The homogeneous electronic state on the surface and the lack of precise electronic state modulation strategies of carbon-based metal-free semiconductor photocatalysts hinder the efficient photocatalytic reduction of CO. Here, one electronic state reconfiguration strategy was proposed to develop a non-metal catalyst consisting of resorcinol-melamine-formaldehyde (M) covalently connected to O-doped carbon nitride (OCN) for yielding methanol with high selectivity. The metal-free composite catalyst (O-M) exhibited an excellent methanol production rate of 22.27 μmol g h, approximately 50 and 3 times higher than that of OCN and M, respectively. Spectroscopic analysis and theoretical calculation revealed that the constructed covalent bond between OCN and M served as an electron channel for rapid electron transfer. Based on these electron channels, introducing O broke uniform electron distribution and led to electronic state reconfiguration on the surface of O-M, which accelerated charge transfer and improved CO photoreduction. This work provides valuable insights into significantly improving photocatalytic performance through the modulating the electronic state of carbon-based metal-free photocatalyst.

中文翻译：

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氧掺杂氮化碳共价连接间苯二酚-三聚氰胺-甲醛光催化剂的电子态重构用于高选择性二氧化碳还原成甲醇

碳基非金属半导体光催化剂表面的均匀电子态和缺乏精确的电子态调制策略阻碍了CO的有效光催化还原。这里，提出了一种电子态重构策略来开发一种非金属催化剂，该催化剂由间苯二酚-三聚氰胺-甲醛（M）与氧掺杂氮化碳（OCN）共价连接，以高选择性产生甲醇。无金属复合催化剂（OM）表现出优异的甲醇产率，达到 22.27 μmol g·h，分别比 OCN 和 M 高约 50 倍和 3 倍。光谱分析和理论计算表明，OCN和M之间构建的共价键可作为快速电子转移的电子通道。基于这些电子通道，引入O打破了均匀的电子分布，导致OM表面电子态重构，从而加速了电荷转移并改善了CO光还原。这项工作为通过调节碳基无金属光催化剂的电子态来显着提高光催化性能提供了宝贵的见解。