First-Principles Insights into Pt_(n)/ZnO(0001)Catalyst:Regulation of Metal-Support Interaction through Surface Polarity  

Pt_(n)/ZnO(0001)催化剂的第一性原理研究:表面极性对金属-载体相互作用的调控作用

作　　者：Yue-Tong Sun Ju-Fang Zheng Ya-Hao Wang Xiao-Shun Zhou Qiang Wan 孙月同;郑菊芳;王亚浩;周小顺;万强(浙江师范大学物理化学研究所,先进催化材料教育部重点实验室,金华321004)

机构地区：[1]Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,Institute of Physical Chemistry,Zhejiang Normal University,Jinhua 321004,China

出　　处：《Chinese Journal of Chemical Physics》2024年第5期582-590,I0018-I0027,I0099,共20页化学物理学报（英文）

基　　金：This work was financially supported by the National Natural Science Foundation of China(Nos.22303085,22102150 and 22172146);the Zhejiang Provincial Natural Science Foundation of China(LQ24B030014 andLQ21B030010).

摘　　要：Polar surfaces are prevalent in metal oxides,the interactions between surface species with polar surfaces are different from those with non-polar surfaces,a thorough understanding of the interactions is key to regulate the performance of heterogeneous catalysts.In this work,we delve into the interaction of Pt_(n)(n=1-4)with polar ZnO(0001)-Zn and ZnO(0001)-O,and the influence of the surface polarity on the electronic structures and reactivity of Pt_(n) by using density functional theory calculations.The results suggest distinct differences in electronic structures of two exposed terminations,leading to different interactions with Pt_(n).The interaction between Pt_(n) and two terminations not only stabilizes the surface and clusters through polar compensation,but also induces opposite charges on the cluster at two terminations.Remarkably,the Pearson correlation coefficient reveals the interdependency between the electronic states of Pt_(n) and its performance in terms of small molecule adsorption/activation.These observations demonstrate the crucial role of surface polarity in regulating the electronic states and catalytic performance of active sites,and offer a possible design principle for supported catalysts.摘要:极性表面在金属氧化物中普遍存在,表面物种和极性表面的相互作用与其和非极性表面的相互作用截然不同,深入理解它们之间的相互作用对于多相催化剂的性能调控至关重要.本文通过密度泛函理论计算,深入研究了Pt_(n)(n=1~4)与极性ZnO(0001)-Zn和ZnO(0001)-O面的具体相互作用,以及表面极性对Pt电子结构和活性的影响机制.结果表明,两个表面的电子结构存在明显差异并导致它们与Pt_(n)相互作用截然不同.Pt_(n),与两个极性面间的相互作用不仅通过极性补偿机制稳定了表面和Pt_(n),还导致两个表面上的Pt_(n),携带相反电荷.值得注意的是,Pearson相关系数揭示了Pt_(n),的电子结构与其吸附活化小分子方面表现之间的关联性,这些结果表明表面极性在调控活性位点的电子态和催化性能具有关键作用,为负载型催化剂的提供了一个可能的设计策略.

关 键 词：Electronic structures Surface polarity Wurtzite ZnO Metal-support interaction 

分 类 号：O64[理学—物理化学]