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通过促进伏尔默反应制备的具有共掺杂的镍/钼双金属氧化物衍生的富含异质界面的硫化物纳米片用于高效碱性析氢反应

Ni/Mo Bimetallic-Oxide-Derived Heterointerface-Rich Sulfide Nanosheets with Co-Doping for Efficient Alkaline Hydrogen Evolution by Boosting Volmer Reaction.

作者信息

Zhang Liyang, Zheng Yujie, Wang Jiacheng, Geng Yang, Zhang Ben, He Junjie, Xue Junmin, Frauenheim Thomas, Li Meng

机构信息

MOE Key Laboratory of Low-Grade Energy Utilization Technologies and Systems, CQU-NUS Renewable Energy Materials & Devices Joint Laboratory, School of Energy & Power Engineering, Chongqing University, Chongqing, 400044, China.

Bremen Center for Computational Materials Science, University of Bremen, Am Fallturm 1, 28359, Bremen, Germany.

出版信息

Small. 2021 Mar;17(10):e2006730. doi: 10.1002/smll.202006730. Epub 2021 Feb 16.

DOI:10.1002/smll.202006730
PMID:33590691
Abstract

Molybdenum disulfide (MoS ) is a promising alternative to Pt-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in an acidic environment. However, alkaline HER activity for molybdenum disulfide is limited by its slow water dissociation kinetics. Interface engineering is an effective strategy for the design of alkaline HER catalysts. However, the restricted heterointerfaces of current catalysts have significantly limited their alkaline HER performance. Herein, a novel assembly of cobalt-doped interface- and defect-rich MoS /Ni S hetero-nanosheet anchoring on hierarchical carbon framework for alkaline HER is reported by directly vulcanizing NiMoO nanosheets. In the heterostructure nanosheet, Ni S acts as a water dissociation promoter and MoS acts as a hydrogen acceptor. Density functional theory calculations find that redistribution of charges at the heterointerface can reduce hydrogen adsorption Gibbs free energy (∆G ) and water decomposition energy barrier. The resulting hierarchical electrode with the synergistic effect of both hybrid components shows a low overpotential of 89 mV at -10 mA cm in 1 m KOH, a Tafel slope as low as 62 mV dec , and can run at -100 mA cm for at least 50 h without obvious voltage change. This study provides a potentially feasible strategy for the design of heterostructure-based electrocatalysts with abundant active interfaces.

摘要

二硫化钼(MoS₂)是在酸性环境中用于电催化析氢反应(HER)的一种很有前景的铂基催化剂替代物。然而,二硫化钼的碱性析氢活性受其缓慢的水解离动力学限制。界面工程是设计碱性析氢催化剂的一种有效策略。然而,当前催化剂有限的异质界面显著限制了它们的碱性析氢性能。在此,通过直接硫化NiMoO₄纳米片,报道了一种新型的钴掺杂的富含界面和缺陷的MoS₂/Ni₃S₂异质纳米片组装体,其锚定在分级碳框架上用于碱性析氢。在异质结构纳米片中,Ni₃S₂作为水解离促进剂,MoS₂作为氢受体。密度泛函理论计算发现,异质界面处电荷的重新分布可以降低氢吸附吉布斯自由能(∆G)和水分解能垒。所得的具有两种混合组分协同效应的分级电极在1 M KOH中-10 mA cm⁻²时显示出89 mV的低过电位,塔菲尔斜率低至62 mV dec⁻¹,并且可以在-100 mA cm⁻²下运行至少50小时而无明显电压变化。这项研究为设计具有丰富活性界面的基于异质结构的电催化剂提供了一种潜在可行的策略。

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