Universal Ligand-Assisted Supermolecular Strategy to Synthesize Single-Atom Catalysts for Solar-to-Ethanol Conversion

作者：Longshuai Zhang, Feiyao Wu, Xunheng Jiang, Fanqi Meng, Haiyan Liu, Qing Sun, Shimin Yu, Mei‐Feng Wu, Shun He, Xin Lü, Yi‐Tao Cui, Weili Dai, Tianyi Ma, Hui Li, Jian‐Ping Zou, Xubiao Luo · 发表于：Research Square · 年份：2022 · DOI：10.21203/rs.3.rs-1665965/v1 · 研究领域：Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts、Advanced Photocatalysis Techniques

Abstract Single-atom catalysts (SACs) have attracted significant attention; however, their catalytic properties are not satisfactory due to the sparse and inhomogeneity of the single-atom sites. Herein, we report a novel ligand-assisted supermolecular (LASM) strategy for the preparation of carbon nitride (CN)-supported SACs (M 1 -CNs) with controllable and high active metal loadings. The ligands in the metal chelates can immobilise the metal and control their type and content, while the formed hydrogen-bonded supermolecules can inhibit the fusion of the CN precursor. Therefore, M 1 -CN SACs (M: Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, and Cd) and multiple-metals SACs (Mα 1/Mβ 1-CNs: Fe/Cu and Cu/Zn/Ag) were successfully prepared. The as-synthesizd Cu 1 -CN have a record-high loading of 9.75 at.%. Notably, Cu 1 -CNs with high loadings achieved highly selective solar-driven photoreduction of CO 2 to ethanol, a breakthrough result in the field of 100% C 2+ product construction using SACs, which stands among the best solar-to-ethanol single-atom photocatalysts up to date. Combining experimental evidence including X-ray absorption analysis and theoretical calculations, revealed that the Cu 1 -CN with high loading promoted the C–C coupling of *CO intermediate products. This work provides a novel strategy for the controllable preparation of M 1 -CNs and for the design of SACs with high selectivity and efficiency for the photoreduction of CO 2 to C 2+ products.