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.

Strategies for developing transition metal phosphides as heterogeneous electrocatalysts for water splitting

Biomass-derived carbon materials (BCMs) are encountering the most flourishing moment because of their versatile properties and wide potential applications. Numerous BCMs, including 0D carbon spheres and dots, 1D carbon fibers and tubes, 2D carbon sheets, 3D carbon aerogel, and hierarchical carbon materials have been prepared. At the same time, their structure-property relationship and applications have been widely studied. This paper aims to present a review on the recent advances in the controllable preparation and potential applications of BCMs, providing a reference for future work. First, the chemical compositions of typical biomass and their thermal degradation mechanisms are presented. Then, the typical preparation methods of BCMs are summarized and the relevant structural management rules are discussed. Besides, the strategies for improving the structural diversity of BCMs are also presented and discussed. Furthermore, the applications of BCMs in energy, sensing, environment, and other areas are reviewed. Finally, the remaining challenges and opportunities in the field of BCMs are discussed.

Biomass-Derived Carbon Materials: Controllable Preparation and Versatile Applications.

Tubular-structured nanomaterials with tailorable crystal structures and shell architectures whose properties can be tuned without changing their chemical compositions are attractive in electrochemical energy conversion and storage fields. Herein, we report the fabrication of tubular-structured orthorhombic CoSe2 (o-CoSe2) and cubic CoSe2 (c-CoSe2) by calcining monoclinic Co3Se4 nanotubes (Co3Se4 NTs) prepared by a facile precursor transformation method. Benefiting from advantageous structural features, including functional shells and well-defined interior voids, the tubular-structured o-CoSe2 showed a high power conversion efficiency of 9.34% as a counter electrode catalyst for dye-sensitized solar cells (DSSCs), superior to that of a Pt counter electrode (8.15%), under AM 1.5 G irradiation. In addition, the o-CoSe2 nanotubes also demonstrated excellent electrocatalytic activity in terms of low onset overpotential (∼54 mV) and small Tafel slope (∼65.9 mV per decade) as a hydrogen evolution reaction (HER) catalyst in alkaline medium. Hence, this work provides a promising strategy to selectively design and synthesize highly active electrocatalysts for energy conversion.

Template synthesis of CoSe2/Co3Se4 nanotubes: tuning of their crystal structures for photovoltaics and hydrogen evolution in alkaline medium

Hierarchical porous carbon (HPC) materials contain organized pores having different scales of diameters. These materials exhibit surprisingly high performance in various applications due to the functional combination of hierarchical pores. This paper reviews the preparation of HPC from waste and biomass, and their potential applications. Biomass with naturally organized hierarchical structure, such as wood, grass and nut shell, have been widely used as raw materials, from which, hierarchical porosity can be formed through simple pyrolysis-activation. Influences of the types and dosages of activating agent, as well as the pyrolysis/activation conditions on the specific surface area, pore volume and hierarchical porous structure of the structured biomass-based HPC are discussed. For non-structured raw materials such as sucrose, pitch and plastics, novel technologies have been developed to prepare HPC; these include hard-/soft-template methods, hydrothermal carbonization, chemical vapor deposition, spray pyrolysis and autogenic pressure carbonization. The approaches to design or control the structures and properties of HPC made from non-structured materials are also reviewed. Moreover, advanced applications of HPC in energy storage, deionization, adsorption and catalysis are summarized.

Preparation and Application of Hierarchical Porous Carbon Materials from Waste and Biomass: A Review

The development of efficient and low-cost hydrogen evolution reaction (HER) catalysts is critical for storing energy in hydrogen via water splitting but still presents great challenges. Herein, we report synthesis of three-dimensional (3-D) hierarchical nanoporous carbon (HNC) supported transition metal phosphides (TMPs) for the first time by in situ growth of CoP nanoparticles (NPs) in CaCO3 NP-templated Cinnamomum platyphyllum leaf extract-derived carbon. They were subsequently employed as a HER catalyst, showing an onset potential of 7 mV and an overpotential of 95.8 mV to achieve 10 mA cm–2, a Tafel plot of 33 mV dec–1, and an exchange current density of 0.1182 mA cm–2, of which the onset overpotential and the Tafel plot are the lowest reported for non-noble-metal HER catalysts, and the overpotential to achieve 10 mA cm–2 and the exchange current density also compare favorably to most reported HER catalysts. In addition, this catalyst exhibits excellent durability with negligible loss in current densi...

CoP Nanoparticles in Situ Grown in Three-Dimensional Hierarchical Nanoporous Carbons as Superior Electrocatalysts for Hydrogen Evolution

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/celc.201600035

Biomass‐Derived Hierarchical Nanoporous Carbon with Rich Functional Groups for Direct‐Electron‐Transfer‐Based Glucose Sensing

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CoP Nanoparticles in Situ Grown in Three-Dimensional Hierarchical Nanoporous Carbons as Superior Electrocatalysts for Hydrogen Evolution

Biomass‐Derived Hierarchical Nanoporous Carbon with Rich Functional Groups for Direct‐Electron‐Transfer‐Based Glucose Sensing