基于金属氧化物/金属复合纳米管二氧化碳的高效转化及其机理研究

The solar energy, wind energy and other renewable energy conversion into electrical energy, again by electroreduction of CO2 into high value-added chemicals, is one of the effective ways to reduce the greenhouse effect and realize the recycling of carbon resource. To solve the bottleneck problems such as low efficiency, poor selectivity and so on in the CO2 electroreduction transformation, this project will use heterogeneous interface to promote the electrocatalytic performance for CO2 transformation. By constructing metal oxide/metal interface to regulate electronic structure of metal, change the adsorption behavior of CO2 on the metal surface and decrease the activation energy of CO2, the reaction pathway of CO2 electroreduction will be changed, and the formation energy barriers of intermediate species and products will be decreased, and accordingly the efficiency and selectivity of CO2 electroreduction transformation will be improved. This project will firstly perform the theoretical calculation of electrocatalyst for guiding rational design, and then realize the controllable synthesis metal oxide/metal (CoO/Co, MnO2/Mn, SnO2/Sn, etc.) core-shell nanoparticle tube arrays by electrodeposition method. Finally, the electrocatalytic mechanism of CO2 reduction will be revealed by combining in-situ characterization and theoretical simulations, and the surface and interface effects of metal oxide/metal on electrocatalytic activity, selectivity and stability of CO2 reduction will be clarified. This project will provide a new way for CO2 efficient transformation.

将大阳能、风能等可再生能源转化为电能，再通过电还原将CO2转化为高附加值的化学品，是减少温室效应和实现碳资源循环利用的有效途径之一。针对CO2电还原效率低、选择性差等瓶颈问题，本项目将利用异质界面促进电催化性能的思想应用于CO2转化，通过构筑金属氧化物/金属异质界面调节金属的电子结构，改变金属表面对CO2的吸附行为和降低CO2活化能，从而导向性地调控CO2电还原反应途径和降低中间物种及产物的形成能垒，提高CO2电还原转化效率和选择性。本项目将首先通过理论模拟计算指导电催化剂的理性设计，通过电沉积方法实现金属氧化物/金属(CoO/Co、MnO2/Mn、SnO2/Sn等)核-壳纳米粒子堆积的复合纳米管催化剂的可控制备，然后将理论模拟和原位动态表征相结合揭示CO2还原的电催化机理，阐明金属氧化物/金属复合纳米管的表界面效应对CO2电还原催化活性、选择性及稳定性的影响，为CO2高效转化提供新途径。

将大阳能、风能等可再生能源转化为电能，再通过电还原将CO2转化为高附加值的化学品，是减少温室效应和实现碳资源循环利用的有效途径之一。针对CO2电还原效率低、选择性差等瓶颈问题，本项目将利用异质界面促进电催化性能的思想应用于CO2转化，通过构筑金属氧化物/金属异质界面调节金属的电子结构，改变金属表面对CO2的吸附行为和降低CO2活化能，从而导向性地调控CO2电还原反应途径和降低中间物种及产物的形成能垒，提高CO2电还原转化效率和选择性。本项目通过理论模拟计算指导电催化剂的理性设计，通过电沉积方法实现金属氧化物/金属(MnO2/Ni、TiO2/Co、Cu2O/Cu等)异质结构的催化剂可控制备，然后将理论模拟和原位动态表征相结合揭示CO2还原、H2O还原、H2O氧化的电催化机理，阐明金属氧化物/金属异质界面效应对CO2还原、H2O还原、H2O氧化的催化活性、选择性及稳定性的影响，为高效电化学转化提供新途径。