Cu纳米片/CuxMy(M=MOFs, P)纳米阵列分级结构构筑及电催化分解水研究

In order to effectively improve the conductivity and prevent the loss of non-noble metal catalysts for electrolysis water reaction, a novel Cu nanosheets /CuxMy(M=MOFs, P) nanoarray hierarchical composites are fabricated by using two-dimensional Cu nanosheets as self-template and conductive substrate. Cu-MOFs and Cu3P nanoarray hierarchical structures are respectively fabricated on the surfaces of copper nanosheets. The functional assembly of the hierarchical structure in the conducting/catalytic active regions enables efficient conversion of the electrocatalytic decomposition of the water reaction. Density functional theory (DFT) was used to calculate the electronic density structure and the minimum energy path of the materials to explore the catalytic active sites, identify the active sites and establish the catalytic reaction kinetics model. The mechanism of electrocatalytic reaction will be studied, the synergistic effect mechanism between the conductive interface, the electrocatalytic active components, as well as the hierarchical nanoarray structures will also be explored. This work not only provides design criteria and manufacturing principle for high quality electrocatalytic materials, but also promote their application in the field of electrocatalytic water decomposition.

针对目前常用的Pt、Ir/IrO2、Ru/RuO2电催化剂价格昂贵，而非贵金属催化剂导电性能差、反应中催化剂容易团聚、流失等问题，本项目提出了构筑Cu nanosheets/ CuxMy (M= MOFs、P)纳米阵列分级结构的新思路，巧妙地以二维铜纳米片作为自模板和导电基底，在铜纳米片表面分别生长Cu-MOFs和Cu3P纳米阵列材料，通过导电区/催化活性区分级结构的功能组装，实现电催化分解水反应的高效转化。利用密度泛函理论(DFT)计算分析材料的电子密度结构、最小能量路径等探究催化活性位，明确活性中心，建立催化反应动力学模型，揭示电催化反应机理，探讨导电界面和电催化活性组分及纳米阵列分级结构间协同效应机制。此项工作能为开发性能优异的电催化材料提供设计准则与制备原理，推动其在电催化分解水领域的应用。

本项目针对目前常用的电催化剂Pt、Ir/IrO2、Ru/RuO2价格昂贵，而非贵金属催化剂导电性差、反应中催化剂容易团聚、流失等问题，提出了构筑Cu nanosheets/ CuxMy (M= MOFs、P)纳米阵列分级结构的新思路，通过原位生长、自组装和结构调控等方法在Cu纳米片基底上构筑了Cu nanosheets/Cu3P纳米片阵列、三角形Cu nanosheets@Cu3P纳米柱阵列、Cu nanosheets/Cu-BTC纳米柱阵列、Cu nanosheets/Cu-NBDC纳米片阵列、Cu nanosheets/Cu-BTEC纳米阵列等多种纳米Cu 基电催化复合材料。掌握了Cu纳米片/CuxMy(M=MOFs, P)纳米阵列的分级结构构筑原则和调控规律，揭示了Cu纳米片、Cu3P及MOFs间的协同作用机制。经DFT计算，Cu纳米片作为导电基底和自模板的引入，能够改变Cu3P上单个氢原子的吸附自由能，使其更接近0，从而实现优异的电催化性能。所开发的Cu nanosheets/Cu3P纳米片阵列材料用于酸性条件下电催化析氢催化反应，展现出优异的电催化活性和稳定性。开发的系列Cu nanosheets/Cu-MOFs纳米阵列材料在碱性条件下具备析氢、析氧双重催化活性。其中Cu nanosheets/Cu-BTC纳米柱阵列在碱性条件下的OER反应中，电流密度为10 mA/cm2时，Cu nanosheets/Cu-BTC纳米阵列的过电位仅为170mV。本项目为可持续、低价、双功能非贵电催化材料的定向设计与制备提供理论基础。