|
|||||
|
|
Modulating the Reaction Configuration by Breaking the Structural Symmetry of Active Sites for Efficient Photocatalytic Reduction of Low-concentration CO2 |
|
| Authors: | Wenyuan Lyu Dr Yang Liu Jingyi Zhou Datong Chen Dr Xin Zhao Dr Ruiqi Fang Dr Fengliang Wang Prof Yingwei Li |
| Institution: | 1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 China
Contribution: Data curation (lead), Formal analysis (lead), Investigation (lead), Methodology (lead), Writing - original draft (equal), Writing - review & editing (equal);2. Guangdong Provincial Key Laboratory of Petrochemical Pollution Process and Control, School of Environmental Science and Engineering, Guangdong University of Petrochemical Technology, Maoming, Guangdong, 525000 China Contribution: Methodology (equal), Software (lead);3. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 China Contribution: Formal analysis (equal), Investigation (equal);4. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 China Contribution: Formal analysis (supporting), Investigation (equal);5. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 China Contribution: Formal analysis (supporting);6. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 China |
| Abstract: | Photocatalytic conversion of low-concentration CO2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, the weak CO2 adsorption and tough CO2 activation process seriously compromise the CO production, due to the chemical inertness of CO2 molecule and the formed fragile metal-C/O bond. Herein, we designed and fabricated oxygen vacancy contained Co3O4 hollow nanoparticles on ordered macroporous N-doped carbon framework (Vo−HCo3O4/OMNC) towards photoreduction of low-concentration CO2. In situ spectra and ab initio molecular dynamics simulations reveal that the constructed oxygen vacancy is able to break the local structural symmetry of Co−O−Co sites. The formation of asymmetric active site switches the CO2 configuration from a single-site linear model to a multiple-sites bending one with a highly stable configuration, enhancing the binding and structural polarization of CO2 molecules. As a result, Vo−HCo3O4/OMNC shows unprecedent activity in the photocatalytic conversion of low-concentration CO2 (10 % CO2/Ar) under laboratory light source or even natural sunlight, affording a syngas yield of 337.8 or 95.2 mmol g−1 h−1, respectively, with an apparent quantum yield up to 4.2 %. |
| Keywords: | CO2 Reduction Metal–Organic Frameworks Oxygen Vacancy Photocatalysis Synthesis Gas |