Theoretical Insights into Dual-Metal-Site Catalysts for the Nonoxidative Coupling of Methane

Huang，Zheng Qing1; Chen，You Tao1,2; Chang，Chun Ran1; Li，Jun3,4

2021

10.1021/acscatal.1c02597

ACS Catalysis   影响因子和分区

2155-5435

2155-5435

Direct conversion of methane to C2 hydrocarbons under nonoxidative conditions is an attractive technology but is challenging due to high reaction temperature, severe coke deposition, and low selectivity. Here, we report three dual-metal-site catalysts (DMSCs) based on nitrogen-doped graphene (FeCo-N-C, Fe2-N-C, and Co2-N-C) for nonoxidative coupling of methane to C2 hydrocarbons from a theoretical perspective. Our calculated results reveal that DMSCs present universally better performance in methane activation than single-metal-site catalysts (Fe-N-C and Co-N-C). Among the three DMSCs, Co2-N-C exhibits the best catalytic activity and superior selectivity to ethane in the whole reaction pathway. Our microkinetic modeling reveals that the Co2-N-C catalyst can convert methane to CH3, C2H6, and H2 at 1200 K. The electronic structure analysis and ab initio molecular dynamics simulations demonstrate that Co2-N-C possesses both intrinsic stability and high-temperature stability. Moreover, Co2-N-C also manifests better coke resistance compared with larger Co clusters, indicated by the difficult kinetics of methane deep dehydrogenation to naked carbon. This work provides a potential catalyst prototype for the selective conversion of methane to C2 hydrocarbons under nonoxidative conditions.

AIMD DFT dual-metal site methane nonoxidative coupling

SCI ; EI

英语

其他

National Natural Science Foundation of China[22078257,2210080405] ; China Postdoctoral Science Foundation["2018T111034","2021M692548"] ; Fundamental Research Funds for the Central Universities["xtr0218016","cxtd2017004"] ; Rising Star Program in Science and Technology of Shaanxi Province[2020KJXX-079] ; Shaanxi Creative Talents Promotion Plan-Technological Innovation Team[2019TD039] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Physical

WOS:000716773800030

AMER CHEMICAL SOC

20214411096100

Carbon dioxide ; Catalyst activity ; Coke ; Doping (additives) ; Electronic structure ; Iron compounds ; Metals ; Molecular dynamics ; Reaction kinetics

Solid Fuels:524 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2

2-s2.0-85118145494

Scopus

1.Shaanxi Key Laboratory of Energy Chemical Process Intensification,School of Chemical Engineering and Technology,Xi'An Jiaotong University,Xi'an,710049,China
2.Shaanxi Yanchang Petroleum (Group) Corp. Ltd.,Xi'an,710069,China
3.Department of Chemistry,Key Laboratory of Organic Optoelectronics and Molecular Engineering,Ministry of Education,Tsinghua University,Beijing,100084,China
4.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Huang，Zheng Qing,Chen，You Tao,Chang，Chun Ran,et al. Theoretical Insights into Dual-Metal-Site Catalysts for the Nonoxidative Coupling of Methane[J]. ACS Catalysis,2021,11(21):13149-13159.

Huang，Zheng Qing,Chen，You Tao,Chang，Chun Ran,&Li，Jun.(2021).Theoretical Insights into Dual-Metal-Site Catalysts for the Nonoxidative Coupling of Methane.ACS Catalysis,11(21),13149-13159.

Huang，Zheng Qing,et al."Theoretical Insights into Dual-Metal-Site Catalysts for the Nonoxidative Coupling of Methane".ACS Catalysis 11.21(2021):13149-13159.