Replacing PVP by macrocycle cucurbit[6]uril to cap sub-5 nm Pd nanocubes as highly active and durable catalyst for ethanol electrooxidation

Pd nano cubes(NCs)en closed by six{100}facets are fasci nating model materials for both fun dame ntal studies and practical applicati ons.However,the only available method to prepare well-defined sub-10 nm Pd NCs was developed by Xia et al.more than 10 years ago,un avoidably using polyvinyl pyrrol id one(PVP)polymer to preve nt particle aggregati on.The strongly adsorbed PVP extremely deteriorates the catalysts*efficiency because of the high coverage of accessible surface-active sites.Numerous efforts have been devoted to replacing PVP with weaker capping agents but with limited progress predominately due to the difficulties in tuning the growth kinetics of Pd NCs.For the first time,we report that macrocycle cucurbit[6]uril(CB[6])can replace PVP in the synthesis of Pd NCs by dedicatedly controlling the growth parameters.CB[6]capped Pd NCs showed 1.1-1.5 times in creased specific surface area compared to the surfactant-free commercial Pd catalysts.Moreover,X-ray photoelectron spectroscopy dem on strated the modified electronic structure of Pd NCs through the carb onyl group of CB[6].Consequently,compared to the commercial catalysts,the obtained Pd NCs exhibited 7 times higher current density towards ethanol oxidation reaction.Remarkably,after 17 h of continuous work,it reduced deactivation by up to 1-4 orders of magnitude.