从第一性原理理解金属二聚体上的CH转化

Understanding the CH Conversion over Metal Dimers from First Principles.

作者信息

Meng Haihong, Han Bing, Li Fengyu, Zhao Jingxiang, Chen Zhongfang

机构信息

School of Physical Science and Technology, Inner Mongolia University, Hohhot 010021, China.

Key Laboratory of Photonic and Electronic Bandgap Materials, College of Chemistry and Chemical Engineering, Ministry of Education, Harbin Normal University, Harbin 150025, China.

出版信息

Nanomaterials (Basel). 2022 Apr 29;12(9):1518. doi: 10.3390/nano12091518.

DOI:10.3390/nano12091518

PMID:35564225

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9100024/

Abstract

Inspired by the advantages of bi-atom catalysts and recent exciting progresses of nanozymes, by means of density functional theory (DFT) computations, we explored the potential of metal dimers embedded in phthalocyanine monolayers (M-Pc), which mimics the binuclear centers of methane monooxygenase, as catalysts for methane conversion using HO as an oxidant. In total, 26 transition metal (from group IB to VIIIB) and four main group metal (M = Al, Ga, Sn and Bi) dimers were considered, and two methane conversion routes, namely *O-assisted and *OH-assisted mechanisms were systematically studied. The results show that methane conversion proceeds via an *OH-assisted mechanism on the Ti-Pc, Zr-Pc and Ta-Pc, a combination of *O- and *OH-assisted mechanism on the surface of Sc-Pc, respectively. Our theoretical work may provide impetus to developing new catalysts for methane conversion and help stimulate further studies on metal dimer catalysts for other catalytic reactions.

摘要

受双原子催化剂的优势以及纳米酶近期令人振奋的进展启发，借助密度泛函理论（DFT）计算，我们探索了嵌入酞菁单层（M-Pc）中的金属二聚体作为使用HO作为氧化剂的甲烷转化催化剂的潜力，该金属二聚体模拟了甲烷单加氧酶的双核中心。总共考虑了26种过渡金属（从IB族到VIIIB族）和四种主族金属（M = Al、Ga、Sn和Bi）二聚体，并系统研究了两条甲烷转化途径，即O辅助和OH辅助机制。结果表明，甲烷转化分别通过Ti-Pc、Zr-Pc和Ta-Pc上的OH辅助机制以及Sc-Pc表面上的O和*OH辅助机制的组合进行。我们的理论工作可能为开发用于甲烷转化的新型催化剂提供动力，并有助于激发对用于其他催化反应的金属二聚体催化剂的进一步研究。