磷掺杂剂和石墨烯包覆层对NiCo_(2)S_(4)电催化剂析氢活性和耐久性的协同影响  

Synergetic effect of phosphorus-dopant and graphene-covering layer on hydrogen evolution activity and durability of NiCo_(2)S_(4)electrocatalysts

作　　者：陈杰 毛梁 徐家琛 顾修全 Zakhar I.Popov 赵宇龙 凌意瀚 隋艳伟 应鹏展 蔡晓燕 张俊英 Jie Chen;Liang Mao;Jiachen Xu;Xiuquan Gu;Zakhar I.Popov;Yulong Zhao;Yihan Ling;Yanwei Sui;Pengzhan Ying;Xiaoyan Cai;Junying Zhang(School of Materials Science and Physics,China University of Mining and Technology,Xuzhou 221116,China;Emanuel Institute of Biochemical Physics RAS,119334,4 Kosigin st.,Moscow,Russian Federation;School of Physics,Beihang University,Beijing 100191,China)

机构地区：[1]School of Materials Science and Physics,China University of Mining and Technology,Xuzhou 221116,China [2]Emanuel Institute of Biochemical Physics RAS,119334,4 Kosigin st.,Moscow,Russian Federation [3]School of Physics,Beihang University,Beijing 100191,China

出　　处：《Science China Materials》2023年第10期3875-3886,共12页中国科学（材料科学（英文版）

基　　金：supported by the National Key R&D Program of China(2021YFA1501900);the National Natural Science Foundation of China-Yunnan Joint Fund(U2102215);the National Natural Science Foundation of China(22209203);China Postdoctoral Science Foundation(2021M693419);Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization(PCSX202202);the Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology(CUMTMS202202 and CUMTMS202207);the Open Sharing Fund for the Large-scale Instruments and Equipment of China University of Mining and Technology。

摘　　要：探索具有优异导电性和稳定性的非贵金属电催化剂对氢经济至关重要.本研究将杂原子掺杂和石墨烯包覆相结合,以控制NiCo_(2)S_(4)(NCS)蛋黄壳微球的电子性能,并抵抗酸性介质中H_(2)O和O_(2)的腐蚀.密度泛函理论(DFT)模拟结合综合表征和实验首次揭示了在NCS中引入P杂原子不仅加速了电子从体相向表面的转移动力学,而且降低了掺杂P原子附近活性S位上的析氢反应势垒.利用DFT计算的穿透能垒预测了rGO覆盖层在P掺杂NCS(P-NCS)表面对质子的渗透性和对H_(2)O和O_(2)分子的抵抗性等重要功能,并用X射线光电子能谱对新催化剂和回收催化剂进行了验证.利用P掺杂剂和rGO覆盖层分别辅助电荷传递和质子传递,通过二者的协同作用获得了催化活性和耐久性之间的平衡.因此,优化后的P-NCS/rGO在70 mV的低过电位下实现了10 mA cm^(-2)的电流密度,并具有令人满意的80小时耐用性.本工作阐明了石墨烯覆盖硫化物催化剂可通过调控电子结构和质子/分子穿透提高电催化性能.The investigation of highly conductive and stable non-noble metal electrocatalysts is imperative for promoting the hydrogen economy.Herein,we employed heteroatom-doping and graphene-covering techniques to enhance the electronic properties of NiCo_(2)S_(4)(NCS)yolk-shell microspheres,boosting their resistance to H_(2)O and O_(2) corrosion in acidic environments.Based on the results of density functional theory(DFT)simulations and comprehensive characterizations,P heteroatom introduction into NCS was found to expedite electron transfer from bulk to surface,reducing the barrier for the hydrogen evolution reaction(HER)on neighboring active S sites.DFT-calculated energy barriers and X-ray photoelectron spectrometer analysis substantiated that the reduced graphene oxide(rGO)-covering layer played a vital role by facilitating proton permeability in HER while hindering H_(2)O and O_(2) molecule penetration.By leveraging charge transfer and mass transfer,a balanced catalyst with high activity and corrosion resistance was achieved.The optimized P-NCS/rGO catalyst exhibited a current density of 10 mA cm^(-2) at a low overpotential of 70 mV,demonstrating excellent durability over 80 h.This study exemplified the rational design of graphene-covered sulfide catalysts,enhancing electrocatalyst performance through the regulation of electronic structures and proton/molecule penetration.

关 键 词：ELECTROCATALYSIS elemental doping proton penetration hydrogen evolution corrosion resistance 

分 类 号：TQ116.2[化学工程—无机化工] TQ426