Tsang Shik Chi, Cailuo Nick, Oduro William, Kong Adam T S, Clifton L, Yu K M Kerry, Thiebaut Benedicte, Cookson James, Bishop Peter
Wolfson Catalysis Centre, Inorganic Chemistry, University of Oxford, Oxford, U.K.
ACS Nano. 2008 Dec 23;2(12):2547-53. doi: 10.1021/nn800400u.
Bimetallic heterostructures are used as industrial catalysts for many important transformations. However, conventional catalysts are primarily prepared in cost-effective manners without much appreciation in metal size control and metal-metal interaction. By employing recent nanotechnology, Pt nanocrystals with tailored sizes can be decorated with Co atoms in a controlled manner in colloid solution as preformed nanocatalysts before they are applied on support materials. Thus, we show that the terminal CO hydrogenation can be achieved in high activity, while the undesirable hydrogenation of the CC group can be totally suppressed in the selective hydrogenation of alpha,beta-unsaturated aldehydes to unsaturated alcohols, when Co decorated Pt nanocrystals within a critical size range are used. This is achieved through blockage of unselective low coordination sites and the optimization in electronic influence of the Pt nanoparticle of appropriate size by the Co decoration. This work clearly demonstrates the advantage in engineering preformed nanoparticles via a bottom-up construction and illustrates that this route of catalyst design may lead to improved catalytic processes.
双金属异质结构被用作许多重要转化反应的工业催化剂。然而,传统催化剂主要以具有成本效益的方式制备,而对金属尺寸控制和金属-金属相互作用的重视程度不高。通过采用最新的纳米技术,在将预制的纳米催化剂应用于载体材料之前,可以在胶体溶液中以可控的方式用钴原子修饰具有定制尺寸的铂纳米晶体。因此,我们表明,当使用临界尺寸范围内的钴修饰铂纳米晶体时,在α,β-不饱和醛选择性加氢制备不饱和醇的反应中,可以实现高活性的末端CO加氢,同时完全抑制CC基团的不希望的加氢反应。这是通过阻断非选择性的低配位位点以及通过钴修饰对适当尺寸的铂纳米颗粒的电子影响进行优化来实现的。这项工作清楚地展示了通过自下而上的构建方式来设计预制纳米颗粒的优势,并表明这种催化剂设计路线可能会带来改进的催化过程。