The Key Role of Support Surface Hydrogenation in the CH4 to CH3OH Selective Oxidation by a ZrO2-Supported Single-Atom Catalyst

Harrath, Karim1,2; Yu, Xiaohu3,4; Xiao, Hai1,2; Li, Jun1,2,5

2019-10

10.1021/acscatal.9b02093

ACS Catalysis   影响因子和分区

2155-5435

Direct conversion of methane to methanol has attracted much interest and yet remains a challenge. Here, we investigate the catalytic mechanisms for methane oxidation on the Rh single-atom catalyst (SAC) dispersed on zirconia support Rh-1/ZrO2 by first-principles calculations. We find that, by comparison with other metal SACs dispersed on ZrO2, the spontaneous dissociative adsorption of H2O2 on the Rh-1/ZrO2 surface is a key factor that initiates the active site and hydrogenates the surrounding oxide support surface. We further reveal that the hydrogenation of the oxide support surface plays a key role in suppressing the further production of CH3OOH and CO2. Additionally, we propose a non-noble-metal Fe-1/ZrO2 SAC as an active and selective catalyst for direct CH4 to CH3OH conversion, potentially performing better than the current best Rh-1/ZrO2 SAC. Our findings provide insights for the design of highly selective and efficient catalysts for direct CH4 to CH3OH conversion.

methane to methanol selectivity single-atom catalyst support surface hydrogenation density functional theory calculations

SCI ; EI

英语

通讯

Natural Science Basic Research Program of Shaanxi Province[2019JM-226]

Chemistry

Chemistry, Physical

WOS:000489204000007

AMER CHEMICAL SOC

20193907479614

Atoms ; Calculations ; Catalyst selectivity ; Catalytic oxidation ; Density functional theory ; Hydrogenation ; Methane ; Methanol ; Precious metals ; Rhodium compounds ; Zirconia

Precious Metals:547.1 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Mathematics:921 ; Atomic and Molecular Physics:931.3

Web of Science

1.Tsinghua Univ, Minist Educ, Dept Chem, Beijing 100084, Peoples R China
2.Tsinghua Univ, Minist Educ, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China
3.Shaanxi Univ Technol, Shaanxi Key Lab Catalysis, Hanzhong 723000, Peoples R China
4.Shaanxi Univ Technol, Sch Chem & Environm Sci, Hanzhong 723000, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Harrath, Karim,Yu, Xiaohu,Xiao, Hai,et al. The Key Role of Support Surface Hydrogenation in the CH4 to CH3OH Selective Oxidation by a ZrO2-Supported Single-Atom Catalyst[J]. ACS Catalysis,2019,9(10):8903-8909.

Harrath, Karim,Yu, Xiaohu,Xiao, Hai,&Li, Jun.(2019).The Key Role of Support Surface Hydrogenation in the CH4 to CH3OH Selective Oxidation by a ZrO2-Supported Single-Atom Catalyst.ACS Catalysis,9(10),8903-8909.

Harrath, Karim,et al."The Key Role of Support Surface Hydrogenation in the CH4 to CH3OH Selective Oxidation by a ZrO2-Supported Single-Atom Catalyst".ACS Catalysis 9.10(2019):8903-8909.