近日，中国科学技术大学熊宇杰团队实现了通过原子工程光催化剂在水相中太阳能驱动大规模生产二聚亚胺。2025年4月15日，《德国应用化学》杂志发表了这一成果。

有机物的光催化选择性氧化是可持续生产增值化学品的一条有前景的途径，但存在电荷分离缓慢和选择性操作困难的问题。特别是，肖特基势垒诱导的预期有机产物在还原位点的吸附往往会引发氢化副反应，由于极性不同，这在理想的水环境中更为明显。

研究组报告了一种在原子水平上对ZnIn₂S₄（ZIS）光催化剂的精确助催化剂策略，以消除ZIS和助催化剂之间的肖特基势垒，从而在水介质中实现光催化二聚亚胺生产的卓越活性（565μmol h^-1）和选择性（99%），其效率是负载Pt纳米粒子的ZIS的五倍。通过有效衰减Pt位点附近光生空穴的积累，然后抑制不需要的氢化副反应，实现了优异的性能。

研究组进一步证明，该系统可以直接扩大到0.5平方米，用于可扩展的室外实验，并在太阳照射下实现太阳能驱动的苄基亚胺生产，产量为125毫升，纯度为97wt%，持续两周。该研究提出了一种界面原子设计策略，用于光催化剂在温和和绿色条件下有效生产与H₂偶联的高价值亚胺。

附：英文原文

Title: Solar-Driven Massive Production of Dimerized Imine in Aqueous Phase via an Atomically Engineered Photocatalyst

Author: Nengcong Yang, Zixi Yin, Zhian Chen, Chao Gao, Zhuwei Cao, Yi Zheng, Zhenhua Pan, Haiqun Cao, Sheng Ye, Yujie Xiong

Issue&Volume: 2025-04-15

Abstract: Photocatalytic selective oxidation of organics represents a promising avenue for the sustainable production of value-added chemicals, but suffers from sluggish charge separation and difficult selectivity manipulation. In particular, the Schottky barrier-induced adsorption of expected organic products at reduction sites tends to trigger the hydrogenation side reaction, which is more pronounced in the ideal aqueous environment due to distinct polarity. Here, we report a precise cocatalyst strategy on ZnIn2S4 (ZIS) photocatalyst at the atomic level to eliminate the Schottky barrier between ZIS and cocatalyst, thus achieving exceptional activity (565 μmol h1) and selectivity (99%) for photocatalytic dimerized imine production in aqueous media, which is five times more effective than ZIS loaded with Pt nanoparticles. The excellent performance is achieved by effectively attenuating the accumulation of photogenerated holes near the Pt sites and then suppressing the unwanted hydrogenation side reaction. We further demonstrate that our system can be directly scaled up to 0.5 m2 for scalable outdoor experiment and achieve solar-driven production of benzylimine with 125 mL yield and 97 wt% purity for two weeks under solar irradiation. This study presents an interfacial atomical design strategy for photocatalysts to efficiently produce high-value imine coupled with H2 under mild and green conditions.

DOI: 10.1002/anie.202502202

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202502202