Photoredox dual reaction for selective alcohol oxidation and hydrogen evolution over nickel surface-modified ZnIn2S4
Photoredox dual reaction for selective alcohol oxidation and hydrogen evolution over nickel surface-modified ZnIn2S4
复制标题
镍表面改性 ZnIn2S4 选择性醇氧化和析氢的光氧化还原双反应
DOI：
10.1016/j.apcatb.2020.118946
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发表时间：
2020-08-15
影响因子：
22.1
通讯作者：
Xu, Yi-Jun
中科院分区：
文献类型：
--
作者：
Lin, Qiong;Li, Yue-Hua;Xu, Yi-Jun
光催化耦合反应可以一锅法进行，实现电子和空穴的同时利用，从而获得高附加值的精细化工品和燃料。本文报道了一种镍修饰的ZnIn 2S 4（Ni：ZIS）光催化剂，用于高效选择性氧化苯甲醇（BA）生成苯甲醛（BAD），并结合放氢（H-2），其中Ni可以促进光生电荷转移，从而提高光催化活性。特别地，在相同的反应条件下，在空白ZnIn_2S_4（ZIS）和Ni：ZIS上将BA转化为芳香族化合物的产物显示出显著的差异。氢苯偶姻（HB）是空白ZIS的主要产品。在引入Ni后，HB的形成被显著抑制，导致BAD的更高选择性，因为Ni的引入促进了α-H的提取。此外，在Ni基化合物改性的ZIS（如NixP和NiS）上也观察到类似的现象。希望这项工作将提供一个可行的范例，改性的光催化剂的表面，以调整产品导向的醇类氧化与H-2的析出耦合在水中的选择性。
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 (H-2) 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 alpha-H abstraction. In addition, an analogous phenomenon has been observed on Ni-based compounds modified ZIS, such as NixP 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 H-2 evolution in water.