Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Mg/MgO interfaces as efficient hydrogen evolution cathodes causing accelerated corrosion of additive manufactured Mg alloys:A DFT analysis

The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide inclusions.Scanning Kelvin Probe Force Microscopy demonstrated that MgO inclusions could act as cathodes for Mg corrosion,but their low conductivity likely precludes this.However,the density of state calculations through density functional theory using hybrid HSE06 functional revealed overlapping electronic states at the Mg/MgO interface,which facilitates electron transfers and participates in redox reactions.Subsequent determination of the hydrogen absorption energy at the Mg/MgO interface reveals it to be an excellent catalytic site,with HER being found to be a factor of 23x more efficient at the interface than on metallic Mg.The results not only support the plausibility of the Mg/MgO interface being an effective cathode to the adjacent anodic Mg matrix during corrosion but also contribute to the understanding of the enhanced cathodic activities observed during the anodic dissolution of magnesium.

Heterostructured Pt-Ni_(3)Mo_(3)N formed via ammonia-containing polyoxometalates for highly efficient electrocatalytic hydrogen evolution in acid medium

Constructing heterostructured nanohybrid is considered as a prominent route to fabricate alternative electrocatalysts to commercial Pt/C for hydrogen evolution reaction(HER).In this work,(NH_(4))_(4)[NiH_(6)Mo_(6)O_(4)]·5H_(2)O polyoxometalates(NiMo_(6))are adopted as the cluster precursors for simple fabrication of heterostructured Pt-Ni_(3)Mo_(3)N nanohybrids supported by carbon black(Pt-Ni_(3)Mo_(3)N/C)without using additional N sources.The improved porosity and enhanced electronic interaction of Pt-Ni_(3)Mo_(3)N/C should be attributed to the integration of Pt with NiMo_(6),which favors the mass transport,promotes the formation of exposed catalytic sites,and benefits the regulation of intrinsic activity.Thus,the as-obtained Pt-Ni_(3)Mo_(3)N/C exhibits impressive and durable HER performance as indicated by the low overpotential of 13.7 mV at the current density of 10 mA cm^(-2) and the stable overpotential during continuous working at 100 mA cm^(-2) for 100 h.This work provides significant insights for the synthesis of new highly active heterostructured electrocatalysts for renewable energy devices.

Enhancing hydrogen evolution and oxidation kinetics through oxygen insertion into nickel lattice

Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.

Unsaturated bi-heterometal clusters in metal-vacancy sites of 2D MoS2 for efficient hydrogen evolution

The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.

Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Fundamental Understanding of Hydrogen Evolution Reaction on Zinc Anode Surface:A First‑Principles Study

Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.

In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.

Multifunctional catalytic sites regulation of atomic-scale iridium on orthorhombic-CoSe_(2)for high efficiency dual-functional alkaline hydrogen evolution and organic degradation

The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.

The effect of the carbon components on the performance of carbonbased transition metal electrocatalysts for the hydrogen evolution reaction

The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.

Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)_(2)Nanosheets with Promoted Hydrogen Absorption in Hydrogen Evolution

Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates,which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts.In this work,Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)_(2)nanosheet arrays.Based on the X-ray absorption fine structure analysis and first-principles calculations,Pt SA was bonded with Ni sites of amorphous Ni(OH)_(2),rather than conventional O sites,resulting in negatively charged Pt^(δ-).In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms,which were the essential intermediate for alkaline hydrogen evolution reaction.The hydrogen spillover process was revealed from amorphous Ni(OH)_(2)that effectively cleave the H-O-H bond of H_(2)O and produce H atom to the Pt SA sites,leading to a low overpotential of 48 mV in alkaline electrolyte at-1000 mA cm^(-2)mg^(-1)_(Pt),evidently better than commercial Pt/C catalysts.This work provided new strategy for the control-lable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.

Exploring the Cation Regulation Mechanism for Interfacial Water Involved in the Hydrogen Evolution Reaction by In Situ Raman Spectroscopy

Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.

Atomic-level coupled RuO_(2)/BaRuO_(3) heterostructure for efficient alkaline hydrogen evolution reaction

The slow water dissociation is the rate-determining step that slows down the reaction rate in alkaline hydrogen evolution reaction(HER).Optimizing the surface electronic structure of the catalyst to lower the energy barrier of water dissociation and regulating the binding strength of adsorption intermediates are crucial strategy for boosting the catalytic performance of HER.In this study,RuO_(2)/BaRuO_(3)(RBRO)heterostructures with abundant oxygen vacancies and lattice distortion were in-situ constructed under a low temperature via the thermal decomposition of gel-precursor.The RBRO heterostructures obtained at 550℃ exhibited the highest HER activity in 1 M KOH,showing an ultra-low overpotential of 16 mV at 10 mA cm^(-2)and a Tafel slope of 33.37 m V dec^(-1).Additionally,the material demonstrated remarkable durability,with only 25 mV of degradation in overpotential after 200 h of stability testing at 10 mA cm^(-2).Density functional theory calculations revealed that the redistribution of charges at the heterojunction interface can optimize the binding energies of H*and OH*and effectively lower the energy barrier of water dissociation.This research offers novel perspectives on surpassing the water dissociation threshold of alkaline HER catalysts by means of a systematic design of heterogeneous interfaces.

Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.

Recent advances in design of hydrogen evolution reaction electrocatalysts at high current density:A review

The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.

Accelerating H^(*)desorption of hollow Mo_(2)C nanoreactor via in-situ grown carbon dots for electrocatalytic hydrogen evolution

Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.

Insights into the hydrogen evolution reaction in vanadium redox flow batteries:A synchrotron radiation based X-ray imaging study

The parasitic hydrogen evolution reaction(HER)in the negative half-cell of vanadium redox flow batteries(VRFBs)causes severe efficiency losses.Thus,a deeper understanding of this process and the accompanying bubble formation is crucial.This benchmarking study locally analyzes the bubble distribution in thick,porous electrodes for the first time using deep learning-based image segmentation of synchrotron X-ray micro-tomograms.Each large three-dimensional data set was processed precisely in less than one minute while minimizing human errors and pointing out areas of increased HER activity in VRFBs.The study systematically varies the electrode potential and material,concluding that more negative electrode potentials of-200 m V vs.reversible hydrogen electrode(RHE)and lower cause more substantial bubble formation,resulting in bubble fractions of around 15%–20%in carbon felt electrodes.Contrarily,the bubble fractions stay only around 2%in an electrode combining carbon felt and carbon paper.The detected areas with high HER activity,such as the border subregion with more than 30%bubble fraction in carbon felt electrodes,the cutting edges,and preferential spots in the electrode bulk,are potential-independent and suggest that larger electrodes with a higher bulk-to-border ratio might reduce HER-related performance losses.The described combination of electrochemical measurements,local X-ray microtomography,AI-based segmentation,and 3D morphometric analysis is a powerful and novel approach for local bubble analysis in three-dimensional porous electrodes,providing an essential toolkit for a broad community working on bubble-generating electrochemical systems.

Preparation of Flower-like Copper Foam Supported Co_(3)O_(4) Electrocatalyst and Its Hydrogen Evolution Performance

Flower-like copper foam Co_(3)O_(4) catalysts(Co_(3)O_(4)/CF) were prepared by hydrothermal method.The crystalline structure and microscopic morphology of the prepared samples were characterized by using X-ray diffractometer(XRD) and scanning electron microscope(SEM),and the electrochemical properties were investigated by an electrochemical workstation.The experimental results show that the Co_(3)O_(4) catalysts are successfully prepared on the foamed copper support by hydrothermal method,and the material’s morphology is mainly flower cluster.When the current density is 10 mA·cm^(-2),the overpotential value of the Co_(3)O_(4)/CF catalyst is 141 mV,lower than that of blank support.The electrochemical impedance(EIS) spectrum shows that the R_(ct )value of the Co_(3)O_(4)/CF catalyst decreases,and the Coulomb curves of double-layer show that the electrochemically active area of the Co_(3)O_(4)/CF catalyst efficiently increases compared with that of the blank support.Therefore,the as-obtained Co_(3)O_(4)/CF catalyst exhibits a good hydrogen evolution rate,showing great applicability potential in the catalytic electrolysis of water for hydrogen production.

Unraveling the Harmonious Coexistence of Ruthenium States on a Self-Standing Electrode for Enhanced Hydrogen Evolution Reaction

The development of cost-effective,highly efficient,and durable electrocatalysts has been a paramount pursuit for advancing the hydrogen evolution reaction(HER).Herein,a simplified synthesis protocol was designed to achieve a self-standing electrode,composed of activated carbon paper embedded with Ru single-atom catalysts and Ru nanoclusters(ACP/Ru_(SAC+C))via acid activation,immersion,and high-temperature pyrolysis.Ab initio molecular dynamics(AIMD)calculations are employed to gain a more profound understanding of the impact of acid activation on carbon paper.Furthermore,the coexistence states of the Ru atoms are confirmed via aberration-corrected scanning transmission electron microscopy(AC-STEM),X-ray photoelectron spectroscopy(XPS),and X-ray absorption spectroscopy(XAS).Experimental measurements and theoretical calculations reveal that introducing a Ru single-atom site adjacent to the Ru nanoclusters induces a synergistic effect,tuning the electronic structure and thereby significantly enhancing their catalytic performance.Notably,the ACP/Ru_(SAC+C)exhibits a remarkable turnover frequency(TOF)of 18 s^(−1)and an exceptional mass activity(MA)of 2.2 A mg^(−1),surpassing the performance of conventional Pt electrodes.The self-standing electrode,featuring harmoniously coexisting Ru states,stands out as a prospective choice for advancing HER catalysts,enhancing energy efficiency,productivity,and selectivity.