Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory for Nano Technology, National Laboratory of Solid State Microstructures, School of Physics, Nanjing University, No. 22 Hankou Road, Nanjing, Jiangsu 210093, P. R. China.
Eco-materials and Renewable Energy Research Center (ERERC), Collaborative Innovation Center of Advanced Microstructures, College of Engineering and Applied Sciences, Nanjing University, No. 22 Hankou Road, Nanjing, Jiangsu 210093, P. R. China.
Dalton Trans. 2023 May 30;52(21):7129-7135. doi: 10.1039/d3dt00144j.
The sluggish kinetics of CO activation and reduction severely limit the energy conversion efficiency of electrocatalytic CO reduction into fuels. Here, ZnSn(OH) with an alternating arrangement of Zn(OH) and Sn(OH) octahedral units and SrSn(OH) with an alternating arrangement of SrO and Sn(OH) octahedral units were adopted to check the effects of frustrated Lewis pairs (FLPs) on electrochemical CO reduction. The FLPs were electrochemically reconstructed on ZnSn(OH) by reducing the electrochemically unstable Sn-OH to Sn-oxygen vacancies (Sn-O) as a Lewis acid site, which are able to create strong interactions with the adjacent electrochemically stable Zn-OH, a Lewis base site. Compared to SrSn(OH) without FLPs, the higher formate selectivity of ZnSn(OH) originates from the strong ability of FLPs to capture protons and activate CO the electrostatic field of FLPs triggering better electron transfer and strong orbital interactions under negative potentials. Our findings may guide the design of electrocatalysts for CO reduction with high catalytic performances.
CO 的活化和还原动力学缓慢，严重限制了电催化 CO 还原为燃料的能量转换效率。在这里，采用具有交替排列的 Zn(OH) 和 Sn(OH) 八面体单元的 ZnSn(OH) 和具有交替排列的 SrO 和 Sn(OH) 八面体单元的 SrSn(OH) 来检查受阻路易斯对 (FLP) 对电化学 CO 还原的影响。通过将电化学不稳定的 Sn-OH 还原为路易斯酸位 Sn-氧空位 (Sn-O)，在 ZnSn(OH) 上电化学重建了 FLP，该路易斯酸位能够与相邻的电化学稳定的 Zn-OH 形成强相互作用，即路易斯碱位。与没有 FLP 的 SrSn(OH) 相比，ZnSn(OH) 具有更高的甲酸盐选择性，这源于 FLP 捕获质子和激活 CO 的能力较强，在静电场下，FLP 触发了更好的电子转移和强轨道相互作用，在负电势下。我们的研究结果可能为设计具有高催化性能的 CO 还原电催化剂提供指导。
