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

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.

Hydrogen (H2) is one of the most important clean and renewable energy sources for future energy sustainability. Nowadays, photocatalytic and electrocatalytic hydrogen evolution reactions (HERs) from water splitting are considered as two of the most efficient methods to convert sustainable energy to the clean energy carrier, H2. Catalysts based on transition metal dichalcogenides (TMDs) are recognized as greatly promising substitutes for noble-metal-based catalysts for HER. The photocatalytic and electrocatalytic activities of TMD nanosheets for the HER can be further improved after hybridization with many kinds of nanomaterials, such as metals, oxides, sulfides, and carbon materials, through different methods including the in situ reduction method, the hot-injection method, the heating-up method, the hydro(solvo)thermal method, chemical vapor deposition (CVD), and thermal annealing. Here, recent progress in photocatalytic and electrocatalytic HERs using 2D TMD-based composites as catalysts is discussed.

2D Transition‐Metal‐Dichalcogenide‐Nanosheet‐Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions

We study the synthesis and electrochemical and mechanical performance of layered free-standing papers composed of acid-exfoliated few-layer molybdenum disulfide (MoS2) and reduced graphene oxide (rGO) flakes for use as a self-standing flexible electrode in sodium-ion batteries. Synthesis was achieved through vacuum filtration of homogeneous dispersions consisting of varying weight percent of acid-treated MoS2 flakes in GO in DI water, followed by thermal reduction at elevated temperatures. The electrochemical performance of the crumpled composite paper (at 4 mg cm–2) was evaluated as counter electrode against pure Na foil in a half-cell configuration. The electrode showed good Na cycling ability with a stable charge capacity of approximately 230 mAh g–1 with respect to total weight of the electrode with Coulombic efficiency reaching approximately 99%. In addition, static uniaxial tensile tests performed on crumpled composite papers showed high average strain to failure reaching approximately 2%.

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MoS2/Graphene Composite Paper for Sodium-Ion Battery Electrodes

A highly active and stable electrocatalyst for hydrogen evolution is developed based on the in situ formation of MoS2 nanoparticles on mesoporous graphene foams (MoS2/MGF). Taking advantage of its high specific surface area and its interconnected conductive graphene skeleton, MGF provides a favorable microenvironment for the growth of highly dispersed MoS2 nanoparticles while allowing rapid charge transfer kinetics. The MoS2/MGF nanocomposites exhibit an excellent electrocatalytic activity for the hydrogen evolution reaction with a low overpotential and substantial apparent current densities. Such enhanced catalytic activity stems from the abundance of catalytic edge sites, the increase of electrochemically accessible surface area and the unique synergic effects between the MGF support and active catalyst. The electrode reactions are characterized by electrochemical impedance spectroscopy. A Tafel slope of ≈42 mV per decade is measured for a MoS2/MGF modified electrode, suggesting the Volmer-Heyrovsky mechanism of hydrogen evolution.

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Marcos A. L. Cordeiro

Papers

Graphene oxide as a highly selective substrate to synthesize a layered MoS2 hybrid electrocatalyst