Peng Hong-Jie, Tang Michael T, Halldin Stenlid Joakim, Liu Xinyan, Abild-Pedersen Frank
SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA.
SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, CA, 94305, USA.
Nat Commun. 2022 Mar 17;13(1):1399. doi: 10.1038/s41467-022-29140-8.
The electrochemical conversion of carbon di-/monoxide into commodity chemicals paves a way towards a sustainable society but it also presents one of the great challenges in catalysis. Herein, we present the trends in selectivity towards specific dicarbon oxygenate/hydrocarbon products from carbon monoxide reduction on transition metal catalysts, with special focus on copper. We unveil the distinctive role of electrolyte pH in tuning the dicarbon oxygenate/hydrocarbon selectivity. The understanding is based on density functional theory calculated energetics and microkinetic modeling. We identify the critical reaction steps determining selectivity and relate their transition state energies to two simple descriptors, the carbon and hydroxide binding strengths. The atomistic insight gained enables us to rationalize a number of experimental observations and provides avenues towards the design of selective electrocatalysts for liquid fuel production from carbon di-/monoxide.
将二氧化碳/一氧化碳电化学转化为商品化学品为迈向可持续社会铺平了道路，但这也是催化领域的重大挑战之一。在此，我们展示了过渡金属催化剂上一氧化碳还原生成特定二碳含氧化合物/碳氢化合物产物的选择性趋势，特别关注铜。我们揭示了电解质pH值在调节二碳含氧化合物/碳氢化合物选择性方面的独特作用。这种理解基于密度泛函理论计算的能量学和微观动力学模型。我们确定了决定选择性的关键反应步骤，并将它们的过渡态能量与两个简单的描述符——碳和氢氧化物结合强度联系起来。由此获得的原子层面的见解使我们能够合理解释一些实验观察结果，并为设计用于从二氧化碳/一氧化碳生产液体燃料的选择性电催化剂提供了途径。
