| Affiliation: | 1. School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials/Huangpu Hydrogen Innovation Center/Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou Higher Education Mega Center, No. 230 Wai Huan Xi Road, Guangzhou, 510006 P. R. China School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013 P. R. China;2. School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials/Huangpu Hydrogen Innovation Center/Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou Higher Education Mega Center, No. 230 Wai Huan Xi Road, Guangzhou, 510006 P. R. China;3. School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013 P. R. China;4. School of Environmental Science and Engineering, Qingdao University, Qingdao, Shandong, 266071 P. R. China |
| Abstract: | Breaking the trade-off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H2O2) photosynthesis, especially the side-on configuration of oxygen (O2) on the catalyst surface will cause the cleavage of O−O bonds, which drastically hinders the H2O2 production performance. Herein, we present an atomically heteroatom P doped ZnIn2S4 catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar-driven H2O2 production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn2S4 at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O−O bonds and reducing the energy barriers to H2O2 production. As a result, the oxygen adsorption configuration is regulated from side-on (Yeager-type) to end-on (Pauling-type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g−1 h−1. This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst. |
