Facilitating alkaline hydrogen evolution kinetics via interfacial modulation of hydrogen-bond networks by porous amine cages

The electrode-electrolyte interface is pivotal in the electrochemical kinetics. However, modulating the electrochemical interface at the atomic or molecular level is challenging due to the lack of efficient interfacial regulators. Here, we employ a porous amine cage as an interfacial modifier to Pt cluster in a confining configuration, largely enhancing alkaline HER kinetics by facilitating charge transfer. In situ electrochemical surface-enhanced Raman spectra, in combination with the ab initio molecular dynamics simulation, elucidates that the interaction between water and the -NH- moiety of cage frame softens the H-bonds net of interfacial water, making it more flexible for charge transfer. Moreover, our investigation pinpointed that the -NH- moiety acted as a pump for charge transfer by Grotthuss mechanism, lowering the kinetic barrier for hydrogen adsorption. Our findings highlight the strategy of establishing a soft-confining interfacial modifier by porous cage, offering opportunities to optimize electrochemical interfaces and promote reaction kinetics in a targeted way.