摘要
载体上孤立的Pd原子作为乙炔半加氢反应的催化活性位点,由于具有独特的反应性和高效的金属利用率而备受关注.特别是在金属氧化物表面的不同位点掺杂Pd单原子,可以通过调节其局部配位环境来调控其电子和催化性能.本文采用密度泛函理论计算,研究了TiO_(2)负载Pd单原子的局域配位环境对Pd_(1)/TiO_(2)催化剂上乙炔半加氢反应的活性和选择性的影响.综合考虑反应活性和选择性,发现具有负电荷Pd^(δ-)位点的Pd_(1)Ti_(3)/TiO_(2)四原子单团簇催化剂展现出优异的催化性能.此外,活性和选择性与表面性质如d-带中心指数和表面功函数等密切相关.本文为未来设计可还原氧化物载体上的高效单团簇催化剂以用于类似的多相催化反应提供了理论参考.
Acetylene semi-hydrogenation is a vital process where the utilization of supported isolated Pd atoms as catalytic active sites is promising due to their unique reactivity and metal atom efficacy.In particular,doping Pd single atoms at different sites on metal-oxide surfaces provides an opportunity to regulate their local coordination environments and modulate their electronic and catalytic properties.In this study,we conduct extensive density functional theory calculations to investigate the influence of single Pd atom coordination environments and surface properties on the activity and selectivity of Pd_(1)/TiO_(2) catalysts for acetylene semihydrogenation.Considering the activity and selectivity,a fouratom single-cluster catalyst(SCC)of Pd_(1)Ti_(3)/TiO_(2) with negatively charged Pd^(δ-)sites is found to exhibit excellent catalytic performance.Moreover,both activity and selectivity are highly correlated with the surface properties,including the dband center index and surface work function.Our work provides theoretical guidance for the future design of heterogeneous SCC on reducible oxide supports for similar reactions in heterogeneous catalysis.
作者
赵姝
汤妍
于小虎
李隽
Shu Zhao;Yan Tang;Xiaohu Yu;Jun Li(Institute of Advanced Battery Materials and Devices,Faculty of Materials and Manufacturing,Beijing University of Technology,Beijing 100124,China;Key Laboratory of Advanced Functional Materials,Ministry of Education,Beijing University of Technology,Beijing 100124,China;Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education,Tsinghua University,Beijing 100084,China;Shaanxi Key Laboratory of Catalysis,School of Chemical&Environment Sciences,Shaanxi University of Technology,Hanzhong 723000,China;Department of Chemistry,Southern University of Science and Technology,Shenzhen 518055,China)
基金
supported by the Foundation of Key Laboratory of Low-Carbon Conversion Science&Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences(KLLCCSE201902,SARI,CAS)
the National Natural Science Foundation of China(22033005,22002004,22273053 and 92261203)
the National Key R&D Project(2022YFA1503900 and 2022YFA1503000)
the NSFC Center for Single-Atom Catalysis
the Natural Science Basic Research Program of Shaanxi(S2020-JC-WT-0001 and S2021JCW-20)
Support of Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
