Two-dimensional B7P2: Dual-purpose functional material for hydrogen evolution reaction/hydrogen storage

It is well known that the development of dual-purpose materials is more significant and valuable than single-use materials due to the diversity of their use purposes. Based on density functional theory (DFT), the hydrogen evolution/hydrogen storage characteristics of two-dimensional (2D) B₇P₂ monolayer are systematically studied in this paper, focusing on the key word of clean energy-“hydrogen”. The results show that the B₇P₂ monolayer can be used as a stable metal-free decorated catalyst for hydrogen evolution reaction (HER), which is renewable and environmentally friendly. The calculated Gibbs free energy (ΔG_H1) is 0.06 eV, which is comparable or even better than that of Pt catalyst (ΔG_H1 = ?0.09 eV). In addition, we also found that the increase of hydrogen coverage and strain driving (?2%–2%) did not further enhance the HER activity of B₇P₂ monolayer, showing a poor ΔG_H1. In the aspect of hydrogen storage, we have investigated the hydrogen storage performances of alkali-metal (Li, Na and K) doped B₇P₂. It is found that in the fully loaded case, B₇P₂Li₆ is a promising hydrogen storage material with a 7.5 wt% H₂ content and 0.15 eV/H₂ average hydrogen adsorption energy (E_ave). Moreover, ab initio molecular dynamics (AIMD) calculations show that there is no dynamic barrier for H₂ desorption of Li-decorated B₇P₂ monolayer. In conclusion, our results indicate that the B₇P₂ monolayer is not only an excellent catalyst for HER, but also a promising hydrogen storage medium.     

Edge terminated and interlayer expanded pristine MoS2 nanostructures with 1T on 2H phase,for enhanced hydrogen evolution reaction

Pristine molybdenum disulfide (MoS₂) nanostructures with 1T on 2H phase have been prepared by tuning the growth time in hydrothermal synthesis. The optimized sample has an expanded interlayer and it exhibits striking kinetic metrics with an onset potential of - 0.13 V, Tafel slope of 49 mV/decade, and an exchange current density of 3.98 × 10^?3 mA, performing best among the pristine MoS₂ based hydrogen evolution reaction (HER) catalysts reported so far. The edge terminated structure, together with the expanded interlayer, is believed to modify the electronic structure to enhance the conductivity of the compound. The Mott-Schottky analysis of the optimized sample indicated a decrease in band bending and an enhancement in the charge transfer. The promising HER response obtained with sufficiently low growth time and growth temperature for the pristine MoS₂ nanostructures suggests a potential way to design high-performance HER catalysts based on the compound.     

Encapsulation of Pt nanocatalyst with N-containing carbon layer for improving catalytic activity and stability in the hydrogen evolution reaction

As hydrogen emerges as a next-generation clean energy source, the production of hydrogen is generating much research interest. Water electrolysis, one of the promising methods of hydrogen production, has the advantage of no resource depletion or carbon dioxide emissions. In this study, a Pt@C core–shell catalyst in which an N-containing carbon layer covers individual Pt nanoparticles was applied to the hydrogen evolution reaction (the cathodic reaction of water electrolysis), and the effect of the carbon shell on the activity and stability of the catalyst was investigated. The catalyst was synthesized by simple annealing of Pt-aniline complexes at 600 °C in a N₂ atmosphere. The thermal decomposition of aniline during annealing resulted in N-containing carbon shells. The carbon shell had a positive effect on both the activity and stability of the catalyst in the hydrogen evolution reaction. Graphitic N and pyridinic N on the carbon shell, along with Pt, served as active sites for the hydrogen evolution reaction, increasing the catalytic activity. The carbon shell also effectively protected the Pt core from dissolution and agglomeration while allowing the transport of the reactant protons through the shell, improving stability with minimal loss of catalytic activity.     

Flower-like CoS2/MoS2 nanocomposite with enhanced electrocatalytic activity for hydrogen evolution reaction

Molybdenum sulfide (MoS₂) has received tremendous attracts for its promising performance in the aspects of hydrogen evolution reaction (HER). To improve the HER activity of MoS₂, we designed a flower-shaped CoS₂/MoS₂ nanocomposite with enhanced HER electroactivity compared with MoS₂ nanosheets by a simple one-step hydrothermal method. The facile approach brings about distinct transformation of the morphology from nanosheets to nanoflower structures. The introduction of Co element into MoS₂ results in the larger active surface area, more edge-terminated structures, and higher conductivity of the CoS₂/MoS₂ nanocomposite, which are good for improving the HER electroactivity. In brief, the optimized catalyst exhibits the low overpotential of 154 mV at 10 mA cm^?2, small Tafel slope of 61 mV dec^?1, and excellent stability in acidic solution.     

Investigating hydrogen evolution reaction properties of a new honeycomb 2D AlC

The hydrogen due to its high mass energy density is a new renewable, economically viable and clean resource. The most eco-friendly and economical approaches for the generation of hydrogen through hydrogen evolution is electrochemical water splitting. The two-dimensional (2D) nanomaterials have been recently found as potential candidates as non-noble metal catalyst for hydrogen evolution. In this work, we have systematically studied the structural and electronic properties of the newly predicted hexagonal-aluminium carbide monolayer (h-AlC ML) under the framework of dispersion-corrected density functional theory (DFT) calculations. The calculated electronic total density of states (TDOS) of h-AlC ML predict its metallic nature in contrast to other polar honeycomb 2D materials which are either semiconducting or semimetallic. The metallic behavior of h-AlC monolayer which motivates us to investigate its HER activity results due to the presence of delocalized charge density near Fermi level. Thus, we have investigated the HER activity of h-AlC ML by calculating hydrogen (H) adsorption energy (ΔE_H) and Gibbs free energy (ΔG_H) at three different sites of the 3 × 3 and 4 × 4 supercells of h-AlC ML; top of carbon atom (E_H-C), top of aluminium atom (E_H-Al) and hollow site (E_H-Hollow). Our results show that the hollow site is most catalytically active site in both supercells of h-AlC ML. We believe that our results will inspire experimentalists to fabricate this new 2D material for achieving the desired range of HER activity.     

Self-standing,hybrid three-dimensional-porous MoS2/Ni3S2 foam electrocatalyst for hydrogen evolution reaction in alkaline medium

Self-standing and hybrid MoS₂/Ni₃S₂ foam is fabricated as electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium. The Ni₃S₂ foam with a unique surface morphology results from the sulfurization of Ni foam showing a truncated-hexagonal stacked sheets morphology. A simple dip coating of MoS₂ on the sulfurized Ni foam results in the formation of self-standing and hybrid electrocatalyst. The electrocatalytic HER performance was evaluated using the standard three-electrode setup in the de-aerated 1 M KOH solution. The electrocatalyst shows an overpotential of 190 mV at ?10 mA/cm² with a Tafel slope of 65.6 mV/dec. An increased surface roughness originated from the unique morphology enhances the HER performance of the electrocatalyst. A density functional approach shows that, the hybrid MoS₂/Ni₃S₂ heterostructure synergistically favors the hydrogen adsorption-desorption steps. The hybrid electrocatalyst shows an excellent stability under the HER condition for 12 h without any performance degradation.     

Ultrathin-layered MoS2 hollow nanospheres decorating Ni3S2 nanowires as high effective self-supporting electrode for hydrogen evolution reaction

High-activity and cost-effective transition metal sulfides (TMSs) have attracted tremendous attention as promising catalysts for hydrogen evolution reaction (HER). However, a significant challenge is the simultaneous construction of abundant electrochemical active sites and the fast electronic transmission path to boost a high-efficient HER. Herein, we demonstrate a facile one-step hydrothermal preparation of MoS₂ hollow nanospheres decorating Ni₃S₂ nanowires supported on Ni foam (NF), without any other additional template, surfactant or annealing. In this three-dimensional (3D) heterostructure, the ultrathin-layered MoS₂ hollow nanospheres contribute to the promotion of the total surface area and the electrochemical active sites. Meanwhile, the Ni₃S₂ nanowires are beneficial to the high electrical conductivity. Consequently, the optimized MoS₂/Ni₃S₂/NF-200-24 electrocatalyst presents an extremely superior HER activity to that of individual MoS₂/NF and Ni₃S₂/NF. The HER overpotentials are 85 mV at 10 mA cm⁻² and 189 mV at 100 mA cm⁻², which are also comparable with the state-of-the-art 20% Pt/C/NF electrode at both low and high current.     

Improving the catalytic activity of two-dimensional Mo2C for hydrogen evolution reaction by doping and vacancy defects

Molybdenum carbide (Mo₂C) has high catalytic activities toward electrocatalytic hydrogen evolution reaction (HER) owing to its high surface activity and electrochemical properties. However, the defects modification of Mo₂C, which plays an important role in the HER activity, is relatively scarce in the theoretical research. Herein, in this work, based on first-principles calculations, we screen the influences of vacancies, nonmetal doping (X_C/T, X = N, O, F, P and S) and metal substitutional doping (Y_Mo, Y = Re and W) on HER of two-dimensional Mo₂C. The results reveal that vacancies of Mo₆C (0.02 eV) and Mo₃C (0.22 eV), substitutional dopants of O_C, S_C, Re_Mo (?0.33～0.08 eV) and adsorptive dopants of N_T, F_T, P_T, S_T (?0.26～0.14 eV) show enhanced catalytic activity with the absolute value of hydrogen adsorption free energy $(\Delta GH1)$ smaller than 0.33 eV. A negative linear relationship is observed between $\Delta GH1$ and d band center of transition metals in vacancies and metal dopants, but not in the configurations with nonmetal doping. The results provide more insight and guidance for the design of Mo₂C electrocatalyst.     

Synergy between in-situ immobilized MoS2 nanosheets and TiO2 nanotubes for efficient electrocatalytic hydrogen evolution

MoS₂ electrocatalyst exhibits a significant potential to substitute platinum in hydrogen evolution reaction (HER), but its immobilization on practical supports is still challenging. Herein, a facile hydrothermal method is developed for in-situ immobilizing MoS₂ nanosheets on titanium nanotubes (TNTs) support. Easy to mount electrodes with a uniform and dense layer of MoS₂ on TNTs are achieved. An overpotential of ?200 mV_RHE is ample to deliver ?10 mA/cm² from an acidic medium. This overpotential is much lower than those of the electrodes developed by drop-casting MoS₂ on TNTs, glassy carbon (274 mV), and in-situ immobilized on Ti foil (264 mV). The results revealed that the synergy between the in-situ immobilized MoS₂ and TNTs enhances the electrochemical surface area and the adsorption capacity of hydronium ions. The electronic interaction between MoS₂ and TNTs facilitates the mobility of electrons and reduces the charge transfer resistance at the electrode/electrolyte interface.     

Recent advances in CoSe2 electrocatalysts for hydrogen evolution reaction

Hydrogen as a sustainable alternative fuel is recognized as a primary choice for future energy supply due to its high gravimetric energy density and zero carbon emission upon combustion. Electrochemical water splitting is a promising strategy for effective and sustainable hydrogen production. Nowadays, research is focused on developing non-precious, stable, and highly efficient electrocatalysts for hydrogen evolution reaction (HER). Among them, CoSe₂ has attracted tremendous attention as HER electrocatalyst due to its unique electronic configuration that ensures fast charge transport, excellent catalytic activity, and good chemical stability. So far, a lot of reviews on electrocatalytic water splitting based on transition metal dichalcogenides and cobalt-based materials are reported. However, the review on CoSe₂ electrocatalyst for hydrogen evolution reaction is limited up-to-date. Hence in the present review, a comprehensive literature survey on CoSe₂ electrocatalyst for hydrogen evolution reaction is done and reported. In this review, the crystal structures of CoSe₂, their phase transformation strategy, their hydrogen evolution reaction mechanism in acidic and alkaline electrolytes are highlighted. The various synthesis procedures adopted to produce CoSe₂ based materials, the relation between its structure and composition with their electrocatalytic activities are discussed. Moreover, the effective ways to enhance the electrocatalytic performance of CoSe₂ based materials such as its morphological modification, constructing heterostructures, and heteroatom doping are reviewed.     

Boosting electrochemical hydrogen evolution activity of MoS2 nanosheets via facile decoration of Au overlayer

--Owing to its unique physicochemical properties, two-dimensional (2D) layered MoS₂ has been proposed as a potential catalyst for efficient hydrogen evolution reaction (HER). However, their large-scale application is still hindered due to limited active sites, poor conductivity, and restacking during synthesis. Herein, we report a one-step hydrothermal route to grow MoS₂ nanosheets on molybdenum (Mo) foil substrate followed by Au decoration as an active cocatalyst to enhance the HER performance of MoS₂ nanosheets. A facile, quick, and controlled decoration of stable Au overlayer with different mass loadings was performed using a sputtering Au coating unit for different deposition times (10s, 30s, and 50s), thus paving the way for producing efficient and inexpensive HER electrocatalysts. Electrochemical studies of different Au–MoS₂/Mo hybrids demonstrate that the optimized Au–MoS₂/Mo-30s sample exhibits ultralow onset potential (52 ± 2 mV vs. RHE), small overpotentials of 136 ± 6 and 318 ± 3 mV (vs. RHE) at current densities of 10 and 100 mA cm^?2, a small Tafel slope (46.23 ± 6 mV/dec), along with an outstanding electrochemical stability over a couple of days. Presence of metallic 1T-phase of MoS₂, as well as the synergistic effect between MoS₂ and Au, result in enhanced electrical conductivity, high density of active sites, large electrochemically accessible surface area, and fast charge transfer at the catalyst-electrolyte interface for boosting HER activity of the hybrid catalyst.     

High-throughput screening of transition metal single-atom catalyst anchored on Janus MoSSe basal plane for hydrogen evolution reaction

Considerable efforts have been made to enhance the hydrogen evolution reaction (HER) catalytic performance of Janus MoSSe monolayer, which have been considered to be a promising candidate due to the unique asymmetry structure. However, the activation effect remains non-optimal for the inert Janus MoSSe basal plane at present. Herein, a train of transition metal (TM) atoms were anchored on the S-/Se-/Mo-defective MoSSe basal plane to screen effective TM single-atom catalysts for HER through density functional theory (DFT) computations. Interestingly, the single Co atom anchored on Mo-defective MoSSe and the single Zn or Cd atom anchored on S-defective MoSSe were judged to possess excellent HER performance yielding a near-zero ΔG_H (ΔG_H = ?0.050, ?0.095, ?0.098 eV, respectively), which is comparable to the optimized Pt-SACs. The enhanced HER activity is attributed to the doping of TM atoms (Co, Zn and Cd) which improves the conductivity of the original MoSSe and offers unoccupied states near the Fermi level decreasing the energy barrier of electrons transfer between H and TMs@MoSSe surface. In addition, the change of unoccupied antibonding states of active atoms leads to appropriate interaction between the active sites and H. The hybridization between H-s orbital and the TMs@MoSSe systems around the Fermi level also suggests the formation of stable bonding-antibonding hydrogen adsorption states. This work reveals an effective way of activating MoSSe basal plane for HER.     

Activating basal plane of Janus VSSe for efficient hydrogen evolution reaction by non-noble metal element doping: A first-principal study

Searching electrocatalysts with excellent hydrogen evolution reaction (HER) performance is very important for developing clean hydrogen energy. Two-dimensional (2D) materials have been widely studied as HER electrocatalysts, however, the basal planes of 2D materials, which dominate the surface area, are usually with poor activity. In this work, we theoretically studied the HER activity of Janus 2H–VSSe with or without non-noble metal element doping. Density functional theory (DFT) calculations suggest that doping As and Si atoms in the S or Se sites of VSSe and the C and Ge atoms in the Se site of VSSe greatly promote the HER performance of the basal plane of VSSe, resulting in hydrogen adsorption free energy close to zero (i.e. ?0.022, ?0.040, 0.066, 0.065, ?0.030, 0.058 eV, respectively), which are better than the Pt catalyst (?0.09 eV). The doped atoms strengthen the interaction between their pz-orbital and the hydrogen s-orbital, resulting in a lower bonding state in energy and higher bind strength for the hydrogen atom. This work opens up a new way to design highly efficient and low-cost catalysts for HER.     

Synthesis and electrocatalytic activity of Ni0.85Se/MoS2 for hydrogen evolution reaction

Recently, the replacement of expensive platinum-based catalytic materials with non-precious metal materials to electrolyze water for hydrogen separation has attracted much attention. In this work, Ni_0.85Se, MoS₂ and their composite Ni_0.85Se/MoS₂ with different mole ratios are prepared successfully, as electrocatalysts to catalyze the hydrogen evolution reaction (HER) in water splitting. The result shows that MoS₂/Ni_0.85Se with a molar ratio of Mo/Ni = 30 (denoted as M30) has the best catalytic performance towards HER, with the lowest overpotential of 118 mV at 10 mA cm⁻², smallest Tafel slope of 49 mV·dec⁻¹ among all the synthesized materials. Long-term electrochemical testing shows that M30 has good stability for HER over at least 30 h. These results maybe due to the large electrochemical active surface area and high conductivity. This work shows that transition metal selenides and sulfides can form effective electrocatalyst for HER.     

Facile preparing composite of CoSe2 wrapping N-doped mesoporous carbon with highly electrocatalytic activity for hydrogen evolution reaction

The composites of cobalt selenide (CoSe₂) wrapping nitrogen self-doped mesoporous graphitic carbon were facilely prepared by hydrothermally wrapping CoSe₂ on the carbon material derived from pyrolysis of N-containing zeolitic imidazolate framework. The composites exhibit excellent catalytic activities and durability for electrochemical hydrogen evolution reaction (HER) in 0.5 M H₂SO₄. The optimum composite catalyst needs only low overpotential of 159 mV to approach 10 mA/cm² and as low as 83 mV/dec of Tafel slope can be obtained. The results are among the most active for HER based on non-noble materials in acidic solution.     

Potential and support-dependent hydrogen evolution reaction activation energies on sulfur vacancies of MoS2 from GC-DFT

We present a detailed mechanistic study of HER at the sulfur vacancy V_S of 2H–MoS₂. We evaluate the Volmer, Tafel, and Heyrovsky transition states for the different possible reaction steps, determining the activation energy as a function of the electrochemical potential via grand-canonical density functional theory. The results show that the Volmer and Heyrovsky steps depend on the electrochemical potential and the activation energies decrease for more negative potentials, while this is not the case for the Tafel step, for which the activation energy is constant. From the activation energies at ?0.2 V vs SHE, it can be concluded that during HER on V_S a first hydrogen atom is adsorbed as a spectator via a Volmer step. Then, the catalytic cycle consists of a Volmer and a Heyrovsky step, with the latter being rate determining. In addition, we investigate for the first time the effect of a conductive support on the HER activity of these sulfur vacancies. Our results show that copper, gold and graphite supports have little effects on the activation energies of all steps. Hence, we conclude that cheap, acid-stable, high-surface area carbon supports are well suited for MoS₂-based HER catalysts.     

A new hyperbranched water-splitting technique based on Co3O4/MoS2 nano composite catalyst for High-Performance of hydrogen evolution reaction

Due to the extensive use of fossil fuels & their direct influence on the environment, new ways of producing energy sources are highly needed. Hydrogen is the perfect candidate for renewable energy; however, H₂ gas production is associated with disadvantages due to a lack of efficient and active catalysts that could be cost-effective and comparable to platinum performance. Active hydrogen evolution reaction catalysts are needed to advance the development of a cheaper generation of solar fuels. Thus, outperformance, and stable earth abundant. And inexpensive catalysts are highly demanded. That is H₂ gas production from the electrolysis of water through HER. In this work, we present different analytical techniques that characterize an efficient and highly stable catalyst based on transition metal oxide Co₃O₄/MoS₂ nanostructures. And their composites for water splitting in harsh acidic conditions time and material chemical composition as like SEM, EDS, XRD, HRTEM & XPS. The composite material is highly best to produce HER at 10 mA cm^?2 and obtained 268 mV overpotential of nano Co₃O₄/MoS₂ (S3) and Tafel slope of 56 mv/dec. Faraday efficiencies of the hydrogen gas production measured for the 60 min and catalyst is highly durable for the 20 h. The presented catalysts are up to the mark of platinum metal performance and superior to several transition metal oxides. This fabrication technology is a new roadmap for developing active and scalable hydrogen-evolving catalysts by overcoming the issues of fewer catalytic edges, low density, and poor conductivity.