理论计算辅助FLP催化CO2分子还原反应研究

CO2分子是一类经济性较高、可循环利用且无毒性的碳源，一直以来被视为构筑部分化合物及燃料分子的潜在C1合成砌块。使用“受阻路易斯酸碱对”（FLP）能够对CO2分子进行化学固定，由于其同时能够异裂氢气分子，普遍认为使用FLP实现对CO2分子的活化，再经历后续分步氢化还原过程得到富氢的C1化合物具有较高的可能性。但在已有的报道中，由于Lewis酸的亲氧性，往往需要当量的FLP催化系统参与且该还原反应存在转化率低、产物选择性较差等不足。我们希望结合理论计算与实验研究手段，利用Mayr方程对本课题组所发展经硼氢化反应原位生成的FLP系统酸-碱强度进行定量分析并建立针对CO2还原反应的库，完成对CO2还原反应势能面的构建，设计、优化FLP系统并寻找合适的O-捕获剂，以实现对CO2分子的高效、高选择性催化还原。

The general concern over the control of greenhouse gas CO2, which has been treated as a valuable, recyclable and non-toxic C1 feedstock to synthesize some important carbonyl molecules and fuels, has led to the development of carbon capture and transformation technologies. Frustrated Lewis pairs (FLP), emerging as a milestone in the metal-free bifunctional activation of H2 and CO2, has also shown a potential to drive CO2 to hydrogen-enrich C1 product via a stepwise hydrogenation reduction. The major challenge originates from the requirement of a stoichiometric amount of FLP, the low conversion rate and a poor product-selectivity. Here, we combine the theoretical calculation and experimental studies to explore the PES of in situ generated-FLPs (originated from the hydroboration of alkene/alkyne and HBR2) triggered CO2 reductions, make a quantitative analysis to the Lewis acidity/basicity. Based on the calculation results, some sequential work, such as the design and optimization of FLP systems, will be conducted to realize the FLP catalyzed CO2 reduction.