Photocatalytic reduction of CO into fuel represents a promising approach for achieving carbon neutrality, while realizing high selectivity in this process is challenging due to uncontrollable reaction intermediate and retarded desorption of target products. Engineering the interface microenvironment of catalysts has been proposed as a strategy to exert a significant influence on reaction outcomes, yet it remains a significant challenge. In this study, amino alkylation was successfully integrated into the melem unit of polymeric carbon nitrides (PCN), which could efficiently drive the photocatalytic CO reduction. Experimental characterization and theoretical calculations revealed that the introduction of amino alkylation lowers the energy barrier for CO reduction into *COOH intermediate, transforming the adsorption of *COOH intermediate from the endothermic to an exothermic process. Notably, the as-prepared materials demonstrated outstanding performance in photocatalytic CO reduction, yielding CO at a rate of 152.8 μmol h with a high selectivity of 95.4% and a quantum efficiency of 6.6%.

中文翻译：

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通过氨基烷基化工程调节 *COOH 中间体，实现极其有效的光催化 CO2 还原

光催化将二氧化碳还原成燃料是实现碳中和的一种有前景的方法，但由于反应中间体不可控和目标产物解吸延迟，实现该过程的高选择性具有挑战性。设计催化剂的界面微环境已被提议作为对反应结果产生重大影响的策略，但这仍然是一个重大挑战。在这项研究中，氨基烷基化成功地集成到聚合氮化碳（PCN）的梅勒姆单元中，可以有效地驱动光催化CO还原。实验表征和理论计算表明，氨基烷基化的引入降低了CO还原为*COOH中间体的能垒，将*COOH中间体的吸附从吸热过程转变为放热过程。值得注意的是，所制备的材料在光催化CO还原方面表现出出色的性能，CO生成率为152.8 μmol h，选择性高达95.4%，量子效率为6.6%。