机构地区:[1]School of Materials Science and Engineering,Anhui University of Technology,Maanshan 243002,China [2]Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials,Ministry of Education,Anhui University of Technology,Maanshan 243002,China
出 处:《Chinese Journal of Chemical Physics》2025年第2期199-211,I0040,共14页化学物理学报(英文)
基 金:financially supported by the National Natural Science Foundation of China(No.51971002);National Natural Science Foundation of Anhui,China(No.2108085QE188);Natural Science Foundation of Anhui Provincial Education Department(No.KJ2021A0361)。
摘 要:Currently,single atom(SA),quantum dots(QDs)and heterogeneous interfaces have been extensively em-ployed for the design of nov-el catalysts for overall water splitting.However,there are still few literatures about the hydrogen(HER)and oxygen(OER)evolution perfor-mances for three different morphologies of the same metal loaded on MXenes substrates.Herein,the HER and OER per-formances of Mo_(2)CO_(2)modified by transition metals(TM,TM=Fe,Co,and Ni)with differ-ent SA loading(STM/Mo_(2)CO_(2)),QDs(QTM/Mo_(2)CO_(2))and heterogeneous interface(ITM/Mo_(2)CO_(2)),and TM loading and N3(TMN_(3)/Mo_(2)CO_(2))or N4 doping co-modification(TMN4/Mo_(2)CO_(2))are investigated by density functional theory(DFT)calculations.The re-sults show that the HER and OER performances of STM/Mo_(2)CO_(2)are better than those of ITM/Mo_(2)CO_(2)and QTM/Mo_(2)CO_(2).Especially,SNi/Mo_(2)CO_(2)exhibits the best HER and OER properties among the studied structures,with the correspondingΔGH*andηOER of−0.04 eV and 0.53 V,respectively.It is noteworthy that theΔGH*absolute value,ηOER,work function(Φ)and TM valence charges are significantly correlated,whereΔGH*absolute value,ηOER,andΦall present an increase trend following the order of STM/Mo_(2)CO_(2),ITM/Mo_(2)CO_(2),and QTM/Mo_(2)CO_(2),whereas TM valence charges exhibit a decrease trend with the above order.Furthermore,integral crystal orbital Hamilton population(ICOHP)results indicate that the more negative the ICOHP,the stronger bonding strength between TM and H atoms,and the better the corresponding HER performance in STM/Mo_(2)CO_(2).Campared with SNi/Mo_(2)CO_(2),Ni loading and N3 doping co-modification Mo_(2)CO_(2)(NiN_(3)/Mo_(2)CO_(2))shows better HER(ΔGH*=−0.01 eV)and OER catalytic activities(ηOER=0.36 V).Molecular dynamics simula-tions results indicate that most of the modified systems are stable at reaction temperature.In summary,NiN_(3)/Mo_(2)CO_(2)can be used as an efficient electrocatalyst for overall water splitting.目前,单原子、量子点和异质界面已被广泛用于设计整体水分解的新型催化剂.然而,目前鲜有文献报道三种不同形貌的同一金属负载在MXenes基底的析氢和析氧性能.本文通过密度泛函理论计算研究了单金属TM(Fe、Co和Ni)负载(STM/Mo2CO2),量子点(QTM/Mo2CO2),界面(ITM/Mo2CO2)以及TM负载与N3(TMN3/Mo2CO2)或N4掺杂(TMN4/Mo2CO2)共改性对Mo2CO2析氢和析氧性能的影响规律.研究结果表明,负载的析氢和析氧性能均优于界面和量子点.其中,SNi/Mo2CO2具有最佳的析氢和析氧性能,相应的氢吸附的吉布斯自由能ΔGH*和析氧反应的过电位ηOER分别为-0.04 eV和0.53 V.值得注意的是,ΔGH*绝对值、ηOER和Φ均呈现出按照负载、界面和量子点顺序的递增变化规律,而TM价电子转移量则与之相反.此外,晶体轨道哈密顿布居积分结果表明,晶体轨道哈密顿布居积分越负,TM和H原子之间的键合强度越强,析氢性能越好.与SNi/Mo2CO2相比,Ni负载和N3掺杂共改性Mo2CO2(NiN3/Mo2CO2)表现出更好的析氢(ΔGH*=-0.01 eV)和析氧催化活性(ηOER=0.36 V).分子动力学模拟结果表明,大多数改性体系在反应温度下是稳定的.综上所述,NiN3/Mo2CO2可以作为整体水分解的高效电催化剂.
关 键 词:Single-atom catalysts Quantum dot Heterogeneous interface Density function-al theory Mo_(2)CO_(2)MXene
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