Abstract
Developing energy production, storage, and conversion technologies based on sustainable or renewable energy is essential to address the energy and environmental crisis. Electrochemical water splitting is one of the most promising approaches to realize the production of green hydrogen. The design of catalytic materials with low cost, high activity, and long-term stability and the exploration of specific reaction mechanisms are the key focus for the involved electrochemical hydrogen evolution reaction (HER). Recently, substantial efforts have been devoted to the rational design and synthesis of non-noble metallic heterostructures with fascinating synergistic effects among different components. These heterostructured materials demonstrate comprehensive properties exceeding the estimations by the rule of mixtures and display high activity and long-term stability in industrial conditions for HER. Herein, the reaction mechanism and key parameters for improving catalytic performance in the HER process are discussed in detail. The latest advances in heterostructures based on synthetic methods and electrocatalytic characteristics from experimental and computational perspectives are summarized according to the role of various components. Herein, insights are provided in this review into an in-depth understanding of the heterostructures as HER electrocatalysts, and the opportunities and challenges to scale up future-oriented developments are highlighted.