Tailoring the Active-Site Spacing of a Single-Atom Catalyst for CH₄-to-CH₃OH Conversion: The Co₁/UiO-66 MOF as an Exemplary Model

Harrath, Karim1; Yao, Zhen1; Jiang, Ya-Fei1; Wang, Yang-Gang1; Li, Jun1,2,3,4

2024-03-25

10.1021/acs.jpcc.4c00742

JOURNAL OF PHYSICAL CHEMISTRY C   影响因子和分区

1932-7447

1932-7455

Developing catalysts for the mild and selective oxidation of methane to methanol (CH4-to-CH3OH) is a challenging yet crucial endeavor for the industry. In this study, we propose a strategy to enhance the selective methane oxidation reaction, focusing on the crucial step of metal-oxo active-site formation. Our findings demonstrate that optimizing the spacing between active metal sites can facilitate efficient charge transfer from the metal sites to O-2, thereby kinetically enhancing O-2 activation and leading to the formation of highly reactive O (oxo) species capable of activating the methane C-H bond. Through the screening of different metals at varying metal site spacings, we find that the Co single atom exhibits favorable properties and performance, characterized by the duality of a low O-2 activation energy and the radical character of the formed metal-oxo species. Utilizing a Co single-atom catalyst dispersed on the UiO-66 MOF as a probe catalyst, we have showcased the potential of tailoring the active-site spacing to enhance the activity and selectivity toward methane oxidation to methanol. Notably, the newly designed catalyst surpasses the activity of a known catalyst, achieving an observable turnover frequency (>1 s(-1) site(-1)) at 350 K while also enhancing its selectivity by inhibiting continuous methane dehydrogenation. This strategic approach could provide valuable insights for further exploration of MOF-supported single-atom catalysts or other support morphologies for the selective oxidation of CH4 to CH3OH with excellent activity in the gas phase.

SCI ; EI

英语

第一 ; 通讯

Guangdong Provincial Pearl River Talents Program[2022YFA1503102] ; National Key R&D Program of China[22033005] ; NSFC[22388102] ; NSFC Center for Single-Atom Catalysis[JCYJ20220818100410023] ; Shenzhen Science and Technology Program[2019QN01L353] ; Guangdong "Pearl River" Talent Plan[2020B121201002]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:001191201000001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
3.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
4.Ganjiang Innovat Acad, Chinese Acad Sci, Fundamental Sci Ctr Rare Earths, Ganzhou 341000, Peoples R China

Harrath, Karim,Yao, Zhen,Jiang, Ya-Fei,et al. Tailoring the Active-Site Spacing of a Single-Atom Catalyst for CH₄-to-CH₃OH Conversion: The Co₁/UiO-66 MOF as an Exemplary Model[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2024,128(13).

Harrath, Karim,Yao, Zhen,Jiang, Ya-Fei,Wang, Yang-Gang,&Li, Jun.(2024).Tailoring the Active-Site Spacing of a Single-Atom Catalyst for CH₄-to-CH₃OH Conversion: The Co₁/UiO-66 MOF as an Exemplary Model.JOURNAL OF PHYSICAL CHEMISTRY C,128(13).

Harrath, Karim,et al."Tailoring the Active-Site Spacing of a Single-Atom Catalyst for CH₄-to-CH₃OH Conversion: The Co₁/UiO-66 MOF as an Exemplary Model".JOURNAL OF PHYSICAL CHEMISTRY C 128.13(2024).