Wang Zeyu, Jia Yaling, Zhao Shangqing, Zheng Huiling, Rajendran Antony, Li Wen-Ying
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China.
J Colloid Interface Sci. 2025 Aug 15;692:137528. doi: 10.1016/j.jcis.2025.137528. Epub 2025 Apr 5.
SnO-based materials are promising electrocatalysts for the conversion of CO to formate however increasing their activity further is challenging due to the suboptimal CO adsorption and activation capacity. The interfacial engineering has proven effective in modulating the electronic structure and adsorption behavior of electrocatalysts. Herein, a heterostructure Bi/SnO was constructed for the CO electroreduction to formate in which a formate Faraday efficiency of 94.9% and single-pass carbon efficiency of 40.3% were achieved at -1.0 V versus reversible hydrogen electrode in 1.0 M KOH. During a 30-hour stability test, the current density was nearly constant without a significant decrease while the formate Faraday efficiency was maintained around 90%. This remarkable activity is attributed to the strong electronic interaction arising from p-p orbital coupling at the Bi/SnO interface, according to the experimental and theoretical investigations. The computational insights suggest that the p-p orbital coupling promotes the electron transfer from Bi to SnO and optimizes the adsorption strength of the intermediate (*OCHO) to enhance the catalytic activity. The formation of *OCHO during formate generation was confirmed by the in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy. This work might contribute key insights into the mechanisms underlying activity enhancement via strong electronic interaction between dual p-block metal catalysts.
基于SnO的材料是将CO转化为甲酸盐的有前景的电催化剂，然而，由于CO吸附和活化能力欠佳，进一步提高其活性具有挑战性。界面工程已被证明在调节电催化剂的电子结构和吸附行为方面是有效的。在此，构建了一种异质结构Bi/SnO用于CO电还原制甲酸盐，在1.0 M KOH中，相对于可逆氢电极在-1.0 V时，甲酸盐法拉第效率达到94.9%，单程碳效率达到40.3%。在30小时的稳定性测试中，电流密度几乎保持恒定，没有显著下降，而甲酸盐法拉第效率保持在90%左右。根据实验和理论研究，这种显著的活性归因于Bi/SnO界面处p-p轨道耦合产生的强电子相互作用。计算结果表明，p-p轨道耦合促进了电子从Bi转移到SnO，并优化了中间体(OCHO)的吸附强度，从而提高了催化活性。原位衰减全反射表面增强红外吸收光谱证实了甲酸盐生成过程中OCHO的形成。这项工作可能为通过双p区金属催化剂之间的强电子相互作用提高活性的潜在机制提供关键见解。
