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Molecular Functionalization of NiO Nanocatalyst for Enhanced Water Oxidation by Electronic Structure Engineering
Author(s) -
Fan Lizhou,
Zhang Biaobiao,
Qiu Zhen,
Dharanipragada N. V. R. Aditya,
Timmer Brian J. J.,
Zhang Fuguo,
Sheng Xia,
Liu Tianqi,
Meng Qijun,
Inge A. Ken,
Edvinsson Tomas,
Sun Licheng
Publication year - 2020
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.202001716
Subject(s) - surface modification , catalysis , non blocking i/o , electron transfer , molecule , electronic structure , nanomaterials , nanotechnology , materials science , chemical engineering , nanoparticle , water splitting , chemistry , photochemistry , computational chemistry , organic chemistry , photocatalysis , engineering
Tuning the local environment of nanomaterial‐based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure‐activity relationship was discovered: the increasing electron‐withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron‐withdrawing modification facilitates the charge‐transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high‐valent γ‐NiOOH reactive species generation. The NiO−C 6 F 5 catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well‐designed and effective approach for heterogeneous catalyst fabrication under the molecular level.

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