Unveiling the promotion of accelerated water dissociation kinetics on the hydrogen evolution catalysis of NiMoO_(4) nanorods

Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.Herein,we successfully accelerate the water dissociation kinetics of NiMoO_(4)for prominent HER catalytic properties via simultaneous in situ interfacial engineering with molybdenum dioxide(MoO_(2))and doping with phosphorus(P).The as-synthesized P-doped NiMoO_(4)/MoO_(2)heterostructure nanorods exhibit outstanding HER performance with an extraordinary low overpotential of-23 m V at a current density of 10 m A cm^(-2),which is highly comparable to the performance of the state-of-art Pt/C coated on nickel foam(NF)catalyst.The density functional theory(DFT)analysis reveals the enhanced performance is attributed to the formation of MoO_(2)during the in situ epitaxial growth that substantially reduces the energy barrier of the Volmer pathway,and the introduction of P that provides efficient hydrogen desorption of Ni MoO_(2).This present work creates valuable insight into the utilization of interfacial and doping systems for hydrogen evolution catalysis and beyond.

A Simple Model to Determine the Trends of Electric Field Enhanced Water Dissociation in a Bipolar Membrane

This work is concentrated on elucidating the mechanism of the electric field enhanced water dissociation. A simple model was established for the theoretical current-voltage characteristics in water dissociation process on a bipolar membrane based on the existence of a depletion layer and Onsager's theory. Particular attention was given to the influence of applied voltage on depletion thickness and the dissociation constant. The factors on the water splitting process, such as water diffusivity, water content, ion exchange capacity, temperature, relative permittivity, etc. Were adequately analysed based on the derived model equations and several suggestions were proposed for decreasing the applied voltage in practical operation. The water dissociation tests were conducted and compared with both the theoretical calculation and the measured current-voltage curves reported in the literature, which showed a very good prediction to practical current-voltage behavior of a bipolar membrane at high current densities when the splitting of water actually commenced.

Regulating local charges of atomically dispersed Moδ+ sites by nitrogen coordination on cobalt nanosheets to trigger water dissociation for boosted hydrogen evolution in alkaline media

Now,Pt-based materials are still the best catalysts for hydrogen evolution reaction(HER).Nevertheless,the scarcity of Pt makes it impossible for the large-scale applications in industry.Although cobalt is taken as an excellent HER catalyst due to its suitable H*binding,its alkali HER catalytic property need to be improved because of the sluggish water dissociation kinetics.In this work,nitrogen with small atomic radius and metallophilicity is employed to adjust local charges of atomically dispersed Mo^(δ+)sites on Co nanosheets to trigger water dissociation.Theoretical calculations suggest that the energy barrier of water dissociation can be effectively reduced by introducing nitrogen coordinated Mo^(δ+)sites.To realize this speculation,atomically dispersed Mo^(δ+)sites with nitrogen coordination of Mo(N)/Co were prepared via reconstruction of CoMoO_(4).High angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)and X-ray absorption spectroscopy(XAS)demonstrate the coordination of N atoms with atomically dispersed Mo atoms,leading to the local charges of atomically dispersed Mo^(δ+)sites in Mo(N)/Co.The measurement from ambient pressure X-ray photoelectron spectroscopy(AP-XPS)reveals that the Mo^(δ+)sites promote the adsorption and activation of water molecule.Therefore,the Mo(N)/Co exhibits an excellent activity,which need only an overpotential of 39 mV to reach the current density of 10 mA cm^(-2).The proposed strategy provides an advance pathway to design and boost alkaline HER activity at the atomic-level.

Water Dissociation Phenomena on a Bipolar Membrane──Current-voltage Curve in Relation with IonicTransport and Limiting Current Density

The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were com

Oxygen vacancy promoting artificial atom(RuPd)by d-orbital coupling for efficient water dissociation

Rational design of highly active catalysts for breaking hydrogen-oxygen bonds is of great significance in energy chemical reactions involving water.Herein,an efficient strategy for the artificial atom(RuPd)established by d-orbital coupling and adjusted by oxygen vacancy(V_(O))is verified for water dissociation.As an experimental verification,the turnover frequency of RuPd-TiO_(2)-VO(RuPdTVO)catalyst in ammonia borane hydrolysis reaches up to 2750 min^(−1)(26,190 min−1 based on metal dispersion)in the absence of alkali,exceeding the highest active catalysts(Rh-based catalysts).The d-orbital coupling effect between Ru and Pd simulates the outer electronic structure of Rh.Electron transfer from V_(O) to(RuPd)constructs an electron-rich state of active sites that further enhances the ability of the artificial atom to dissociate water.This work provides an effective electronic regulation strategy from V_(O) and artificial atom constructed by d-orbital coupling effect for efficient water dissociation.

Accelerating water dissociation at carbon supported nanoscale Ni/NiO heterojunction electrocatalysts for high-efficiency alkaline hydrogen evolution

The synergistic catalysis of heterojunction electrocatalysts for the multi-step process in hydrogen evolution reaction(HER)is a promising approach to enhance the kinetics of alkaline HER.Herein,we proposed a strategy to form nanoscale Ni/NiO heterojunction porous graphitic carbon composites(Ni/NiO-PGC)by reduction-pyrolysis of the preformed Ni-metal-organic framework(MOF)under H2/N2 atmosphere.Benefiting from low electron transfer resistance,increased number of active sites,and unique hierarchical micro-mesoporous structure,the optimized Ni/NiO-PGC_(10-1-400)exhibited excellent electrocatalytic performance and robust stability for alkaline HER(η10=30 mV,65 h).Density functional theory(DFT)studies revealed that the redistribution of electrons at the Ni/NiO interface enables the NiO phase to easily initiate the dissociation of alkaline H_(2)O,and shifts down the d-band center of Ni and optimizes the H*adsorption-desorption process of Ni,thereby leading to extremely high HER activity.This work contributes to a further understanding of the synergistic promotion of the multi-step HER processes by heterojunction electrocatalysts.

V-doped Ni_(3)N/Ni heterostructure with engineered interfaces as a bifunctional hydrogen electrocatalyst in alkaline solution:Simultaneously improving water dissociation and hydrogen adsorption

Alkali-water electrolyzers and hydroxide exchange membrane fuel cells are emerging as promising technologies to realize hydrogen economy.Developing cost-effective electrode materials with high activities towards corresponding hydrogen evolution(HER)and oxidation(HOR)reactions plays a crucial role in commercial hydrogen production and utilization.Herein,we fabricated a V-doped Ni_(3)N/Ni heterostructure(V-Ni_(3)N/Ni)through a controlled nitridation treatment on a V-incorporated nickel hydroxide precursor.The resultant catalyst exhibits comparable catalytic activity and durability to commercial Pt/C in terms of both HER(a low overpotential of 44 mV at the current density of 10 mA·cm^(-2))and HOR(a high current density of 1.54 mA·cm^(-2)at 0.1 V versus reversible hydrogen electrode)under alkaline conditions.The superior activity of V-Ni_(3)N/Ni grown on different substrates further implies its intrinsic performance.Density functional theory(DFT)calculations reveal that the coupled metallic Ni and doped V can promote the water adsorption,accelerate the Volmer step of alkaline HER,as well as optimize the adsorption and desorption of hydrogen intermediate(H^(*))to reach a balancedΔGH*value.

Reduced water dissociation barrier on constructing Pt-Co/CoO_(x)interface for alkaline hydrogen evolution

Water dissociation process is generally regarded as the rate-limiting step for alkaline hydrogen evolution reaction(HER),and severely inhibits the catalytic efficiency of Pt based catalysts.To overcome this problem,the in-situ constructed interfaces of PtCo alloy and amorphous cobalt oxide(CoO_(x))on the carbon powder are designed.The amorphous CoO_(x)at Pt-Co/CoO_(x)interfaces not only provide active sites for water dissociation to facilitate Volmer step,but also produce the strong electronic transfer with Pt-Co.Accordingly,the obtained interfacial catalysts exhibit outstanding alkaline HER performance with a Tafel slope of 29.3 mV·dec^(−1)and an ultralow overpotential of only 28 mV at 10 mA·cm^(−2).Density functional theory(DFT)reveals that the electronic accumulation on the interfacial Co atom in Pt-Co/CoO_(x)constructing the novel active site for water dissociation.Compared to the Pt-Co,all of the energy barriers for water adsorption,water dissociation and hydrogen adsorption/desorption are reduced in Pt-Co/CoO_(x)interfaces,suggesting a boosted HER kinetics for alkaline HER.

Rational design of Ru species on N-doped graphene promoting water dissociation for boosting hydrogen evolution reaction

In this study,the morphological distribution of Ru on nitrogen-doped graphene(NG)could be rationally regulated via modulating the combination mode between Ru precursor and the zeolite imidazolate framework-8(ZIF-8).The cation exchange and host-guest strategies respectively resulted in two different combination modes between Ru precursor and ZIF-8 anchored on graphene.Following pyrolysis of the above precursors,Ru single-atom sites(SASs)with and without Ru nanoparticles(NPs)were formed selectively on NG(denoted as Ru SASs+NPs/NG and Ru SASs/NG,respectively).Ru SASs+NPs/NG exhibited excellent hydrogen evolution reaction(HER)performance in alkaline solutions(η_(10)=12 mV,12.57 A mg^(-1)_(Ru) at 100 mV),which is much better than Ru SASs/NG.The experimental and theoretical study revealed that Ru SASs could adsorb hydrogen with optimal adsorption strength,while Ru NPs could lower the barrier of water molecule dissociation,and thus Ru SASs and Ru NPs could synergistically promote the catalytic performance of HER in alkaline solutions.

Water transfer characteristics during methane hydrate formation and dissociation processes inside saturated sand

Gas hydrates formation and dissociation processes inside porous media are always accompanied by water transfer behavior, which is similar to the water behavior of ice freezing and thawing processes. These processes have been studied by many researchers, but all the studies are so far on the water transfer characteristics outside porous media and the water transfer characteristics inside porous media have been little known. In this study, in order to study the water transfer characteristics inside porous media during methane hydrate formation and dissociation processes, a novel apparatus with three pF-meter sensors which can detect water content changes inside porous media was applied. It was experimentally observed that methane hydrate formation processes were accompanied by water transfer from bottom to top inside porous media, however, the water behavior during hydrate dissociation processes was abnormal, for which more studies are needed to find out the real reason in our future work.

Aviation-oriented Micromachining Technology—Micro-ECM in Pure Water

This article proposes a precise and ecofriendly micromachining technology for aerospace application called electrochemical machining in pure water （PW-ECM）. On the basis of the principles of water dissociation, a series of test setups and tests are devised and performed under different conditions. These tests explain the need for technological conditions realizing PW-ECM, and further explore the technological principles. The results from the tests demonstrate a successful removal of electrolytic slime by means of ultrasonic vibration of the workpiece. To ensure the stability and reliability of PW-ECM process, a new combined machining method of PW-ECM assisted with ultrasonic vibration （PW-ECM/USV） is devised. Trilateral and square cavities and holes as well as a group of English alphabets are worked out on a stainless steel plate. It is confirmed that PW-ECM will be probably an efficient new aviation precision machining method.

Structure transformation induced bi-component Co–Mo/A-Co(OH)_(2)as highly efficient hydrogen evolution catalyst in alkaline media

Elucidating the inherent origins of the sluggish hydrogen evolution reaction(HER)kinetics in alkaline media and developing high-performance electrocatalysts are fundamental for the advances of conventional alkaline water electrolyzers and emerging anion exchange membrane(AEM)electrolyzers.Here we present a facile electrochemical modification strategy for the synthesis of bi-component Co–Mo_((18%))/A-Co(OH)_(2)catalyst toward efficient HER catalysis in alkaline media.Porous Co–Mo alloys with adjustable Mo/Co atomic ratio are first prepared by H2-assisted cathodic electrodeposition.By virtue of the appropriate electronic structure and hydrogen binding energy,Co–Mo_((18%))is the most HER active among the alloys and is further activated by a constant-current electrochemical modification process.Physical characterizations reveal the formation of amorphous Co(OH)_(2)nanoparticles on the surface.Electrokinetic analysis combined with theoretical calculations reveal that the in-situ formed Co(OH)_(2)can efficiently promote the water dissociation,resulting in accelerated Volmer-step kinetics.As a result,the Co–Mo_((18%))/A-Co(OH)_(2)simultaneously achieves the optimization of the two factors dominating alkaline HER activity,i.e.,water dissociation and hydrogen adsorption/desorption via the bifunctional synergy of the bi-components.The high HER activity(η10 of 47 mV at 10 mA cm^(-2))of Co–Mo_((18%))/A-Co(OH)_(2)is close to benchmark Pt/C catalyst and comparable or superior to the most active non-noble metal catalysts.

Mechanism study of reduction of CO_2 into formic acid by in-situ hydrogen produced from water splitting with Zn: Zn/ZnO interface autocatalytic role

We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.

Adsorption and dissociation of H_2O on Cu_2O(100): A computational study

The adsorption and dissociation of water on Cu2O（100） have been investigated by the density functional theory-generalized gradient approximation （DFT-GGA） method. The corresponding reaction energies, the structures of the transition states and the activation energies were determined. Calculations with and without dipole correction were both studied to get an understanding of the effect of the dipole moment on the adsorption and reaction of water on dipole surface Cu2O（100）. When dipole correction was added, the adsorption energies of H2O on different sites generally decreased. The calculated activation barriers for HxO （x = 1, 2） dehydrogenation are 0.42 eV （1.01 eV without the dipole correction） and 1.86 eV, respectively, including the zero point energy correction. The first dehydrogenation outcome is energetically the most stable product.

Coupling interface engineering with electronic interaction toward high-efficiency H_(2) evolution in pH-universal electrolytes

Herein,the merits of heterojunction,CeO_(2),and W are employed to design and prepare the PtCoW@CeO_(2)heterojunction catalyst,which can accelerate water dissociation and improve the desorption of OHad,displaying efficient hydrogen evolution reaction(HER)performance in pH-universal conditions.Density functional theory calculation results reveal that the electronic structure of Pt is regulated by CeO_(2)and W,which tunes the Pt-Hadbond strength to boost HER intrinsic activity.Consequently,electrochemical results display that it has low potentials of-26,-25,and-23 mV at-10 mA cm^(-2)in alkaline,neutral,and acidic solutions,respectively,and it can stably cycle for 50,000 cycles.Thus,this work provides the guidance for developing high-performance Pt-based catalysts in pH-universal environments.

Engineering Vacancy-Atom Ensembles to Boost Catalytic Activity toward Hydrogen Evolution

The dissociation of water is the rate-determining step of several energy-relating reactions due to high energy barrier in homolysis of H-O bond.Herein,engineering vacancy-atom ensembles via injecting oxygen vacancy(V O)into single facet-exposed TiO_(2)-Pd catalyst to form V_(O)-Pd ensemble is proposed and implemented.The outstanding activity of as-prepared catalyst,1.5-PdTV_(O),toward water dissociation is established with a turnover frequency of 240 min^(−1) in ammonia borane hydrolysis at 298 K.Density functional theory simulation suggests that the V_(O)-Pd ensemble is responsible for the high intrinsic catalytic activity.Water molecules tend to be dissociated on V_(O) sites and ammonia borane molecules on Pd atoms.Those H atoms from water dissociation on V_(O) combine with H atoms from ammonia borane on Pd atoms to generate H_(2).This insights into engineering vacancy-atom ensembles catalysis provide a new avenue to design catalytic materials for important energy chemical reactions.

Promoting CO_(2) and H_(2)O activation on O-vacancy regulated In-Ti dual-sites for enhanced CH_(4) photo-production

Engineering the specific active sites of photocatalysts for simultaneously promoting CO_(2)and H_(2)O activation is important to achieve the efficient conversion of CO_(2)to hydrocarbon with H_(2)O as a proton source under sunlight.Herein,we delicately design the In/TiO_(2)-VOphotocatalyst by engineering In single atoms(SAs)and oxygen vacancies(VOs)on porous TiO_(2).The relation between structure and performance of the photocatalyst is clarified by both experimental and theoretical analyses at the atomic levels.The In/TiO_(2)-VOphotocatalyst furnish a high CH_(4)production rate up to 35.49μmol g^(-1)h^(-1)with a high selectivity of 91.3%under simulated sunlight,while only CO is sluggishly generated on TiO_(2)-VO.The combination of in situ spectroscopic analyses with theoretical calculations reveal that the VOsites accelerate H_(2)O dissociation and increase proton feeding for CO_(2)reduction.Furthermore,the VOregulated In-Ti dual sites enable the formation of a stable adsorption conformation of In-C-O-Ti intermediate,which is responsible for the highly selective reduction of CO_(2)to CH_(4).This work demonstrates a new strategy for the development of effective photocatalysts by coupling metal SA sites with the adjacent metal sites of support to synergistically enhance the activity and selectivity of CO_(2)photoreduction.

Edge dislocation-induced strains break the limit of PtNi alloys in boosting Pt mass activity for efficient alkaline hydrogen evolution

Creating lattice defects and alloying to produce strain effect in Pt-based bimetallic alloys are both effective methods to optimize the crystal and electronic structure and improve the electrocatalytic performance.Unfortunately,the principles that govern the alkaline hydrogen evolution reaction(HER)performance remain unclear,which is detrimental to the rational design of efficient Pt-based electrocatalysts.Herein,PtNi alloys with different Pt/Ni ratios and edge dislocations were synthesized,and the effects of Pt/Ni composition and edge dislocations on the alkaline HER electrocatalytic activity of PtNi alloys were systematically studied.Combined experimental and theoretical investigations reveal that tuning Pt/Ni ratio results in only 1.1 times enhancements in Pt mass activity,whereas edge dislocations-induced extra tensile strain on Ni site and compressive strain on Pt site further boost the alkaline HER intrinsic activity at all Pt/Ni ratios.Impressively,the introduction of edge dislocations in PtNi alloys could break the limit of alloying in boosting Pt mass activity and result in up to 13.7-fold enhancement,in the case that Pt and Ni contents are nearly identical and thus edge dislocation density reaches the maximum.Fundamental mechanism studies demonstrate that the edge dislocation strategy could make a breakthrough in facilitating water dissociation kinetics of PtNi alloys.

Surface reconstruction of heterostructures in alkaline medium towards enhanced electrocatalytic hydrogen evolution

Constructing heterostructures has proved to be a successful strategy to fabricate electrocatalysts with high efficiency for water splitting.However,the structure evolution in alkaline hydrogen evolution reaction lacks investigation and the specific active center remains disputable.Herein,we take the well-designed Ni_(3)S_(2)@VO_(2) heterostructures as a model to investigate the electrocatalytic activity and the surface reconstruction process of heterostructure catalysts in alkaline electrolyte.The Ni_(3)S_(2)@VO_(2) heterostructures,with Ni_(3)S_(2) nanorods as the core and VO_(2) nanoflakes as the shell,coupled with the high conductive Ni_(3)S_(2),the hydrophilic VO_(2) and modulated electronic structures at the interfaces,exhibited prominent activity and superior stability at various current densities.Further,the ex-situ characterizations confirmed that the surface reconstruction from Ni_(3)S_(2)@VO_(2) into Ni_(3)S_(2)@amorphous-Ni(OH)_(2) in alkaline media could optimize the water dissociation barrier and exposed large active area,thereby contributing to improved electrocatalytic performance.Our study not only introduces novel high-performance electrocatalysts for hydrogen evolution reaction(HER),but also provides a new avenue for re-examining hetero-structural catalysts in alkaline solutions.

Dual active sites engineering of electrocatalysts for alkaline hydrogen evolution

Hydrogen evolution reaction(HER)in alkaline medium plays an important role in producing green hydrogen but suffers from sluggish reaction kinetics owing to additional water dissociation step.Extensive research interest has been placed on engineering dual active sites(i.e.,water-dissociation sites and hydrogen-adsorption/recombination sites)within a catalyst to enhance the HER activity.This article reviews recent progress in developing alkaline HER catalysts with high-efficiency dual active sites via strategies of heterogeneous interfaces constructing and heteroatoms doping or alloying.The latest advances in the component design,synthetic strategy,catalytic performance,and mechanistic understanding are discussed with selective examples of the hybrid between metal/alloy or metal phosphide/nitride/sulfide and transition metal hydroxides,oxyhydroxide or bicarbonates.Furthermore,remaining challenges and perspectives in the field of dualsite engineering are highlighted for future development of better alkaline HER electrocatalysts.