[1]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,(01):67-74.[doi:10.16357/j.cnki.issn1000-5862.2021.01.10]
 QIN Yu,FANG Zhigang*,ZHAO Lulu,et al.The Study on the Dynamics and Thermodynamics of Isomeric Transformation of Cluster Co3NiB2[J].Journal of Jiangxi Normal University:Natural Science Edition,2021,(01):67-74.[doi:10.16357/j.cnki.issn1000-5862.2021.01.10]
点击复制

团簇Co3NiB2异构化反应的动力学与热力学研究()
分享到:

《江西师范大学学报》(自然科学版)[ISSN:1006-6977/CN:61-1281/TN]

卷:
期数:
2021年01期
页码:
67-74
栏目:
出版日期:
2021-02-10

文章信息/Info

Title:
The Study on the Dynamics and Thermodynamics of Isomeric Transformation of Cluster Co3NiB2
文章编号:
1000-5862(2021)01-0067-08
作者:
秦 渝方志刚*赵璐璐廖 薇许 友
辽宁科技大学化学工程学院,辽宁 鞍山 114051
Author(s):
QIN YuFANG Zhigang*ZHAO LuluLIAO WeiXU You
School of Chemical Engineering,University of Science and Technology of Liaoning,Anshan Liaoning 114051,China
关键词:
团簇Co3NiB2 异构化反应 密度泛函理论 过渡态理论 范特荷夫方程 阿伦尼乌斯方程
Keywords:
cluster Co3NiB2 isomerization reaction density functional theory transition state theory Van’t Hoff equation Arrhenius equation(责任编辑:刘显亮)
分类号:
O 641.12
DOI:
10.16357/j.cnki.issn1000-5862.2021.01.10
文献标志码:
A
摘要:
为确定团簇Co3NiB2最终能稳定存在的优化构型并探究不同异构化反应在不同温度下与平衡常数、指前因子之间的关系,基于密度泛函理论与过渡态理论在B3LYP/Lanl2dz水平下结合范特荷夫方程与阿伦尼乌斯方程,分别从化学动力学与化学热力学角度对团簇Co3NiB2的异构化反应进行深入讨论.研究结果表明:构型1(4)~4(4)能大量稳定存在,且连串反应7(4)→5(4)→4(2)→1(2)最容易发生; 依据范特荷夫方程积分式可知平衡常数的对数ln K与1/T呈线性关系,依据阿伦尼乌斯方程的衍生公式可知ln A与1/T同样呈线性关系; 当T=298.15 K时,ln K与反应物和生成物的能量差ΔE呈正相关关系,且同时满足线性方程ln K(T)=0.404 31ΔE+0.388 26.研究预测团簇各个优化构型所能发生异构化反应的平衡常数K的取值范围为0.946 0~9.431 9×1019.
Abstract:
In order to determine the optimized configurations of cluster Co3NiB2 and explore the relationship between different isomerization reactions and equilibrium constants,pre-exponential factors at different temperatures,the isomerization of cluster Co3NiB2 is thoroughly discussed from the view of chemical dynamics and thermodynamics,based on the density functional theory and transition state theory and combined with Van’t Hoff equation and Arrhenius equation at the B3LYP/Lanl2dz level.The results show that configuration 1(4)—4(4) can exist in a large amount,and the reaction 7(4)→5(4)→4(2)→1(2) is most easily to occur.According to the integral formula of Van’t Hoff equation,the ln K and 1/T of the equilibrium constant show a linear relationship.According to the derivative formula of Arenius equation,ln A and 1/T also show a linear relationship.When T=298.15 K,the ln K of the equilibrium constant is positively correlated with the energy difference(ΔE)of reactants and products,and meets the linear equation that is ln K(T)=0.404 31ΔE+0.388 26.At the same time,the range of the equilibrium constant K of the isomerization reaction of the optimized configurations is from 0.946 0 to 9.431 9×1019.

参考文献/References:

[1] Yin Xueli,Wang Quan,Duan Donghong,et al.Amorphous NiB alloy decorated by Cu as the anode catalyst for a direct borohydride fuel cell[J].International Journal of Hydrogen Energy,2019,44(21):10971-10981.
[2] Yu Wanqiu,Zhou Qinglei,Liu Zuoshan,et al.Effect of heat treatment on the microstructure and magnetic properties of amorphous alloy Fe60Co19Zr9B12[J].Metal Science and Heat Treatment,2019,61(1/2):27-31.
[3] Yousaf A B,Imran M,Farooq M,et al.Synergistic effect of Co-Ni co-bridging with MoS2 nanosheets for enhanced electrocatalytic hydrogen evolution reactions[J].Rsc Advances,2018,8(7):3374-3380.
[4] Duwez P,Willens R H,Klement W,et al.Continuous series of metastable solid solutions in silver-copper alloys[J].Journal of Applied Physics,1960,31(6):1136-1137.
[5] Klement W,Willens R H,Duwez P,et al.Non-crystalline structure in solidified gold-silicon alloys[J].Nature,1960,187(4740):869-870.
[6] Novikov V V,Zhemoedov N A,Mitroshenkov N V,et al.Anomalies in thermal expansion and heat capacity of TmB50 at low temperatures:magnetic phase transition and crystal electric field effect[J].Dalton Transactions,2016,45(43):17447-17452.
[7] Sun Hongming,Meng Jing,Jiao Lifang,et al.A review of transition-metal boride/phosphide-based materials for catalytic hydrogen generation from hydrolysis of boron-hydrides[J].Inorganic Chemistry Frontiers,2018,5(4):760-772.
[8] Yang Yisu,Zhuang Linzhou,Rufford T E,et al.Efficient water oxidation with amorphous transition metal boride catalysts synthesized by chemical reduction of metal nitrate salts at room temperature[J].RSC Advances,2017,7(52):32923-32930.
[9] Bourourou Y,Beldi L,Bentria B,et al.Structure and magnetic properties of the 3d transition-metal mono-borides TM-B(TM=Mn,Fe,Co)under pressures[J].Journal of Magnetism and Magnetic Materials,2014,365(1):23-30.
[10] Chen Qiang,Zhao Yanxia,Jiang Lixue,et al.Thermal activation of methane by vanadium boride cluster cations VB+n(n=3—6)[J].Physical Chemistry Chemical Physics,2018,20(7):4641-4645.
[11] Zhu Qiaohong,Qiu Bocheng,Du Mengmeng,et al.Nickel boride co-catalyst boosting efficient photocatalytic hydrogen evolution reaction[J].Industrial and Engineering Chemistry Research,2018,57(24):8125-8130.
[12] 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.
[13] Sun Hongming,Xu Xiaobin,Yan Zhenhua,et al.Superhydrophilic amorphous Co-B-P nanosheet electrocatalysts with Pt-like activity and durability for the hydrogen evolution reaction[J].Journal of Materials Chemistry,2018,6(44):22062-22069.
[14] Drisko G L,Gatel C,Fazzini P F,et al.Air-stable anisotropic monocrystalline nickel nanowires characterized using electron holography[J].Nano Letters,2018,18(3):1733-1738.
[15] 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.
[16] Eyring H.The quantum theory of activation and absolute reaction rates of photochemical processes[C]∥Cold Spring Harbor Symposia on Quantitative Biology.New York:Cold Spring Harbor Laboratory Press,1935,3:10-18.
[17] Fernades R,Patel N,Miotell O A,et al.Studies on catalytic behavior of Co-Ni-B in hydrogen production by hydrolysis of NaBH4[J].Journal of Molecular Catalysis A:Chemical,2009,298(1/2):1-6.
[18] Yu Xuegang.Hyperbolic multi-topology and the basic principle in quantum mechanics[J].Advances in Applied Clifford Algebras,1999,9(1):109-118.
[19] Hay P J.Gaussian basis sets for molecular calculations:the representation of 3d orbitals in transition-metal atoms[J].The Journal of Chemical Physics,1977,66(10):4377-4384.
[20] Hay P J,Wadt W R.Ab initio effective core potentials for molecular calculations:potentials for the transition metal atoms Sc to Hg[J].The Journal of Chemical Physics,1985,82(1):270-283.
[21] Peng Chunyang,Schlegel H B.Combining synchronous transit and quasi-newton methods to find transition states[J].Isr J Chem,1993,33(4):449-454.
[22] Cohen N,Westberg K R.The use of transition-state theory to extrapolate rate coefficients for reactions of O atoms with alkanes[J].International Journal of Chemical Kinetics,1986,18(1):99-140.
[23] Zanoelo E F,Beninca C.Chemical kinetics of 5-o-caffeoylquinic acid in superheated steam:effect of isomerization on mate(Ilex paraguariensis)manufacturing[J].Journal of Agricultural and Food Chemistry,2009,57(24):11564-11569.

备注/Memo

备注/Memo:
收稿日期:2020-03-16
基金项目:国家自然科学基金重点课题(51634004),国家级大学生创新创业训练计划(201910146032,201910146034,201910146037,202010146009,202010146016)和辽宁省大学生创新创业训练计划(201910146039)资助项目.
通信作者: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方面的研究.E-mail:lnfzg@163.com
更新日期/Last Update: 2021-04-10