State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, and National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China.
Nat Commun. 2018 Aug 22;9(1):3367. doi: 10.1038/s41467-018-05757-6.
Metal-support interaction is one of the most important parameters in controlling the catalysis of supported metal catalysts. Silica, a widely used oxide support, has been rarely reported as an effective support to create active metal-support interfaces for promoting catalysis. In this work, by coating Cu microparticles with mesoporous SiO, we discover that Cu/SiO interface creates an exceptional effect to promote catalytic hydrogenation of esters. Both computational and experimental studies reveal that Cu-H and SiO-H species would be formed at the Cu-O-SiO interface upon H dissociation, thus promoting the ester hydrogenation by stablizing the transition states. Based on the proposed catalytic mechanism, encapsulting copper phyllosilicate nanotubes with mesoporous silica followed by hydrogen reduction is developed as an effective method to create a practical Cu nanocatalyst with abundant Cu-O-SiO interfaces. The catalyst exhibits the best performance in the hydrogenation of dimethyl oxalate to ethylene glycol among all reported Cu catalysts.
金属-载体相互作用是控制负载金属催化剂催化作用的最重要参数之一。二氧化硅作为一种广泛使用的氧化物载体，很少有报道将其作为一种有效的载体来创造活性的金属-载体界面以促进催化作用。在这项工作中，通过在 Cu 微粒表面包覆介孔 SiO，我们发现 Cu/SiO 界面能产生一种促进酯类催化加氢的特殊效果。通过计算和实验研究发现，在 H 原子的解离过程中，Cu-O-SiO 界面会形成 Cu-H 和 SiO-H 物种，从而通过稳定过渡态来促进酯的加氢反应。基于所提出的催化机理，通过介孔硅对铜层状硅酸盐纳米管进行封装，然后进行氢气还原，开发了一种有效方法来制备具有丰富 Cu-O-SiO 界面的实用 Cu 纳米催化剂。该催化剂在所有报道的 Cu 催化剂中，在草酸二甲酯加氢制乙二醇的反应中表现出最好的性能。
