天津理工大学袁阔团队报道了基于MOF的双层Pickering乳液——利用H₂O作为氢源，在水油界面进行分子水平的水输送门控，以实现高效的光催化加氢。相关论文发表在2025年1月2日出版的《德国应用化学》。

双体系不仅为复杂的催化过程提供了有前景的机会，也是高效串联反应的巨大挑战。作为一种新兴的太阳能到化学的转换，可见光驱动和供水氢化结合了光催化的可持续性和氢化的经济价值。然而，关键和挑战点是将水溶性光催化析氢反应（HER）与油溶性氢化结合起来。

该文中，研究人员采用金属有机框架（MOFs）和CdS纳米棒构建了MOF-CdS双层Pickering乳液（油包水，W/O），该乳液将用于光催化HER的水相和用于氢化的油相分隔开来。疏水性MOF和亲水性CdS分别在W/O乳液的内层和外层分离。MOF的分子调节疏水性控制了CdS光催化剂上的水分输送，实现了HER和氢化的协同调节。

在肉桂醛的光催化加氢反应中，MOF-CdS-Pickering乳液的最高收率达到187.37 mmol·g^-1·h^-1，是无乳液对应物（6.44 mmol·g^-1·h^-1）的30倍。在没有助催化剂的情况下，其表观量子产率达到43.24%。到目前为止，这一表现处于最高水平。

该工作实现了水-油界面的精确调节，有效地耦合了不同相中的两个反应，为挑战串联催化提供了新的视角。

附：英文原文

Title: MOF-based Dual-Layer Pickering Emulsion: Molecular-Level Gating of Water Delivery at Water-Oil Interface for Efficient Photocatalytic Hydrogenation Using H2O as a Hydrogen Source

Author: Kuo Yuan, Ying Zhang, Zhuang Yan, Qinbai Yun, Tianqun Song, Jun Guo, Jie Feng, Zheng Chen, Xiaotao Zhang, Zhiyong Tang, Wenping Hu, Tongbu Lu

Issue&Volume: 2025-01-02

Abstract: Biphasic system not only presents a promising opportunity for complex catalytic processes, but also is a grand challenge in efficient tandem reactions. As an emerging solar-to-chemical conversion, the visible-light-driven and water-donating hydrogenation combines the sustainability of photocatalysis and economic-value of hydrogenation. However, the key and challenging point is to couple water-soluble photocatalytic hydrogen evolution reaction (HER) with oil-soluble hydrogenation. Herein, we employed metal-organic frameworks (MOFs) and CdS nanorods to construct a MOF-CdS dual-layer Pickering emulsion (water in oil, W/O), which compartmented aqueous phase for photocatalytic HER and oil phase for hydrogenation. The hydrophobic MOF and hydrophilic CdS were isolated at the inner and outer layers of W/O emulsion, respectively. The molecularly regulated hydrophobicity of MOF controlled the water delivery onto CdS photocatalysts, which realized the synergistic regulation of HER and hydrogenation. In the photocatalytic hydrogenation of cinnamaldehyde, the highest yield of MOF-CdS Pickering emulsion reached 187.37 mmol·g-1·h-1, 30 times that of the counterpart without emulsion (6.44 mmol·g-1·h-1). Its apparent quantum yield reached 43.24% without co-catalysts. To our knowledge, this performance is at a top-level so far. Our work realized the precise regulation of water-oil interface to effectively couple two reactions in different phases, providing new perspective for challenging tandem catalysis.

DOI: 10.1002/anie.202421341

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202421341