Air-stable and reusable porous silica-supported ultrafine Nix-NiO nanoparticles for semi-hydrogenation of alkynes
Air-stable and reusable porous silica-supported ultrafine Nix-NiO nanoparticles for semi-hydrogenation of alkynes
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DOI：
10.1016/j.apsusc.2024.159411
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发表时间：
2024
影响因子：
6.7
通讯作者：
Yaxin Xing;Yatao Su;Luyao Li;Zengli Jia;Gang Feng;Hongchao Wang;Yuangong Zhang;Xinyu Wen
中科院分区：
文献类型：
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作者：
Yaxin Xing;Yatao Su;Luyao Li;Zengli Jia;Gang Feng;Hongchao Wang;Yuangong Zhang;Xinyu Wen
非贵金属基加氢催化剂活性低，在空气中易氧化，限制了其实际应用。通过Michael加成/席夫碱反应和三乙氧基硅烷的水解制得有机-无机杂化3D纳米材料，制备了多孔二氧化硅负载超细氧化镍(NiO)。由于邻苯三酚/氨基单元与Ni2+的配位作用以及Si-O-Si网络的隔离作用，直径约2.6 nm的NiO纳米粒子均匀分散并限制在共生的介孔二氧化硅骨架中。所制备的催化剂具有中孔结构和较高的比表面积(715×m2/g)，并具有良好的催化活性、选择性和重复使用性能。半加氢过程中在NiO纳米颗粒表面形成的少量金属镍(Nix-NiO)起到了活性物种的作用，Nix-NiO上中等的吸附/脱附能有利于活性的提高。最重要的是，它在空气中长期储存后表现出恒定的催化活性和选择性。这项工作为制备空气稳定性和可重复使用的超细金属载体催化剂提供了一种绿色可行的策略，可以替代传统的浸渍方法。
The practical application of non-noble metal-based hydrogenation catalysts is limited because of their low activity and easy oxidation in air. Here, porous silica-supported ultrafine nickel oxide (NiO) was prepared by calcining an organic–inorganic hybrid 3D nanomaterial that was formed via the Michael addition/Schiff’s base reaction, and hydrolyzation of triethoxysilane. NiO nanoparticles with ca. 2.6 nm diameter was uniformly dispersed and confined in the cogenerated mesoporous SiO2skeleton, thanks to the coordination between pyrogallol/amino units and Ni2+ions, and the isolation effect of Si-O-Si network. The as-prepared catalyst featured mesoporous structure and high specific surface area (715 m2/g), and exhibited excellent activity, selectivity and reusability in the semi-hydrogenation of alkynes. Small amount of metallic nickel (Nix-NiO) that formed on the surface of NiO nanoparticles during the semi-hydrogenation acted as the active species, and the moderate adsorption/desorption energies on Nix-NiO facilitated the activity enhancement. Most importantly, it showed constant catalytic activity and selectivity after a long-term storage in air. This work provides a green and feasible strategy, as an alternative to the traditional impregnation method, for the preparation of ultrafine metal-supported catalysts with air-stability and reusability.