The photocatalytic coupling reaction can be conducted in one pot to realize the simultaneous utilization of electrons and holes, thereby obtaining value-added fine chemicals and fuels. Herein, we report a binary nickel modified ZnIn₂S₄ (Ni:ZIS) for highly efficient photocatalytic selective oxidation of benzyl alcohol (BA) to benzaldehyde (BAD) integrated with hydrogen (H₂) evolution, in which Ni can promote photogenerated charge transfer for enhancing photoactivity. Particularly, the products of converting BA to aromatic compounds over blank ZnIn₂S₄ (ZIS) and Ni:ZIS show a marked difference under the same reaction conditions. Hydrobenzoin (HB) is the primary product over blank ZIS. After the introduction of Ni, the formation of HB is dramatically suppressed, resulting in higher selectivity of BAD, because the introduction of Ni facilitates the α-H abstraction. In addition, an analogous phenomenon has been observed on Ni-based compounds modified ZIS, such as Ni_xP and NiS. It is hoped that this work would provide a feasible paradigm for modifying the surface of photocatalysts to tune the selectivity of product-oriented alcohols oxidation coupled with H₂ evolution in water.

光催化偶联反应可在一个罐中进行，以实现电子和空穴的同时利用，从而获得增值的精细化学品和燃料。本文中，我们报道了一种二元镍改性的ZnIn ₂ S ₄（Ni：ZIS），用于高效光催化将苄醇（BA）选择性氧化为苯甲醛（BAD），并与氢（H ₂）逸出结合，其中Ni可以促进光生电荷转移以增强光活性。特别是在空白ZnIn ₂ S ₄上将BA转化为芳族化合物的产物（ZIS）和Ni：ZIS在相同的反应条件下显示出明显的差异。氢苯偶姻（HB）是空白ZIS的主要产品。引入Ni后，HB的形成被显着抑制，导致BAD的选择性更高，因为引入Ni有助于α-H的抽象。另外，在Ni基化合物改性的ZIS上观察到类似现象，例如Ni _x P和NiS。希望这项工作将提供一个可行的范式，以修饰光催化剂的表面，以调节产物导向的醇氧化的选择性以及在水中H _2的释放。