Loading cocatalysts can effectively enhance the surface hydrogen reduction in photocatalytic water splitting by introducing a positive Schottky barrier. NiS is regarded as a promising cocatalyst to replace the noble metals due to its low cost and equivalent or even better performance. However, there is a huge controversy over whether the NiS cocatalyst is used to trap electrons or holes in the photocatalytic process. Herein, a new type of NiS‐decorated ZnO/ZnS (ZnOS) nanorod heterostructure photocatalysts is first designed from the corresponding bimetallic organic frameworks (ZnNi–MOFs). The Zn species in the bimetallic–MOFs can spatially separate the Ni species to restrain their aggregation, which is beneficial for the formation of NiS with a small enough size. The optimal heterostructure photocatalysts exhibit an excellent hydrogen production rate of 27 mmol g−1 h−1, which is about seven times higher than that of the ZnOS heterostructure. X‐ray photoelectron spectroscopy and open‐circuit potential characterizations disclose that NiS can effectively facilitate the migration of the electrons. Density functional theory calculations, including differential charge density, Mulliken population analyses, and d‐band center, intuitively reveal that the real role of NiS in the photocatalytic process is to capture the electrons rather than the holes.
The design and development of site-isolating and multifunctional catalysts for multistep sequential reactions at the molecular level is a significant challenge. Herein, we first report bifunctional metal NPs@chiral MOFs catalysts for asymmetric sequential reactions. Pd nanoparticles and chiral proline were successfully added to NH 2 -UiO-66 to construct two chiral bifunctional catalysts, in which active Pd nanoparticles were encapsulated into the frameworks via the "bottle-around-ship" method, and chiral proline was introduced into NH 2 -UiO-66 by coordination to zirconium nodes and postsynthetic modification (PSM) of the organic linkers. The chiral proline-decorated bifunctional Pd@NH 2 -UiO-66 catalysts were applied to sequential Suzuki coupling/asymmetric aldol reactions with excellent coupling performance (yields up to 99.9%) and good enantioselectivities (ee anti values up to 97%). The heterogeneous catalyst by coordination of proline can be reused, and the reaction activity was not significantly reduced after four cycles.
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