Center for Environmentally Beneficial Catalysis, Department of Chemical & Petroleum Engineering, University of Kansas, 1501 Wakarusa Drive, Lawrence, Kansas 66047, USA.
ACS Nano. 2013 Feb 26;7(2):1309-16. doi: 10.1021/nn304820v. Epub 2013 Jan 16.
A bimetallic nanocatalyst with unique surface configuration displays extraordinary performance for converting biomass-derived polyols to chemicals, with potentially much broader applications in the design of novel catalysts for several reactions of industrial relevance. The synthesis of nanostructured metal catalysts containing a large population of active surface facets is critical to achieve high activity and selectivity in catalytic reactions. Here, we describe a new strategy for synthesizing copper-based nanocatalysts on reduced graphene oxide support in which the catalytically active {111} facet is achieved as the dominant surface by lattice-match engineering. This method yields highly active Cu-graphene catalysts (turnover frequency = 33-114 mol/g atom Cu/h) for converting biopolyols (glycerol, xylitol, and sorbitol) to value-added chemicals, such as lactic acid and other useful co-products consisting of diols and linear alcohols. Palladium incorporation in the Cu-graphene system in trace amounts results in a tandem synergistic system in which the hydrogen generated in situ from polyols is used for sequential hydrogenolysis of the feedstock itself. Furthermore, the Pd addition remarkably enhances the overall stability of the nanocatalysts. The insights gained from this synthetic methodology open new vistas for exploiting graphene-based supports to develop novel and improved metal-based catalysts for a variety of heterogeneous catalytic reactions.
一种具有独特表面结构的双金属纳米催化剂在将生物质衍生的多元醇转化为化学品方面表现出非凡的性能，在设计用于几种工业相关反应的新型催化剂方面具有潜在的更广泛应用。合成含有大量活性表面晶面的纳米结构金属催化剂对于在催化反应中实现高活性和选择性至关重要。在这里，我们描述了一种在还原氧化石墨烯载体上合成铜基纳米催化剂的新策略，其中通过晶格匹配工程实现了催化活性 {111} 面作为主要表面。该方法得到了高活性的 Cu-石墨烯催化剂（周转频率=33-114 mol/g 原子 Cu/h），可将生物多元醇（甘油、木糖醇和山梨糖醇）转化为附加值化学品，如乳酸和其他由二醇和直链醇组成的有用联产。钯以痕量形式掺入 Cu-石墨烯体系中，形成串联协同体系，其中多元醇原位产生的氢气用于进料本身的顺序氢解。此外，Pd 的加入显著提高了纳米催化剂的整体稳定性。从这种合成方法中获得的见解为利用基于石墨烯的载体开发用于各种多相催化反应的新型和改进的金属基催化剂开辟了新的前景。
