Concentrated C<sub>2+</sub> Alcohol Production Enabled\nby Post-Intermediate Modulation and Augmented CO Adsorption in CO\nElectrolysis

The electrocatalytic synthesis of multicarbon products\nfrom CO<sub>2</sub>/CO feedstock represents a sustainable method for\nchemical\nproduction with a reduced carbon footprint. Traditional copper catalysts\npredominantly produce alkenes, but generating valuable and versatile\nC<sub>2+</sub> alcohols, especially high-energy-density C<sub>3</sub> alcohols, has been challenging due to issues with selectivity, activity,\nand stability. Here, we present the construction of Ru-doped Cu nanowires\nthat enhance the selectivity of <i>n</i>-PrOH and C<sub>2+</sub> alcohols. In situ Raman spectroscopy shows that our approach\npromotes both *CO binding and availability, particularly facilitating\nthe formation of high-frequency-bound *CO (*CO<sub>HFB</sub>) and\nmaintaining multiple *CO adsorption modes on Ru-modified and bare\nlow-coordinated Cu nanowires. Density-functional theory (DFT) simulations\nillustrate that introducing Ru species onto a low-coordinated Cu step\nsurface simultaneously stabilizes CO and alcohol-related intermediates,\nshifting the dominant reaction pathway toward alcohols and facilitating\nCO–C<sub>2</sub> coupling at the expense of ethylene selectivity.\nIn an alkaline gas-diffusion electrolyzer, we attained a maximum Faradaic\nefficiency (FE) of 35.9% for <i>n</i>-PrOH and 62.4% for\nthe total C<sub>2+</sub> alcohols. Optimizing parameters in the membrane\nelectrode assembly (MEA) system enabled the one-pot generation and\nseparation of C<sub>2+</sub> alcohols, achieving a record concentration\nof 18.8 wt % (4.2 wt % <i>n</i>-PrOH and 14.6 wt % EtOH)\nwith nearly 100% purity at 200 mA/cm<sup>2</sup> over 100 h. This\nwork not only provides new insights and guidance for the development\nof future catalysts from the perspectives of surface science and mechanisms\nbut also highlights the importance of coupling material engineering\nwith reactor engineering to optimize the production process of high-value\nalcohol products.