基于耗散结构理论的层次阵列锰氧化物电合成过程强化研究

The electro-synthesis is an important industrial synthetic strategy for functional manganese oxide. A ubiquitous issue in chemical process engineering and product engineering is the feature failing of nano materials during mass production. An origin for the failure of nano features is the step-wise destruction of the nano\micro hybrid ordered structure during the scaling-up process from nano unit to macro materials. We have previously found a plenty of nonlinear kinetic steps in the electro-synthesis of manganese oxide, which will be further enhanced when the reaction system goes far from the dynamic equilibrium, and strongly affect the structural order of the reaction system and the oxide product. In search for an efficient electro-synthesis strategy for highly-active functional manganese oxides, this project plans to analyze and control the mechanism of ordered self-assembling in the nonequilibrium electro-reaction-diffusion coupled system, under the guiding of typical nonequilibrium physicochemical theory, like dissipative-structure theory; to develop new process-intensifying and process-monitoring methods for the scaling-up process from nano to macro; to design and synthesize novel hierarchical array-like manganese oxide. Our researches will not only develop controllable designing and synthesis strategies for new functional materials to improve its reproductivity and controllability, but also explore the application of new fundamental theories in industrial electrochemistry, in order to provide new ideas for researches on the process engineering and product engineering of nano functional materials.

电合成是锰氧化物工业合成的一种重要方法。纳米材料在规模化合成中的特性失效是当前化学加工及产品工程领域亟待攻克的重大课题，而导致失效的根源之一就是纳米单元跨尺度组装构成宏观材料过程中的介观结构有序性逐级耗失问题。申请人前期发现，锰氧化物电合成过程富含非线性动力学机制，并且其作用会随体系远离平衡而强化，从而深刻影响产物结构有序性。为提高锰氧化物电合成过程的介观跨尺度组装效率，本项目拟基于以耗散结构理论为代表的非平衡态物理化学理论，分析并调控非平衡态电反应-扩散耦合体系的时空有序动力学机制，开发跨尺度可控组装过程强化及监控新方法，设计合成高活性的新型层次阵列结构锰氧化物。研究将有助于创新多尺度产品结构设计及调控方法，拓展非平衡态物理化学基础理论在电反应工程中的应用，从而为纳米功能材料加工工程及产品工程研究提供新思路和新方法。

纳米材料在化工合成及规模化应用中的特性失效是化工领域亟待攻克的重大课题。导致功能失效的一大根源就是纳米单元跨尺度组装构成宏观材料时，结构有序性逐级耗失。电合成是工业制备锰氧化物的一种重要方法。申请人基于前期发现锰氧化物电合成过程富含非线性动力学机制，并且其作用会随体系远离平衡而强化，从而深刻影响产物结构有序性。通过非线性动力学机制的调控，可以指导开发新的过程强化方法，提高电合成过程的介观跨尺度组装效率，并制备高性能锰氧化物材料等。本项目基于耗散结构理论为代表的非平衡态物理化学理论，分析并调控了电反应-扩散耦合体系的非平衡态时空有序机制，开发了系列跨尺度组装过程强化及监控新方法，设计合成了新型层次阵列结构锰氧化物。研究创新了多尺度产品结构设计及调控方法，拓展非平衡态基础理论在电反应工程中的应用。发表SCI论文13篇，申请专利5项，授权2项，论文入选了《Matter》评选的2020年度论文。电解二氧化锰过程强化技术正在广西中信大锰等企业的生产线推广。纤维织物结构高性能锌锰二次电池正在与华为等单位接洽合作。