RhCu催化剂中限域环境调控合成气转化生成CH x 反应性能

doi:10.16085/j.issn.1000-6613.2023-2179

摘要/Abstract

摘要：

合成气制C₂含氧化合物的选择性目前仍面临巨大挑战。本研究基于密度泛函理论计算方法，探究了4种RhCu限域催化剂中Rh活性位限域环境对合成气转化生成CH _x 反应性能的影响，揭示了RhCu限域催化剂中限域效应调控催化性能的本质。结果表明，RhCu限域催化剂中Rh活性位限域环境能够调控合成气转化生成CH _x 的活性和选择性。筛选获得催化剂具有最高的生成CH _x （x=1~3）单体活性，归因于适中的限域效应使得表层原子d带中心远离费米能级，导致CH₂OH解离过渡态与RhCu表面之间呈现适当的电子转移，利于CH₂OH解离，从而呈现良好的CH _x 生成活性。本研究为通过调变单原子限域环境实现调控合成气转化生成C₂含氧化合物反应的催化性能提供了理论依据，并为单原子限域金属催化剂设计提供了结构线索。

关键词: 限域催化剂, 限域环境, 合成气, 碳氢化合物, 密度泛函理论

Abstract:

The selectivity of syngas-to-C₂ oxygenates still faces a big challenge. Using density functional theory calculation methods, this study explores the influence of the confined environment of Rh active sites on the reaction performance of syngas conversion to CH _x over four types of RhCu confined catalysts, which further reveals the essential reasons of the confinement effect to regulate the catalytic performance. The results showed that the confined environment of Rh active sites in the RhCu confined catalysts can regulate the activity and selectivity of syngas conversion to generate CH _x . The screened catalyst could perform the highest catalytic activity toward syngas conversion to generate CH _x (x=1—3) monomer. The moderate confinement effect of catalyst made the d-band center of surface atoms far away from the Fermi level, leading to an appropriate electron gain and loss between the transition state of CH₂OH dissociation and RhCu surface, which was conducive to the dissociation of CH₂OH into CH₂ and thus exhibited excellent CH _x formation activity. This study provides theoretical basis for improving the catalytic performance of syngas conversion to C₂ oxygenates by adjusting the confined environment of active site and provides the structural clues for the design of the confined metal single-atom catalysts.

Key words: confined catalyst, confined environment, syngas, CH _x, density functional theory

中图分类号:

O643.3

李娜, 赵婉彤, 凌丽霞, 王宝俊, 章日光. RhCu催化剂中限域环境调控合成气转化生成CH _x 反应性能[J]. 化工进展, 2024, 43(5): 2684-2695.

LI Na, ZHAO Wantong, LING Lixia, WANG Baojun, ZHANG Riguang. Confined environment of RhCu catalyst to regulate the reaction performance for synthesis gas conversion to CH _x[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2684-2695.

图/表 12

图1 不同限域环境的RhCu催化剂模型

图2 合成气转化生成关键中间体CH x （x=1~3）的可能路径

图3 RhGCN7.5、RhGCN6.7、RhGCN5.5和RhGCN5.8催化剂上CO活化势能及基元反应的初始、过渡态和末态结构

图4 RhCu催化剂上C、H和O原子的态密度

图5 RhGCN7.5、RhGCN6.7、RhGCN5.5和RhGCN5.8催化剂上CH生成反应势能

图6 RhGCN7.5、RhGCN6.7、RhGCN5.5和RhGCN5.8催化剂上CH2生成反应势能

图7 RhGCN7.5、RhGCN6.7、RhGCN5.5和RhGCN5.8催化剂上CH3生成反应势能

图8 RhGCN7.5、RhGCN6.7、RhGCN5.5和RhGCN5.8催化剂上CH3OH生成反应势能

图9 RhCu催化剂上CH x （x=1~3）和CH3OH最有利路径的总能垒及相应的CH x （x=1~3）选择性

图10 RhCu催化剂上CH2相关反应势能

图11 RhGCN7.5、RhGCN6.7、RhGCN5.8和RhGCN5.5催化剂上Cu金属表面对Rh活性位施加不同的限制作用(a)及Econfinement与Rh原子的Bader电荷和CH2生成总能垒火山曲线关系(b)

图12 RhGCN7.5、RhGCN6.7、RhGCN5.8和RhGCN5.5催化剂表层原子d带中心与CH2OH解离生成CH2和OH的活性和该反应过渡态分子[TS(CH2OH)]Bader电荷之间的关系

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