双原子催化剂TM2@C3N4电催化CO2生成双碳产物的理论探究

二氧化碳的资源化利用对于缓解温室效应、实现国家“双碳目标”具有重要的意义，为实现碳循环和能源长期储存提供了可行途径。其中，对于二氧化碳还原反应机理的研究是指导生产不同碳产品的重要理论基础。近年来，单原子催化剂由于其有均匀分散、丰富、可调控的活性金属位点而成为有潜力的电化学反应催化剂；双原子催化剂除具有单原子催化剂的优点外，其两个金属原子活性位点间的协同作用使得其可能具备更优秀的催化活性。本课题应用密度泛函理论计算系统地进行了由g-C₃N₄负载同核和异核双金属原子组成的催化剂（TM₂@C₃N₄）催化二氧化碳还原反应的研究。通过计算证实该系列双原子催化剂均具有较好的稳定性，并且对二氧化碳有很强的活化吸附作用。进一步系统研究了CO₂电催化还原形成多碳产物的反应自由能路径，包括CO-CO、CO-CHO、CHO-CHO和CO-COH耦合方式。本课题先考察了15种催化剂碳碳耦合前各耦合方式进行反应所需的最低电势能和碳碳耦合过程中的自由能变化，筛选得到1种同核催化剂和5种异核催化剂进行完整的反应路径计算，以最终确定催化剂的极限电势。在分析反应路径时，考虑了异核双原子催化剂对中间体的异核吸附效应。最终筛选得到了五种具有低极限电势的高活性异核双原子催化剂MnFe@C₃N₄、MnCo@C₃N₄、MnNi@C₃N₄、MnCu@C₃N₄和FeCo@C₃N₄，同时可以有效抑制析氢竞争反应的进行，有望成为高校的二氧化碳的催化剂材料。本论文的研究对于实验合成高性能二氧化碳还原催化剂具有一定的指导意义，还为其它理论计算中探讨不同耦合方式、异核吸附、反应路径筛选等问题提供了参考。

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