Single transition metal atoms anchored on a two-dimensional polyimide covalent-organic framework as single-atom catalysts for photocatalytic CO2 reduction: A first-principles study

• Published in: Catalysis communications Vol. 175; p. 106604
• Main Authors: Gong, Minghao, Yin, Huang, Lyu, Pengbo, Sun, Lizhong
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2023; Elsevier
• Subjects: Covalent-organic framework; Density functional theory; Photocatalytic carbon dioxide reduction; Reaction mechanism; Single-atom catalyst; Reaction mechanism; Density functional theory; Photocatalytic carbon dioxide reduction; Single-atom catalyst; Covalent-organic framework
• ISSN: 1566-7367; 1873-3905
• DOI: 10.1016/j.catcom.2023.106604

We systematically investigated single transition metal atoms anchored on a two-dimensional polyimide (M@2DPI) monolayer as single-atom catalysts (SACs) for photocatalytic CO2 reduction reaction (CO2RR) with first-principles calculations. The stability of M@2DPI systems is investigated first, followed by the hybrid HSE06 functional calculations on electronic structures to determine their thermodynamic feasibility for photocatalytic CO2RR. Then the optimal reaction pathways of CO2RR are identified and the highest activity is found for M@2DPI (M = Sc, Zr and La). The electronic origin of the catalytic activity is further analyzed. Finally, we found that the candidate systems except Mn-based system are able to suppress the hydrogen evolution reaction. [Display omitted] •The anchoring of single La, Sc, Y, Zr, Ti, Hf, V and Mn atoms are stable.•Hybrid functional calculations reveal their feasibility for photocatalysis.•The activities of candidate systems are among the best of available literature.•The electronic origin of catalytic activity is explored with COHP analysis.•The candidate systems show selectivity towards CO2RR rather than HER.