Photocatalytic conversion of benzyl alcohol (BA) is a promising means to coproduce H2 with value‐added chemicals. However, there is a lack of an efficient strategy to regulate the selectivity of the BA conversion products. Here, by a simple cocatalyst engineering technique, the selective conversion of BA over Zn2In2S5 nanosheets (ZIS) is maneuvered. Two types of cocatalysts, i.e., Pt and Cd, are photo‐deposited onto ZIS that can shift the selectivity to diverse products, namely, Pt to benzaldehyde (BAD) and Cd to the carbon‐carbon (C─C) coupling compounds. Mechanistic studies indicate that Cd has a high reducing capacity to convert BAD back to the ketyl radical (C𝛼 radical), favoring the construction of the C─C bonds. Pt, however, facilitates the generation of C𝛼 radicals but is energetically unfavorable for their coupling reactions, resulting in the generation of BAD as the main product. Theoretical calculation reveals that the distinct catalytic behaviors of Pt and Cd stem from their different electronic structures that govern the adsorption strength to the reaction intermediates and the reaction energy barriers of the C─C coupling step. This work not only addresses the challenge of selectivity regulation for BA conversion but also brings fresh mechanistic insights into the role of the cocatalysts.

中文翻译：

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Zn2In2S5 纳米片上的助催化剂工程对苯甲醇增值进行选择性光催化


苯甲醇 （BA） 的光催化转化是一种很有前途的 H2 与增值化学品共产的方法。然而，缺乏一种有效的策略来调节 BA 转化产品的选择性。在这里，通过简单的助催化剂工程技术，操纵 BA 在 Zn2In2S5 纳米片 （ZIS） 上的选择性转化。两种类型的助催化剂，即 Pt 和 Cd，光沉积到 ZIS 上，可以将选择性转移到不同的产物上，即 Pt 到苯甲醛 （BAD） 和 Cd 到碳-碳 （C─C） 偶联化合物。机理研究表明，Cd 具有很高的还原能力，可将 BAD 转化回酮基自由基（Cα 自由基），有利于 C─C 键的构建。然而，Pt 促进 Cα 自由基的产生，但在能量上不利于它们的偶联反应，导致产生 BAD 作为主要产物。理论计算表明，Pt 和 Cd 不同的催化行为源于它们不同的电子结构，这些电子结构决定了对反应中间体的吸附强度和 C─C 偶联步骤的反应能垒。这项工作不仅解决了 BA 转化选择性调控的挑战，还为助催化剂的作用带来了新的机制见解。