碳层卡镶超小铂钴纳米颗粒的可控制备及其在生物质加氢脱氧反应中的构效研究

5-羟甲基糠醛加氢脱氧制2,5-二甲基呋喃是实现生物质催化转化的关键反应之一。然而该反应面临副产物多、催化条件苛刻等问题。设计并合成高选择性、高活性与高稳定性的催化剂是解决该问题的一种关键方案。前期研究表明，铂钴合金具有优异的催化选择性，减小铂钴粒径能够有效提升催化活性。因此，构建超小铂钴纳米颗粒可控合成方案，利用铂钴粒径的调控实现其催化活性的最优化；化学吸附与物理限域结合的机制实现超小铂钴颗粒的稳定化，是实现该反应长效高收率的途径之一。本项目拟利用酚醛树脂化学吸附铂盐并可控还原，耦合二氧化硅包覆煅烧、硝酸除碳优化传质与铂钴合金化等技术手段，实现碳层卡镶超小铂钴纳米颗粒的可控合成；随后利用第一性原理计算、化学吸附实验与表征结合手段对该反应中的尺寸效应与催化过程展开研究；最后考察碳层卡镶稳定策略的稳定化构效。本项目的成功实施将助力生物质转化催化剂的研究与合成，助力该反应的工业化生产。

Hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is one of the key reactions to achieve biomass conversion, but the reaction still faces problems of low catalytic selectivity and harsh catalytic conditions. Design and synthesis of catalysts with high selectivity, activity and stability is a key solution to resolve this problem. Many researches show that the catalytic selectivity of HMF hydrodeoxygenation to DMF reaction could be effectively enhanced by PtCo alloy, and reducing the size of PtCo nanoparticles can effectively enhance the catalytic activity. To realize the long-term and high yield of this reaction, it is necessary to control the size of PtCo nanoparticles and stabilize the ultra-small PtCo nanoparticle by combining chemical adsorption and physical confinement to optimize their catalytic activity by using the regulation of platinum cobalt particle size, and to stabilize the ultra-small PtCo nanoparticles. In this project, firstly, the carbon layer inlaid with ultra-small PtCo nanoparticles will be synthesis by slow reduction of phenolic resin and platinum salt, coupled with silica coating protection calcination, etching carbon layer, cobalt salt adsorption and alloying. Secondly, the size effect and catalytic process of catalyst in HMF hydrodeoxygenation to DMF reaction will be studied. Finally, the structure-activity relationship of carbon layer under mild and severe reaction conditions will be investigated. The successful implementation of the project will reduce the difficulty of the reaction, realize the long-term and high activity biomass conversion, and help the reaction to achieve industrial application.