Song Bowen, Xia Xueqian, Ma Zengying, Li Renjie, Wang Xiufeng, Zhou Lin, Huang Yucheng
College of Chemistry and Material Science, Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Normal University, Wuhu 241000, China.
Anhui Key Laboratory of Molecule-Based Materials, Anhui Carbon Neutrality Engineering Center, Anhui Normal University, Wuhu 241000, China.
J Phys Chem Lett. 2024 Sep 19;15(37):9342-9348. doi: 10.1021/acs.jpclett.4c02088. Epub 2024 Sep 5.
The electrochemical CO reduction reaction (CORR) to HCOOH provides an avenue for reducing global accelerated CO emissions and producing high-value-added chemicals. Nevertheless, the presence of an inherent linear scaling relationship (LSR) between *OCHO and *HCOOH leads to the electrosynthesis of HCOOH being achieved at high cathodic potentials. In this work, by adjusting the different Cu:Sn ratio of SnCu alloys, we comprehensively explored the electrocatalytic 2e CORR performance toward the production of HCOOH. Combining density functional theory calculations with the constant-potential implicit solvent model, the SnCu surface alloy was posited to be a promising electrocatalyst with superior HCOOH selectivity and an ultralow limiting potential of -0.20 V in an environment of pH = 7.2. The high performance was found to originate from the breaking of the LSR, which is a result of an extraordinary electronic property of the active Cu site. This work not only advances a global-searched strategy for the rational design of efficient catalysts toward HCOOH production but also provides in-depth insights into the underlying mechanism for the enhanced performance of microalloy electrocatalysts.
将电化学CO还原反应（CORR）转化为HCOOH为减少全球加速的CO排放和生产高附加值化学品提供了一条途径。然而，OCHO和HCOOH之间存在固有的线性标度关系（LSR），导致HCOOH的电合成在高阴极电位下才能实现。在这项工作中，通过调整SnCu合金的不同Cu:Sn比例，我们全面探索了电催化2e CORR生成HCOOH的性能。结合密度泛函理论计算和恒电位隐式溶剂模型，推测SnCu表面合金是一种有前景的电催化剂，在pH = 7.2的环境中具有优异的HCOOH选择性和-0.20 V的超低极限电位。发现这种高性能源于LSR的打破，这是活性Cu位点特殊电子性质的结果。这项工作不仅推进了一种用于合理设计高效HCOOH生产催化剂的全局搜索策略，还为微合金电催化剂性能增强的潜在机制提供了深入见解。
