Hydrogen fuel is considered as the cleanest renewable resource and the primary alternative to fossil fuels for future energy supply. Sustainable hydrogen generation is the major prerequisite to realize future hydrogen economy. The electrocatalytic hydrogen evolution reaction (HER), as the vital step of water electrolysis to H2 production, has been the subject of extensive study over the past decades. In this comprehensive review, we first summarize the fundamentals of HER and review the recent state-of-the-art advances in the low-cost and high-performance catalysts based on noble and non-noble metals, as well as metal-free HER electrocatalysts. We systemically discuss the insights into the relationship among the catalytic activity, morphology, structure, composition, and synthetic method. Strategies for developing an effective catalyst, including increasing the intrinsic activity of active sites and/or increasing the number of active sites, are summarized and highlighted. Finally, the challenges, perspectives, and research directions of HER electrocatalysis are featured.

Recent Advances in Electrocatalytic Hydrogen Evolution Using Nanoparticles.

Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state-of-the-art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active-sites with improved electrochemical efficiencies in future.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201700464

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions

The persistently increasing energy consumption and the low abundance of conventional fuels have raised serious concerns all over the world. Thus, the development of technology for clean-energy production has become the major research priority worldwide. The globalization of advanced energy conversion technologies like rechargeable metal–air batteries, regenerated fuel cells, and water-splitting devices has been majorly benefitted by the development of apposite catalytic materials that can proficiently carry out the pertinent electrochemical processes like oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and water hydrolysis. Despite a handful of superbly performing commercial catalysts, the high cost and low electrochemical stability of precursors have consistently discouraged their long-term viability. As a promising substitute of conventional platinum-, palladium-, iridium-, gold-, silver-, and ruthenium-based catalysts, various transition-metal (TM) i...

Nickel-Based Electrocatalysts for Energy-Related Applications: Oxygen Reduction, Oxygen Evolution, and Hydrogen Evolution Reactions

Mixed metal sulfides (MMSs) have attracted increased attention as promising electrode materials for electrochemical energy storage and conversion systems including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), hybrid supercapacitors (HSCs), metal–air batteries (MABs), and water splitting. Compared with monometal sulfides, MMSs exhibit greatly enhanced electrochemical performance, which is largely originated from their higher electronic conductivity and richer redox reactions. In this review, recent progresses in the rational design and synthesis of diverse MMS-based micro/nanostructures with controlled morphologies, sizes, and compositions for LIBs, SIBs, HSCs, MABs, and water splitting are summarized. In particular, nanostructuring, synthesis of nanocomposites with carbonaceous materials and fabrication of 3D MMS-based electrodes are demonstrated to be three effective approaches for improving the electrochemical performance of MMS-based electrode materials. Furthermore, some potential challenges as well as prospects are discussed to further advance the development of MMS-based electrode materials for next-generation electrochemical energy storage and conversion systems.

Mixed Metal Sulfides for Electrochemical Energy Storage and Conversion

0D to 3D carbon-based networks combined with pseudocapacitive electrode material for high energy density supercapacitor: A review

Facile synthesis of CuCo2S4 as a novel electrode material for ultrahigh supercapacitor performance

Transforming Nickel Hydroxide into 3D Prussian Blue Analogue Array to Obtain Ni2P/Fe2P for Efficient Hydrogen Evolution Reaction

Fabrication of stable, efficient, and inexpensive bifunctional electro-catalysts for water splitting has become increasingly attractive. Herein, for the first time, the direct growth of Mo-doped Ni3S2 on Ni foams using sodium molybdate as the Mo source at different temperatures is demonstrated. Effects of temperature on the morphology and water splitting performance of Mo-doped Ni3S2 were discussed in detail. It is found that the atomic stoichiometric ratios of Mo and Ni can be controlled by the adjusting of reaction temperature, while the obtained electro-catalysts demonstrate various morphologies, capacitances and chemisorption free energies of hydrogen, which lead to different current densities and hydrogen evolution efficiencies. The electro-catalyst synthesized at 200 °C (200-SMN/NF) demonstrates the best regular morphology and electrochemical properties. When employed in oxygen evolution reactions, 200-SMN/NF demonstrates a low over-potential of 180 mV at 100 mA cm−2. Adapting it as a bifunctional electro-catalyst, a current density of 10 mA cm−2 at a very low cell voltage of 1.53 V and cycling lifespan of more than 15 h was delivered. Further results indicated elevated hydrogen evolution reaction activity, consisting of a moderate 278 mV over-potential at a 100 mA cm−2 hydrogen production current density, a small 72.9 mV dec−1 Tafel slope, and a superior current density compared to that of precious catalyst Pt/C (40%) after −0.53 V. These results underscore the fact that 200-SMN/NF is a high-performance, precious-metal-free electro-catalyst, and provide the foundation for exciting opportunities in water splitting applications.

Controlled synthesis of Mo-doped Ni3S2 nano-rods: an efficient and stable electro-catalyst for water splitting

Synthesis of highly efficient and robust catalysts with earth-abundant resources for overall water splitting is essential for large-scale energy conversion processes. Herein, a series of highly active and inexpensive Co–Ni–P films were fabricated by a one-step constant current density electrodeposition method. These films were demonstrated to be efficient bifunctional catalysts for both H2 and O2 evolution reactions (HER and OER), while deposition time was deemed to be the crucial factor governing electrochemical performance. At the optimal deposition time, the obtained Co–Ni–P-2 catalyst performed remarkably for both HER and OER in alkaline media. In particular, it requires −103 mV overpotential for HER and 340 mV for OER to achieve the current density of 10 mA cm–2, with corresponding Tafel slopes of 33 and 67 mV dec–1. Moreover, it outperforms the Pt/C//RuO2 catalyst and only needs −160 mV (430 mV) overpotential for HER (OER) to achieve 200 mA cm–2 current density. Co–Ni–P electrodes were also conducte...

Controlled Electrodeposition Synthesis of Co–Ni–P Film as a Flexible and Inexpensive Electrode for Efficient Overall Water Splitting

Herein, we describe the preparation and testing of Co-doped FeSe2 hybridized with graphene (Fe1–xCoxSe2/RGO), a high-active yet stable electrocatalyst for hydrogen evolution reactions (HERs) in acidic solutions. First, we systematically analyze the composition and morphology of Fe1–xCoxSe2/RGO and attribute its excellent electrochemical performance to its unique architecture—a base of highly conductive graphene with fully exposed active edges that enhances conductivity and facilitates ion/electron transfer. Our experimental measurements indicate elevated HER activity with a moderate overpotential of ∼166 mV at a hydrogen production current density of 10 mA cm–2, a small Tafel slope of ∼36 mV dec–1, and long cycling lifespan more than 20 h. The promising results, in addition to the fact that Fe1–xCoxSe2/RGO is a high-performance, precious-metal-free electrocatalyst, pave the way for exciting opportunities in renewable hydrogen production applications.

Yuancai Ge

Papers

Facile synthesis of CuCo2S4 as a novel electrode material for ultrahigh supercapacitor performance

Transforming Nickel Hydroxide into 3D Prussian Blue Analogue Array to Obtain Ni2P/Fe2P for Efficient Hydrogen Evolution Reaction

Controlled synthesis of Mo-doped Ni3S2 nano-rods: an efficient and stable electro-catalyst for water splitting

Controlled Electrodeposition Synthesis of Co–Ni–P Film as a Flexible and Inexpensive Electrode for Efficient Overall Water Splitting

Cobalt-Doped FeSe2-RGO as Highly Active and Stable Electrocatalysts for Hydrogen Evolution Reactions