[1]方志刚,许 友,王智瑶,等.基于量子化学的团簇Co4P非晶态合金析氢反应研究[J].江西师范大学学报(自然科学版),2022,(03):221-226.[doi:10.16357/j.cnki.issn1000-5862.2022.03.01]
　FANG Zhigang,XU You,WANG Zhiyao,et al.The Study on Hydrogen Evolution Reaction of Cluster Co4P Amorphous Alloy Based on Quantum Chemistry[J].Journal of Jiangxi Normal University:Natural Science Edition,2022,(03):221-226.[doi:10.16357/j.cnki.issn1000-5862.2022.03.01]
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基于量子化学的团簇Co4P非晶态合金析氢反应研究()
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《江西师范大学学报》（自然科学版）[ISSN:1006-6977/CN:61-1281/TN]

卷:
期数:
2022年03期
页码:
221-226
栏目:
化学
出版日期:
2022-05-25

文章信息/Info

Title:
The Study on Hydrogen Evolution Reaction of Cluster Co4P Amorphous Alloy Based on Quantum Chemistry
文章编号:
1000-5862(2022)03-0221-06
作者:
方志刚; 许 友; 王智瑶; 毛智龙; 郑新喜; 曾鑫渔; 吴庭慧
辽宁科技大学化学工程学院,辽宁 鞍山 114051
Author(s):
FANG Zhigang; XU You; WANG Zhiyao; MAO Zhilong; ZHENG Xinxi; ZENG Xinyu; WU Tinghui
School of Chemical Engineering,University of Science and Technology Liaoning,Anshan Liaoning 114051,China
关键词:
团簇Co4P;  催化析氢;  密度泛函理论;  前线轨道理论
Keywords:
cluster Co4P;  catalytic hydrogen evolution;  density functional theory;  frontier orbital theory
分类号:
O 641.12
DOI:
10.16357/j.cnki.issn1000-5862.2022.03.01
文献标志码:
A
摘要:
为寻找在团簇Co4P中具有最优催化析氢性能的构型,该文根据密度泛函理论于B3LYP/lanl2dz水平下对团簇Co4P分别进行在二、四重态下的计算,根据前线轨道理论对优化后团簇Co4P的HOMO图、水分子的LUMO图以及能级差进行分析,发现构型1(2)、2(2)的β电子与构型1(4)、2(4)的α电子的HOMO负相位对催化析氢反应的第1步提供了较大的贡献.此外,综合分析析氢反应的各步骤发现:构型2(2)具有较好的吸附能力,且该构型在吸附1个氢原子后在电化学解吸和化学重组解吸中均具有最优解析性质.因此,构型2(2)是在团簇Co4P各优化构型中最优的催化析氢构型.
Abstract:
In order to find the configuration with the optimal catalytic hydrogen evolution performance in the cluster Co4P,according to the density functional theory at the B3LYP/lanl2dz level,the cluster Co4P is calculated in the double and quartet states,and then the optimized cluster is calculated according to the frontier orbit theory.The HOMO diagram of cluster Co4P,the LUMO diagram of water molecules and the energy level difference are analyzed,and it is found that the HOMO is generated by the β electrons of configuration 1(2) and 2(2) and α electrons of configuration 1(4) and 2(4).The negative phase provides a greater contribution to the first step of the catalytic hydrogen evolution reaction.In addition,comprehensive analysis of the various steps of the hydrogen evolution reaction finds that configuration 2(2) has better adsorption capacity,and this configuration has the best desorption properties in both electrochemical desorption and chemical recombination desorption after adsorbing a hydrogen atom.Therefore,configuration 2(2) is the optimal catalytic hydrogen evolution configuration among the optimized configurations of cluster Co4P.

参考文献/References:

[1] SUN Minghao,JI Jiapeng,HU Mingyu,et al.Overwhelming the performance of single atoms with atomic clusters for platinum-catalyzed hydrogen evolution[J].ACS Catalysis,2019, 9(9):8213-8223.
[2] PEI Yan,ZHOU Gongbing,LUAN N,et al.Synthesis and catalysis of chemically reduced metal-metalloid amorphous alloys[J].Chemical Society Reviews,2012,41(24):8140-8162.
[3] CHANG Bing,YANG Yingchun,YE Zhixiang,et al.Enhancement of alkaline water splitting activity by Co-P coating on a copper oxide nanowire[J].Dalton Transactions,2019,48(3):891-897.
[4] HOU Chunchao,CAO Shuang,FU Wenfu,et al.Ultrafine CoP nanoparticles supported on carbon nanotubes as highly active electrocatalyst for both oxygen and hydrogen evolution in basic media[J].ACS Applied Materials & Interfaces,2015,7(51):28412-28419.
[5] RYU J,JUNG N,JANG J H,et al.In situ transformation of hydrogen-evolving CoP nanoparticles:toward efficient oxygen evolution catalysts bearing dispersed morphologies with Co-oxo/hydroxo molecular units[J].ACS Catalysis,2015,5(7):4066-4074.
[6] ZHANG Junchang,SU Feijing,WEN Peng,et al.In-situ growth of Co2P nanocrystal on g-C3N4 for efficient and stable photocatalytic hydrogen evolution[J].Energy & Fuels,2021,35(2):1859-1865.
[7] SUN Qianqian,YU Zebin,JIANG Ronghua,et al.CoP QD anchored carbon skeleton modified CdS nanorods as a co-catalyst for photocatalytic hydrogen production[J].Nanoscale,2020,12(37):19203-19212.
[8] SHAO Qi,LI Tianjiao,WANG Hengguo,et al.A facile one-pot synthesis of Co2P nanoparticle-encapsulated doped carbon nanotubes as bifunctional electrocatalysts for high-performance rechargeable Zn-air batteries[J].Cryst Eng Comm,2021,23(4):1013-1018.
[9] JI Pengxia,LUO Xu,CHEN Ding,et al.Significantly improved water oxidation of CoP catalysts by electrochemical activation[J].ACS Sustainable Chemistry & Engineering,2020,8(48):17851-17859.
[10] XU Shaohong,WANG Jingfeng,VALÉRIO A,et al.Activating Co nanoparticles on graphitic carbon nitride by tuning the Schottky barrier via P doping for the efficient dehydrogenation of ammonia-borane[J].Inorganic Chemistry Frontiers,2021,8(1):48-58.
[11] LI Ruiqian,HOU Yuanyuan,DONG Qiujing,et al.Wear and corrosion resistance of Co-P coatings:the effects of current modes[J].RSC Advances,2018,8(2):895-903.
[12] 吕孟娜,方志刚,秦渝,等.团簇Ni4P催化析氢性能研究[J].化学通报,2022,85(5):624-629.
[13] TOUZANI R S,REHORN C W G,FOKWA B P T.Influence of chemical bonding and magnetism on elastic properties of the A2MB2 borides(A=Nb,Ta; M=Fe,Ru,Os)from first-principles calculations[J].Computational Materials Science,2015,104:52-59.
[14] 秦渝,方志刚,赵璐璐,等.团簇Co3NiB2异构化反应的动力学与热力学研究[J].江西师范大学学报(自然科学版),2021,45(1):67-74.
[15] 秦渝,方志刚,张伟,等.团簇Co3NiB催化析氢活性研究[J].江西师范大学学报(自然科学版),2020,44(1):56-62.
[16] 郑新喜,方志刚,侯欠欠,等.团簇Fe3Ni3的极化率与催化性质[J].江西师范大学学报(自然科学版),2021,45(5):473-479.
[17] 李历红,方志刚,赵振宁,等.团簇Ni3CoP电子性质与磁性研究[J].江西师范大学学报(自然科学版),2019,43(2):160-166.
[18] 郑新喜,方志刚,秦渝,等.团簇Fe3Ni3电子性质[J].贵州大学学报(自然科学版),2021,38(5):7-12,19.
[19] 方志刚,王智瑶,郑新喜,等.团簇Co3NiB2极化率、偶极矩及态密度研究[J].贵州大学学报(自然科学版),2022,39(1):17-24.
[20] 侯欠欠,方志刚,秦渝,等.团簇Fe4P的成键及极化率探究[J].广西师范大学学报(自然科学版),2021,39(6):140-146.
[21] CHECK C E,FAUST T O,BAILEY J M,et al.Addition of polarization and diffuse functions to the LANL2DZ basis set for p-block elements[J].The Journal of Physical Chemistry A,2001,105(34):8111-8116.
[22] FUKUI K,YONEZAWA T,SHINGU H.A molecular orbital theory of reactivity in aromatic hydrocarbons[J].The Journal of Chemical Physics,1952,20(4):722-725.
[23] FUKUI K.Recognition of stereochemical paths by orbital interaction[J].Accounts of Chemical Research,1971,4(2):57-64.

相似文献/References:

[1]秦 渝,方志刚*,张 伟,等.团簇Co3NiB催化析氢活性研究[J].江西师范大学学报(自然科学版),2020,(01):56.[doi:10.16357/j.cnki.issn1000-5862.2020.01.10]
　QIN Yu,FANG Zhigang*,ZHANG Wei,et al.The Study on the Catalytic Properties of Cluster Co3NiB in the Hydrogen Evolution Reaction[J].Journal of Jiangxi Normal University:Natural Science Edition,2020,(03):56.[doi:10.16357/j.cnki.issn1000-5862.2020.01.10]

备注/Memo

备注/Memo:
收稿日期:2022-03-15
基金项目:国家自然科学基金(51634004),国家级大学生创新创业训练计划(202110146027,202010146009,202010146016)和辽宁省大学生创新创业训练计划(S202110146030,S202110146056,S202110146052,S202110146055,S202110146040,S202110146049)资助项目.
作者简介:方志刚(1964—),男,辽宁鞍山人,教授,博士,博士生导师,主要从事量子化学、物理化学及表面催化研究.E-mail:lnfzg@163.com
更新日期/Last Update: 2022-05-25