Transition metal nitrides(TMN)have recently grabbed immensely appealing as ideal active materials in energy storage and catalysis fields on account of their remarkable electrical conductivity,excellent chemical stabil...Transition metal nitrides(TMN)have recently grabbed immensely appealing as ideal active materials in energy storage and catalysis fields on account of their remarkable electrical conductivity,excellent chemical stability,wide band gap and tunable morphology.Both pure TMN and TMN-based materials have been extensively studied concerned with their preparation approaches,nanostructures,and favored performance in various applications.However,the processes towards synthesis of TMN are numerous and complex.Choosing appropriate method to obtain target TMN with desired structure is crucial,which further affects its practical application performance.Herein,this review offers a timely and comprehensive summary of the synthetic ways to TMN and their application in energy related domains.The synthesis section is categorized into in-situ and ex-situ based on where the N element in TMN origins from.Then,overviews on the energy related applications including energy storage,electrocatalysis and photocatalysis are discussed.In the end,the problems to be solved and the development trend of the synthesis and application of transition metal nitrides are prospected.展开更多
Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optim...Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.展开更多
Faraday pseudocapacitors take both advantages of secondary battery with high energy density and supercapacitors with high power density,and electrode material is the key to determine the performance of Faraday pseudoc...Faraday pseudocapacitors take both advantages of secondary battery with high energy density and supercapacitors with high power density,and electrode material is the key to determine the performance of Faraday pseudocapacitors.Transition metal oxides and nitrides,as the two main kinds of pseudocapacitor electrode materials,can enhance energy density while maintaining high power capability.Recent advances in designing nanostructured architectures and preparing composites with high specific surface areas based on transition metal oxides and nitrides,including ruthenium oxides,nickel oxides,manganese oxides,vanadium oxides,cobalt oxides,iridium oxides,titanium nitrides,vanadium nitrides,molybdenum nitrides and niobium nitrides,are addressed,which would provide important significances for deep researches on pseudocapacitor electrode materials.展开更多
A series of transition metal nitrides(MxNy,M=Fe,Co,Ni)nanoparticle(NP)composites caged in N-doped hollow porous carbon sphere(NHPCS)were prepared by impregnation and heat treatment methods.These composites combine the...A series of transition metal nitrides(MxNy,M=Fe,Co,Ni)nanoparticle(NP)composites caged in N-doped hollow porous carbon sphere(NHPCS)were prepared by impregnation and heat treatment methods.These composites combine the high catalytic activity of nitrides and the high-efficiency mass transfer characteristics of NHPCS.The oxygen reduction reaction results indicate that Fe2N/NHPCS has the synergistic catalytic performance of higher onset potential(0.96 V),higher electron transfer number(~4)and higher limited current density(1.4 times as high as that of commercial Pt/C).In addition,this material is implemented as the air catalyst for zinc−air battery that exhibits considerable specific capacity(795.1 mA·h/g)comparable to that of Pt/C,higher durability and maximum power density(173.1 mW/cm2).展开更多
Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunc...Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunctional electrocatalysts for air-cathode oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes,the practical application of rechargeable ZABs is seriously hindered.In the effort of developing high active,stable and cost-effective electrocatalysts,transition metal nitrides(TMNs)have been regarded as the candidates due to their high conductivity,strong corrosion-resistance,and bifunctional catalytic performance.In this paper,the research progress in TMNs-based material as ORR and OER electrocatalysts for ZABs is discussed with respect to their synthesis,chemical/physical characterization,and performance validation/optimization.The surface/interface nanoengineering strategies such as defect engineering,support binding,heteroatom introduction,crystal plane orientation,interface construction and small size effect,the physical and chemical properties of TMNs-based electrocatalysts are emphasized with respect to their structures/morphologies,composition,electrical conductivity,specific surface area,chemical stability and corrosion resistance.The challenges of TMNs-based materials as bifunctional air-cathode electrocatalysts in practical application are evaluated,and numerous research guidelines to solve these problems are put forward for facilitating further research and development.展开更多
Three transition metal-like facet centered cubic structured transition metal nitrides,γ-Mo_(2)N,β-W_(2)N andδ-NbN,are synthesized and applied in the reaction of CO_(2)hydrogenation to CO.Among the three nitride cat...Three transition metal-like facet centered cubic structured transition metal nitrides,γ-Mo_(2)N,β-W_(2)N andδ-NbN,are synthesized and applied in the reaction of CO_(2)hydrogenation to CO.Among the three nitride catalysts,theγ-Mo_(2)N exhibits superior activity to target product CO,which is 4.6 and 76 times higher than the other two counterparts ofβ-W_(2)N andδ-NbN at 600℃,respectively.Additionally,γ-Mo_(2)N exhibits excellent stability on both cyclic heating-cooling and high space velocity steady state operation.The deactivation degree of cyclic heating-cooling evaluation after 5 cycles and long-term stability performance at 773 and 873 K in 50 h are all less than 10%.In-situ XRD and kinetic studies suggest that theγ-Mo_(2)N itself is able to activate both of the reactants CO_(2)and H_(2).Below 400℃,the reaction mainly occurs at the surface ofγ-Mo_(2)N catalyst.CO_(2)and H_(2)competitively adsorbe on the surface of catalyst and CO_(2)is the relatively stronger surface adsorbate.At a higher temperature,the interstitial vacancies of theγ-Mo_(2)N can be reversibly filled with the oxygen from CO_(2)dissociation.Both of the surface and bulk phase sites ofγ-Mo_(2)N participate in the high temperature CO_(2)hydrogenation pathway.展开更多
Large-scale deployment of Internet of Things (IoT),a revolutionary innovation for a better world,is hampered by the limitation of energy self-sufficiency.Constructing transition metal nitride (TMN)-based micro-superca...Large-scale deployment of Internet of Things (IoT),a revolutionary innovation for a better world,is hampered by the limitation of energy self-sufficiency.Constructing transition metal nitride (TMN)-based micro-supercapacitors is a possible solution by taking advantage of the high conductivity,large specific capacitance,and large tap density of the materials.However,the pseudocapacitive storage mechanism of TMNs is still unclear consequently impeding the design of microdevices.Herein,the functions and mechanism of TMNs with different metal oxynitride (TMNO_(x)) concentrations in pseudocapacitive electrodes are investigated systematically by in situ Raman scattering,ex situ X-ray photoelectron spectroscopy,as well as ion isolation and substitution cyclic voltammetry.It is found that the specific capacitances of TMNs depend on the TMNO_(x) concentrations and the N–M–O site is responsible for the large pseudocapacitance via the Faradic reaction between TMNO_(x) and OH^(-).Our study elucidates the mechanism pertaining to pseudocapacitive charge storage of TMNs and provides insights into the design and optimization of TMNO_(x) as well as other electrode materials for pseudocapacitors.展开更多
Transition metal nitrides(TMNs)are considered as viable alternatives to noble metal catalysts owing to their versatile electronic structure and favorable catalytic performance.However,the conventional synthetic proces...Transition metal nitrides(TMNs)are considered as viable alternatives to noble metal catalysts owing to their versatile electronic structure and favorable catalytic performance.However,the conventional synthetic processes for TMNs suffer from high energy consumption and low production yield.In this study,a range of TMNs and their hetero-composite arrays were successfully synthesized via an ultrafast flash Joule heating technology within 0.5 s.As a proof concept,the nitrides and hetero-composites were applied for the electrocatalytic hydrazine oxidation reaction(HzOR),in which the Co_(4)N/Mo_(16)N_(7)arrays shows the best performance with a geometric current density of 100 mA cm^(-2)at 23 mV(vs.reversible hydrogen electrode(RHE)).This work paves a new way for the ultrafast synthesis of TMNs which could meet the ever-increased energy crisis.展开更多
The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"...The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"volcanic"relationship between the catalytic activity and the adsorption energy of the catalyst to the intermediates is first demonstrated based on the first-principles calculation,which meets the Sabatier principle and can be used to design the cathode catalysts.The increases in the number of nitrogenvacancy in WN shift the d-band center and increase the interaction with the reactants.The catalytic activity increases first and then decreases with the increase of adsorption energy,which was proved in the experiment.The optimal catalyst for moderate adsorption of intermediate makes the thin LiaCO_(3) distribute evenly.It exhibits a median voltage difference of 0.68 V and an energy efficiency of 84.33%at20μA cm^(-2)with a limited capacity of 200μA h cm^(-2).展开更多
Electrocatalytic water splitting provides a potentially sustainable approach for hydrogen production,but is typically restrained by kinetically slow anodic oxygen evolution reaction(OER)which is of lesser value.Here,f...Electrocatalytic water splitting provides a potentially sustainable approach for hydrogen production,but is typically restrained by kinetically slow anodic oxygen evolution reaction(OER)which is of lesser value.Here,free-standing,hetero-structured Ni_(3)N-Ni_(0.2)Mo_(0.8)N nanowire arrays are prepared on carbon cloth(CC)electrodes for hydrogen evolution reaction(HER)and glycerol oxidation reaction(GOR)to formate with a remarkably high Faradaic efficiency of 96%.A two-electrode electrolyzer for GOR-assisted hydrogen production operates with a current density of 10 mA cm^(-2)at an applied cell voltage of 1.40 V,220 mV lower than for alkaline water splitting.In-situ Raman measurements identify Ni(Ⅲ)as the active form of the catalyst for GOR rather than Ni(IV)and in-situ Fourier transform infrared(FTIR)spectroscopy measurements reveal pathways for GOR to formate.From density functional theory(DFT)calculations,the Ni_(3)N-Ni_(0.2)Mo_(0.8)N heterostructure is beneficial for optimizing adsorption energies of reagents and intermediates and for promoting HER and GOR activities by charge redistribution across the heterointerface.The same electrode also catalyzes conversion of ethylene glycol from polyethylene terephthalate(PET)plastic hydrolysate into formate.The combined results show that electrolytic H_(2) and formate production from alkaline glycerol and ethylene glycol solutions provide a promising strategy as a cost-effective energy supply.展开更多
Adsorption and activation of dinitrogen(N_(2)) is an indispensable process in nitrogen fixation.Metal nitride species continue to attract attention as a promsing catalyst for ammonia synthesis.However,the detailed mec...Adsorption and activation of dinitrogen(N_(2)) is an indispensable process in nitrogen fixation.Metal nitride species continue to attract attention as a promsing catalyst for ammonia synthesis.However,the detailed mechanisms at a molecular level between reactive nitride species and N_(2) remain unclear at elevated temperature,which is important to understand the temperature effect and narrow the gap between the gas phase system and condensed phase system.Herein,the ^(15)N/^(14)N isotopic exchange in the reaction between tantalum nitride cluster anions Ta_(3)^(14)N_(3)^(-) and ^(15)N_(2) leading to the regeneration of ^(14)N_(2)/^(14)N^(15)N was observed at elevated temperature(393-593 K)using mass spectrometry.With the aid of theoretical calculations,the exchange mechanism and the effect of temperature to promote the dissociation of N_(2) on Ta_(3)N_(3)^(-) were elucidated.A comparison experiment for Ta_(3)^(14)N_(4)^(-)/^(15)N_(2) couple indicated that only desorption of ^(15)N_(2) from Ta_(3)^(14)N_(4)^(15)N_(2)^(-) took place at elevated temperature.The different exchange behavior can be well understood by the fact that nitrogen vacancy is a requisite for the dinitrogen activation over metal nitride species.This study may shed light on understanding the role of nitrogen vacancy in nitride species for ammonia synthesis and provide clues in designing effective catalysts for nitrogen fixation.展开更多
First principles calculations are preformed to systematically investigate the elastic and thermodynamic properties of Re2N at high pressure and high temperature. The Re2N exhibits a clear elastic anisotropy and the el...First principles calculations are preformed to systematically investigate the elastic and thermodynamic properties of Re2N at high pressure and high temperature. The Re2N exhibits a clear elastic anisotropy and the elastic constants C11 and C33 vary rapidly in comparison with the variations in C12, C13 and C44 at high pressure. In addition, bulk modulus B, elastic modulus E, and shear modulus Gas a function of crystal orientations for Re2N are also investigated for the first time. The tensile directional dependences of the elastic modulus obey the following trend： [0001] [1211] [1010] [1011]EEEE〉〉〉 . The shear moduli of Re2N within the （0001） basal plane are the smallest and greatly reduce the resistance of against large shear deformations. Based on the quasi-harmonic Debye model, the dependences of Debye temperature, Grüneisen parameter, heat capacity and thermal expansion coefficient on the temperature and pressure are explored in the whole pressure range from 0 to 50 GPa and temperature range from 0 to 1600 K.展开更多
With the increasing demand for energy, various emerging energy storage/conversion technologies have gradually penetrated human life, providing numerous conveniences. The practical application efficiency is often affec...With the increasing demand for energy, various emerging energy storage/conversion technologies have gradually penetrated human life, providing numerous conveniences. The practical application efficiency is often affected by the slow kinetics of hydrogen or oxygen electrocatalytic reactions(hydrogen evolution and oxidation reactions, oxygen evolution and reduction reactions) among the emerging devices. Therefore, the researchers devote to finding cost-effective electrocatalysts. Non-noble metal catalysts have low cost and good catalytic activity, but poor stability, agglomeration, dissolution, and other problems will occur after a long cycle, such as transition metal oxides and carbides. Transition metal nitrides(TMNs) stand out among all kinds of non-noble metal catalysts because of the intrinsic platinum-like electrocatalytic activities, relatively high conductivity, and wide range of tunability. In this review, the applications of TMNs in electrocatalytic fields are summarized based on the number of metals contained in TMNs. The practical application potentials of TMNs in fuel cell, water splitting, zinc-air battery and other electrochemical energy storage/conversion devices are also listed. Finally, the design strategies and viewpoints of TMNs-based electrocatalyst are summarized. The potential challenges of TMNs-based electrocatalyst in the development of electrocatalytic energy devices in the future are prospected.展开更多
Transition metal nitrides have been suggested to have both high hardness and good thermal stability with large potential application value, but so far stable superhard transition metal nitrides have not been synthesiz...Transition metal nitrides have been suggested to have both high hardness and good thermal stability with large potential application value, but so far stable superhard transition metal nitrides have not been synthesized. Here, with our newly developed machine-learning accelerated crystal structure searching method, we designed a superhard tungsten nitride, h-WN6, which can be synthesized at pressure around 65 GPa and quenchable to ambient pressure. This h-WN6 is constructed with single-bonded armchair-like N6 rings and presents ionic-like features, which can be formulated as W^2.4＋N^2.4-. It has a band gap of 1.6 eV at 0GPa and exhibits an abnormal gap broadening behavior under pressure. Excitingly, this h-WN6 is found to be the hardest among transition metal nitrides known so far （Vickers hardness around 57 GPa） and also has a very high melting temperature （around 1,900 K）. Additionally, the good gravimet- ric （3.1 kJ/g/and volumetric （28.0 kJ/cm3） energy densities make this nitrogen-rich compound a potential high-energy-density material, These predictions support the designing rules and may stimulate future experiments to synthesize superhard and high-energy-density material.展开更多
Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion effici...Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion efficiency,the smart design of efficient catalysts by the right combination of semiconductor light harvesters and cocatalyst is highly required.Herein,we report a composite photocatalyst composed of noble metal-free transition metal nitride Ni_(3)FeN decorated on 2D ultrathin ZnIn_(2)S_(4)(ZIS)nanosheets for selective oxidation of aromatic alcohols to aldehydes pairing with H_(2)production.In the composite,ultrathin ZIS serves as a light harvester that greatly shortens the diffusion length of photogenerated charges,while the metallic nitride Ni_(3)FeN acts as an advanced cocatalyst which not only captures the photoelectrons generated from the ultrathin ZIS to promote the charge separation,but also provides active sites to lower the overpotential and accelerate the H_(2)reduction.The best photocatalytic performance is found on ZIS/1.5%M-Ni_(3)FeN,which shows a H_(2)generation rate of 2427.9μmol g^(^(-1))h^(-1)and a benzaldehyde(BAD)production rate of 2460μmol g^(-1)h^(-1),about 7.8-fold as high as that of bare ZIS.This work is anticipated to endorse the exploration of transition metal nitrides as high-performance cocatalysts to promote the coupled photocatalytic organic transformation and H_(2)production.展开更多
Titanium-aluminum-nitride（TiAlN） films were grown by plasma-enhanced atomic layer deposition（PEALD）on 316 L stainless steel at a deposition temperature of 200 °C. A supercycle, consisting of one AlN and ten T...Titanium-aluminum-nitride（TiAlN） films were grown by plasma-enhanced atomic layer deposition（PEALD）on 316 L stainless steel at a deposition temperature of 200 °C. A supercycle, consisting of one AlN and ten TiN subcycles, was used to prepare TiAlN films with a chemical composition of Ti（0.25）Al（0.25）N（0.50）. The addition of AlN to TiN resulted in an increased electrical resistivity of TiAlN films of 2800 μΩ cm, compared with 475 μΩ cm of TiN films, mainly due to the high electrical resistivity of AlN and the amorphous structure of TiAlN. However, potentiostatic polarization measurements showed that amorphous TiAlN films exhibited excellent corrosion resistance with a corrosion current density of 0.12 μA/cm^2, about three times higher than that of TiN films, and about 12.5 times higher than that of 316 L stainless steel.展开更多
Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N h...Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method.The heterogeneous interface between NiCo and Mo_(2)N induces electron redistribution,regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates.Consequently,NiCo–Mo_(2)N/NF exhibits superior catalytic activity with a potential of 1.14 V_(RHE)/−17 mV_(RHE)(HMFOR/HER)at±10 mA cm^(−2),and the HMF conversion rate,FDCA yield,and Faradaic efficiency(FE)are∼100%,99.98%,and 98.65%,respectively.Besides,it only requires a low voltage of 1.36 V to achieve 100 mA cm^(−2)for HMFOR-assisted H2 production.This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.展开更多
Ni-based transition metal nitrides(TMNs)have been regarded as promising substitutes for noble-metal electrocatalysts towards the hydrogen evolution reaction(HER)due to their low cost,excellent chemical stability,high ...Ni-based transition metal nitrides(TMNs)have been regarded as promising substitutes for noble-metal electrocatalysts towards the hydrogen evolution reaction(HER)due to their low cost,excellent chemical stability,high electronic conductivity,and unique electronic structure.However,facile green synthesis and rational microstructure design of Ni-based TMNs electrocatalysts with high HER activity remain challenging.In this work,we report the fabrication of Ni/Ni_(3)N heterostructure nanoarrays on carbon paper via a one-step magnetron sputtering method under low temperature and N2 atmosphere.The Ni/Ni_(3)N hierarchical nanoarrays exhibit an excellent HER catalytic activity with a low overpotential of 37 mV at 10 mA·cm^(−2)and robust long-term durability over 100 h.Furthermore,the Ni/Ni_(3)N||NiFeOH(NiFeOH=NiFe bimetallic hydroxide)electrolyzer requires a small voltage of 1.54 V to obtain 10 mA·cm^(−2)for water electrolysis.Density functional theory(DFT)calculations reveal that the heterointerface between Ni and Ni_(3)N could directly induce electron redistribution to optimize the electronic structure,which accelerates the dissociation of water molecules and the subsequent hydrogen desorption,and thus boosting the HER kinetics.展开更多
As a new type of two-dimensional material,MXene’s unique layered structure,outstanding electrical conductivity,low density,tunable surface chemistry,and solution processability make it receive extensive attention in ...As a new type of two-dimensional material,MXene’s unique layered structure,outstanding electrical conductivity,low density,tunable surface chemistry,and solution processability make it receive extensive attention in various fields,especially for the lightweight shielding mate rials since the report on electromagnetic interference(EMI) shielding of 2D Ti3 C2 Tx in 2016.In this review,the progress on the MXe nes material including their synthetic strategies,prope rties and EMI application is highlighted.First,the recent advance on the different synthesis methods and properties of MXene is summarized.According to their intrinsic characteristics,the application of MXene in EMI fields is then discussed.Finally,the challenges and perspective on the future development of MXene in low-cost preparation and practical application are proposed.展开更多
基金support offered by National Natural Science Foundation of China(NSFC,Grant No.21403091)。
文摘Transition metal nitrides(TMN)have recently grabbed immensely appealing as ideal active materials in energy storage and catalysis fields on account of their remarkable electrical conductivity,excellent chemical stability,wide band gap and tunable morphology.Both pure TMN and TMN-based materials have been extensively studied concerned with their preparation approaches,nanostructures,and favored performance in various applications.However,the processes towards synthesis of TMN are numerous and complex.Choosing appropriate method to obtain target TMN with desired structure is crucial,which further affects its practical application performance.Herein,this review offers a timely and comprehensive summary of the synthetic ways to TMN and their application in energy related domains.The synthesis section is categorized into in-situ and ex-situ based on where the N element in TMN origins from.Then,overviews on the energy related applications including energy storage,electrocatalysis and photocatalysis are discussed.In the end,the problems to be solved and the development trend of the synthesis and application of transition metal nitrides are prospected.
基金financially supported by the National Key R&D Program of China(2022YFA1503003)the National Natural Science Foundation of China(91961111,22271081)+3 种基金the Natural Science Foundation of Heilongjiang Province(ZD2021B003)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2020004)The Basic Research Fund of Heilongjiang University in Heilongjiang Province(2021-KYYWF-0039)the Heilongjiang University Excellent Youth Foundation。
文摘Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.
基金Project(51274248) supported by the National Natural Science Foundation of ChinaProjects(2015DFR50580,2013DFA31440) supported by the International Scientific and Technological Cooperation Projects of China
文摘Faraday pseudocapacitors take both advantages of secondary battery with high energy density and supercapacitors with high power density,and electrode material is the key to determine the performance of Faraday pseudocapacitors.Transition metal oxides and nitrides,as the two main kinds of pseudocapacitor electrode materials,can enhance energy density while maintaining high power capability.Recent advances in designing nanostructured architectures and preparing composites with high specific surface areas based on transition metal oxides and nitrides,including ruthenium oxides,nickel oxides,manganese oxides,vanadium oxides,cobalt oxides,iridium oxides,titanium nitrides,vanadium nitrides,molybdenum nitrides and niobium nitrides,are addressed,which would provide important significances for deep researches on pseudocapacitor electrode materials.
基金the National Natural Science Foundation of China(Nos.51702137,51802128)the Natural Science Foundation of Jiangsu Province,China(No.BK20181013)+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutions,China(No.18KJB430013)the Foundation of State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering,China(No.2020-KF-20).
文摘A series of transition metal nitrides(MxNy,M=Fe,Co,Ni)nanoparticle(NP)composites caged in N-doped hollow porous carbon sphere(NHPCS)were prepared by impregnation and heat treatment methods.These composites combine the high catalytic activity of nitrides and the high-efficiency mass transfer characteristics of NHPCS.The oxygen reduction reaction results indicate that Fe2N/NHPCS has the synergistic catalytic performance of higher onset potential(0.96 V),higher electron transfer number(~4)and higher limited current density(1.4 times as high as that of commercial Pt/C).In addition,this material is implemented as the air catalyst for zinc−air battery that exhibits considerable specific capacity(795.1 mA·h/g)comparable to that of Pt/C,higher durability and maximum power density(173.1 mW/cm2).
基金financial support from the National Key Research and Development Program of China(2017YFB0102900)
文摘Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunctional electrocatalysts for air-cathode oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes,the practical application of rechargeable ZABs is seriously hindered.In the effort of developing high active,stable and cost-effective electrocatalysts,transition metal nitrides(TMNs)have been regarded as the candidates due to their high conductivity,strong corrosion-resistance,and bifunctional catalytic performance.In this paper,the research progress in TMNs-based material as ORR and OER electrocatalysts for ZABs is discussed with respect to their synthesis,chemical/physical characterization,and performance validation/optimization.The surface/interface nanoengineering strategies such as defect engineering,support binding,heteroatom introduction,crystal plane orientation,interface construction and small size effect,the physical and chemical properties of TMNs-based electrocatalysts are emphasized with respect to their structures/morphologies,composition,electrical conductivity,specific surface area,chemical stability and corrosion resistance.The challenges of TMNs-based materials as bifunctional air-cathode electrocatalysts in practical application are evaluated,and numerous research guidelines to solve these problems are put forward for facilitating further research and development.
基金financially supported by the National Natural Science Foundation of China(22002140)Zhejiang Provincial Natural Science Foundation of China(LR21B030001 and LR22b030003)+1 种基金Young Elite Scientist Sponsorship Program by CAST(No.2019QNRC001)Use of the Advanced Photon Source(beamlines 17-BM,for in-situ XRD characterization)was supported by the U.S.DOE under contract no.DE-AC02-06CH11357。
文摘Three transition metal-like facet centered cubic structured transition metal nitrides,γ-Mo_(2)N,β-W_(2)N andδ-NbN,are synthesized and applied in the reaction of CO_(2)hydrogenation to CO.Among the three nitride catalysts,theγ-Mo_(2)N exhibits superior activity to target product CO,which is 4.6 and 76 times higher than the other two counterparts ofβ-W_(2)N andδ-NbN at 600℃,respectively.Additionally,γ-Mo_(2)N exhibits excellent stability on both cyclic heating-cooling and high space velocity steady state operation.The deactivation degree of cyclic heating-cooling evaluation after 5 cycles and long-term stability performance at 773 and 873 K in 50 h are all less than 10%.In-situ XRD and kinetic studies suggest that theγ-Mo_(2)N itself is able to activate both of the reactants CO_(2)and H_(2).Below 400℃,the reaction mainly occurs at the surface ofγ-Mo_(2)N catalyst.CO_(2)and H_(2)competitively adsorbe on the surface of catalyst and CO_(2)is the relatively stronger surface adsorbate.At a higher temperature,the interstitial vacancies of theγ-Mo_(2)N can be reversibly filled with the oxygen from CO_(2)dissociation.Both of the surface and bulk phase sites ofγ-Mo_(2)N participate in the high temperature CO_(2)hydrogenation pathway.
基金financially supported by the Hong Kong Scholars Program (XJ2018009)the City University of Hong Kong Strategic Research Grant (SRG) (7005505)+3 种基金the Shenzhen – Hong Kong Innovative Collaborative Research and Development Program (SGLH20181109110802117 and CityU 9240014)the National Natural Science Foundation of China(U2004210, 21875080, 51572100 and 52003129)the Innovative Research Group Project of the Natural Science Foundation of Hubei Province (2019CFA020)the Shandong Provincial Natural Science Foundation (ZR2019BB006)。
文摘Large-scale deployment of Internet of Things (IoT),a revolutionary innovation for a better world,is hampered by the limitation of energy self-sufficiency.Constructing transition metal nitride (TMN)-based micro-supercapacitors is a possible solution by taking advantage of the high conductivity,large specific capacitance,and large tap density of the materials.However,the pseudocapacitive storage mechanism of TMNs is still unclear consequently impeding the design of microdevices.Herein,the functions and mechanism of TMNs with different metal oxynitride (TMNO_(x)) concentrations in pseudocapacitive electrodes are investigated systematically by in situ Raman scattering,ex situ X-ray photoelectron spectroscopy,as well as ion isolation and substitution cyclic voltammetry.It is found that the specific capacitances of TMNs depend on the TMNO_(x) concentrations and the N–M–O site is responsible for the large pseudocapacitance via the Faradic reaction between TMNO_(x) and OH^(-).Our study elucidates the mechanism pertaining to pseudocapacitive charge storage of TMNs and provides insights into the design and optimization of TMNO_(x) as well as other electrode materials for pseudocapacitors.
基金supported by the National Natural Science Foundation of China(22375001)the Natural Science Foundation of Anhui Province(2208085Y03,2208085QB30)+2 种基金the University Synergy Innovation Program of Anhui Province(GXXT-2023-036)the Key Scientific Research Foundation of the Education Department of Anhui Province(2023AH050113)the Start-up Grant from Anhui University。
文摘Transition metal nitrides(TMNs)are considered as viable alternatives to noble metal catalysts owing to their versatile electronic structure and favorable catalytic performance.However,the conventional synthetic processes for TMNs suffer from high energy consumption and low production yield.In this study,a range of TMNs and their hetero-composite arrays were successfully synthesized via an ultrafast flash Joule heating technology within 0.5 s.As a proof concept,the nitrides and hetero-composites were applied for the electrocatalytic hydrazine oxidation reaction(HzOR),in which the Co_(4)N/Mo_(16)N_(7)arrays shows the best performance with a geometric current density of 100 mA cm^(-2)at 23 mV(vs.reversible hydrogen electrode(RHE)).This work paves a new way for the ultrafast synthesis of TMNs which could meet the ever-increased energy crisis.
基金supported by the National Natural Science Foundation of China (51972225)。
文摘The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"volcanic"relationship between the catalytic activity and the adsorption energy of the catalyst to the intermediates is first demonstrated based on the first-principles calculation,which meets the Sabatier principle and can be used to design the cathode catalysts.The increases in the number of nitrogenvacancy in WN shift the d-band center and increase the interaction with the reactants.The catalytic activity increases first and then decreases with the increase of adsorption energy,which was proved in the experiment.The optimal catalyst for moderate adsorption of intermediate makes the thin LiaCO_(3) distribute evenly.It exhibits a median voltage difference of 0.68 V and an energy efficiency of 84.33%at20μA cm^(-2)with a limited capacity of 200μA h cm^(-2).
基金supported by the National Natural Science Foundation of China(22072107,21872105)the Science&Technology Commission of Shanghai Municipality(19DZ2271500)the Fundamental Research Funds for the Central Universities。
文摘Electrocatalytic water splitting provides a potentially sustainable approach for hydrogen production,but is typically restrained by kinetically slow anodic oxygen evolution reaction(OER)which is of lesser value.Here,free-standing,hetero-structured Ni_(3)N-Ni_(0.2)Mo_(0.8)N nanowire arrays are prepared on carbon cloth(CC)electrodes for hydrogen evolution reaction(HER)and glycerol oxidation reaction(GOR)to formate with a remarkably high Faradaic efficiency of 96%.A two-electrode electrolyzer for GOR-assisted hydrogen production operates with a current density of 10 mA cm^(-2)at an applied cell voltage of 1.40 V,220 mV lower than for alkaline water splitting.In-situ Raman measurements identify Ni(Ⅲ)as the active form of the catalyst for GOR rather than Ni(IV)and in-situ Fourier transform infrared(FTIR)spectroscopy measurements reveal pathways for GOR to formate.From density functional theory(DFT)calculations,the Ni_(3)N-Ni_(0.2)Mo_(0.8)N heterostructure is beneficial for optimizing adsorption energies of reagents and intermediates and for promoting HER and GOR activities by charge redistribution across the heterointerface.The same electrode also catalyzes conversion of ethylene glycol from polyethylene terephthalate(PET)plastic hydrolysate into formate.The combined results show that electrolytic H_(2) and formate production from alkaline glycerol and ethylene glycol solutions provide a promising strategy as a cost-effective energy supply.
基金supported by the National Natural Science Foundation of China(No.21973101 and No.21833011)the Youth Innovation Promotion Association CAS(No.2020034)the K.C.Wong Education Foundation。
文摘Adsorption and activation of dinitrogen(N_(2)) is an indispensable process in nitrogen fixation.Metal nitride species continue to attract attention as a promsing catalyst for ammonia synthesis.However,the detailed mechanisms at a molecular level between reactive nitride species and N_(2) remain unclear at elevated temperature,which is important to understand the temperature effect and narrow the gap between the gas phase system and condensed phase system.Herein,the ^(15)N/^(14)N isotopic exchange in the reaction between tantalum nitride cluster anions Ta_(3)^(14)N_(3)^(-) and ^(15)N_(2) leading to the regeneration of ^(14)N_(2)/^(14)N^(15)N was observed at elevated temperature(393-593 K)using mass spectrometry.With the aid of theoretical calculations,the exchange mechanism and the effect of temperature to promote the dissociation of N_(2) on Ta_(3)N_(3)^(-) were elucidated.A comparison experiment for Ta_(3)^(14)N_(4)^(-)/^(15)N_(2) couple indicated that only desorption of ^(15)N_(2) from Ta_(3)^(14)N_(4)^(15)N_(2)^(-) took place at elevated temperature.The different exchange behavior can be well understood by the fact that nitrogen vacancy is a requisite for the dinitrogen activation over metal nitride species.This study may shed light on understanding the role of nitrogen vacancy in nitride species for ammonia synthesis and provide clues in designing effective catalysts for nitrogen fixation.
基金Project (11204007) supported by the National Natural Science Foundation of ChinaProject (2012JQ1005) supported by Natural Science Basic Research Plan of Shaanxi Province,ChinaProject (2013JK0638) supported by the Education Committee Natural Science Foundation of Shaanxi Province,China
文摘First principles calculations are preformed to systematically investigate the elastic and thermodynamic properties of Re2N at high pressure and high temperature. The Re2N exhibits a clear elastic anisotropy and the elastic constants C11 and C33 vary rapidly in comparison with the variations in C12, C13 and C44 at high pressure. In addition, bulk modulus B, elastic modulus E, and shear modulus Gas a function of crystal orientations for Re2N are also investigated for the first time. The tensile directional dependences of the elastic modulus obey the following trend： [0001] [1211] [1010] [1011]EEEE〉〉〉 . The shear moduli of Re2N within the （0001） basal plane are the smallest and greatly reduce the resistance of against large shear deformations. Based on the quasi-harmonic Debye model, the dependences of Debye temperature, Grüneisen parameter, heat capacity and thermal expansion coefficient on the temperature and pressure are explored in the whole pressure range from 0 to 50 GPa and temperature range from 0 to 1600 K.
基金supported by the Natural Science Foundation of Jiangsu Province (No. BK20191430)Six Talent Peaks Project in Jiangsu Province (No. XNY-009)+2 种基金High-tech Research Key Laboratory of Zhenjiang (No. SS2018002)Jiangsu Province Key Laboratory of Intelligent Building Energy Efficiency (No. BEE201904)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘With the increasing demand for energy, various emerging energy storage/conversion technologies have gradually penetrated human life, providing numerous conveniences. The practical application efficiency is often affected by the slow kinetics of hydrogen or oxygen electrocatalytic reactions(hydrogen evolution and oxidation reactions, oxygen evolution and reduction reactions) among the emerging devices. Therefore, the researchers devote to finding cost-effective electrocatalysts. Non-noble metal catalysts have low cost and good catalytic activity, but poor stability, agglomeration, dissolution, and other problems will occur after a long cycle, such as transition metal oxides and carbides. Transition metal nitrides(TMNs) stand out among all kinds of non-noble metal catalysts because of the intrinsic platinum-like electrocatalytic activities, relatively high conductivity, and wide range of tunability. In this review, the applications of TMNs in electrocatalytic fields are summarized based on the number of metals contained in TMNs. The practical application potentials of TMNs in fuel cell, water splitting, zinc-air battery and other electrochemical energy storage/conversion devices are also listed. Finally, the design strategies and viewpoints of TMNs-based electrocatalyst are summarized. The potential challenges of TMNs-based electrocatalyst in the development of electrocatalytic energy devices in the future are prospected.
基金financially supported by the Ministry of Science and Technology of the People’s Republic of China (2016YFA0300404 and 2015CB921202)the National Natural Science Foundation of China (51372112 and 11574133)+2 种基金the NSF of Jiangsu Province (BK20150012)the Fundamental Research Funds for the Central Universities,the Science Challenge Project (TZ2016001)Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) under Grant No.U1501501
文摘Transition metal nitrides have been suggested to have both high hardness and good thermal stability with large potential application value, but so far stable superhard transition metal nitrides have not been synthesized. Here, with our newly developed machine-learning accelerated crystal structure searching method, we designed a superhard tungsten nitride, h-WN6, which can be synthesized at pressure around 65 GPa and quenchable to ambient pressure. This h-WN6 is constructed with single-bonded armchair-like N6 rings and presents ionic-like features, which can be formulated as W^2.4＋N^2.4-. It has a band gap of 1.6 eV at 0GPa and exhibits an abnormal gap broadening behavior under pressure. Excitingly, this h-WN6 is found to be the hardest among transition metal nitrides known so far （Vickers hardness around 57 GPa） and also has a very high melting temperature （around 1,900 K）. Additionally, the good gravimet- ric （3.1 kJ/g/and volumetric （28.0 kJ/cm3） energy densities make this nitrogen-rich compound a potential high-energy-density material, These predictions support the designing rules and may stimulate future experiments to synthesize superhard and high-energy-density material.
基金National Natural Science Foundation of China(21905049 and 22178057)Natural Science Foundation of Fujian Province(2020J01201 and 2021J01197)Award Program for Minjiang Scholar Professorship.S.Liu thanks the support from the Fundamental Research Funds for the Central Universities(Grant No.DUT21RC(3)114).
文摘Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion efficiency,the smart design of efficient catalysts by the right combination of semiconductor light harvesters and cocatalyst is highly required.Herein,we report a composite photocatalyst composed of noble metal-free transition metal nitride Ni_(3)FeN decorated on 2D ultrathin ZnIn_(2)S_(4)(ZIS)nanosheets for selective oxidation of aromatic alcohols to aldehydes pairing with H_(2)production.In the composite,ultrathin ZIS serves as a light harvester that greatly shortens the diffusion length of photogenerated charges,while the metallic nitride Ni_(3)FeN acts as an advanced cocatalyst which not only captures the photoelectrons generated from the ultrathin ZIS to promote the charge separation,but also provides active sites to lower the overpotential and accelerate the H_(2)reduction.The best photocatalytic performance is found on ZIS/1.5%M-Ni_(3)FeN,which shows a H_(2)generation rate of 2427.9μmol g^(^(-1))h^(-1)and a benzaldehyde(BAD)production rate of 2460μmol g^(-1)h^(-1),about 7.8-fold as high as that of bare ZIS.This work is anticipated to endorse the exploration of transition metal nitrides as high-performance cocatalysts to promote the coupled photocatalytic organic transformation and H_(2)production.
基金supported by the Global Frontier R&D Program (2013M3A6B1078874) on Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, ICT & Future Planning, Republic of Koreasupported by a grant from the Industrial R&D Program for Core Technology of Materials funded by the Ministry of Industry and Energy (10060331), Republic of Korea
文摘Titanium-aluminum-nitride（TiAlN） films were grown by plasma-enhanced atomic layer deposition（PEALD）on 316 L stainless steel at a deposition temperature of 200 °C. A supercycle, consisting of one AlN and ten TiN subcycles, was used to prepare TiAlN films with a chemical composition of Ti（0.25）Al（0.25）N（0.50）. The addition of AlN to TiN resulted in an increased electrical resistivity of TiAlN films of 2800 μΩ cm, compared with 475 μΩ cm of TiN films, mainly due to the high electrical resistivity of AlN and the amorphous structure of TiAlN. However, potentiostatic polarization measurements showed that amorphous TiAlN films exhibited excellent corrosion resistance with a corrosion current density of 0.12 μA/cm^2, about three times higher than that of TiN films, and about 12.5 times higher than that of 316 L stainless steel.
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011).
文摘Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction(HMFOR)and hydrogen evolution reaction(HER)is meaningful but remains a challenge.Herein,the NiCo–Mo_(2)N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method.The heterogeneous interface between NiCo and Mo_(2)N induces electron redistribution,regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates.Consequently,NiCo–Mo_(2)N/NF exhibits superior catalytic activity with a potential of 1.14 V_(RHE)/−17 mV_(RHE)(HMFOR/HER)at±10 mA cm^(−2),and the HMF conversion rate,FDCA yield,and Faradaic efficiency(FE)are∼100%,99.98%,and 98.65%,respectively.Besides,it only requires a low voltage of 1.36 V to achieve 100 mA cm^(−2)for HMFOR-assisted H2 production.This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.
基金supported by the National Natural Science Foundation of China(Nos.51601163,22001081,and 22075236)the Natural Science Foundation of Fujian Province(No.2021J011211)+1 种基金the Xiamen Municipal Bureau of Science and Technology(No.3502Z20206070)the Open Fund of Fujian Provincial Key Laboratory of Functional Materials and Applications(No.fma2018012),and Xiamen University.
文摘Ni-based transition metal nitrides(TMNs)have been regarded as promising substitutes for noble-metal electrocatalysts towards the hydrogen evolution reaction(HER)due to their low cost,excellent chemical stability,high electronic conductivity,and unique electronic structure.However,facile green synthesis and rational microstructure design of Ni-based TMNs electrocatalysts with high HER activity remain challenging.In this work,we report the fabrication of Ni/Ni_(3)N heterostructure nanoarrays on carbon paper via a one-step magnetron sputtering method under low temperature and N2 atmosphere.The Ni/Ni_(3)N hierarchical nanoarrays exhibit an excellent HER catalytic activity with a low overpotential of 37 mV at 10 mA·cm^(−2)and robust long-term durability over 100 h.Furthermore,the Ni/Ni_(3)N||NiFeOH(NiFeOH=NiFe bimetallic hydroxide)electrolyzer requires a small voltage of 1.54 V to obtain 10 mA·cm^(−2)for water electrolysis.Density functional theory(DFT)calculations reveal that the heterointerface between Ni and Ni_(3)N could directly induce electron redistribution to optimize the electronic structure,which accelerates the dissociation of water molecules and the subsequent hydrogen desorption,and thus boosting the HER kinetics.
文摘As a new type of two-dimensional material,MXene’s unique layered structure,outstanding electrical conductivity,low density,tunable surface chemistry,and solution processability make it receive extensive attention in various fields,especially for the lightweight shielding mate rials since the report on electromagnetic interference(EMI) shielding of 2D Ti3 C2 Tx in 2016.In this review,the progress on the MXe nes material including their synthetic strategies,prope rties and EMI application is highlighted.First,the recent advance on the different synthesis methods and properties of MXene is summarized.According to their intrinsic characteristics,the application of MXene in EMI fields is then discussed.Finally,the challenges and perspective on the future development of MXene in low-cost preparation and practical application are proposed.
