CO/OH诱导的TiO_(2)(110)上贵金属纳米粒子分解的第一性原理热力学研究  

First-Principles Thermodynamics Study of CO/OH Induced Disintegration of Precious Metal Nanoparticles on TiO_(2)(110)

作　　者：曹士彦 胡素磊 李微雪 Shiyan Cao;Sulei Hu;Wei-Xue Li(Department of Chemical Physics,School of Chemistry and Materials Science,Hefei National Research Center for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学技术大学化学与材料科学学院,合肥微尺度物质科学国家研究中心,合肥230026

出　　处：《Chinese Journal of Chemical Physics》2023年第4期411-418,I0001-I0005,I0034,共14页化学物理学报（英文）

基　　金：supported by the National Key R&D Program of China(2021YFB3502000,2018YFA0208603);National Program for Support of Top-notch Young Professional,Chinese Academy of Sciences Youth Innovation Promotion Association,Anhui Outstanding Youth Fund(No.2208085J27);the National Natural Science Foundation of China(No.22221003,No.91945302,No.21903077);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450102);Innovation Program for Quantum Science and Technology(2021ZD0303302);Chinese Academy of Sciences(QYZDJ-SSW-SLH054);K.C.Wong Education(GJTD-2020-15);the Dalian National Laboratory For Clean Energy(DNL)Cooperation Fund,the CAS(DNL201920);the China Postdoctoral Science Foundation,the Fundamental Research Funds for the Central Universities,USTC Research Funds of the Double First-Class Initiative(KY9990000170,YD9990002008)。

摘　　要：本文揭示了反应气氛诱导的负载型金属纳米粒子分解的机制及其对金属组分与气氛的依赖关系,对于改进负载型金属纳米催化剂和单原子催化剂的稳定性至关重要.为此使用了第一性原理方法,研究了在完整和氧桥位缺陷的TiO_(2)(110)上CO和OH诱导的Ag、Cu、Au、Ni、Pt、Rh、Ru和Ir纳米粒子分解为金属-反应物复合物(M(CO)n,M(OH)n,n=1和2)的分解热力学.结果表明,相比OH来说,CO与这些过渡金属的相互作用更强,从而拥有更低的形成能,对分解为金属-反应物复合物具有更大的促进作用.反应物的吸附能与金属内聚能表现出线性依赖关系,拥有更高的内聚能的金属,由于其与气氛和载体的结合更强,表现出更高的原子稳定性。进一步的熟化自由能计算表明只有CO诱导的Ni、Rh、Ru和Ir的纳米粒子的分解是热力学可行的.这些结果为反应气氛诱导的金属纳米粒子分解为热力学稳定的金属单原子催化剂提供了进一步的理解.Revealing the fundamental mechanisms governing reactant-induced disintegration of supported metal nanoparticles and their dependences on the metal component and reactant species is vital for improving the stability of supported metal nanocatalysts and single-atom catalysts.Here we use first-principlesbased disintegration thermodynamics to study the CO-and OH-induced disintegration of Ag,Cu,Au,Ni,Pt,Rh,Ru,and Ir nanoparticles into metal-reactantcomplexes(M(CO)n,M(OH)n,n=1 and 2)on the pristine and bridge oxygen vacancy site of TiO_(2)(110).It was found that CO has a stronger interaction with these considered transition metals compared to OH,resulting in lower formation energy and a larger promotion effect on the disintegration of nanoparticles(NPs).The corresponding reactant adsorption energy shows a linear dependence on the metal cohesive energy,and metals with higher cohesive energies tend to have higher atomic stability due to their stronger binding with reactant and support.Further disintegration free energy calculations of NPs into metal-reactant complexes indicate only COinduced disintegration of Ni,Rh,Ru,and Ir nanoparticles is thermodynamically feasible.These results provide a deeper understanding of reactant-induced disintegration of metal nanoparticles into thermodynamically stable metal single-atom catalysts.

关 键 词：热力学 分解 密度泛函理论 金属纳米粒子 

分 类 号：O647.3[理学—物理化学] O641.4[理学—化学]