Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generatio...Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generation,is an important strategy to improve the production and selectivity of the C_(2)products.In this study,we determined that the local electric field can promote the C-C coupling reaction and enhance CO_(2)electroreduction to C_(2)products.First,finite-element simulations indicated that the high curvature of the Cu nanoneedles results in a large local electric field on their tips.Density functional theory(DFT)calculations proved that a large electric field can promote C-C coupling.Motivated by this prediction,we prepared a series of Cu catalysts with different curvatures.The Cu nanoneedles(NNs)exhibited the largest number of curvatures,followed by the Cu nanorods(NRs),and Cu nanoparticles(NPs).The Cu NNs contained the highest concentration of adsorbed K+,which resulted in the highest local electric field on the needles.CO adsorption sensor tests indicated that the Cu NNs exhibited the strongest CO adsorption ability,and in-situ Fourier-transform infrared spectroscopy(FTIR)showed the strongest*COCO and*CO signals for the Cu NNs.These experimental results demonstrate that high-curvature nanoneedles can induce a large local electric field,thus promoting C-C coupling.As a result,the Cu NNs show a maximum FEC_(2)of 44%for CO_(2)RR at a low potential(-0.6 V vs.RHE),which is approximately 2.2 times that of the Cu NPs.This work provides an effective strategy for enhancing the production of multi-carbon products during CO_(2)RR.展开更多
文摘Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generation,is an important strategy to improve the production and selectivity of the C_(2)products.In this study,we determined that the local electric field can promote the C-C coupling reaction and enhance CO_(2)electroreduction to C_(2)products.First,finite-element simulations indicated that the high curvature of the Cu nanoneedles results in a large local electric field on their tips.Density functional theory(DFT)calculations proved that a large electric field can promote C-C coupling.Motivated by this prediction,we prepared a series of Cu catalysts with different curvatures.The Cu nanoneedles(NNs)exhibited the largest number of curvatures,followed by the Cu nanorods(NRs),and Cu nanoparticles(NPs).The Cu NNs contained the highest concentration of adsorbed K+,which resulted in the highest local electric field on the needles.CO adsorption sensor tests indicated that the Cu NNs exhibited the strongest CO adsorption ability,and in-situ Fourier-transform infrared spectroscopy(FTIR)showed the strongest*COCO and*CO signals for the Cu NNs.These experimental results demonstrate that high-curvature nanoneedles can induce a large local electric field,thus promoting C-C coupling.As a result,the Cu NNs show a maximum FEC_(2)of 44%for CO_(2)RR at a low potential(-0.6 V vs.RHE),which is approximately 2.2 times that of the Cu NPs.This work provides an effective strategy for enhancing the production of multi-carbon products during CO_(2)RR.
