当前位置: X-MOL 学术Annu. Rev. Chem. Biomol. Eng. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Dynamic Interconversion of Metal Active Site Ensembles in Zeolite Catalysis
Annual Review of Chemical and Biomolecular Engineering ( IF 7.6 ) Pub Date : 2021-06-07 , DOI: 10.1146/annurev-chembioeng-092120-010920
Siddarth H Krishna 1 , Casey B Jones 1 , Rajamani Gounder 1
Affiliation  

Catalysis science is founded on understanding the structure, number, and reactivity of active sites. Kinetic models that consider active sites to be static and noninteracting entities are routinely successful in describing the behavior of heterogeneous catalysts. Yet, active site ensembles often restructure in response to their external environment and even during steady-state catalytic turnover, sometimes requiring non-mean-field kinetic treatments to describe distance-dependent interactions among sites. Such behavior is being recognized more frequently in modern catalysis research, with the advent of experimental methods to quantify turnover rates with increasing precision, an expanding arsenal of operando characterization tools, and computational descriptions of atomic structure and motion at chemical potentials and timescales increasingly relevant to reaction conditions. This review focuses on dynamic changes to metal active site ensembles on zeolite supports, which are silica-based crystalline materials substituted with Al that generate binding sites for isolated and low-nuclearity metal site ensembles. Metal sites can become solvated and mobilized during reaction, facilitating interactions among sites that change their nuclearity and function. Such intersite communication can be regulated by the zeolite support, resulting in non-single-site and potentially non-mean-field kinetic behavior arising from mechanisms of catalytic action that combine elements of those canonically associated with homogeneous and heterogeneous catalysis.We discuss recent literature examples that document dynamic active site behavior in metal-zeolites and outline methodologies to identify and interpret such behavior. We conclude with our outlook on future research directions to develop this evolving branch of catalysis science and harness it for practical applications.

中文翻译:


沸石催化中金属活性位点集合的动态互变

催化科学建立在了解活性位点的结构、数量和反应性的基础上。将活性位点视为静态和非相互作用实体的动力学模型通常成功地描述了非均相催化剂的行为。然而,活性位点集合通常会根据其外部环境甚至在稳态催化转换期间进行重构,有时需要非平均场动力学处理来描述位点之间依赖于距离的相互作用。这种行为在现代催化研究中被更频繁地识别出来,随着实验方法的出现以越来越高的精度量化周转率,操作表征工具的扩展库,化学势和时间尺度上原子结构和运动的计算描述与反应条件越来越相关。本综述重点关注沸石载体上金属活性位点集合的动态变化,沸石载体是用 Al 取代的二氧化硅基晶体材料,可为孤立的低核金属位点集合生成结合位点。金属位点可以在反应过程中被溶剂化和移动,促进位点之间的相互作用,从而改变其核数和功能。这种位点间的通讯可以通过沸石载体进行调节,导致非单点和潜在的非平均场动力学行为产生于催化作用机制,这些机制结合了与均相和非均相催化相关的元素。我们讨论了最近的文献实例,这些实例记录了金属沸石中的动态活性位点行为,并概述了识别和解释这种行为的方法。我们总结了对未来研究方向的展望,以发展这一不断发展的催化科学分支并将其用于实际应用。

更新日期:2021-06-08
down
wechat
bug