The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous elec...The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.展开更多
Electrochemical production of hydrogen from water requires the development ofelectrocatalysts that are active,stable,and low-cost for water splitting.To address these challenges,researchers are increasingly exploring ...Electrochemical production of hydrogen from water requires the development ofelectrocatalysts that are active,stable,and low-cost for water splitting.To address these challenges,researchers are increasingly exploring binder-free electrocatalytic integratedelectrodes (IEs) as an alternative to conventional powder-based electrode preparation methods,for the former is highly desirable to improve the catalytic activity and long-term stability for large-scale applications of electrocatalysts.Herein,we demonstrate a laser-inducedhydrothermal reaction (LIHR) technique to grow NiMoO4nanosheets on nickel foam,which is then calcined under H2/Ar mixed gases to prepare the IE IE-NiMo-LR.This electrode exhibits superior hydrogen evolution reaction performance,requiring overpotentials of 59,116 and143 mV to achieve current densities of 100,500 and 1000 mA·cm-2.During the 350 h chronopotentiometry test at current densities of 100 and 500 m A·cm-2,the overpotentialremains essentially unchanged.In addition,NiFe-layered double hydroxide grown on Ni foam is also fabricated with the same LIHR method and coupled with IE-NiMo-IR to achieve water splitting.This combination exhibits excellent durability under industrial current density.The energy consumption and production efficiency of the LIHR method are systematicallycompared with the conventional hydrothermal method.The LIHR method significantly improves the production rate by over 19 times,while consuming only 27.78%of the total energy required by conventional hydrothermal methods to achieve the same production.展开更多
To maximize the catalytic performance of MoS_(2) in the hydrogen evolution reaction,we investigate the electrocatalytic and photocatalytic performance of monolayer MoS_(2) doped with noble metal(Ag,Au,Cu,Pd,and Pt)usi...To maximize the catalytic performance of MoS_(2) in the hydrogen evolution reaction,we investigate the electrocatalytic and photocatalytic performance of monolayer MoS_(2) doped with noble metal(Ag,Au,Cu,Pd,and Pt)using first principles calculation combined with the climbing image nudged elastic band method.We find the band gap of the monolayer MoS_(2) is reduced significantly by the noble metal doping,which is unfavorable to improving its photocatalytic performance.The optical absorption coefficient shows that the doping does not increase the ability of the monolayer MoS_(2) to absorb visible light.The monolayer MoS_(2) doped with the noble metal is not a potential photocatalyst for the hydrogen evolution reaction because the band edge position of the conduction band minimum is lower than-4.44 eV,the reduction potential of H^(+)/H_(2).Fortunately,the band gap reduction increases the electron transport performance of the monolayer MoS_(2),and the activation energy of water splitting is greatly reduced by the noble metal doping,especially the Pt doping.On the whole,noble metal doping can enhance the electrocatalytic performance of the monolayer MoS_(2).展开更多
Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was pr...Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was prepared by solvothermal method,and then used as precursor to prepare NiFe-based MOF-derived materials by pyrolysis.The effects of different metal ratios and pyrolysis temperatures on the sample structure and OER electrocatalytic performance were investigated and compared.The experimental results showed that when the metal molar ratio was Fe:Ni=1:5 and the pyrolysis temperature was 450℃,the sample(FeNi_(5)-MOF-450)exhibits a composite structure of Ni Fe_(2)O_(4)/FeNi_(3)/C and owns the superior electrocatalytic activity in OER.When the current density is 100 mA·cm^(-2),the overpotential of the sample was 377 mV with Tafel slope of 56.2 mV·dec^(-1),which indicates that FeNi_(5)-MOF-450 exhibits superior electrocatalytic performance than the commercial RuO_(2).Moreover,the long-term stability of FeNi_(5)-MOF-450 further promotes its development in OER.This work demonstrated that the regulatory methods such as component optimization can effectively improve the OER catalytic performance of NiFe-based MOF-derived materials.展开更多
Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via el...Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.展开更多
The investigation of highly effective,durable,and cost-effective electrocatalysts for the hydrogen evolution reaction(HER)is a prerequisite for the upcoming hydrogen energy society.To establish a new hydrogen energy s...The investigation of highly effective,durable,and cost-effective electrocatalysts for the hydrogen evolution reaction(HER)is a prerequisite for the upcoming hydrogen energy society.To establish a new hydrogen energy system and gradually replace the traditional fossil-based energy,electrochemical water-splitting is considered the most promising,environmentally friendly,and efficient way to produce pure hydrogen.Compared with the commonly used platinum(Pt)-based catalysts,ruthenium(Ru)is expected to be a good alternative because of its similar hydrogen bonding energy,lower water decomposition barrier,and considerably lower price.Analyzing and revealing the HER mechanisms,as well as identifying a rational design of Ru-based HER catalysts with desirable activity and stability is indispensable.In this review,the research progress on HER electrocatalysts and the relevant describing parameters for HER performance are briefly introduced.Moreover,four major strategies to improve the performance of Ru-based electrocatalysts,including electronic effect modulation,support engineering,structure design,and maximum utilization(single atom)are discussed.Finally,the challenges,solutions and prospects are highlighted to prompt the practical applications of Rubased electrocatalysts for HER.展开更多
Molybdenum carbide(MO_(2)C)materials are promising electrocatalysts with potential applications in hydrogen evolution reaction(HER)due to low cost and Pt-like electronic structures.Nevertheless,their HER activity is u...Molybdenum carbide(MO_(2)C)materials are promising electrocatalysts with potential applications in hydrogen evolution reaction(HER)due to low cost and Pt-like electronic structures.Nevertheless,their HER activity is usually hindered by the strong hydrogen binding energy.Moreover,the lack of water-cleaving site's makes it difficult for the catalysts to work in alkaline solutions.Here,we designed and synthesized a B and N dual-doped carbon layer that encapsulated on MO_(2)C nanocrystals(MO_(2)C@BNC)for accelerating HER under alkaline condition.The electronic interactions between the MO_(2)C nanocrystals and the multiple-doped carbon layer endow a near-zero H adsorption Gibbs free energy on the defective C atoms over the carbon shell.Meanwhile,the introduced B atoms afford optimal H_2O adsorption sites for the water-cleaving step.Accordingly,the dual-doped MO_(2)C catalyst with synergistic effect of non-metal sites delivers superior HER performances of a low overpotential(99 mV@10 mA cm^(-2))and a small Tafel slope(58.1 mV dec^(-1))in 1 M KOH solution.Furthermore,it presents a remarkable activity that outperforming the commercial 10%Pt/C catalyst at large current density,demonstrating its applicability in industrial water splitting.This study provides a reasonable design strategy towards noble-metal-free HER catalysts with high activity.展开更多
The perovskite transition metal oxide(TMO) has been considered in electrocatalysis for the modern clean energy technologies as its high electrochemical activity and low cost. The atomic scale engineering to the local ...The perovskite transition metal oxide(TMO) has been considered in electrocatalysis for the modern clean energy technologies as its high electrochemical activity and low cost. The atomic scale engineering to the local stoichiometry of single crystal TMO provides a clue of the relation between electronic structure and catalytic performance. Here we report a hydrogen evolution reaction(HER) activity enhancement ~ 1761% of Bi_(0.85)Sr_(0.15)FeO_3 compared to the pure BiFeO_3. By the systemic investigation of the Sr doping level of Bi_(1-x)Sr_xFeO_3(BSFO), it is found that the HER enhancement originates from the improvement of ferromagnetism of BSFO without obvious scarification of the ferroelectricity at the room temperature. The multiple ferroic orderings in BSFO are beneficial for HER activity, which offers the strengthen of hybridization of Fe 3d and O2 p orbitals from the view of ferromagnetism, and the assistance of electron drift by spontaneous electric polarization. Our study not only affords the strategy of developing multiple ferroic orderings in TMO, but also facilitates the atomic scale understanding of the improved HER activity.展开更多
Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to...Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.展开更多
Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.P...Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.Polyoxometalates(POMs)with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts.Herein,a series of transition metal-doped MoS_(2)materials with different surface engineered structures(Fe,Cr,V doping and S vacancies)(M-MoS_(2)/CC,M=Fe,Cr and V)were fabricated by a simple hydrothermalvulcanization strategy using Keplerate polyoxomolybdate nanoball({Mo_(72)Fe_(30)},{Mo_(72)Cr_(30)},{Mo_(72)V_(30)},{Mo_(132)})as precursors.The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS_(2)/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media.The optimized Fe-MoS_(2)/CC afford current densities of 10 and 50 mA/cm^(2)at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH aqueous solution,respectively,outperforming most of reported typical transition metal sulfide-based catalysts.This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.展开更多
The rational design of the catalysts with easily-accessible surface and high intrinsic activity is desirable for electrocatalytic hydrogen evolution reaction(HER).Here,we reported the construction of two-dimensional(2...The rational design of the catalysts with easily-accessible surface and high intrinsic activity is desirable for electrocatalytic hydrogen evolution reaction(HER).Here,we reported the construction of two-dimensional(2D)Co-Mo nitrides based heterojunctional catalyst for efficient HER based on a“mediated molecular”assisted route.The 2D Co(OH)_(2)sheet reacted partially with the“mediated molecular”(2-methylimidazole(2-MIM))to form zeolitic imidazolate framework(ZIF)-67 at surface,giving ZIF-67/Co(OH)_(2)sheets.The ZIF-67 combines with[PMo_(12)O_(40)]^(3−)cluster(PMo_(12))due to the interaction of mediated molecular with PMo_(12),producing 2D Mo-Co-2MIM/Co(OH)_(2)bimetallic precursor.After controlled nitriding,the Mo_(2)N islands dispersed on 2D porous Co-based sheets were formed.A series of characterizations and density functional theory(DFT)calculation indicated the formation of a close contact interface,which promotes the electron transfer between Mo and Co components,enhances the electron migration/redistribution and redistribution and down-shift of d-band center and thus gives a high intrinsic activity.The 2D characteristics make the catalyst more accessible contact sites,which is favourable to promot the HER.The tests showed that the optimized catalyst exhibits an onset potential of 0 mV and an overpotential of 10 mA·cm^(−2)at 35.0 mV,which is quite close to that of Pt/C catalyst.It also exhibits an activity superior to Pt/C at high current density(>100 mA·cm^(−2)).A good stability of the catalyst was achieved with no significant decay for 100 h of continuous operation.The electrolytic cell composed of optimized catalyst and P-NiFe-layered double hydroxide(LDH)can be driven by low voltage(only 1.47 V)to reach a current density of 10 mA·cm^(−2).展开更多
The Ni-Fe-TiO_(2) overlayers on mild steel strips were prepared by electrochemical deposition.The layers were characterized morphologically by confocal laser scanning microscopy and scanning electron microscopy(SEM) c...The Ni-Fe-TiO_(2) overlayers on mild steel strips were prepared by electrochemical deposition.The layers were characterized morphologically by confocal laser scanning microscopy and scanning electron microscopy(SEM) coupled with energy-dispersive spectroscopy(EDS)analysis.The layers exhibit a quasi-three-dimensional(3D)morphology in which the crystalline,TiO_(2),is embedded.Electrocatalytic activity of the Ni-Fe-TiO_(2) layers for the hydrogen evolution reaction(HER) was assessed by using pseudo-steady-state polarization curves and electrochemical impedance spectroscopy(EIS) in alkaline solution.The results were compared with the properties of Ni-Fe electrodes and used for determining the mechanism and kinetics of HER.In comparison with Ni-Fe electrodes,the synthesized Ni-Fe-TiO_(2) electrodes present higher catalytic activity for HER due to the increase in the real surface area and high intrinsic elec trocatalytic activity of titanium dioxide.The present study provides valuable insight for exploring practical applications of Ni-based alloys as hydrogen evolution electrodes.展开更多
Collecting green hydrogen(H2)from water splitting driven by renewable energy is a new competition to implement the construction of H2 energy industry and promote new economic growth for global governments.The common s...Collecting green hydrogen(H2)from water splitting driven by renewable energy is a new competition to implement the construction of H2 energy industry and promote new economic growth for global governments.The common strategy to enhance the efficiency of H2 production is to reduce the potential of electrolytic cell that is the mainstream way to prepare efficient electrocatalysts.Layered double hydroxides(LDHs)are one of the most active electrocatalysts with adjustable active sites in contemporary research.In this review,we discuss the recent advanced progress of LDHs for hydrogen evolution reaction(HER)on cathode and oxygen evolution reaction(OER)or organic oxidation on anode and emphasize the influence of LDHs structure regulation in water electrolysis process(HER/OER)as well as the current development status of organic oxidation catalyzed by active oxygen species on anode.Finally,we propose the current challenges of LDHs in electrocatalysis and prospect their developing tendency and further application.展开更多
Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity...Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity of MoS2,this may lower its electrocatalytic activity.In this paper we present a method that we developed to directly produce solid S,N co‐doped carbon(SNC)with a graphite structure and multiple surface groups through a hydrothermal route.When Na2MoO4was added to the reaction,polymolybdate could be anchored into the carbon materials via a chemical interaction that helps polymolybdate disperse uniformly into the SNC.After a high temperature treatment,polymolybdate transformed into MoS2at800°C for6h in a N2atmosphere at a heating rate of5°C/min,owing to S2?being released from the SNC during the treatment(denoted as MoS2/SNC‐800‐6h).The SNC effectively prevents MoS2from aggregating into large particles,and we successfully prepared highly dispersed MoS2in the SNC matrix.Electrochemical characterizations indicate that MoS2/SNC‐900‐12h exhibits a low onset potential of115mV and a low overpotential of237mV at a current density of10mA/cm2.Furthermore,MoS2/SNC‐900‐12h also had an excellent stability with only^2.6%decay at a current density of10mA/cm2after5000test cycles.展开更多
The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack o...The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack of simple,cheap,highefficient electrocatalysts.Here,we successfully develop a simple and scalable electro-deposition and subsequent phosphorization route to fabricate Ni-doped Co_(2)P(Ni-Co_(2)P)nanosheets catalyst using the in-situ released Ni species from defective Ni foam as metal source.Impressively,the as-synthesized Ni-Co_(2)P catalyst exhibits excellent electrochemical 5-hydroxymethylfurfural oxidation reaction(HOR)performance with>99%2,5-furandicarboxylic acid yield and>97%Faradaic efficiency at an ultralow potential of 1.29 V vs.reversible hydrogen electrode(RHE).Experimental characterization and theoretical calculation reveal that the atomically doped Ni species can enhance the adsorption of reactant and thus lower the reaction energy barriers.By coupling the electrocatalytic HOR with HER,the employed two-electrode system using Ni-Co_(2)P and commercial Ni foam as anode and cathode,respectively,exhibits a low cell voltage of 1.53 V to drive a current density of 10 mA·cm^(−2),which is 90 mV lower than that of pure water splitting.This work provides a facile and efficient approach for the preparation of high-performance earth-abundant electrocatalysts toward the concurrent production of H_(2)and value-added chemicals.展开更多
基金support from the National Natural Science Foundation of China(21802120,21872121,and 21908189)the National Key R&D Program of China(2016YFA0202900)+3 种基金the Key R&D Project of Zhejiang Province(2020C01133)the Fundamental Research Funds for the Central Universities(G2019KY05119)the China Postdoctoral Science Foundation(2021 M692634)the Natural Science Basic Research Program of Shaanxi Province(2022JQ-118)are greatly appreciated.
文摘The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.
基金financial support from The University of Manchester to cover his PhD tuition fees for him to carry out this workChina National High-end Foreign Experts Recruitment Plan Project (G2023018001L) for partially supporting the work。
文摘Electrochemical production of hydrogen from water requires the development ofelectrocatalysts that are active,stable,and low-cost for water splitting.To address these challenges,researchers are increasingly exploring binder-free electrocatalytic integratedelectrodes (IEs) as an alternative to conventional powder-based electrode preparation methods,for the former is highly desirable to improve the catalytic activity and long-term stability for large-scale applications of electrocatalysts.Herein,we demonstrate a laser-inducedhydrothermal reaction (LIHR) technique to grow NiMoO4nanosheets on nickel foam,which is then calcined under H2/Ar mixed gases to prepare the IE IE-NiMo-LR.This electrode exhibits superior hydrogen evolution reaction performance,requiring overpotentials of 59,116 and143 mV to achieve current densities of 100,500 and 1000 mA·cm-2.During the 350 h chronopotentiometry test at current densities of 100 and 500 m A·cm-2,the overpotentialremains essentially unchanged.In addition,NiFe-layered double hydroxide grown on Ni foam is also fabricated with the same LIHR method and coupled with IE-NiMo-IR to achieve water splitting.This combination exhibits excellent durability under industrial current density.The energy consumption and production efficiency of the LIHR method are systematicallycompared with the conventional hydrothermal method.The LIHR method significantly improves the production rate by over 19 times,while consuming only 27.78%of the total energy required by conventional hydrothermal methods to achieve the same production.
基金the Joint Funds of the National Natural Science Foundation of China(Grant No.U1967212)the National Science and Technology Major Project of China(Grant No.2019XS06004009)the Fundamental Research Funds for the Central Universities(Grant No.2018ZD10).
文摘To maximize the catalytic performance of MoS_(2) in the hydrogen evolution reaction,we investigate the electrocatalytic and photocatalytic performance of monolayer MoS_(2) doped with noble metal(Ag,Au,Cu,Pd,and Pt)using first principles calculation combined with the climbing image nudged elastic band method.We find the band gap of the monolayer MoS_(2) is reduced significantly by the noble metal doping,which is unfavorable to improving its photocatalytic performance.The optical absorption coefficient shows that the doping does not increase the ability of the monolayer MoS_(2) to absorb visible light.The monolayer MoS_(2) doped with the noble metal is not a potential photocatalyst for the hydrogen evolution reaction because the band edge position of the conduction band minimum is lower than-4.44 eV,the reduction potential of H^(+)/H_(2).Fortunately,the band gap reduction increases the electron transport performance of the monolayer MoS_(2),and the activation energy of water splitting is greatly reduced by the noble metal doping,especially the Pt doping.On the whole,noble metal doping can enhance the electrocatalytic performance of the monolayer MoS_(2).
基金supported by the Shandong Natural Science Fund (No.ZR2020KB010)the Fundamental Research Funds for the Central Universities (No.22CX 07010A)。
文摘Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was prepared by solvothermal method,and then used as precursor to prepare NiFe-based MOF-derived materials by pyrolysis.The effects of different metal ratios and pyrolysis temperatures on the sample structure and OER electrocatalytic performance were investigated and compared.The experimental results showed that when the metal molar ratio was Fe:Ni=1:5 and the pyrolysis temperature was 450℃,the sample(FeNi_(5)-MOF-450)exhibits a composite structure of Ni Fe_(2)O_(4)/FeNi_(3)/C and owns the superior electrocatalytic activity in OER.When the current density is 100 mA·cm^(-2),the overpotential of the sample was 377 mV with Tafel slope of 56.2 mV·dec^(-1),which indicates that FeNi_(5)-MOF-450 exhibits superior electrocatalytic performance than the commercial RuO_(2).Moreover,the long-term stability of FeNi_(5)-MOF-450 further promotes its development in OER.This work demonstrated that the regulatory methods such as component optimization can effectively improve the OER catalytic performance of NiFe-based MOF-derived materials.
文摘Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.
基金supported by the Key Research and Development Project of Hainan Province(ZDYF2020037,ZDYF2020207)the National Natural Science Foundation of China(21805104)+1 种基金Innovative Research Projects for Graduate Students of Hainan Province(Hyb2020-05)the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084)。
文摘The investigation of highly effective,durable,and cost-effective electrocatalysts for the hydrogen evolution reaction(HER)is a prerequisite for the upcoming hydrogen energy society.To establish a new hydrogen energy system and gradually replace the traditional fossil-based energy,electrochemical water-splitting is considered the most promising,environmentally friendly,and efficient way to produce pure hydrogen.Compared with the commonly used platinum(Pt)-based catalysts,ruthenium(Ru)is expected to be a good alternative because of its similar hydrogen bonding energy,lower water decomposition barrier,and considerably lower price.Analyzing and revealing the HER mechanisms,as well as identifying a rational design of Ru-based HER catalysts with desirable activity and stability is indispensable.In this review,the research progress on HER electrocatalysts and the relevant describing parameters for HER performance are briefly introduced.Moreover,four major strategies to improve the performance of Ru-based electrocatalysts,including electronic effect modulation,support engineering,structure design,and maximum utilization(single atom)are discussed.Finally,the challenges,solutions and prospects are highlighted to prompt the practical applications of Rubased electrocatalysts for HER.
基金supported by the National Natural Science Foundation of China(Grant No.52202310)Natural Science Foundation of Jiangsu Province(Grant No.BK20191443)+7 种基金the Qinglan ProjectYouth Hundred Talents Programthe Toptalent Program of Yangzhou Universitythe Innovation technology platform project(YZ2020268)jointly built by Yangzhou City and Yangzhou UniversityPostgraduate Research&Practice Innovation Program of Jiangsu Province(SJCX22_1703)the Key Research and Development Projects of Sichuan Province(23ZDYF0466)“Tianfu Emei”Science and Technology Innovation Leader Program in Sichuan ProvinceUniversity of Electronic Science and Technology of China Talent Start-up Funds(A1098531023601208)。
文摘Molybdenum carbide(MO_(2)C)materials are promising electrocatalysts with potential applications in hydrogen evolution reaction(HER)due to low cost and Pt-like electronic structures.Nevertheless,their HER activity is usually hindered by the strong hydrogen binding energy.Moreover,the lack of water-cleaving site's makes it difficult for the catalysts to work in alkaline solutions.Here,we designed and synthesized a B and N dual-doped carbon layer that encapsulated on MO_(2)C nanocrystals(MO_(2)C@BNC)for accelerating HER under alkaline condition.The electronic interactions between the MO_(2)C nanocrystals and the multiple-doped carbon layer endow a near-zero H adsorption Gibbs free energy on the defective C atoms over the carbon shell.Meanwhile,the introduced B atoms afford optimal H_2O adsorption sites for the water-cleaving step.Accordingly,the dual-doped MO_(2)C catalyst with synergistic effect of non-metal sites delivers superior HER performances of a low overpotential(99 mV@10 mA cm^(-2))and a small Tafel slope(58.1 mV dec^(-1))in 1 M KOH solution.Furthermore,it presents a remarkable activity that outperforming the commercial 10%Pt/C catalyst at large current density,demonstrating its applicability in industrial water splitting.This study provides a reasonable design strategy towards noble-metal-free HER catalysts with high activity.
基金supported by the National Natural Science Foundation of China (Nos. 51772126 and 21978110)the Jilin Province Science and Technology Department Program (Nos. 20200201277JC, 20200201279JC, 20190201309JC and 20190101009JH)+4 种基金the National Science Foundation of Heilongjiang Province (E2017031)the Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education (Nos. 2017002, 2016010, 2015003 and 2015011)the Jilin Province Development and Reform Commission Program (Nos. 2019C042-1 and 2020C026-3)the ‘‘13th five-year” science and technology project of Jilin provincial education department (No. JJKH20200407KJ)the Jilin Province Fund for Talent Development Program (No. [2019] 874)。
文摘The perovskite transition metal oxide(TMO) has been considered in electrocatalysis for the modern clean energy technologies as its high electrochemical activity and low cost. The atomic scale engineering to the local stoichiometry of single crystal TMO provides a clue of the relation between electronic structure and catalytic performance. Here we report a hydrogen evolution reaction(HER) activity enhancement ~ 1761% of Bi_(0.85)Sr_(0.15)FeO_3 compared to the pure BiFeO_3. By the systemic investigation of the Sr doping level of Bi_(1-x)Sr_xFeO_3(BSFO), it is found that the HER enhancement originates from the improvement of ferromagnetism of BSFO without obvious scarification of the ferroelectricity at the room temperature. The multiple ferroic orderings in BSFO are beneficial for HER activity, which offers the strengthen of hybridization of Fe 3d and O2 p orbitals from the view of ferromagnetism, and the assistance of electron drift by spontaneous electric polarization. Our study not only affords the strategy of developing multiple ferroic orderings in TMO, but also facilitates the atomic scale understanding of the improved HER activity.
基金financially supported by the National Natural Science Foundation of China(21975100).
文摘Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.52171210,21978110 and 22201097)the Program for the Development of Science and Technology of Jilin Province(Nos.20220201130GX and YDZJ202201ZYTS313)。
文摘Rationally designed novel cost-effective hydrogen evolution reaction(HER)electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance.Polyoxometalates(POMs)with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts.Herein,a series of transition metal-doped MoS_(2)materials with different surface engineered structures(Fe,Cr,V doping and S vacancies)(M-MoS_(2)/CC,M=Fe,Cr and V)were fabricated by a simple hydrothermalvulcanization strategy using Keplerate polyoxomolybdate nanoball({Mo_(72)Fe_(30)},{Mo_(72)Cr_(30)},{Mo_(72)V_(30)},{Mo_(132)})as precursors.The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS_(2)/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media.The optimized Fe-MoS_(2)/CC afford current densities of 10 and 50 mA/cm^(2)at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH aqueous solution,respectively,outperforming most of reported typical transition metal sulfide-based catalysts.This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.
基金We gratefully acknowledge the support of this research by the National Key R&D Program of China(No.2022YFA1503003)the National Natural Science Foundation of China(Nos.U20A20250,91961111,and 22271081)+1 种基金the Natural Science Foundation of Heilongjiang Province(No.ZD2021b003)University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2020004).
文摘The rational design of the catalysts with easily-accessible surface and high intrinsic activity is desirable for electrocatalytic hydrogen evolution reaction(HER).Here,we reported the construction of two-dimensional(2D)Co-Mo nitrides based heterojunctional catalyst for efficient HER based on a“mediated molecular”assisted route.The 2D Co(OH)_(2)sheet reacted partially with the“mediated molecular”(2-methylimidazole(2-MIM))to form zeolitic imidazolate framework(ZIF)-67 at surface,giving ZIF-67/Co(OH)_(2)sheets.The ZIF-67 combines with[PMo_(12)O_(40)]^(3−)cluster(PMo_(12))due to the interaction of mediated molecular with PMo_(12),producing 2D Mo-Co-2MIM/Co(OH)_(2)bimetallic precursor.After controlled nitriding,the Mo_(2)N islands dispersed on 2D porous Co-based sheets were formed.A series of characterizations and density functional theory(DFT)calculation indicated the formation of a close contact interface,which promotes the electron transfer between Mo and Co components,enhances the electron migration/redistribution and redistribution and down-shift of d-band center and thus gives a high intrinsic activity.The 2D characteristics make the catalyst more accessible contact sites,which is favourable to promot the HER.The tests showed that the optimized catalyst exhibits an onset potential of 0 mV and an overpotential of 10 mA·cm^(−2)at 35.0 mV,which is quite close to that of Pt/C catalyst.It also exhibits an activity superior to Pt/C at high current density(>100 mA·cm^(−2)).A good stability of the catalyst was achieved with no significant decay for 100 h of continuous operation.The electrolytic cell composed of optimized catalyst and P-NiFe-layered double hydroxide(LDH)can be driven by low voltage(only 1.47 V)to reach a current density of 10 mA·cm^(−2).
基金financially supported by the Program of International S&T Cooperation of China (No. 2014DFR51130)the Science and Technology Planning Project of Beijing (No.Z161100001116080)the Science and Technology Major Project of Beijing (No.Z171100002017014)。
文摘The Ni-Fe-TiO_(2) overlayers on mild steel strips were prepared by electrochemical deposition.The layers were characterized morphologically by confocal laser scanning microscopy and scanning electron microscopy(SEM) coupled with energy-dispersive spectroscopy(EDS)analysis.The layers exhibit a quasi-three-dimensional(3D)morphology in which the crystalline,TiO_(2),is embedded.Electrocatalytic activity of the Ni-Fe-TiO_(2) layers for the hydrogen evolution reaction(HER) was assessed by using pseudo-steady-state polarization curves and electrochemical impedance spectroscopy(EIS) in alkaline solution.The results were compared with the properties of Ni-Fe electrodes and used for determining the mechanism and kinetics of HER.In comparison with Ni-Fe electrodes,the synthesized Ni-Fe-TiO_(2) electrodes present higher catalytic activity for HER due to the increase in the real surface area and high intrinsic elec trocatalytic activity of titanium dioxide.The present study provides valuable insight for exploring practical applications of Ni-based alloys as hydrogen evolution electrodes.
基金supported by the National Key Research and Development Program of China(No.2022YFA1504200)the National Natural Science Foundation of China(Nos.22090031,22108008,22288102)+1 种基金the Young Elite Scientist Sponsorship Program by the China Association for Science and Technology(No.2021QNRC001)the Fundamental Research Funds for the Central Universities,China(No.buctrc202011).
文摘Collecting green hydrogen(H2)from water splitting driven by renewable energy is a new competition to implement the construction of H2 energy industry and promote new economic growth for global governments.The common strategy to enhance the efficiency of H2 production is to reduce the potential of electrolytic cell that is the mainstream way to prepare efficient electrocatalysts.Layered double hydroxides(LDHs)are one of the most active electrocatalysts with adjustable active sites in contemporary research.In this review,we discuss the recent advanced progress of LDHs for hydrogen evolution reaction(HER)on cathode and oxygen evolution reaction(OER)or organic oxidation on anode and emphasize the influence of LDHs structure regulation in water electrolysis process(HER/OER)as well as the current development status of organic oxidation catalyzed by active oxygen species on anode.Finally,we propose the current challenges of LDHs in electrocatalysis and prospect their developing tendency and further application.
基金supported by the National Natural Science Foundation of China(21671011)Beijing High-Level Talent program~~
文摘Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity of MoS2,this may lower its electrocatalytic activity.In this paper we present a method that we developed to directly produce solid S,N co‐doped carbon(SNC)with a graphite structure and multiple surface groups through a hydrothermal route.When Na2MoO4was added to the reaction,polymolybdate could be anchored into the carbon materials via a chemical interaction that helps polymolybdate disperse uniformly into the SNC.After a high temperature treatment,polymolybdate transformed into MoS2at800°C for6h in a N2atmosphere at a heating rate of5°C/min,owing to S2?being released from the SNC during the treatment(denoted as MoS2/SNC‐800‐6h).The SNC effectively prevents MoS2from aggregating into large particles,and we successfully prepared highly dispersed MoS2in the SNC matrix.Electrochemical characterizations indicate that MoS2/SNC‐900‐12h exhibits a low onset potential of115mV and a low overpotential of237mV at a current density of10mA/cm2.Furthermore,MoS2/SNC‐900‐12h also had an excellent stability with only^2.6%decay at a current density of10mA/cm2after5000test cycles.
基金the National Key Research and Development(R&D)Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(NSFC)(Nos.21725102,51902311,22122506,91961106,22075267,and 21803002)+5 种基金Strategic Priority Research Program of the CAS(No.XDPB14)Anhui Provincial Natural Science Foundation(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Open Funding Project of National Key Laboratory of Human Factors Engineering(No.SYFD062010K)Users with Excellence Program of Hefei Science Center CAS(No.2020HSCUE003)Fundamental Research Funds for the Central Universities(No.WK2060000039).
文摘The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack of simple,cheap,highefficient electrocatalysts.Here,we successfully develop a simple and scalable electro-deposition and subsequent phosphorization route to fabricate Ni-doped Co_(2)P(Ni-Co_(2)P)nanosheets catalyst using the in-situ released Ni species from defective Ni foam as metal source.Impressively,the as-synthesized Ni-Co_(2)P catalyst exhibits excellent electrochemical 5-hydroxymethylfurfural oxidation reaction(HOR)performance with>99%2,5-furandicarboxylic acid yield and>97%Faradaic efficiency at an ultralow potential of 1.29 V vs.reversible hydrogen electrode(RHE).Experimental characterization and theoretical calculation reveal that the atomically doped Ni species can enhance the adsorption of reactant and thus lower the reaction energy barriers.By coupling the electrocatalytic HOR with HER,the employed two-electrode system using Ni-Co_(2)P and commercial Ni foam as anode and cathode,respectively,exhibits a low cell voltage of 1.53 V to drive a current density of 10 mA·cm^(−2),which is 90 mV lower than that of pure water splitting.This work provides a facile and efficient approach for the preparation of high-performance earth-abundant electrocatalysts toward the concurrent production of H_(2)and value-added chemicals.