulation of H-loading and O-coordination((TM-NxO4-x)@g-C16N3-H3,x=0-4).Together a"four-step procedure"screening mechanism with the first-principles high-throughput calculations,we find that(Rh-N4)and(Ir-N2O2-Ⅱ)distributed on g-C16N3-H3 can modulate the adsorption strength of the adsorbates,thus achieving the best HER/OER/ORR performance among 216 candidates,and the lowest overpotential of 0.098/0.3/0.46 V and 0.06/0.48/0.45 V,respectively.Additionally,the d-band center,crystal orbital Hamilton population(COHP),and molecular orbitals are used to reveal the OER/ORR activity source.Particularly,the Rh/Ir-d orbital is dramatically hybridized with the O-p orbital of the oxygenated adsorbates,so that the lone-electrons incipiently locate at the antibonding orbital pair up and populate the downward bonding orbital,allowing oxygenated intermediates to be adsorbed onto(TM-NxO4-x)@g-C16N3-H3 appropriately.
single atom catalystsloading and coordinationhydrogen evolution reactionoxygen evolution reactionoxygen reduction reaction
Chunyao Fang、Xian Wang、Qiang Zhang、Xihang Zhang、Chenglong Shi、Jingcheng Xu、Mengyu Yang
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Department of Physics,University of Shanghai for Science and Technology,Shanghai 200093,China
School of Materials and Chemistry,University of Shanghai for Science and Technology,Shanghai 200093,China
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