文献类型：期刊文献

英文题名：Achieving Theory-Experiment Parity for Activity and Selectivity in Heterogeneous Catalysis Using Microkinetic Modeling

作者：Xie, Wenbo[1];Xu, Jiayan[1];Chen, Jianfu[2,3];Wang, Haifeng[2,3];Hu, P.[1,2,3]

机构：[1]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland;[2]East China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2022

卷号：55

期号：9

起止页码：1237

外文期刊名：ACCOUNTS OF CHEMICAL RESEARCH

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000800139900005)】；

基金：We acknowledge the NSFC (92045303) and NKRDPC (2021YFA1500700) . We are grateful for computational support from the UK National High-Performance Computing Service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC grant ref EP/P022561/1. We are grateful to the UK Materials and Molecular Modeling Hub for computational resources, which is partially funded by the EPSRC (EP/P020194/1) . We are grateful for access to the Queen's University Belfast Kelvin HPC service, which is partially funded by ESPRC (EP/T022175/1) .

语种：英文

摘要：Microkinetic modeling based on density functional theory (DFT) energies plays an essential role in heterogeneous catalysis because it reveals the fundamental chemistry for catalytic reactions and bridges the microscopic understanding from theoretical calculations and experimental observations. Microkinetic modeling requires building a set of ordinary differential equations (ODES) based on the calculation results of thermodynamic properties of adsorbates and kinetic parameters for the reaction elementary steps. Solving a microkinetic model can extract information on catalytic chemistry, including critical reaction intermediates, reaction pathways, the surface species distribution, activity, and selectivity, thus providing vital guidelines for altering catalysts. However, the quantitative reliability of traditional microkinetic models is often insufficient to conclusively extrapolate the mechanistic details of complex reaction systems. This can be attributed to several factors, the most important of which is the limitation of obtaining an accurate estimation of the energy inputs via traditional calculation methods. These limitations include the difficulty of using static DFT methods to calculate reaction energies of adsorption/desorption processes, often rate-controlling or selectivity-determining steps, and the inadequate consideration of surface coverage effects. In addition, the robust microkinetic software is rare, which also complicates the resolution of complex catalytic systems. In this Account, we review our recent works toward refining the predictions of microkinetic modeling in heterogeneous catalysis and achieving theory-experiment parity for activity and selectivity. First, we introduce CATKINAS, a microkinetic software developed in our group, and show how it disentangles the problem that traditional microkinetic software has and how it can now be applied to obtain kinetic results for more sophisticated reaction systems. Second, we describe a molecular dynamics method developed recently to obtain the free-energy changes for the adsorption/desorption process to fill in the missing energy inputs. Third, we show that a rigorous consideration of surface coverage effects is pivotal for building more realistic models and obtaining accurate kinetic results. Following a series of studies on acetylene hydrogenation reactions on Pd catalysts, we demonstrate how this new approach can provide an improved quantitative understanding of the mechanism, active site, and intrinsic structural sensitivity. Finally, we conclude with a brief outlook and the remaining challenges in this field.