多元锰基复合氧化物的受控组装及其氧还原应用研究

Due to the special atomic arrangement and excellent catalytic performance, doped manganese oxides are drawing increasing attentions in wide areas such as organic synthesis, chlor-alkali industry, and low temperature fuel cell. Developing the multi-level, multi-dimensional assembly strategy and coupling their catalytic characteristics is an important research direction for manganese oxide based non platinum electrocatalytic materials. The project plans to take the electrochemical oxygen reduction (ORR ) characteristics of MxMn3-xO4 ( M = Zn, Fe, Co, Ni etc.) materials as the main object and conduct their facile synthesis under mild conditions in a controlled manner. The main contents include: 1st, synthesis and surface modification of monodisperse manganese oxide nanocrystals based on the micro-confinement effect of molecular templates; ( 2) preparation of hierarchically nanostructured manganese oxide composites and their assemblies; ( 3) kinetic research on the electrocatalytic oxygen reduction performance of the manganese oxide composites; (4 ) synergy effects of crystal assembly and surface modification on the ORR electrocatalytic mechanism...This project attempts to explore the simple, environment friendly wet chemical synthesis of nanostructured manganese oxide composites, and study the multi-component synergistic catalytic mechanism for the realization of the efficient, stable ORR electric catalytic applications. It is expected that the successful implementation of this project can provide some preliminary but novel theoretical and experimental basis for developing manganese oxide composite electrocatalyst.

锰基复合氧化物因其特殊的原子排列方式及优异的催化性能而在有机合成、氯碱工业、低温燃料电池领域受到广泛关注，发展其多层次、多维度的组装方法并实现其催化特性耦合是当前非铂锰氧化物电催化材料研究的重要方向。本项目拟以MxMn3-xO4（M = Zn、Fe、Co、Ni等）为研究对象，开展其温和条件下可控制备及电化学氧还原（ORR）特性研究，主要内容包括：（1）基于分子模板微限域效应的单分散锰复合氧化物纳米晶合成及表面修饰；（2）制备复杂结构多元锰复合氧化物及其组装体；（3）锰氧化物电催化氧还原过程动力学研究；（4）复杂组装及功能分子修饰的氧还原协同效应机制。.本项目试图探索操作简单、环境友好的锰复合氧化物有序纳米结构材料的湿化学合成方法，并在多组分协同催化机制的基础上实现其高效、稳定氧还原电催化应用，从而为新型锰复合氧化物电催化材料的开发及应用提供初步的理论和实验依据。

本项目主要探索了具有高催化活性、选择性和耐久性的锰基复合氧化物纳米电催化剂的湿化学合成及其多层次、多维度的异质界面组装和催化特性耦合，主要内容包括：.1. 以Fe、Co、Ni 等过渡金属为取代原子，开展了复合锰氧化物的水溶液制备及组装研究，主要关注基于分子模板微限域效应的单分散锰复合氧化物纳米晶合成及表面修饰；.2. 研究溶液体系中反应物前驱体存在形态、扩散速度等参数对锰氧化物复合纳米晶成核与生长速度的关系，通过选择性加入表面活性剂获得锰氧化物多级结构纳米晶有序自组装体。.3. 利用浸渍、刻蚀、外延等手段，基于晶格匹配和非均相成核机制，在锰氧化物单分散纳米晶的基础上制备复杂结构多元锰复合氧化物及其组装体；.4. 重点研究复合锰氧化物催化剂纳米相结构对材料性能的调控作用和机制，通过解析双金属氧化物催化剂体系中氧还原反应活化能、反应路径等动力学参数的影响，探索复合锰氧化物催化剂的协同催化效应。.. 本项目通过探索锰复合氧化物有序纳米结构材料的简单、快速湿化学合成方法，在多组分协同催化机制的基础上尝试实现其高效氧还原电催化应用，从而为新低铂电催化材料的开发、应用提供实验依据。