Department of Chemistry , Tsinghua University , Beijing 100084 , China.
State Key Laboratory of Green Building Materials , China Building Materials Academy , Beijing 100041 , China.
J Am Chem Soc. 2018 Jun 20;140(24):7407-7410. doi: 10.1021/jacs.8b03121. Epub 2018 Jun 11.
The hydrosilylation reaction is one of the largest-scale application of homogeneous catalysis and is widely used to enable the commercial manufacture of silicon products. However, considerable issues including disposable platinum consumption, undesired side reactions and unacceptable catalyst residues still remain. Here, we synthesize a heterogeneous partially charged single-atom platinum supported on anatase TiO (Pt/TiO) catalyst via an electrostatic-induction ion exchange and two-dimensional confinement strategy, which can catalyze hydrosilylation reaction with almost complete conversion and produce exclusive adduct. Density functional theory calculations reveal that unexpected property of Pt/TiO originates from atomic dispersion of active species and unique partially positive charge Pt electronic structure that conventional nanocatalysts do not possess. The fabrication of single-atom Pt/TiO catalyst accomplishes a reasonable use of Pt through recycling and maximum atom-utilized efficiency, indicating the potential to achieve a green hydrosilylation industry.
硅氢加成反应是均相催化中规模最大的应用之一，被广泛用于实现硅产品的商业化制造。然而，仍存在一些问题，包括铂的一次性消耗、不希望的副反应和不可接受的催化剂残留。在这里，我们通过静电感应离子交换和二维限域策略合成了一种负载在锐钛矿 TiO 上的部分带电的单原子铂（Pt/TiO）催化剂，该催化剂可以催化硅氢加成反应，几乎实现完全转化，并生成专一的加合物。密度泛函理论计算表明，Pt/TiO 的意外性质源于活性物质的原子分散和独特的部分正电荷 Pt 电子结构，这是传统纳米催化剂所不具备的。单原子 Pt/TiO 催化剂的制备通过回收和最大限度地提高原子利用率实现了铂的合理利用，表明有可能实现绿色硅氢加成工业。
