Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
Faraday Discuss. 2017 Sep 21;202:79-98. doi: 10.1039/c7fd00041c.
The search for and exploitation of efficient catalytic systems for selective conversion of furfural into various high value-added chemicals remains a huge challenge for green synthesis in the chemical industry. Here, novel Pt nanoparticles supported on bamboo shoot-derived porous heteroatom doped carbon materials were designed as highly active catalysts for controlled hydrogenation of furfural in aqueous media. The porous heteroatom doped carbon supported Pt catalysts were endowed with a large surface area with a hierarchical porous structure, a high content of nitrogen and oxygen functionalities, a high dispersion of the Pt nanoparticles, good water dispersibility and reaction stability. Benefiting from these features, the novel Pt catalysts displayed a high activity and controlled tunable selectivity for furfural hydrogenation to produce furfuryl alcohol and cyclopentanone in water. The product selectivity could be easily modulated by controlling the carbonization temperature of the porous heteroatom doped carbon support and the reaction conditions (temperature and H pressure). Under mild conditions (100 °C, 1 MPa H), furfuryl alcohol was obtained in water with complete conversion of the furfural and an impressive furfuryl alcohol selectivity of >99% in the presence of Pt/NC-BS-500. A higher reaction temperature, in water, favored rearrangement of the furfural (FFA) with Pt/NC-BS-800 as the catalyst, which resulted in a high cyclopentanone yield of >76% at 150 °C and 3 MPa H. The surface properties and pore structure of the heteroatom doped carbon support, adjusted using the carbonization temperature, might determine the interactions between the Pt nanoparticles, carbon support and catalytic reactants in water, which in turn could have led to a good selectivity control. The effect of different reaction temperatures and reaction times on the product selectivity was also explored. Combined with exploration of the distribution of the reaction products, a reaction mechanism for furfural reduction has been proposed.
寻找和开发高效的催化体系,用于将糠醛选择性转化为各种高附加值化学品,这对于化学工业中的绿色合成来说仍然是一个巨大的挑战。在这里,设计了一种新型的负载在竹笋衍生的多孔杂原子掺杂碳材料上的 Pt 纳米粒子,作为在水相介质中控制糠醛加氢的高活性催化剂。多孔杂原子掺杂碳负载 Pt 催化剂具有大的比表面积、分级多孔结构、高含量的氮和氧官能团、Pt 纳米粒子的高分散性、良好的水分散性和反应稳定性。得益于这些特点,新型 Pt 催化剂在水相中对糠醛加氢生成糠醇和环戊酮表现出高活性和可控可调的选择性。通过控制多孔杂原子掺杂碳载体的碳化温度和反应条件(温度和 H2 压力),可以很容易地调节产物的选择性。在温和条件(100°C,1 MPa H2)下,在 Pt/NC-BS-500 的存在下,糠醛在水中完全转化,糠醇的选择性>99%。在更高的反应温度(水)下,用 Pt/NC-BS-800 作为催化剂有利于糠醛的重排,导致在 150°C 和 3 MPa H2 下环戊酮的收率>76%。通过碳化温度调节杂原子掺杂碳载体的表面性质和孔结构,可能决定了 Pt 纳米粒子、碳载体和催化反应物之间在水中的相互作用,从而可以很好地控制选择性。还探索了不同反应温度和反应时间对产物选择性的影响。结合对反应产物分布的探索,提出了糠醛还原的反应机理。