Liang, YongxiangZhao, JiankangZhang, HanZhang, AnWang, ShilongLi, JunShakouri, MohsenXiao, QunfengHu, YongfengLiu, ZuhuanGeng, ZhigangLi, FengwangZeng, Jie2021-12-042021-12-042021-12-042021-10-2710.1021/acs.nanolett.1c02719https://infoscience.epfl.ch/handle/20.500.14299/183622WOS:000713060900052CO2 electroreduction powered by renewable electricity represents a promising method to enclose anthropogenic carbon cycle. Current catalysts display high selectivity toward the desired product only over a narrow potential window due primarily to unoptimized intermediate binding. Here, we report a functional ligand modification strategy in which palladium nanoparticles are encapsulated inside metal-organic frameworks with 2,2'- bipyridine organic linkers to tune intermediate binding and thus to sustain a highly selective CO2-to-CO conversion over widened potential window. The catalyst exhibits CO faradaic efficiency in excess of 80% over a potential window from -0.3 to -1.2 V and reaches the maxima of 98.2% at -0.8 V. Mechanistic studies show that the 2,2'- bipyridine on Pd surface reduces the binding strength of both *H and *CO, a too strong binding of which leads to competing formate production and CO poison, respectively, and thus enhances the selectivity and stability of CO product.Chemistry, MultidisciplinaryChemistry, PhysicalNanoscience & NanotechnologyMaterials Science, MultidisciplinaryPhysics, AppliedPhysics, Condensed MatterChemistryScience & Technology - Other TopicsMaterials SciencePhysicspalladiummetal-organic frameworksligand modificationco2 electroreductionintermediate binding strengthefficient co2 electroreductionelectrochemical reductioncarbon-dioxideelectrocatalytic reductionpalladium catalystspdphotosensitizernanosheetsoxidationtext::journal::journal article::research article