Synergistic Modulation of Non-Precious-Metal Electrocatalysts for Advanced Water Splitting.

ConspectusHydrogen is an ideal energy carrier and plays a critical role in the future energy transition. Distinct from steam reforming, electrochemical water splitting, especially powered by renewables, has been considered as a promising technique for scalable production of high-purity hydrogen with no carbon emission. Its commercialization relies on the reduction of electricity consumption and thus hydrogen cost, calling for highly efficient and cost-effective electrocatalysts with the capability of steadily working at high hydrogen output. This requires the electrocatalysts to feature (1) highly active intrinsic sites, (2) abundant accessible active sites, (3) effective electron and mass transfer, (4) high chemical and structural durability, and (5) low-cost and scalable synthesis. It should be noted that all these requirements should be fulfilled together for a practicable electrocatalyst. Much effort has been devoted to addressing one or a few aspects, especially improving the electrocatalytic activity by electronic modulation of active sites, while few reviews have focused on the synergistic modulation of these aspects together although it is essential for advanced electrochemical water splitting.In this Account, we will present recent innovative strategies with an emphasis on our solutions for synergistically modulating intrinsic active sites, electron transportation, mass transfer, and gas evolution, as well as mechanical and chemical durability, of non-precious-metal electrocatalysts, aiming for cost-effective and highly efficient water splitting. The following approaches for coupling these aspects are summarized for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER). (1) . The electronic structure of a catalytic site determines the adsorption/desorption of reactive intermediates and thus intrinsic activity. It can be tuned by heterogeneous doping, strain effect, spin polarization, etc. Coupling these effects to optimize the reaction pathways or target simultaneously the activity and stability would advance electrocatalytic performance. (2) . The crystallinity, crystalline phase, crystalline facets, crystalline defects, etc. affect both activity and stability. Coupling these effects with electronic modulation would enhance the activity together with stability. (3) . It will focus on concurrently modulating electronic structure for improving the intrinsic activity and morphology for increasing accessible active sites, especially through single action or processing. The mass transfer and gas evolution properties can also be enhanced by morphological modulation to enable water splitting at large output. (4) . Electrocatalytic reaction generally consists of a couple of elementary reactions. Each one may need a specific active site. Designing and combining various components targeting every elementary step on a space-limited catalyst surface will balance the intermediates and these steps for accelerating the overall reaction. (5) Taking all these strategies together into account is necessary to integrate all above essential features into one electrocatalyst for enabling high-output water electrolysis. Beyond the progress made to date, the remaining challenges and opportunities is also discussed. With these insights, hopefully, this Account will shed light on the rational design of practical water-splitting electrocatalysts for the cost-effective and scalable production of hydrogen.