负载型金基双金属纳米催化剂Au-M/MOF的控制合成及催化性能

Catalysis by bimetallic nanocatalysts is one of the fastest growing subjects in catalytic science today and is also an interesting topic of research in nanotechnology. In this project, we will design and controllable synthesize a series of supported Au-based bimetallic nanocatalysts supported on metal-organic frameworks (MOFs) Au-M/MOF (M=Ag, Ni; MOF=ZIF-8, UiO-67) with different characteristics (e.g., microstructure, bimetallic component ratio, and active site position) by precipitation-redispersion method, in situ reduction method, and reduction method. Extensively physicochemical characterizations of the synthesized Au-based bimetallic nanocatalysts are carried out. The relationship between the preparation conditions and the size, structure and composition of the core-shell bimetallic nanoparticles Au@Ag and Ag@Au were investigated. Efforts will also be directed to reveal the growth process and formation mechanism of core-shell bimetallic nanoparticles Au@Ag and Ag@Au. The structure–performance relationship between the microstructure, bimetallic component ratio, and active site position of Au-based bimetallic nanocatalysts Au-M/MOF and their catalytic activity were evaluated in the aerobic oxidation of benzyl alcohol and the hydrogenation of 1,3-butadiene. In addition, the nature of Au-M bimetallic nanocatalysts, as well as the aerobic oxidation of benzyl alcohol and the hydrogenation of 1,3-butadiene catalytic mechanism will also be revealed. This work addresses novel strategies for preparation of supported Au-based bimetallic nanocatalysts, providing an insightful guidance for developing novel and efficient Au-based bimetallic nanocatalysts.

双金属纳米催化剂的研究是当前催化科学创新的一个热点。本项目拟选用金属有机骨架（MOFs）作为载体，采用“沉积-重分散法”、“原位还原法”和“还原法”控制合成不同微观结构、金属组分比例和活性位位置（孔道内和孔道外）的金基双金属纳米催化剂Au-M/MOF（M=Ag、Ni；MOF=ZIF-8、UiO-67）。综合多种物理化学表征手段，研究双金属纳米粒子Au@Ag和Ag@Au的尺寸、结构和组成调控规律，揭示其生长过程和形成机理。探索Au-M/MOF在苯甲醇氧化和1,3-丁二烯加氢反应中的催化性能，构建金基双金属纳米催化剂Au-M/MOF的微观结构、金属组分比例和活性位位置与催化性能之间的构效关系，揭示Au-M/MOF催化苯甲醇氧化和1,3-丁二烯加氢反应的机理，揭示双金属组分间协同作用的本质。建立合成负载型Au-M/MOF的新方法，为制备新型高效的金基双金属纳米催化剂提供启示和指导。

双金属纳米催化剂的研究是当前催化科学创新的一个热点。以金属有机骨架为载体，设计制备具有金属组分间协同作用的双金属纳米催化剂为设计制备具有高催化活性、高选择性和高稳定性的新型多相催化剂提供了条件。研究组选用金属有机骨架（ZIF-8、ZIF-67、MIL-101、MIL-100、UiO-67、UiO-66和UiO-66-NH2）作为载体，采用沉积-重分散法、原位还原法和共浸渍还原法控制合成了不同载体性质、微观结构、粒径尺寸、金属组分比例的双金属Au–Ag、Au–Ni、Au–Pt、Au–Pd、Cu–Ni、Pd–Ni、Pd–Cu和Pt–Co纳米催化剂。综合多种物理化学表征手段，研究了合成的双金属纳米催化剂的尺寸、结构和组成调控规律。探索催化剂在苯甲醇选择性氧化反应和1,3-丁二烯选择性加氢反应中的催化性能（包括催化活性、选择性和循环使用性能），构建了双金属催化剂的载体性质、微观结构、粒径尺寸和金属组分比例与催化性能之间的构效关系，研究催化反应动力学，揭示了双金属催化剂催化苯甲醇选择性氧化和1,3-丁二烯选择性加氢反应的机理。通过与单一金属纳米催化剂比较，提供了双金属纳米催化剂的特异性/优点，揭示了双金属组分间的协同作用本质。建立了合成负载型双金属纳米催化剂的新方法（沉积-重分散法和原位还原法），建立了高效、绿色催化苯甲醇氧化和1,3-丁二烯加氢反应体系。为制备新型高效的选择性氧化和选择性加氢的双金属纳米催化剂提供了启示和指导。