The crucial role of electrolyte cations in CO2 electroreduction has received intensive attention. One prevailing theory is that through electrostatic interactions or direct coordination, larger cations such as Cs+ can better stabilize the key intermediate species for CO and multicarbon (C2+) product generation, for example, on silver and copper. Herein, we show that smaller, acidic alkali metal cations greatly enhance CO2-to-methanol conversion kinetics (Li+ > Na+ > K+ > Cs+) on an immobilized molecular cobalt catalyst unlike the trend for CO and C2+. Through kinetic isotope effect studies and electrokinetic analyses, we found that hydration shell of a cation serves as a proton donor in the rate-determining protonation step of adsorbed CHO where acidic cations promote the proton-coupled electron transfer. This study reveals the promotional effect of cation solvation environment on CO2 electroreduction beyond the widely acknowledged stabilizing effect of cations.

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Gold nanoparticle stabilized by adsorption of bipedal thiol whose end is modified with bromoarene is prepared to undergo palladium-mediated deprotonative C-H arylation reaction. Heteroarenes are introduced onto the organic moiety of the nanoparticle.

The high enantioselective arylation was pseudo-biologically accererated by self-inclusion of the Rh complex bearing a γ-cyclodextrin.