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 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.

Liquid phase exfoliation has become an important method for the production of large quantities of two-dimensional (2D) nanosheets. This method is versatile, having been used to produce dozens of different 2D materials in a range of stabilizing liquids. The resultant liquid-suspended nanosheets have been characterized in great detail and have been processed into a number of structures for a wide range of applications. This has led to a growing number of researchers adopting this method. As a result, best practice in terms of experimental procedure has evolved rapidly over recent years. As experimental complexity has increased, it has become more and more difficult to discuss the rational behind a chosen experimental procedure in full detail using standard “Methods” sections due to the frequent use of procedures developed in related prior reports. This can make it difficult to reproduce complex procedures and acts as a barrier to new researchers entering the field. To address this shortcoming, here we descr...

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Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation

Applications of Phosphorene and Black Phosphorus in Energy Conversion and Storage Devices

This work describes silicon nanoparticle-based lithium-ion battery negative electrodes where multiple nonactive electrode additives (usually carbon black and an inert polymer binder) are replaced with a single conductive binder, in this case, the conducting polymer PEDOT:PSS. While enabling the production of well-mixed slurry-cast electrodes with high silicon content (up to 95 wt %), this combination eliminates the well-known occurrence of capacity losses due to physical separation of the silicon and traditional inorganic conductive additives during repeated lithiation/delithiation processes. Using an in situ secondary doping treatment of the PEDOT:PSS with small quantities of formic acid, electrodes containing 80 wt % SiNPs can be prepared with electrical conductivity as high as 4.2 S/cm. Even at the relatively high areal loading of 1 mg/cm2, this system demonstrated a first cycle lithiation capacity of 3685 mA·h/g (based on the SiNP mass) and a first cycle efficiency of ∼78%. After 100 repeated cycles a...

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A Commercial Conducting Polymer as Both Binder and Conductive Additive for Silicon Nanoparticle-Based Lithium-Ion Battery Negative Electrodes.

Here we demonstrate that the performance of catalytic electrodes, fabricated from liquid exfoliated MoS2 nanosheets, can be optimized by maximizing the electrode thickness coupled with the addition of carbon nanotubes. We find the current, and so the H2 generation rate, at a given potential to increase linearly with electrode thickness to up ∼5 μm after which saturation occurs. This linear increase is consistent with a simple model which allows a figure of merit to be extracted. The magnitude of this figure of merit implies that approximately two-thirds of the possible catalytically active edge sites in this MoS2 are inactive. We propose the saturation in current to be partly due to limitations associated with transporting charge through the resistive electrode to active sites. We resolve this by fabricating composite electrodes of MoS2 nanosheets mixed with carbon nanotubes. We find both the electrode conductivity and the catalytic current at a given potential to increase with nanotube content as describ...

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Thickness Dependence and Percolation Scaling of Hydrogen Production Rate in MoS2 Nanosheet and Nanosheet-Carbon Nanotube Composite Catalytic Electrodes

Eoghan O’Malley

Papers

Thickness Dependence and Percolation Scaling of Hydrogen Production Rate in MoS2 Nanosheet and Nanosheet-Carbon Nanotube Composite Catalytic Electrodes