Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

Noble metal-free hydrogen evolution catalysts for water splitting

Increasing demand for finding eco-friendly and everlasting energy sources is now totally depending on fuel cell technology. Though it is an eco-friendly way of producing energy for the urgent requirements, it needs to be improved to make it cheaper and more eco-friendly. Although there are several types of fuel cells, the hydrogen (H2) and oxygen (O2) fuel cell is the one with zero carbon emission and water as the only byproduct. However, supplying fuels in the purest form (at least the H2) is essential to ensure higher life cycles and less decay in cell efficiency. The current large-scale H2 production is largely dependent on steam reforming of fossil fuels, which generates CO2 along with H2 and the source of which is going to be depleted. As an alternate, electrolysis of water has been given greater attention than the steam reforming. The reasons are as follows: the very high purity of the H2 produced, the abundant source, no need for high-temperature, high-pressure reactors, and so on. In earlier days,...

Recent Trends and Perspectives in Electrochemical Water Splitting with an Emphasis on Sulfide, Selenide, and Phosphide Catalysts of Fe, Co, and Ni: A Review

There is a growing interest in the conversion of water and solar energy into clean and renewable H2 fuels using earth-abundant materials due to the depletion of fossil fuel and its serious environmental impact. This critical review highlights some key factors influencing the efficiency of heterogeneous semiconductors for solar water splitting (i.e. improved charge separation and transfer, promoted optical absorption, optimized band gap position, lowered cost and toxicity, and enhanced stability and water splitting kinetics). Moreover, different engineering strategies, such as band structure engineering, micro/nano engineering, bionic engineering, co-catalyst engineering, surface/interface engineering of heterogeneous semiconductors are summarized and discussed thoroughly. The synergistic effects of the different engineering strategies, especially for the combination of co-catalyst loading and other strategies seem to be more promising for the development of highly efficient photocatalysts. A thorough understanding of electron and hole transfer thermodynamics and kinetics at the fundamental level is also important for elucidating the key efficiency-limiting step and designing highly efficient solar-to-fuel conversion systems. In this review, we provide not only a summary of the recent progress in the different engineering strategies of heterogeneous semiconductors for solar water splitting, but also some potential opportunities for designing and optimizing solar cells, photocatalysts for the reduction of CO2 and pollutant degradation, and electrocatalysts for water splitting.

Engineering heterogeneous semiconductors for solar water splitting

The construction of highly active and stable non-noble-metal electrocatalysts for hydrogen and oxygen evolution reactions is a major challenge for overall water splitting. Herein, we report a novel hybrid nanostructure with CoP nanoparticles (NPs) embedded in a N-doped carbon nanotube hollow polyhedron (NCNHP) through a pyrolysis–oxidation–phosphidation strategy derived from core–shell ZIF-8@ZIF-67. Benefiting from the synergistic effects between highly active CoP NPs and NCNHP, the CoP/NCNHP hybrid exhibited outstanding bifunctional electrocatalytic performances. When the CoP/NCNHP was employed as both the anode and cathode for overall water splitting, a potential as low as 1.64 V was needed to achieve the current density of 10 mA·cm–2, and it still exhibited superior activity after continuously working for 36 h with nearly negligible decay in potential. Density functional theory calculations indicated that the electron transfer from NCNHP to CoP could increase the electronic states of the Co d-orbital a...

Core–Shell ZIF-8@ZIF-67-Derived CoP Nanoparticle-Embedded N-Doped Carbon Nanotube Hollow Polyhedron for Efficient Overall Water Splitting

Hydrogen has been hailed as a clean and sustainable alternative to finite fossil fuels in many energy systems. Water splitting is an important method for hydrogen production in high purity and large quantities. To accelerate the hydrogen evolution reaction (HER) rate, it is highly necessary to develop high efficiency catalysts and to select a proper electrolyte. Herein, the performances of non-noble metal-based carbon composites under various pH values (acid, alkaline and neutral media) for HER in terms of catalyst synthesis, structure and molecular design are systematically discussed. A detailed analysis of the structure-activity-pH correlations in the HER process gives an insight on the origin of the pH-dependence for HER, and provide guidance for future HER mechanism studies on non-noble metal-based carbon composites. Furthermore, this Review gives a fresh impetus to rational design of high-performance noble-metal-free composites catalysts and guide researchers to employ the established electrocatalysts in proper water electrolysis technologies.

Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications.

Electrodeposition of nickel–phosphorus nanoparticles film as a Janus electrocatalyst for electro-splitting of water

For the first time, self-supported FeP nanorod arrays were developed on a HCl-treated Ti foil (FeP NAs/Ti) via low-temperature phosphidation of α-FeO(OH)/Ti precursor and were further used as a novel hydrogen evolution cathode (HER), demonstrating exceptional catalytic activity in acidic media, superior to all reported non-Pt HER electrocatalysts, while offering an innovative method to synthesize metal phosphides with well-controlled nanostructure and morphology.

Controlled synthesis of FeP nanorod arrays as highly efficient hydrogen evolution cathode

For the first time we demonstrate the topotactic synthesis of a three-dimensional (3D) interconnected network of nanoporous CoP nanowires directly on a Ti substrate (np-CoP NWs/Ti) via low-temperature phosphidation of a Co2(OH)2(CO3)2/Ti precursor and its further use as a highly efficient hydrogen evolution cathode.

Shuang Gu

Papers

Electrodeposition of nickel–phosphorus nanoparticles film as a Janus electrocatalyst for electro-splitting of water

Controlled synthesis of FeP nanorod arrays as highly efficient hydrogen evolution cathode

Three-dimensional interconnected network of nanoporous CoP nanowires as an efficient hydrogen evolution cathode

Tungsten diphosphide nanorods as an efficient catalyst for electrochemical hydrogen evolution

Highly active and inexpensive iron phosphide nanorods electrocatalyst towards hydrogen evolution reaction