As a promising substitute for fossil fuels, hydrogen has emerged as a clean and renewable energy. A key challenge is the efficient production of hydrogen to meet the commercial-scale demand of hydrogen. Water splitting electrolysis is a promising pathway to achieve the efficient hydrogen production in terms of energy conversion and storage in which catalysis or electrocatalysis plays a critical role. The development of active, stable, and low-cost catalysts or electrocatalysts is an essential prerequisite for achieving the desired electrocatalytic hydrogen production from water splitting for practical use, which constitutes the central focus of this review. It will start with an introduction of the water splitting performance evaluation of various electrocatalysts in terms of activity, stability, and efficiency. This will be followed by outlining current knowledge on the two half-cell reactions, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), in terms of reaction mechanisms in alkaline and acidic media. Recent advances in the design and preparation of nanostructured noble-metal and non-noble metal-based electrocatalysts will be discussed. New strategies and insights in exploring the synergistic structure, morphology, composition, and active sites of the nanostructured electrocatalysts for increasing the electrocatalytic activity and stability in HER and OER will be highlighted. Finally, future challenges and perspectives in the design of active and robust electrocatalysts for HER and OER towards efficient production of hydrogen from water splitting electrolysis will also be outlined.

Alloying noble metals with non-noble metals enables high activity while reducing the cost of electrocatalysts in fuel cells. However, under fuel cell operating conditions, state-of-the-art oxygen reduction reaction alloy catalysts either feature high atomic percentages of noble metals (>70%) with limited durability or show poor durability when lower percentages of noble metals (<50%) are used. Here, we demonstrate a highly-durable alloy catalyst derived by alloying PtPd (<50%) with 3d-transition metals (Cu, Ni or Co) in ternary compositions. The origin of the high durability is probed by in-situ/operando high-energy synchrotron X-ray diffraction coupled with pair distribution function analysis of atomic phase structures and strains, revealing an important role of realloying in the compressively-strained single-phase alloy state despite the occurrence of dealloying. The implication of the finding, a striking departure from previous perceptions of phase-segregated noble metal skin or complete dealloying of non-noble metals, is the fulfilling of the promise of alloy catalysts for mass commercialization of fuel cells.

This paper reports findings of an investigation of the synthesis of monolayer-capped iron oxide and core (iron oxide)–shell (gold) nanocomposite and their assembly towards thin film materials. Pre-synthesized and size-defined iron oxide nanoparticles were used as seeding materials for the reduction of gold precursors, which was shown to be effective for coating the iron oxide cores with gold shells (Fe oxide@Au). The unique aspect of our synthesis is the formation of Fe oxide@Au core–shell nanoparticles with controllable surface properties. The novelty of our assembly strategy is the exploitation of the ligand-exchange reactivity at the gold shells for the thin film assembly of the core–shell nanoparticles. The core–shell nanocomposites and assemblies have been characterized using TEM, XRD, XPS, FTIR, TGA, and DCP-AES techniques. In addition to evidence from TEM detection of the change in particle size, UV-Vis observation of the change in the surface plasmon resonance band, and XRD detection of disappearance of the magnetite diffraction peaks after coating the gold shell, the formation of the core–shell morphology was further confirmed by DCP-AES composition analysis of Au and Fe in the molecularly-mediated thin film assembly of Fe oxide@Au particles. The interparticle ligand exchange–precipitation chemistry at the gold shell is to our knowledge the first example demonstrating the inter-shell reactivity for constructing thin films of Fe oxide@Au particles. The results have provided important insights into the design of interfacial reactivities via core–shell nanocomposites for magnetic, catalytic and biological applications.