Catalytic Performance For Hydrogen Evolution Reaction Research Articles

Effects of strain, pH and oxygen-deficient on catalytic performance of Ruddlesden-Popper oxide Srn+1RunO3n+1 (n=1, 2) for hydrogen evolution reaction

Due to low content of precious metals and good stability, Ruddlesden-Popper (R–P) structure oxides are considered as promising hydrogen evolution reaction (HER) catalysts. However, related research is scarce, hindering its further improvement. In this paper, effects of strain, pH, oxygen-deficient and layer numbers on HER catalytic performance of R–P structure oxides Sr2RuO4, Sr3Ru2O7 and Sr3Ru2O6 were comprehensively calculated for the first time. Our results confirm that oxygen-deficient R–P Sr3Ru2O6 is beneficial for its catalytic performance in alkaline environments. Ranking of catalytic performance in acidic environments: Sr2RuO4>Sr3Ru2O6>Sr3Ru2O7, relatively in alkaline environments: Sr3Ru2O6>Sr3Ru2O7>Sr2RuO4, which means pH actually affects the performance of R–P structure catalysts. In other words, acidic environments are conducive to the catalytic activity of Sr2RuO4, while alkaline environments are beneficial for Sr3Ru2O6 and Sr3Ru2O7. We also calculated the effects of tensile and compressive strains and found that 1% and 3% tensile strain can further enhance the HER catalytic performance of Sr3Ru2O6. Taking into account various practical factors, our work investigated the HER catalytic mechanism of R–P oxides, providing theoretical guidance for the development of R–P structure catalysts.

Hydrogen Evolution Catalysis by Cobalt Complexes of an Aza‐Bridged Bis‐1,10‐Phenanthroline Ligand Bearing Pendant Basic Sites

AbstractA novel series of molecular Co(II) complexes with aza‐bridged bis‐1,10‐phenanthroline (bpa) ligands have been synthesized and reported for the catalytic hydrogen evolution reaction (HER). Various nitrogen donor substituents are introduced at the aza‐bridge of the bis‐phenanthroline moieties render intramolecular basic sites in the complexes’ second‐coordination sphere. Modifying the pendant nitrogen donor significantly influences the catalytic HER performance. Among these, the cobalt complex with the (2‐pyridyl)methyl substituted bis‐phenanthroline ligand (L3) exhibits the most photocatalytic HER efficiency in both organic and aqueous media. Under optimized conditions with [Ru(bpy)3]2+ as a sensitizer and ascorbic acid as an electron donor, [CoII(L3)(TfO−)2] achieves an initial turnover frequency (TOF) of 1882±65 h−1 per catalyst and a turnover number (TON) of 4842±122 in a 3 hour reaction period under the irradiation of visible light. Combined experimental and theoretical evidences illustrate that phenanthroline moieties of the bpa ligands act as electron mediators during the HER catalysis, while the pendant nitrogen donor substituents mediate proton transfer. This work provides a unique example for understanding the activity‐structure relationship of homogeneous HER catalyst concerning the redox‐active properties and second coordination sphere basic sites of organic ligand platforms.

Boosting HER performance by using plasma prepared N-doped CNTs to support Pt nanoparticles

Developing highly-efficient and stable Pt-based catalysts towards alkaline hydrogen evolution reaction (HER) offers a promising strategy for future renewable energy. In this work, radio-frequency (RF) cold plasma-prepared N-doped MWCNTs were adopted to support Pt nanoparticles (NPs) (Pt/NCNTs) via pretreating MWCNTs with RF nitrogen plasma and combining with traditional thermal reduction method. The as-synthesized Pt/NCNT featured an ultra-small size of Pt NPs (1.5 nm) and plentiful doped nitrogen, exhibiting ultra-low overpotential of 28 mV@10 mA cm−2 and ultra-high mass activity of 3.2 A mg Pt−1@100 mA in 1 M KOH solution, which are superior to those of commercial 20 wt% Pt/C catalyst. This is because RF plasma can realize fast, high-efficient and specific N-doping structure of MWCNTs. The lone electron pairs of N species (mainly pyri-N and pyrr-N) on MWCNTs surface transfer to the empty orbitals of Pt NPs, forming a strong coordination effect between Pt and nitrogen, thereby boosting the alkaline HER catalytic performance.

Computational screening of single-atom transition metals on boron-rich boron nitride nanosheets for efficient hydrogen evolution catalysis in all pH range.

Low-cost and high-efficiency catalysts are of crucial importance for the electrocatalytic hydrogen evolution reaction (HER). Two-dimensional (2D) boron nitride (B-N) compounds formed by the combination of boron and nitrogen atoms of group III and V elements are promising candidates for electrocatalytic HER due to their significant electronic properties. Hence, an electrocatalyst is computer-aided designed with isolated single atoms of 3d, 4d, and 5d transition metals supported on 2D B-N (B2N, B5N3, and B7N5) monolayers to fabricate single-atom catalysts (SACs) with an excellent HER performance. Moreover, pH modulations are considered to improve the HER activity theoretically based on first-principles calculation. Our results indicate that B-N compounds surface doping with transition metal atoms can effectively enhance the HER catalytic performance over a wide range of pH. Among all SACs studied, Co-, Ti-, V-, Nb-, Ru-, Tc-, Zr-, and Os-embedded B2N, Sc-, Cr-, Mn-, Ti-, and Y-embedded B5N3, and Sc- and Mn-embedded B7N5 have excellent catalytic activity under acidic conditions, while Mo-, Ir-, Re-, Ta-, and W-embedded B2N and Ti- and Fe-embedded B7N5 show high catalytic activity under alkaline conditions. Interestingly, Hf@B2N and V@B5N3 systems exhibit promising catalytic activity under acidic, neutral, and alkaline conditions. Our work offers cost-effective candidates with a wide pH range HER performance for exploring ideal electrocatalysts.

Transition-metal atoms embedded MoTe2 single-atom catalyst for efficient electrocatalytic hydrogen evolution reaction

As an attractive catalyst for the electrochemical hydrogen evolution reaction(HER), MoTe2 has attracted great interest. However, scarce catalytic sites and unsatisfactory catalytic activity of pristine MoTe2 basal plane impeded its practical application. The incorporation of single metal atom into 2D-substrate have been demonstrated as an effective strategy to tune HER activity of materials. Herein, we systematically investigated a series of transition-metal atoms(Fe, Co, Ni, Cu, Ru, Rh, Pd and Ag) embedded MoTe2 plane and edge single-atom catalysts(SAC, TM-MoTe2) for HER performance by employing density functional theory calculations. All TM-MoTe2 catalysts exhibit good thermodynamically and electrochemical stability. Compared with pristine MoTe2, HER catalytic activity of TM-MoTe2 are significantly enhanced due to effective modulation of charge transfer on embedded metal, which attribute to synergy interaction between embedded TM and surrounding Mo atoms. Specially, 2 candidate catalysts with Ru-MoTe2 plane and Fe-MoTe2 edge are found to show higher HER catalytic performance with low overpotential of only 10 mV and 60 mV, respectively. Furthermore, we found a key descriptor Δdd′ to well predict HER-activity trend of MoTe2-based material, which is closely correlated with H adsorption energy(ΔEH). This work provides in-depth theoretical insights for understanding active sites and designing high-efficiency MoTe2-based HER catalysts.

Edge sites regulation, strain and electric field effect on MoS2/CoS2 heterojunction catalysts for hydrogen evolution reaction.

Heterojunction catalysts in the field of hydrogen evolution reaction (HER) from electrocatalytic water splitting have recently become a hot research topic. In this paper, we systematically calculated the HER catalytic performance of a MoS2/CoS2 heterojunction for the first time, considering the effect of edge sites regulation, strain and electric field. The results indicate that the MoS2/CoS2 heterojunction exhibits synergistic catalytic performance compared to MoS2 and CoS2, the HER catalytic activity of which can be improved by exposing more edge sites or regulating the S content on the edges, with an optimized ratio of 25%. Surprisingly, applying strain has a slight effect on the catalytic activity of the edge, however, an obvious effect on the basal plane. For example, applying 2% tensile strain on the MoS2/CoS2 heterojunction can improve the edge catalytic performance by 13%, and for the basal plane, this value can reach 92%. In this case, the catalytic performance of the basal plane is better than that of the edge with 2% and without strain. Since the basal plane accounts for the majority of the two-dimensional catalysts, the catalytic performance of the basal plane is generally much lower than that of the edge. This discovery is of great significance, which means by adjusting strain, the catalytic performance of the heterojunction catalyst is likely to be improved by orders of magnitude. Moreover, considering the actual experimental process, we also calculated the effect of the electric field and found that 0.7 V/Å electric field can enhance the HER catalytic activity of the MoS2/CoS2 heterojunction by 23%.

Constructing novel Sn-Mo bimetallic sulfide heterostructures for enhanced catalytic performance towards the hydrogen evolution reaction

Understanding the design principles of efficient electrocatalysts using the structure–activity relationship is crucial for the advancement of energy-related applications, and specifically the hydrogen evolution reaction (HER). Non-precious electrocatalysts with low overpotentials are essential for driving the HER and achieving high energy efficiency. In this study, we synthesized and thoroughly investigated various heterostructures combining Mo and Sn sulfides, ranging from complete phase-separated hybrids to homogeneous mixtures: SnS@MoS2 core–shell structures, SnS/MoS2 with edge-rich Mo and (SnxMo1-x)S with uniformly distributed Sn-Mo. Our findings reveal that the SnS@MoS2 structure exhibited relatively high intrinsic activity characterized by a high electrochemical active surface area and rapid charge transfer kinetics, thereby enhancing the HER catalytic performance. The presence of fluffy MoS2 layers provided an abundance of optimized sites for HER, potentially due to strain and defects such as S vacancies, known as active catalytic sites. The optimal structure facilitated efficient charge transfer from the core to the shell, improving conductivity and catalytic activity. Our research highlights the advantages of a core–shell hybrid structure, offering guiding principles for the development of an optimal SnS@MoS2 catalyst.

The influence of temperature and the magnetic field on Ni electrodeposition from citrate bath and its electrocatalytic performance towards hydrogen evolution reaction

The demand for energy surpasses the available supply, leading to various economic, social, and environmental consequences. Hydrogen is one of the most clean and renewable source for energy. Therefore, the electrocatalytic hydrogen evolution reaction (HER) presents a promising eco-friendly approach for generating sustainable hydrogen energy. However, in alkaline conditions, HER encounters slow kinetics due to challenges associated with hydrogen adsorption and hydrolysis. In this article, thin Ni films were synthesized using the electrodeposition technique from citrate electrolyte. Their suitability as electrocatalysts for the hydrogen evolution reaction (HER) in a 1 M NaOH solution was estimated. This research investigates how the uniform magnetic field and temperature affect the process of nickel electrodeposition from a citrate bath and its subsequent influence on surface morphology and catalytic properties for the hydrogen evolution reaction (HER). Additionally, alterations in surface material wettability were examined based on changing the temperature during using the magnetic field for the electrodeposition process and shows how this effect on the catalytic performance towards HER. The outputs show that using the magnetic field for fabrication of Ni thin films at room temperature enhances the surface morphology and its catalytic performance for HER. However, the study reveals that using the temperature for Ni electrodeposition improves its catalytic performance independently of the magnetic field, whereas combining temperature with the magnetic field for Ni thin film fabrication diminishes their catalytic performance for the hydrogen evolution reaction (HER). The nickel thin film produced at 25 °C under the influence of a magnetic field, whether parallel or perpendicular, demonstrates the lowest overpotential of − 268 mV to achieve a current density of 10 mA cm−2. Additionally, it exhibits the smallest Tafel slope values of 106 mV dec−1 and 128 mV dec−1 for the parallel (Bǁ) and perpendicular (BꞱ) directions, respectively. However, the magnetic field effect diminishes at elevated temperatures. Nickel thin films prepared at 35 °C under the influence of perpendicular (BꞱ) and parallel (Bǁ) directions exhibit higher overpotential values of − 314 mV and − 322 mV, respectively.

Electronic-Structure-Modulated Cu,Co-Coanchored N-Doped Nanocarbon as a Difunctional Electrocatalyst for Hydrogen Evolution and Oxygen Reduction Reactions.

To alleviate the problems of environmental pollution and energy crisis, aggressive development of clean and alternative energy technologies, in particular, water splitting, metal-air batteries, and fuel cells involving two key half reactions comprising hydrogen evolution reaction (HER) and oxygen reduction (ORR), is crucial. In this work, an innovative hybrid comprising heterogeneous Cu/Co bimetallic nanoparticles homogeneously dispersed on a nitrogen-doped carbon layer (Cu/Co/NC) was constructed as a bifunctional electrocatalyst toward HER and ORR via a hydrothermal reaction along with post-solid-phase sintering technique. Thanks to the interfacial coupling and electronic synergism between the Cu and Co bimetallic nanoparticles, the Cu/Co/NC catalyst showed improved catalytic ORR activity with a half-wave potential of 0.865 V and an excellent stability of more than 30 h, even compared to 20 wt% Pt/C. The Cu/Co/NC catalyst also exhibited excellent HER catalytic performance with an overpotential of below 149 mV at 10 mA/cm2 and long-term operation for over 30 h.

MoS2 supported Ruthenium nanoparticles with abundant sulfur vacancies significantly improved hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER) has become one of effective ways to produce hydrogen. MoS2 is a promising electrocatalyst for the HER, and loading noble metal atoms on MoS2 support can further enhance its HER activity. In present work, the CO was employed as a structure-directing agent to in situ synthesize MoS2-n (n = 0, 0.5, 1.0, 1.4 and 2.0 MPa, representing the CO pressure). Among them, the MoS2-1.4 with highest amounts of sulfur vacancies and superior alkaline HER performance was selected as the support for Ru loadings. Sulfur vacancies can stabilize Ru nanoparticles, prevent nanoparticles from aggregating, and facilitate the formation of small-sized nanoparticles. By optimizing the loading amounts of Ru, the 5Ru@MoS2-1.4 with the Ru loading of 5 wt.% and nanoparticle size of 2 nm exhibits the best alkaline HER activity by displaying a low overpotential of 55 mV and Tafel slope of 68.6 mV dec−1 at a current density of 10 mA cm−2 in 1.0 M KOH medium. This can be majorly related to the synergistic effect of MoS2-1.4 support and small-sized Ru nanoparticles, wherein the CO plays a significant role in regulating the structure of MoS2-1.4 support that favors dispersion of Ru nanoparticles. Generally, present work provides a strategy to enhance the HER catalytic performance of MoS2, which is favorable for other highly-efficient catalyst design.

Ordered PtNiTiZrHf nanoparticles on carbon nanotubes catalyze hydrogen evolution reaction with high activity and durability

With the scarcity of the earth's natural resources, hydrogen production from electrolyzing water is seen as an alternative energy source. Although platinum (Pt) is an advanced catalyst for hydrogen evolution reaction (HER), its application is limited by high cost and limited electrocatalytic performance. In this article, the five-element alloy nanoparticles are successfully synthesized on carbon nanotubes (CNT) by employing liquid-phase reduction and gas-phase sintering to reduce Pt utilization and improve catalytic performance. For comparison, a series of ordered and disordered (PtNi)x(TiZrHf)100-x/CNT catalysts are obtained. Results show that the ordered samples have more excellent HER catalytic performance and stability than disordered samples in 0.5 M H2SO4 and 1 M KOH electrolytes. In particular, when the electrolyte is acidic, the overpotentials of ordered (PtNi)55(TiZrHf)45/CNT at 10 and 100 mA cm−2 are 11 and 52 mV, with low Tafel slope of 37.73 mV dec−1. At 10 mA cm−2, the stabilization time can reach 58 h, which is much better than commercial Pt/C (20 wt.%). Density functional theory (DFT) calculation shows that ordered (PtNi)55(TiZrHf)45/CNT has lower hydrogen adsorption energy and activated water adsorption energy than disordered one, indicating better performance in both acidic and alkaline electrolytes. It is mainly attributed to the electronic coupling effect after ordering that makes the overall D-band center decrease. This work presents a cost-effective approach to optimize the structural design for acid-base HER electrocatalysts.

Theoretical and experimental investigations of vanadium pentoxide–based electrocatalysts for the hydrogen evolution reaction in alkaline media

A key approach towards better realization of intermittent renewable energy resources, namely, solar and wind, is green electrochemical hydrogen production from water electrolysis. In recent years, there have been increasing efforts aimed at developing noble metal-free electrocatalysts that are earth-abundant and electroactive towards hydrogen evolution reaction (HER) in alkaline electrolytes, wherein an initial water dissociation step is followed by a two-electron transfer cathodic reaction. Although relatively earth-abundant, vanadium-based electrocatalysts have been sparsely reported due to subpar electroactivity and kinetics towards water electrolysis in general and alkaline electrolysis in specific. Herein, we investigate the fine-tuning of orthorhombic V2O5-based electrocatalysts as candidates for HER through a scalable two-step sol–gel calcination procedure. Briefly, surface-induced anionic oxygen deficiencies and cationic dopants are synergistically studied experimentally and theoretically. To that end, first-principle facet-dependent density function theory (DFT) calculations were conducted and revealed that the coupling of certain dopants on V2O5 and co-induction of oxygen vacancies can enhance the catalytic HER performance by the creation of new electronic states near the Fermi level (EF), enhancing conductivity, and modulating surface binding of adsorbed protons, respectively. This was reflected experimentally through kinetically non-ideal alkaline electrochemical HER using Zn0.4V1.6O5 whereby − 194 mV of overpotential was required to attain − 10 mA/cm2 of current density, as opposed to pristine V2O5 which required 32% higher overpotential requirement at the same conditions. The disclosed work can be extended to other intrinsically sluggish transition metal (TM)–based oxides via the presented systematic tuning of surface and bulk microenvironment modulation.Graphical

Micro-mechanism investigation of hydrogen evolution reaction on anti-perovskite Ni3InN considering doping and strain effects

Anti-perovskites are considered as promising high-efficiency catalysts for hydrogen evolution reaction (HER) due to their low cost, adjustable composition, and small water dissociation kinetic barriers. Accounting strain effects, transition metal doping effects and solvent effects, we calculate HER micro-mechanism on anti-perovskite Ni3InN and conclude that HER on Ni3InN can be divided into two steps, rapid proton adsorption at the Bridge site and favorable H2 desorption at the Hollow site. We obtained 2 doping elements (Pt and Ir) from 20 transition metal elements that can enhance HER catalytic performance of Ni3InN. It is worth noting that applying a certain strain is beneficial for the catalytic performance of some doped Ni3InN (e.g. +2 %, +1% for Pt), while harmful for others (e.g. Ir). Our work provides a new perspective for the application of anti-perovskites in HER, which is meaningful for the development of HER catalysts.

Unusual Sabatier principle on high entropy alloy catalysts for hydrogen evolution reactions

The Sabatier principle is widely explored in heterogeneous catalysis, graphically depicted in volcano plots. The most desirable activity is located at the peak of the volcano, and further advances in activity past this optimum are possible by designing a catalyst that circumvents the limitation entailed by the Sabatier principle. Herein, by density functional theory calculations, we discovered an unusual Sabatier principle on high entropy alloy (HEA) surface, distinguishing the “just right” (ΔGH* = 0 eV) in the Sabatier principle of hydrogen evolution reaction (HER). A new descriptor was proposed to design HEA catalysts for HER. As a proof-of-concept, the synthesized PtFeCoNiCu HEA catalyst endows a high catalytic performance for HER with an overpotential of 10.8 mV at −10 mA cm−2 and 4.6 times higher intrinsic activity over the state-of-the-art Pt/C. Moreover, the unusual Sabatier principle on HEA catalysts can be extended to other catalytic reactions.

Facile fabrication of an enhanced electrodeposited nickel electrode for alkaline hydrogen evolution reaction

Electrodeposited nickel (Ni) electrode for alkaline hydrogen evolution reaction (HER) has low cost and high stability advantages, but its catalytic performance is unsatisfactory. In this study, a Ni electrode with a pentagonal pyramid microstructure was first fabricated by electrodeposition, and then the surface microstructure and chemical composition of the electrode were elaborately modified by a simple acid etching treatment which significantly enhanced the HER catalytic performance. The HER over-potential at 10 mA cm−2 on the electrode which was etched for 60 min was reduced from 238 mV to 60 mV compared to the un-etched one. The fabricated electrode could maintain stable catalytic stability at a current density of 100 mA cm−2 beyond 360 h. The surface microstructures and chemical compositions of the electrodes were characterized and the catalytic kinetics were investigated by electrochemical methods. The steps on the pentagonal pyramids on the Ni electrode were preferentially dissolved in the etching treatment and the surface became undulating, which efficiently increased the electrochemically active surface area (ECSA). The etching treatment improved the surface wettability and accelerated the hydrogen bubble detachment speed on the electrode. Meanwhile, the electrode surface was further oxidized in the etching treatment. Metallic Ni and crystal NiO were alternately presented on the electrode surface. The generated NiO could facilitate the Volmer step in the HER, which led to the change of the rate-controlling step from the Volmer step to the Heyrovsky step. Further, the synergistic effect between Ni and NiO with a suitable ratio improved the HER catalytic performance of the electrode.

Defect engineering of 1T′ MX 2 (M = Mo, W and X = S, Se) transition metal dichalcogenide-based electrocatalyst for alkaline hydrogen evolution reaction

The alkaline electrolyzer (AEL) is a promising device for green hydrogen production. However, their energy conversion efficiency is currently limited by the low performance of the electrocatalysts for the hydrogen evolution reaction (HER). As such, the electrocatalyst design for the high-performance HER becomes essential for the advancement of AELs. In this work, we used both hydrogen (H) and hydroxyl (OH) adsorption Gibbs free energy changes as the descriptors to investigate the catalytic HER performance of 1T′ transition metal dichalcogenides (TMDs) in an alkaline solution. Our results reveal that the pristine sulfides showed better alkaline HER performance than their selenide counterparts. However, the activities of all pristine 1T′ TMDs are too low to dissociate water. To improve the performance of these materials, defect engineering techniques were used to design TMD-based electrocatalysts for effective HER activity. Our density functional theory results demonstrate that introducing single S/Se vacancy defects can improve the reactivities of TMD materials. Yet, the desorption of OH becomes the rate-determining step. Doping defective MoS2 with late 3d transition metal (TM) atoms, especially Cu, Ni, and Co, can regulate the reactivity of active sites for optimal OH desorption. As a result, the TM-doped defective 1T′ MoS2 can significantly enhance the alkaline HER performance. These findings highlight the potential of defect engineering technologies for the design of TMD-based alkaline HER electrocatalysts.

Phase control of solid-solution RuIn nanoparticles and their catalytic properties.

The properties of solids could be largely affected by their crystal structures. We achieved, for the first time, the phase control of solid-solution RuIn nanoparticles (NPs) from face-centred cubic (fcc) to hexagonal close-packed (hcp) crystal structures by hydrogen heat treatment. The effect of the crystal structure of RuIn alloy NPs on the catalytic performance in the hydrogen evolution reaction (HER) was also investigated. In the hcp RuIn NPs, enhanced HER catalytic performance was observed compared to the fcc RuIn NPs and monometallic Ru NPs. The intrinsic electronic structures of the NPs were investigated by valence-band X-ray photoelectron spectroscopy (VB-XPS). The d-band centre of hcp RuIn NPs obtained from VB-XPS was deeper than that of fcc RuIn NPs and monometallic Ru NPs, which is considered to enable the hcp RuIn NPs to exhibit enhanced HER catalytic performance.

Pt nanoparticles anchored by oxygen vacancies in MXenes for efficient electrocatalytic hydrogen evolution reaction.

The improvement of the hydrogen evolution reaction (HER) performance of nanomaterials is associated with the interfacial synergistic interaction and their hydrogen adsorption kinetics. Nevertheless, it is still a challenge to accelerate the proton transfer and optimize the HER kinetics by constructing Pt-supported heterostructures based on the hydrogen spillover phenomenon. Herein, oxygen vacancies on the surface of MXene nanosheets were constructed via a high-temperature annealing method, which was employed to anchor/stabilize Pt nanoparticles and fabricate a Pt/MXene heterostructure. EPR and XPS analyses verified the presence of oxygen vacancies, which could enhance the intrinsic HER activity of the MXene. The HER catalytic performance was investigated by taking into account the surface structure of the MXene affected by the annealing temperature, the concentration of Pt and the number of deposition cycles. Electrochemical results showed that Pt/MXene with higher utilization of Pt was obtained at 900 °C and 0.05 mgPt mL-1. The 0.05-Pt/MXene-900 obtained at deposition of 60 cycles in 0.5 M H2SO4 solution exhibited the optimized HER activity. The overpotential was 22 mV at a current density of 10 mA cm-2 and the Tafel slope was 42.41 mV dec-1. Furthermore, the accelerated HER kinetics was mainly due to the electron trapping ability of the MXene, small particles of Pt, as well as the enhanced charge transfer between the oxygen vacancies of the MXene and Pt. This strategy for constructing Pt-supported heterostructures based on the vacancy anchoring effects provides new ideas for the design of well-defined electrocatalysts toward the HER.

Reaction modelling of hydrogen evolution on nickel phosphide catalysts: density functional investigation.

Nickel phosphides (NixPy), particularly Ni2P, are promising catalysts for the acidic hydrogen evolution reaction (HER). Using density functional theory (DFT), we model HER at the potential of zero charge (PZC), incorporating solvation effects via an explicit water cluster and implicit surrounding solvent. Comparing the Volmer, Tafel, and Heyrovsky steps under saturated hydrogen coverage on Ni2P(0001) terminations, we find that the Ni3P2 (pristine) surface termination prefers the Volmer-Volmer-Tafel (VVT) pathway with activation energy (Ea) of 0.57 eV. Conversely, the Ni3P2 + 4P (reconstructed) surface favors the Volmer-Heyrovsky (VH) pathway with Ea = 0.60 eV. For the pristine surface termination, the differential gas-phase hydrogen adsorption free energies (ΔGdiff) correlate with the Volmer and Tafel step reaction energies, and a linear Bell-Evans-Polanyi relationship for the calculated activation and reaction energies validates the usefulness of the ΔGdiff descriptor for the Volmer step under PZC conditions. Nickel atoms play a crucial role in H2 production on both pristine and reconstructed surfaces, suggesting that modifications of the Ni sites can be used for catalyst design. Our findings highlight the importance of considering surface reconstruction and solvation effects on the HER catalytic performance.

S dopant-mediated hydrogen evolution reaction activity of CoSe2

CoSe2 has become one of the most appealing non-noble metal catalysts for hydrogen evolution reaction (HER) in the field of electrolysis water due to its abundant resources and good activity. Inversely, its slow kinetic behavior is still restrained, which plays a negative influence for high-efficiency HER. Herein, a certain of Ni or S was introduced into the (100) crystal facet of CoSe2 on the basis of density functional theory (DFT) calculations. Thermodynamic calculation results reveal that the HER activity for CoSe1S1 is relatively better than those of Ni0.375Co0.625Se2 and pristine CoSe2 when a certain of S atoms were introduced into CoSe2. More strikingly, the active sites of CoSe1S1 are reversed from cationic Co to anion S, which is close to the ideal value (0) of Gibbs free energy. Meanwhile, the kinetic performance of H adsorbed on the anionic S or Se site is optimal, and their migration energy barrier is lower in comparison with 1/2 of the cationic Co site. According to the electronic structure analysis, the conductivity of CoSe1S1 is prominent than other counterparts (such as Ni0.375Co0.625Se2 and CoSe2). This work indicates that CoSe1S1 exhibits an excellent catalytic performance for HER, and offers theoretical guidance in the aspect of experiments for designing high-efficient HER catalysts.