Hydrogen Evolution Reaction Properties Research Articles

Activation of efficient hydrogen evolution on 1T-VS2 nanoribbons by low-cost transition metals: A first-principles study

Electrocatalytic water splitting is a very important energy conversion technology that utilizes renewable energy sources to produce hydrogen for sustainable energy development. In this work, the catalytic performance of 1T-VS2 (1T phase of vanadium disulfide) nanoribbons in the hydrogen evolution reaction (HER) was investigated based on first-principles calculations. It was found that 1T-VS2 nanoribbons have a Gibbs free energy (ΔGH*) of 0.05 eV, demonstrating its excellent HER performance. Moreover, some transition metal substitutions can further improve this performance (e.g. the ΔGH* of the Ti/Fe-1T-VS2 are as low as −0.02/0.04 eV). The mechanism of the performance enhancement is thoroughly investigated. The improved catalytic performance of HER is mainly promoted by hybridization between the V-d and TM-d-orbitals. The crystal orbital Hamiltonian population (COHP) and integral crystal orbital Hamiltonian habitation (ICOHP) calculations show that the HER properties are closely related to the filling of bonding and antibonding states. The differential charge density indicates that the adsorption of H results in an effective charge transfer at the interface and an increase in the conductivity, leading to an increase in the HER. The HER activity of the TM-1T-VS2 (TM stands for transition metal) nanoribbons is also related to the proximity of the adsorption site to the edge. Our work suggests that the TM-1T-VS2 nanoribbons are expected to be low cost and highly efficient catalysts.

Surface Termination (-O, -F or -OH) and Metal Doping on the HER Activity of Mo2CTx MXene.

Two-dimensional MXenes have recently garnered significant attention as electrocatalytic materials for hydrogen evolution reaction (HER). However, previous theoretical studies mainly focused on the effect of pure functional groups while neglecting hybrid functional groups that are commonly observed in experiments. Herein, we investigated the hybrid functionalized Mo2CTx MXene (T = -O, -F or -OH) to probe the HER properties. In binary O/F co-functionalization, the presence of F groups would attenuate the H adsorption and lead to the enhanced HER activity than the fully O-terminated Mo2CO2. However, the surface HER activity of ternary O/F/OH functionalized Mo2CTx is not satisfactory owing to the relatively weak H adsorption capacity. To further enhance the catalytic activity, modification was performed by introducing another metal element into its lattice structure. The doped metal (Fe, Co, Ni, Cu) exhibits reduced charge transfer to O compared to Mo atoms, leading to enhanced H adsorption and improved overall activity. The synergistic effect of hybrid functionalization and TM modification provides useful guidance for achieving feasible Mo2CTx candidates with high HER performance, which can be applied to the electrocatalytic applications of other MXenes.

Exploration of transition metal atom-doped NiSe2 electrocatalysts for efficient alkaline hydrogen precipitation using first principles screening

Transition metal (TM) doping exhibits great potential in designing high-performance two-dimensional (2D) NiSe2-based catalysts for electrocatalytic hydrogen evolution reaction (HER). 22 TM atom-doped 2D-NiSe2 catalysts are screened, and the effects of TM doping on the thermal stability and HER catalytic activity are investigated by first-principles calculations. Among them, Cu doped 2D-NiSe2 might exhibit remarkable HER properties with the water dissociation energy of 1.03 eV and H adsorption Gibbs free energy of −0.05 eV. Furthermore, we elucidate the reasons behind the different HER activities. These findings suggest new possibilities for the application of Cu doped 2D-NiSe2 for alkaline HER, offering new perspectives for future research.

Liquid metal-assisted solid-flame combustion synthesis of transition metal carbide nanocrystals for enhanced hydrogen evaluation reaction

Efficient hydrogen production relies on cost-effective and durable non-noble metal electrocatalysts for the hydrogen evolution reaction (HER). In this work, a liquid metal-assisted solid-flame combustion synthesis (SF-CS) method was used to create transition metal carbide TMC) nanocrystals with exposed facets. The TMCs include TiC, VC, NbC, TaC, Ta2C, WC, and Mo2C. In acidic solutions, the TMC nanocrystals show enhanced conductivity and superior HER performance, as evidenced by their lower Tafel slope, higher current density, and decreased overpotential. In particular, Mo2C nanocrystals exhibit an overpotential of 95 mV and a Tafel slope of 26 mV dec−1. These findings highlight a noteworthy improvement over previously reported nanostructures in recent years in terms of the HER properties of Mo2C with particular facets. This improvement is attributed to the unique surface characteristics, such as energy and active sites, which are impacted by various factors and require more investigation to meet the intended goals.

In Situ Probing the Structure Change and Interaction of Interfacial Water and Hydroxyl Intermediates on Ni(OH)2 Surface over Water Splitting.

There is growing acknowledgment that the properties of the electrochemical interfaces play an increasingly pivotal role in improving the performance of the hydrogen evolution reaction (HER). Here, we present, for the first time, direct dynamic spectral evidence illustrating the impact of the interaction between interfacial water molecules and adsorbed hydroxyl species (OHad) on the HER properties of Ni(OH)2 using Au/core-Ni(OH)2/shell nanoparticle-enhanced Raman spectroscopy. Notably, our findings highlight that the interaction between OHad and interfacial water molecules promotes the formation of weakly hydrogen-bonded water, fostering an environment conducive to improving the HER performance. Furthermore, the participation of OHad in the reaction is substantiated by the observed deprotonation step of Au@2 nm Ni(OH)2 during the HER process. This phenomenon is corroborated by the phase transition of Ni(OH)2 to NiO, as verified through Raman and X-ray photoelectron spectroscopy. The significant redshift in the OH-stretching frequency of water molecules during the phase transition confirms that surface OHad disrupts the hydrogen-bond network of interfacial water molecules. Through manipulation of the shell thickness of Au@Ni(OH)2, we additionally validate the interaction between OHad and interfacial water molecules. In summary, our insights emphasize the potential of electrochemical interfacial engineering as a potent approach to enhance electrocatalytic performance.

The Electrochemical Hydrogen Evolution Reaction Based on Helical Chain Stacked 2D Tellurium Nanoflakes

AbstractA crucial factor in advancing the broad utilization of electrocatalytic hydrogen evolution reaction (HER) is the development of efficient catalysts with sufficient active sites. Herein, a hydrothermal approach is utilized to fabricate helical chain stacked two‐dimensional (2D) tellurium (Te) nanoflakes, whose HER performance hasn't been systematically studied yet. It is found that Te nanoflakes transferred on carbon fiber paper (CFP) exhibit impressive HER properties and show a load dependence. The overpotential required for HER is significantly reduced to 279 mV under a load condition of 0.86 mg cm−2 at a current density of 10 mA cm−2. Density functional theory (DFT) calculations are further systematically carried out on Te catalytic sites along the helical chain at [0001] direction with a threefold screw symmetry. It is found that the Gibbs free energy of adsorbed hydrogen atom (ΔGH*) on Te sites is significantly lower than that of molybdenum disulfide (MoS2). Besides, the active sites based on surface atom density calculation reveal that Te provides more adsorption sites than layered MoS2. The decreased adsorption energy and efficient adsorption sites in Te may highlight the promising application of elemental crystal Te in electrocatalytic hydrogen production and pave the way for developing new types of electrocatalysts.

Enhancing electrocatalytic hydrogen evolution of MoS2 enabled by electrochemical cation implantation for simultaneous surface-defect and phase engineering

The increasing demand for energy-efficient and cost-effective water-splitting systems has prompted research on non-precious-metal-based electrocatalysts for the hydrogen evolution reaction (HER) over a wide pH range. Molybdenum sulfide (MoS2) has received considerable attention owing to its excellent HER activity in acidic media. However, its competitive HER properties must be improved to achieve better performance in alkaline or neutral environments. In this study, we introduced an electrochemical cation implantation (ECI) process as a versatile method to enhance the electrocatalytic properties of MoS2. By modifying the microstructure of MoS2, the ECI process induced vacancies in Mo and S, primarily in the basal planes and facilitated a gradual transition from the semiconducting (2H) to metallic (1T) phase. The optimized ECI-processed MoS2 catalysts exhibited improved HER activities and low overpotentials (η10, 144 mV) over the entire pH range compared with bare MoS2 catalysts, highlighting the potential application of the ECI process for enhanced electrocatalysts.

Synthesis of monolayer SiP via chemical vapor transport toward superior optoelectronic and catalytic performance

Single-layer SiP crystals with excellent photoelectric detection and hydrogen evolution reaction properties were synthesized by the one-step CVT method.

Manganese-cobalt hydroxide nanosheets anchored on a hollow sulfur-doped bimetallic MOF for high-performance supercapacitors and the hydrogen evolution reaction in alkaline media.

Nonmetallic doping and in situ growth techniques for designing electrode materials with excellent electrocatalytic activity are effective strategies to enhance the electrochemical performance. Bifunctional electrode materials for supercapacitors (SCs) and the hydrogen evolution reaction (HER) have attracted great interest due to their potential applications in green energy storage and conversion. Herein, the bimetallic MnCo LDH is anchored on a hollow sulfur (S)-doped MnCo-MOF-74 surface, forming a poplar flower-like 3D composite which is used for SCs and the HER in alkaline media. The fabricated S-MnCo-MOF-74@MnCo LDH/NF electrode exhibits a favorable specific capacitance of 1875.4 F g-1 at 1 A g-1 and steady long-term cycling performance. Moreover, the assembled HSC using S-MnCo-MOF-7@MnCo LDH/NF as the cathode material and active carbon (AC) as the anode material shows 546.4 F g-1 capacitance (1 A g-1) with a maximum energy density of 58 W h kg-1 at 14 000 W kg-1 power density. As an electrocatalyst, S-MnCo-MOF-7@MnCo LDH/NF exhibits excellent HER properties with a small Tafel slope of 128.9 mV dec-1 a low overpotential of 197 mV at 10 mA cm-2 and durable performance for 10 hours in alkaline media. The present work provides insights into understanding and designing active electrode materials for stable hydrogen evolution and high-performing supercapacitors in an alkaline environment.

On the origin of the improved hydrogen evolution reaction in Mn- and Co-doped MoS2.

In the field of hydrogen production, MoS2 demonstrates good catalytic properties for the hydrogen evolution reaction (HER) which improve when doped with metal cations. However, while the role of sulfur atoms as active sites in the HER is largely reported, the role of metal atoms (i.e. molybdenum or the dopant cations) has yet to be studied in depth. To understand the role of the metal dopant, we study MoS2 thin films doped with Co and Mn ions. We identify the contribution of the electronic bands of the Mn and Co dopants to the integral valence band of the material using in situ resonant photoemission measurements. We demonstrate that Mn and Co dopants act differently: Mn doping favors the shift of the S-Mo hybridized band towards the Fermi level, while in the case of Co doping it is the less hybridized Co band that shifts closer to the Fermi level. Doping with Mn increases the effectiveness of S as the active site, thus improving the HER, while doping with Co introduces the metallic site of Co as the active site, which is less effective in improving HER properties. We therefore clarify the role of the dopant cation in the electronic structure determining the active site for hydrogen adsorption/desorption. Our results pave the way for the design of efficient materials for hydrogen production via the doping route, which can be extended to different catalytic reactions in the field of energy applications.

Multinary intermetallic with enhanced catalytic activity and prolonged stability at high current density for electrochemical hydrogen production

Developing robust and efficient nonprecious metal-based electrocatalysts toward hydrogen evolution reaction (HER) is a big challenge for green and sustainable energy since insufficient catalytic activity and poor stability of current catalysts cannot meet the application requirements. This work reports a freestanding HER electrode FeNiCuAlMo prepared by arc-melting and chemical dealloying methods. The HER performance firstly improves and then declines with the increase of dealloying time. When the dealloying time is 3 h, the electrode shows optimal catalytic performance. The fabricated electrode is composed of AlMo3 and Al5CuMo2, where micro-sized AlMo3 particles are embedded in cellular dendritic Al5CuMo2. Impressively, it displays excellent HER performance, including a small overpotential of 173 mV at a current density of 500 mA/cm2 and outstanding long-term stability for 100 h of continuous hydrogen evolution at 1000 mA/cm2 in an alkaline electrolyte without obvious attenuation. The intrinsic activity of the electrodes combined intermetallic compounds with hierarchical porous structure provides several effects, including enhanced massive active sites, electrolyte access, electron transport, and fast gas release that contribute jointly to enhancing HER activities. The micro-sized AlMo3 particles provide robust framework for the dendritic Al5CuMo2 active sites center, allowing the exposure of enough active sites and simultaneously maintaining good stability. The highly stable and active electrocatalytic HER property makes it as a promising candidate for practical hydrogen production.

Enhanced HER Efficiency of Monolayer MoS2 via S Vacancies and Nano-Cones Array Induced Strain Engineering.

Molybdenum disulfide (MoS2) has gained significant attention as a promising catalyst for hydrogen evolution reaction (HER). The catalytic performance of MoS2 can be enhanced by either altering its structure or regulating external conditions. In this study, a novel approach combining the introduction of sulfur vacancy (VS) and biaxial tensile strain to create more active sites and modulate the band structure of monolayer MoS2 is proposed. To achieve the desired strain level, nano-cones (NCs) array substrates facilely fabricated by dip-pen nanolithography (DPN) are employed. The magnitude of the applied tensile strain can be finely tuned via adjusting the height of the NCs. Furthermore, on-chip electrochemical devices are constructed based on artificial structures, enabling precise optimization of HER performance of MoS2 through the synergistic effect of VS and strain. Combined with the d-band theory, it reveals that the HER properties of VS-MoS2 are highly dependent on the degree of tensile strain. This study presents a promising avenue for the design and preparation of high-performance 2D catalysts for energy conversion and storage applications.

Electrochemical activation of CoMo LDH nanosheets driving surface reconstruction for enhanced hydrogen evolution

Surface reconstruction emerging in the electrochemical oxygen evolution process is regarded to be significantly important for the activated catalysis efficiency, however, which is rarely recognized for hydrogen evolution reaction (HER). Here, the electrochemical activation of CoMo layered double hydroxide (CoMo-LDH) nanosheet arrays is demonstrated to significantly activate the electrochemical HER property. The catalysis performance improvement originates from the surface transformation of CoMo-LDH to Co(OH)2/CoOOH, as well as the dissolution of Mo and its adsorption on the catalyst surface in K2Mo3O10 phase. Based on the combined benefits of optimized electronic structure, increased catalysis sites, and promoted charge transfer, the overpotentials at catalysis current densities of 10 and 100 mA cm−2 are as low as 113 and 202 mV. This study demonstrates the electrochemical activation strategy to drive the surface reconstruction of bimetal hydroxides for enhanced HER performance, inspiring the research interests on the reconstruction and activation enhancement behaviors of HER electrocatalysts.

Effect of electron transfer of 2D Ti3C2Tx@MOF heterostructure on hydrogen evolution reaction activity

Metal-organic framework (MOF) layers were grown in situ from 2D transition metal carbides (MXenes, Ti3C2Tx) at room temperature to obtain the two-dimensional (2D) Ti3C2Tx@MOF heterostructures with a tightly connected interface. This interface provided more titanium atoms in the low-valence state in comparison to the original Ti3C2Tx, thus facilitating more electron transfer from Ti3C2Tx to MOF-(Fe/Co) nanosheets. The charge density difference and density functional theory results disclosed that Ti3C2Tx could modulate the electronic density around the active sites and lower ΔGH* energy barrier of 2D MOF-(Fe/Co) nanosheets towards the improved hydrogen evolution reaction (HER) activity. The obtained 2D Ti3C2Tx@MOF heterostructures exhibited a much higher HER activity in 1 M KOH electrolyte (with the overpotential of 104 mV at 10 mA/cm2 and Tafel slope of 79 mV/dec) than those of 2D Ti3C2Tx@MOF-TH, 2D MOF nanosheets, and Ti3C2Tx nanosheets. This research provides a basis for developing superior 2D MOFs, which can enhance HER properties through efficient electronic transport at the heterojunction interface.

Heterogeneous Cu incorporated into Ni6Fe2-LDH/rGO induces spin exchange interaction to enhance alkaline hydrogen evolution

The efficiency of hydrogen evolution reaction (HER) takes an important influence on electrochemical water electrolysis, yet it still delivers sluggish kinetics mainly due to the high kinetic energy barriers. Herein, Cu1Ni5Fe2-Layered double hydroxides/reduced graphene oxide (denoted as Cu1Ni5Fe2-LDHs/rGO) with heterogeneous Cu atoms incorporated into Ni6Fe2-LDHs/rGO is constructed through a hydrothermal method and doping strategy in this works, wherein the subtle lattice distortion is availably regulated and optimized by Cu2+ Jahn-Teller effect, offering more active sites for HER. As benefits of the subtle lattice distortion and the spin exchange interaction, Cu1Ni5Fe2-LDHs/rGO displays ferromagnetism at room temperature and shows superior alkaline HER properties with a relatively low overpotentials of 50 mV at 10 mA cm−2 in 1.0 M KOH. The low Tafel slope of 38 mV dec−1 implies Cu1Ni5Fe2-LDHs/rGO owns an ultra-fast HER kinetic. This study can offer a new strategy to construct high efficient HER catalysts based on transition metal NiFe-LDHs.

Ultrathin and porous CoP nanosheets as an efficient electrocatalyst for boosting hydrogen evolution behavior at a broad range of pH

Designing highly-efficient, stable and low-cost catalysts for electrocatalytic hydrogen evolution reaction (HER) plays an important role in renewable energy conversion technology. The particularly ultrathin and porous 2D architecture can provide plentiful activation sites, short delivery channels to improve reaction kinetic and promote HER procedure. High-performance transition metal phosphide (CoP) combined with unique and holey 2D ultrathin nanosheet structure is prepared by successively hydrothermal reaction, oxidation and phosphorization techniques, which presents remarkable stability and electrocatalytic HER properties in a wide pH range. The thickness and pore dimension of ultrathin and porous CoP nanosheets are ∼15 and 3–17 nm. The optimized CoP nanosheets only require 60, 128, 90 mV overpotentials to drive the current density of 10 mA cm−2 in acidic, neutral and alkaline environment, respectively, much better than those of oxide counterpart and the previously reported transition metal-based electrocatalysts. Moreover, the small Tafel slopes of porous CoP nanosheets are 54, 69.9 and 62.9 mV dec−1 in acidic, neutral and alkaline media. CoP nanosheets also exhibit high conductivity, large Cdl, and long-term stability for 20 h in pH-universal electrolyte.

Designed bifunctional flower-like structural molybdenum disulfide doped with Ag atoms for clean energy and contaminant detection

An efficient bifunctional material still remains a stupendous challenge for the use of Surface-enhanced Raman scattering (SERS) substrate and hydrogen evolution reaction (HER) electrocatalysts and suffer from cost issues. In this study, heteroatom Ag doping instead of Ag compound MoS2 has been used to activate the inert plane of MoS2 and improve charge transfer, modulating the SERS and HER properties of MoS2. As SERS substrate, Ag doped MoS2 can be widely used for the rapid detection of organic dyes (MG, CV, R6G), pesticides (endosulfan and dipterex), and endocrine disrupter Bisphenol A and biological macromolecules bilirubin. Meanwhile, the HER activity of the MoS2 is remarkably boosted by introducing Ag atoms. The low overpotentials of pure MoS2 is 524 mV, while the low overpotentials of the Ag doped MoS2 can be reach 54 mV in alkaline electrolytes. Tafel slope, electrochemically active surface area (ECSA), Turnover frequency (TOF) and the normalized ECSA were analyzed to reveal the real reason for the increasing in electrocatalytic activity. As-synthesized Ag doped MoS2 shows highly efficient hydrogen evolution. This work synthesized low-cost bifunctional materials Ag doped MoS2 not only provides a guidance for MoS2-base SERS substrate design but also facilitates cope with the growing demand for clean energy.

Discrepancy of alkaline/neutral hydrogen evolution activity from NiCoSe2/NC and Co–NiSe/NC derived from in-situ thermal and solution processing selenizations of ZIF-67

Constructing cobalt-based selenide catalyst with accessible active site and superior charge transfer capability by simultaneous tailoring chemical component and structure through the feasible strategy is the key to display improved hydrogen evolution reaction (HER) activity. Herein, the bimetal NiCoSe2/nitrogen-doped carbon (NC) with novel flake structure (NiCoSe2/NC/NF) and particle-like cobalt-doped NiSe/NC (Co–NiSe/NC/NF) were synthesized by the in-situ thermal and solution processing selenizations of ZIF-67/NF, respectively. The intrinsic catalytic activity of NiCoSe2, the further accelerated charge-transfer capability originated from the fresh NC and two-dimensional layer structure, and mutually reinforcing kinetics from the closely integrated NiCoSe2 nanoparticles and NC plate endow NiCoSe2/NC/NF with 141 and 284 mV to reach 10 mA cm−2 under alkaline and neutral electrolytes, respectively, accompanying with Tafel slope of 109 and 206 mV dec−1, which were obviously higher than that of the HER properties of Co–NiSe/NC/NF (η10 = 179 mV and Tafel slope of 127 mV dec−1 at alkaline condition, η10 = 301 mV and Tafel slope of 235 mV dec−1 at neutral condition). Meanwhile, the NiCoSe2/NC/NF and Co–NiSe/NC/NF were exhibited well electrochemical stability under alkaline/neutral conditions. This study offers practicable strategy for intuitive comparing the influence of selenization procedures on the whole alkaline/neutral HER activity of cobalt-based catalysts.

The Marriage of Hydrazone‐Linked Covalent Organic Frameworks and MXene Enables Efficient Electrocatalytic Hydrogen Evolution

Electrochemical water splitting is long regarded as a green and feasible pathway to realize the scalable hydrogen production, while the overall hydrogen evolution reaction (HER) efficiency is largely dependent on the electrocatalytic ability of the cathode catalysts. Herein, the in situ growth of hydrazone‐linked covalent organic framework (COF‐42) nanocrystals with a unique nanoflower‐shaped morphology on 2D ultrathin Ti3C2Tx MXene nanosheets (COF/Ti3C2Tx) is achieved through a convenient and robust stereoassembly strategy. Strikingly, the marriage of COF‐42 and Ti3C2Tx nanosheets not only offers multiscale porous channels for the fast transportation of electrolyte and electrons, but also enables the full exposure and activation of numerous catalytically active centers. As a consequence, the optimized COF/Ti3C2Tx nanoarchitecture displays exceptional HER properties in terms of a very low onset potential of 19 mV, a small Tafel slope of 50 mV dec−1 as well as reliable long‐term durability, which are comparable to those of commercial Pt/C catalyst. Density functional theory calculations further disclose that the rational combination of COF‐42 with Ti3C2Tx provides more diversified active positions with appropriate ΔGH values, thus leading to a boosted hydrogen generation rate.

Cobalt-doped WSe2@conducting polymer nanostructures as bifunctional electrocatalysts for overall water splitting

Designing of high-performance, low-cost, and nonprecious metal-based bifunctional electrocatalysts is highly significant for the development of water splitting process and expanding the practical application of green hydrogen production. Transition metal dichalcogenides (TMDs) with intrinsic physical and chemical properties have been considered potential catalytic materials for electrode fabrication. However, it has remained challenging to develop TMD catalysts that have bifunctional properties for overall water splitting. Herein, WSe2, as a typical representative of TMDs, was utilized to design electrocatalysts using polypyrrole (PPy) or polyaniline (PANI) as a conducting polymer (CP) and cobalt doping. A facile hydrothermal preparation of WSe2 in the presence of CP enabled the construction of cobalt-doped WSe2@CP electrocatalysts. Morphological analysis indicated that the CP played an important role as a conductive template to enhance the distribution of WSe2 nanosheets, leading to higher surface area. In addition, cobalt doping led to the formation of defect structures and boosted the electrocatalytic activities of the catalysts for oxygen evolution reaction (OER). Owing to the increased electrochemical surface area and defect structures, the cobalt-doped WSe2@CP nanostructures exhibited enhanced electrochemical properties for hydrogen evolution reaction (HER) and OER in an alkaline medium. The cobalt-doped WSe2@PANI modified glassy carbon electrode (GCE) exhibited overpotentials down to 308 and 360 mV at a current density of 10 mA cm−2 for the HER and OER, respectively. Furthermore, the cobalt-doped WSe2@CP electrocatalysts demonstrated long-term stability and continuous cycling. More importantly, the Co–WSe2@PANI electrolyzer required cell voltage of 1.87 V at a current density of 10 mA cm−2 for overall water splitting process. This work provides new findings for designing efficient bifunctional electrocatalysts utilizing TMD materials and conducting polymers.