Chromium Single-Atom Catalyst with Graphyne Support: A Theoretical Study of NO Oxidation and Reduction

Talib, Shamraiz Hussain1,2; Hussain, Sajjad5; Baskaran, Sambath3; Lu, Zhansheng4; Li, Jun1,2,3

2020-10-16

10.1021/acscatal.0c01175

ACS Catalysis   影响因子和分区

2155-5435

Catalytic mechanisms and bonding analysis of NO oxidation and reduction on Cr single-atom catalysts (SAC) dispersed on the graphyne (GY) surface have been systematically investigated using the first-principles theoretical methods. GY is a decent support for isolated transition-metal (TM) atom catalysts because the most active sp-hybridized carbon atoms exist on the GY surface. All the single TM atoms are trapped into the void of the GY surface and existed in the isolated form. The molecular geometries and adsorbate binding energies of NO@TM-GY, ON@TM-GY, and O-2@TM-GY configurations are determined. We find that the Cr-GY is the most promising SAC for NO oxidation and reduction compared with the other TM-SACs. Herein, we report an efficient NO oxidation and reduction catalyzed by Cr-GY at ambient temperature. We find that Cr-GY SAC is very reactive for NO oxidation and reduction at ambient temperatures with low activation barriers to the rate-determining steps for Eley-Rideal (0.87, 0.60, and 0.62 eV) and Langmuir-Hinshelwood (0.69, 0.62, and 0.84 eV) mechanisms. The Termolecular Eley-Rideal mechanism for the formation of the NO2 molecule is not thermodynamically favorable. Comparative analysis revealed that the NO reduction (0.62 eV) is more favorable than NO oxidation (0.84 eV). These findings provide valuable perceptions for design of highly efficient and selective heterogeneous SACs for NO oxidation and reduction with TMs.

graphyne heterogeneous catalysis single-atom catalysts DFT studies NO oxidation NO reduction

SCI ; EI

英语

通讯

National Natural Science Foundation of China[21590792,91426302,21433005]

Chemistry

Chemistry, Physical

WOS:000614389200023

AMER CHEMICAL SOC

Web of Science

1.Tsinghua Univ, Dept Chem, Minist Educ, Beijing 100084, Peoples R China
2.Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Henan Normal Univ, Sch Phys, Xinxiang 453007, Henan, Peoples R China
5.Mohi Ud Din Islamic Univ Nerian Sharif, Dept Chem, Azad Jammu and Kashmir 12080, Pakistan

Talib, Shamraiz Hussain,Hussain, Sajjad,Baskaran, Sambath,et al. Chromium Single-Atom Catalyst with Graphyne Support: A Theoretical Study of NO Oxidation and Reduction[J]. ACS Catalysis,2020,10(20):11951-11961.

Talib, Shamraiz Hussain,Hussain, Sajjad,Baskaran, Sambath,Lu, Zhansheng,&Li, Jun.(2020).Chromium Single-Atom Catalyst with Graphyne Support: A Theoretical Study of NO Oxidation and Reduction.ACS Catalysis,10(20),11951-11961.

Talib, Shamraiz Hussain,et al."Chromium Single-Atom Catalyst with Graphyne Support: A Theoretical Study of NO Oxidation and Reduction".ACS Catalysis 10.20(2020):11951-11961.