Theoretical Study on the Catalytic CO2 Hydrogenation over the MOF-808-Encapsulated Single-Atom Metal Catalysts,The Journal of Physical Chemistry C

当前位置： X-MOL 学术 › J. Phys. Chem. C › 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.)

Theoretical Study on the Catalytic CO2 Hydrogenation over the MOF-808-Encapsulated Single-Atom Metal Catalysts
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-02-21 , DOI: 10.1021/acs.jpcc.2c08006
Jinlu Liu ₁ , Wenjuan Xue ₁ , Weiwei Zhang ₁ , Donghai Mei ₂

Affiliation

The search for new catalytic agents for reducing excess CO₂ in the atmosphere is a challenging but essential task. Due to the well-defined porous structures and unique physicochemical properties, metal–organic frameworks (MOFs) have been regarded as one of the promising materials in the catalytic conversion of CO₂ into valuable platform chemicals. In particular, introducing the second metal (M) atom to form the M^II–O–Zr⁴⁺ single-atom metal sites on the Zr nodes of MOF-808 would further greatly improve the catalytic performance. Herein, CO₂ hydrogenation reaction mechanisms and kinetics over a series of MOF-808-encapsulated single-atom metal catalysts, i.e., M^II–MOF-808 (M^II = Cu^II, Fe^II, Pt^II, Ni^II, and Pd^II), were systematically studied using density functional theory calculations. First, it has been found that the stability for the encapsulation of a divalent metal ion follows the trend of Pt^II > Ni^II > Pd^II > Cu^II > Fe^II, while they all possess moderate anchoring stability on the MOF-808 with the Gibbs replacement energies ranging from −233.7 to −310.3 kcal/mol. Two plausible CO₂ hydrogenation pathways on Cu^II–MOF-808 catalysts, i.e., formate and carboxyl routes, were studied. The formate route is more favorable, in which the H₂COOH*-to-H₂CO* step is kinetically the most relevant step over Cu^II–MOF-808. Using the energetic span model, the relative turnover frequencies of CO₂ hydrogenation to various C1 products over M^II–MOF-808 were calculated. The Cu^II–MOF-808 catalyst is found to be the most active catalyst among five M^II–MOF-808 catalysts.

中文翻译：

MOF-808包封单原子金属催化剂催化CO2加氢的理论研究

寻找新的催化剂来减少大气中过量的 CO _{2是一项具有挑战性但必不可少的任务。}_{由于明确定义的多孔结构和独特的物理化学性质，金属有机骨架 (MOF) 被认为是将 CO 2}催化转化为有价值的平台化学品的有前途的材料之一。特别地，引入第二个金属（M）原子在 MOF-808 的 Zr 节点上形成 M ^II –O–Zr ^{4+单原子金属位点将进一步大大提高催化性能。}在此，CO ₂加氢反应机制和动力学在一系列 MOF-808 封装的单原子金属催化剂上，即 M ^II –MOF-808 (M^II = Cu ^II、Fe ^II、Pt ^II、Ni ^II和 Pd ^II )，使用密度泛函理论计算进行了系统研究。^{首先，已经发现二价金属离子的包封稳定性遵循 Pt II} > Ni ^II > Pd ^II > Cu ^II > Fe ^II的趋势，而它们在 MOF-808 上都具有中等的锚定稳定性，吉布斯置换能范围为 -233.7 至 -310.3 kcal/mol。Cu ^II上两种可能的 CO _{2加氢途径}– 研究了 MOF-808 催化剂，即甲酸酯和羧基路线。甲酸盐路线更有利，其中 H ₂ COOH*-to-H _{2 CO* 步骤在动力学上是与 Cu}^II –MOF-808最相关的步骤。使用能量跨度模型，计算了M ^{II –MOF-808 上 CO}_{2加氢生成各种 C1 产物的相对周转频率。}发现Cu ^II –MOF-808 催化剂是五种 M ^II –MOF-808 催化剂中活性最高的催化剂。

更新日期：2023-02-21

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南