Dynamic Electrodeposition on Bubbles: An Effective Strategy toward Porous Electrocatalysts for Green Hydrogen Cycling.

ConspectusClosed-loop cycling of green hydrogen is a promising alternative to the current hydrocarbon economy for mitigating the energy crisis and environmental pollution. It stores energy from renewable energy sources like solar, wind, and hydropower into the chemical bond of dihydrogen (H) via (photo)electrochemical water splitting, and then the stored energy can be released on demand through the reverse reactions in H-O fuel cells. The sluggish kinetics of the involved half-reactions like hydrogen evolution reaction (HER), oxygen evolution reaction (OER), hydrogen oxidation reaction (HOR), and oxygen reduction reaction (ORR) limit its realization. Moreover, considering the local gas-liquid-solid triphase microenvironments during H generation and utilization, rapid mass transport and gas diffusion are critical as well. Accordingly, developing cost-effective and active electrocatalysts featuring three-dimensional hierarchically porous structures are highly desirable to promote the energy conversion efficiency. Traditionally, the synthetic approaches of porous materials include soft/hard templating, sol-gel, 3D printing, dealloying, and freeze-drying, which often need tedious procedures, high temperature, expensive equipment, and/or harsh physiochemical conditions. In contrast, dynamic electrodeposition on bubbles using the formed bubbles as templates can be conducted at ambient conditions with an electrochemical workstation. Moreover, the whole preparation process can be finished within minutes/hours, and the resulting porous materials can be employed as catalytic electrodes directly, avoiding the use of polymeric binders like Nafion and the consequent issues like limited catalyst loading, reduced conductivity, and inhibited mass transport.In this Account, we summarize our contributions to the dynamic electrodeposition on bubbles toward advanced porous electrocatalysts for green hydrogen cycling. These dynamic electrosynthesis strategies include potentiodynamic electrodeposition that linearly scans the applied potentials, galvanostatic electrodeposition that fixes the applied currents, and electroshock which quickly switches the applied potentials. The resulting porous electrocatalysts range from transition metals to alloys, nitrides, sulfides, phosphides, and their hybrids. We mainly focus on the 3D porosity design of the electrocatalysts by tuning the electrosynthesis parameters to tailor the behaviors of bubble co-generation and thus the reaction interface. Then, their electrocatalytic applications for HER, OER, overall water splitting (OWS), biomass oxidation (to replace OER), and HOR are introduced, with a special emphasis on the porosity-promoted activity. Finally, the remaining challenges and future perspective are also discussed. We hope this Account will encourage more efforts into this attractive research field of dynamic electrodeposition on bubbles for various energy catalytic reactions like carbon dioxide/monoxide reduction, nitrate reduction, methane oxidation, chlorine evolution, and others.