Spin-Steered Photosynthesis of H2O2 in Magnetic Single-Atom Modified Covalent Triazine Frameworks: A Density Functional Theory Study

Feng Liao; Zhao Lu; Zhongliao Wang

doi:10.3390/molecules29081840

Spin-Steered Photosynthesis of H₂O₂ in Magnetic Single-Atom Modified Covalent Triazine Frameworks: A Density Functional Theory Study

Molecules. 2024 Apr 18;29(8):1840. doi: 10.3390/molecules29081840.

Authors

Feng Liao^{1

2}, Zhao Lu^{1

3}, Zhongliao Wang^{4

5

6}

Affiliations

¹ HKUST Shenzhen-Hong Kong Collaborative Innovation Research Institute, Shenzhen 515100, China.
² Shenzhen Academy of Disaster Prevention and Reduction, Shenzhen 515100, China.
³ Research and Development Center, Shenzhen Foundation Engineering Co., Ltd., Shenzhen 515100, China.
⁴ Anhui Province Industrial Generic Technology Research Center for Alumics Materials, Huaibei Normal University, Huaibei 235000, China.
⁵ Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Huaibei Normal University, Huaibei 235000, China.
⁶ School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000, China.

Abstract

Covalent Organic Frameworks (COFs) demonstrate promising potential in the photocatalytic synthesis of H₂O₂ owing to favorable light absorption, superior charge separation, and considerable surface area. However, the efficiency of H₂O₂ photosynthesis is impeded by insufficient O₂ adsorption sites and a high reaction barrier. In this work, various metal single atoms (Fe, Co, Ni) are introduced onto covalent triazine frameworks (CTFs) with N-N coordination sites to significantly enhance O₂ adsorption and optimize H₂O₂ synthesis. Computational findings suggest that the presence of Fe, Co, and Ni not only enhances O₂ adsorption but also exerts an influence on the reaction pathway of H₂O₂. Significantly, Fe exhibits a distinct advantage in modulating O₂ adsorption through its unique electron spin state when compared to Co and Ni, as confirmed by crystal orbital Hamilton population (COHP) analysis. Additionally, this integration of metal atoms also improves light absorption and charge separation in CTFs. The study provides strategic insight into elevating H₂O₂ production by incorporating tailored metal single atoms into COFs.

Keywords: CTFs; DFT; magnetic single atom; photosynthesis of H2O2; spin-steered.

Grants and funding

This work was supported by the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone (HZQB-KCZYB-2020083), the Shenzhen Science and Technology Program (No. KCXFZ20211020163816023), the Shenzhen Zhongdi Construction Engineering Co., Ltd. cooperation project (22100245), and the Key Research Project in Natural Sciences for Higher Education Institutions by the Ministry of Education (2022AH050396).