Mechanistic Investigations on Thermal Hydrogenation of CO2 to Methanol by Nanostructured CeO2(100): The Crystal-Plane Effect on Catalytic Reactivity

Zhang, Wei1; Ma, Xue-Lu4; Xiao, Hai2,3; Lei, Ming1; Li, Jun2,3,5

2019-05-09

10.1021/acs.jpcc.9b02120

Journal of Physical Chemistry C   影响因子和分区

1932-7447

As a key structural parameter, a crystal plane has a distinguished impact on the catalytic performance. Different exposed crystal planes exhibit different reactivities. CeO2 nanostructured powders are usually exposed to three low-index surfaces, which are (111), (110), and (100) surfaces. Because of the unique structure and low stability of the (100) surface, the investigation of the catalytic reaction mechanism on this surface is rarely involved. Here, density functional theory calculations suggest that the CeO2(100) surface exhibits the strongest reactivity for H-2 oxidation, attributed to the coordination unsaturation of surface oxygen atoms. For the hydrogenation of CO, to methanol on the defective CeO2(100) surface, CO, is prone to adsorb at the oxygen vacancy in a nearly linear configuration and the formate pathway was verified as the dominant one. The bi-H2COO* can easily convert to bi-H2CO* with the vacancy site filled, in which bi-H2CO* serves as the key intermediate in the methanol synthesis. This study aims at providing a better understanding of the catalytic reactivity of the CeO2(100) surface and theoretical insights into the experimental design of thermal CO2-to-methanol conversion.

SCI ; EI

英语

通讯

Beijing Natural Science Foundation[2184105]

Chemistry ; Science & Technology - Other Topics ; Materials Science

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

WOS:000467781000047

AMER CHEMICAL SOC

20192006938766

Carbon dioxide ; Catalysis ; Cerium oxide ; Density functional theory ; Hydrogenation ; Methanol ; Oxygen

Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Probability Theory:922.1

Web of Science

1.Beijing Univ Chem Technol, State Key Lab Chem Resource Engn, Inst Computat Chem, Coll Chem, Beijing 100029, Peoples R China
2.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
3.Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
4.China Univ Min & Technol, Sch Chem & Environm Engn, Beijing 100083, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Zhang, Wei,Ma, Xue-Lu,Xiao, Hai,et al. Mechanistic Investigations on Thermal Hydrogenation of CO2 to Methanol by Nanostructured CeO2(100): The Crystal-Plane Effect on Catalytic Reactivity[J]. Journal of Physical Chemistry C,2019,123(18):11763-11771.

Zhang, Wei,Ma, Xue-Lu,Xiao, Hai,Lei, Ming,&Li, Jun.(2019).Mechanistic Investigations on Thermal Hydrogenation of CO2 to Methanol by Nanostructured CeO2(100): The Crystal-Plane Effect on Catalytic Reactivity.Journal of Physical Chemistry C,123(18),11763-11771.

Zhang, Wei,et al."Mechanistic Investigations on Thermal Hydrogenation of CO2 to Methanol by Nanostructured CeO2(100): The Crystal-Plane Effect on Catalytic Reactivity".Journal of Physical Chemistry C 123.18(2019):11763-11771.