The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their pot...The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.展开更多
Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic ...Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.展开更多
The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts hav...The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.展开更多
The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly...The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly grown on carbon cloth(Se-NiCoP/CC)was prepared by hydrothermal reaction and phosphorization/selenization process.The experimental results reveal that Se doping could increase the electrochemical active sites and alter the electronic structure of NiCoP.The optimized Se-NiCoP/CC electrode exhibits outstanding HER activity in alkaline electrolyte,which only needs a low overpotential of 79 mV at the current density of 10 mA/cm^(2).When serving as anode and cathode electrode simultaneously,the Se-NiCoP/CC electrodes achieve current density of 50 mA/cm^(2) at a low voltage of only 1.62 V.This work provides a feasible way to rationally design high active HER electrocatalysts.展开更多
Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Amo...Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Among them,5-hydroxymethylfurfural(HMF)is an important biomass-derived platform molecule,which can be converted into various high-value chemicals.One of its oxidation products,2,5-furandicarboxylic acid(FDCA),is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics.The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions,fast reaction rate,and high selectivity.The theoretical potential of the HMF electrooxidation reaction(HMFOR,0.3 V vs.reversible hydrogen electrode,RHE)is also lower than that of the oxygen evolution reaction(OER,1.23 V vs.RHE).Coupling anodic HMFOR with cathodic hydrogen evolution reaction(HER)is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen(H2)evolution.However,the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging.In this study,Co-doped Ni-Mo-O porous nanorods grown on a nickel foam(Co-NiMoO/NF)is prepared by simple hydrothermal and calcination methods for both HMFOR and HER.Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR(E10/100=1.31/1.37 V vs.RHE)and HER(E−10/−100=−35/−123 mV vs.RHE)and shows durable HMFOR/HER stability.In particular,Co-NiMoO/NF maintains high FDCA selectivity(~99.2%)and Faradaic efficiency(~95.7%)for 40 successive cycles at 1.36 V vs.RHE for HMFOR.Conversely,Co-NiMoO/NF maintains stable operation at−200 mA∙cm^(−2)for 50 h with no significant activity attenuation for HER.When coupled as a bifunctional electrode for overall HMF splitting,Co-NiMoO/NF reaches an electric flux of 50 mA∙cm^(−2)at 1.48 V,which is 290 mV lower than that of the overall water splitting.This confirms that the HMFOR-assisted H2 production over Co-NiMoO/NF significantly reduces the energy consumption.Moreover,the two-electrode system maintains good FDCA selectivity(97.6%)for 10 cycles at 1.45 V,implying good stability of HMFOR-assisted H2 evolution.The remarkable catalytic performance of Co-NiMoO/NF could be due to the introduction of Co,which optimizes the electronic structure of Ni-Mo-O and adsorption behaviors of the reactants,thereby enhancing the intrinsic activity and stability of the catalyst.Meanwhile,the porous nanorod structure enhanced the mass transport of substrates and desorption of bubbles,thereby elevating the HMFOR/HER kinetics.This study provides useful insights for designing efficient and durable bifunctional catalysts for HMFOR and HER.展开更多
The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorp...The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorption,non toxicity and industrial applicability.Nevertheless,the photoelectrocatalytic(PEC)performance of Si nanowires photocathodes is still limited by ineffective or deficient active sites on their surfaces.Here,we develop an efficient Si based photocathode modified with Al-porphyrin-based MOF(Al-PMOF),consisted of an earth-abundant metal containing Al(OH)O_(4) cluster bridged by 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin.The assembled Al-PMOF significantly enhances the photocurrent density of bare Si nanowires photocathodes,resulting in a twofold increase under equivalent conditions,alongside a positive shift of 200 mV in the onset potential of the Si/Al-PMOF photocathode.The improved PEC hydrogen evolution performance is ascribed to accelerate surface charge transfer of Si photocathode and provision of favorable active site for the hydrogen evolution reaction.This work provides insights into the fabrication of semiconductor/molecule catalyst hybrid photocathodes,thus facilitating the realization of high-efficiency PEC water splitting.展开更多
Transition metal dichalcogenides(TMDs)recently attracted widespread attention due to their potential application to the electrocatalysis of the hydrogen evolution reaction(HER).However,their HER performance is far inf...Transition metal dichalcogenides(TMDs)recently attracted widespread attention due to their potential application to the electrocatalysis of the hydrogen evolution reaction(HER).However,their HER performance is far inferior to that of platinum(Pt)metal.Preparation of multi-elemental alloy and construction of heterostructure are considered as highly effective methods to enhance hydrogen production activity.Herein,a novel quaternary CoMoSSe alloy with heterostructure was synthesized on the surface of carbon black(CB)particles(CoMoSSe@CB)by a simple Sol-Gel process and thereafter served as HER catalyst.Compared to CoSe@CB and MoS2@CB electrocatalysts,CoMoSSe@CB exhibits superior HER activity with a low overpotential of 190 mV at-10 mA·cm^(-2) and a Tafel slope of 62 mV·dec^(-1).This improvement is attributed to the alloying effects among Co,Mo,S and Se,as well as the heterogeneous structure in the composite material,which regulate the electronic structure and intermediate free energy,thereby increasing the number of active sites and enhancing charge-transfer ability.This work can provide new ideas and concepts for designing novel and efficient TMD electrocatalysts.展开更多
MoS_(2)/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate,thiourea,oxalic acid,and copper nitrate trihydrate as raw materials.The hydrogen pro-d...MoS_(2)/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate,thiourea,oxalic acid,and copper nitrate trihydrate as raw materials.The hydrogen pro-duction performance of MoS_(2)/CuS prepared with different molar ratios of Mo to Cu precursors(n_(Mo)∶n_(Cu))as cathodic catalysts was investigated in the two-chamber microbial electrolytic cell(MEC).X-ray diffraction(XRD),X-ray pho-toelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscope(TEM),linear scanning voltammetry(LSV),electrochemical impedance analysis(EIS),and cyclic voltammetry(CV)were used to characterize the synthesized catalysts for testing and analyzing the hydrogen-producing performance.The results showed that the hydrogen evolution performance of MoS_(2)/CuS-20%(nMo∶nCu=5∶1)was better than that of platinum(Pt)mesh,and the hydrogen production rate of MoS_(2)/CuS-20%as a cathode in MEC was(0.2031±0.0237)m^(3)_(H_(2))·m^(-3)·d^(-1) for 72 h at an applied voltage of 0.8 V,which was slightly higher than that of Pt mesh of(0.1886±0.0134)m^(3)_(H_(2))·m^(-3)·d^(-1).The addition of a certain amount of CuS not only regulates the electron transfer ability of MoS_(2) but also increases the density of active sites.展开更多
Iron(Fe)nanoparticles and graphite(Gr)with different masses of bismuth trisulfide(Bi_(2)S_(3))were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi_(2)S_(3)@Fe-Gr.The...Iron(Fe)nanoparticles and graphite(Gr)with different masses of bismuth trisulfide(Bi_(2)S_(3))were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi_(2)S_(3)@Fe-Gr.The hydrogen evolution reaction and iron passivation process on these iron electrodes were investigated in alkaline and neutral solutions.The iron electrode Bi_(2)S_(3)-3@Fe-Gr(The additional amount of Bi_(2)S_(3)was 3 mg)revealed the strongest ability to inhibit hydrogen evolution among the iron electrodes of the present investigation,while the Bi_(2)S_(3)-6@Fe-Gr electrode(The additional amount of Bi_(2)S_(3)was 6 mg)delivered significant performance in inhibiting anodic passivation.This is because the high-energy ball milling process leads to the well-dispersion of Bi_(2)S_(3)and the changes in the surface of Fe nanoparticles,thereby slowing down the passivation of the iron electrode surface.展开更多
The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly effici...The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.展开更多
Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic ele...Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic element atoms,we prepared four different NiX(X=Cl_(2),(CH_(3)COO)_(2),(NO_(3))2,SO_(4))@CNT catalysts.Additionally,by adjusting the temperature,these four materials were expanded into twelve catalyst materials for comparative optimization of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activity.Ultimately,Ni(NO_(3))2@CNT-900 typically exhibits superior OER and HER activity.In 1 mol/L KOH solution with a current density of 10 mA/cm^(2),the overpotentials of HER and OER of Ni(NO_(3))2@CNT-900 are only 145 mV and 300 mV,respectively.Furthermore,the Ni(NO_(3))2@CNT-900 shows excellent durability in both HER and OER.展开更多
Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydroge...Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydrogen has emerged as a clean energy carrier and is considered an ideal chemical for power generation via fuel cells.Using renewable energy to power hydrogen production is an attractive prospect,and hydrogen production through photoelectrochemical water splitting is considered a promising area of interest;consequently,significant research is being conducted on rationally designed photoelectrodes.Generally,a photocathode for hydrogen evolution must have a conduction band that is more negative than the reduction potential of hydrogen.Numerous photocathode materials have been developed based on this premise;these include p-Si,InP,and GaN.Compared with other photocathode materials,Cu-based compounds are advantageous owing to their low preparation costs and diverse chemical states.For example,Cu_(2)O is a non-toxic p-type metal oxide semiconductor material with an appropriate band structure for water splitting and a direct band gap of 1.9-2.2 eV.Furthermore,the production of Cu_(2)O is facile,and the required materials are abundant;thus,it has attracted significant interest as a material for photocathodes.However,Cu_(2)O suffers from rapid recombination of photogenerated carriers and severe photo-corrosion,leading to unsatisfactory efficiency and poor stability.Intrinsically,the poor photo-stability of Cu_(2)O can be attributed to the location of the redox potential of Cu_(2)O within its bandgap,owing to which photoelectrons tend to preferentially reduce Cu_(2)O to Cu rather than reduce water to reduction.Therefore,Cu_(2)O itself is not an ideal hydrogen evolution catalyst.Thus,co-catalysts are necessary to improve its hydrogen evolution activity and photostability.In addition to co-catalysts,combining Cu_(2)O with tailored n-type semiconductors to generate built-in electric fields of p-n junctions has attracted extensive attention owing to its ability of increasing the separation of photogenerated carriers.Similarly,applying a hole transfer layer on the substrate can promote photocarrier separation.Furthermore,considering that water is indispensable for Cu_(2)O reduction,one effective approach to improve the stability of Cu_(2)O is the addition of a protective/passivation layer to isolate Cu_(2)O from water in aqueous electrolytes.In this review,we provide a brief overview of the mechanism of photoelectrochemical water splitting and the band structure of Cu_(2)O ;preparation methods of Cu_(2)O photocathodes;strategies to improve the efficiency and stability of Cu_(2)O photocathodes,including the construction of p-n junctions,integration with co-catalysts,and modifications using hole transport layers;advanced photoelectrochemical characterization techniques;and a discussion regarding the direction of future photocathode research.展开更多
Exploiting highly active and non-noble metal bifunctional catalysts at large current density is significant for the advancement of water electrolysis.In this work,CeO_(2)electronically structure modulated FeNi bimetal...Exploiting highly active and non-noble metal bifunctional catalysts at large current density is significant for the advancement of water electrolysis.In this work,CeO_(2)electronically structure modulated FeNi bimetallic composite porous nanosheets in-situ grown on nickel foam(NiFe_(2)O_(4)-Fe_(24)N_(10)-CeO_(2)/NF)is synthesized.Electrochemical experiments show that the NiFe_(2)O_(4)-Fe_(24)N_(10)-CeO_(2)/NF exhibited the outstanding activities toward both oxygen and hydrogen evolution reactions(OER and HER)(η1000=352 mV andη1000=429 mV,respectively).When assembled into a two-electrode system for overall water splitting(OWS),it only needs a low cell voltage of 1.81 V to drive 100 mA·cm^(-2).And it can operate stably at±500 mA·cm^(-2)over 30 h toward OER,HER and OWS without significant activity changes.The reason could be assigned to the electronic modulating of CeO_(2)on FeNi composite,which can boost the intrinsic activity and optimize the adsorption of reaction intermediates.Moreover,the porous nanosheets insitu grown on NF could enhance the contact of active site with electrolyte and facilitate the gas release,thus improving its chemical and mechanical stabilities.This study highlights a novel approach to design bifunctional non-noble metal catalysts for water splitting at large current density.展开更多
Non-precious electro catalysts with high-efficiency, cheapness and stablility are of great significance to replace noble metal electro catalysts in the hydrogen evolution reaction(HER) and oxygen evolution reaction(OE...Non-precious electro catalysts with high-efficiency, cheapness and stablility are of great significance to replace noble metal electro catalysts in the hydrogen evolution reaction(HER) and oxygen evolution reaction(OER). In this work, triangular Cu@CuO nanorods on Cu nanosheets were fabricated by a novel in-situ oxidation approach using Cu nanosheets as self-template and conductive nano-substrate in an aqueous solution of NaOH/H2O2, and then by lowtemperature phosphorization treatments. The experimental results show that the phosphating temperature has a significant effect on the morphology, composition and number of active sites of Cu@Cu_(3)P nanorods. The Cu@Cu_(3)P-280 electrode exhibits a good HER catalytic activity of achieving a current density of 10 mA/cm^(2) at 252 mV in acid electrolyte. After catalysis for 14 h, the current density can still reach 72% of the initial value. Moreover, the Cu@Cu_(3)P-280 electrode also shows an excellent OER catalytic activity in basic electrolyte, reaching a current density of 10 mA/cm^(2) at the overpotential value of 200 mV. After catalysis for 12 h, the current density remained more than 93% of the initial value. This work provides a theoretical basis for the directional design and preparation of sustainable, low-cost, bifunctional electrocatalytic materials.展开更多
Continued growth in energy demand and increased environmental pollution constitute major challenges that need to be addressed urgently.The development and utilization of renewable,sustainable,and clean energy sources,...Continued growth in energy demand and increased environmental pollution constitute major challenges that need to be addressed urgently.The development and utilization of renewable,sustainable,and clean energy sources,such as wind and solar,are crucial.However,the instability of these intermittent energy sources makes the need for energy storage systems increasingly urgent.Aqueous zinc-ion batteries(AZIBs)have received widespread attention due to their unique advantages,such as high energy density,cost-effectiveness,environmental friendliness,and safety.However,AZIBs face significant challenges,mainly the formation of zinc dendrites that seriously affect the stability and lifetime of the batteries,leading to battery failure.Therefore,reducing the formation of zinc dendrites is crucial for improving the performance of AZIBs.This review systematically and comprehensively comprehends the current strategies and advances in inhibiting the formation of zinc dendrites.By comprehensively analyzing the latest developments in zinc anode,electrolyte,separator design and modification,as well as other novel mechanisms,it provides researchers with a thorough understanding to guide future research and advance the development of AZIBs.展开更多
Heterojunction catalysts composed of transition metal sulfides exhibited excellent potentials in electrocatalytic water splitting.Herein,we have designed a FeS/Co_(3)S_(4) heterojunction catalyst for hydrogen evolutio...Heterojunction catalysts composed of transition metal sulfides exhibited excellent potentials in electrocatalytic water splitting.Herein,we have designed a FeS/Co_(3)S_(4) heterojunction catalyst for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline water/seawater solution.Three-dimensional nanoarrays were grown on nickel foam,and the successful synthesis of heterojunction endowed excellent activity to the catalyst.In alkaline water/seawater solution,the low overpotentials(at current density of 10 mA/cm^(2))of HER were 120.3 and 135.6 mV and the low overpotentials of OER were 212 and 232 mV,respectively.This work provided an effective method for highly-efficiently electrocatalytic splitting of water via fabrication of heterojunction.展开更多
基金supported by the National Natural Science Foundation of China(22179138).
文摘The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.
基金supported by the National Natural Science Foundation of China(No.52072226,U22A20144)Key Research and Development Program of Shaanxi(2024GX-YBXM-466)+1 种基金Science and Technology Program of Xi'an,China(22GXFW0013)Science and Technology Program of Weiyang District of Xi'an,China(202315)。
文摘Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.
文摘The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.
基金Projects(51772086,51872087,51971089)supported by the National Natural Science Foundation of ChinaProject(2018TP1037-202102)supported by Open Fund of Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion,China+1 种基金Project supported by Student National SIT Innovation Program,ChinaProject(2020CB1007)supported by Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy,China。
文摘The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly grown on carbon cloth(Se-NiCoP/CC)was prepared by hydrothermal reaction and phosphorization/selenization process.The experimental results reveal that Se doping could increase the electrochemical active sites and alter the electronic structure of NiCoP.The optimized Se-NiCoP/CC electrode exhibits outstanding HER activity in alkaline electrolyte,which only needs a low overpotential of 79 mV at the current density of 10 mA/cm^(2).When serving as anode and cathode electrode simultaneously,the Se-NiCoP/CC electrodes achieve current density of 50 mA/cm^(2) at a low voltage of only 1.62 V.This work provides a feasible way to rationally design high active HER electrocatalysts.
文摘Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Among them,5-hydroxymethylfurfural(HMF)is an important biomass-derived platform molecule,which can be converted into various high-value chemicals.One of its oxidation products,2,5-furandicarboxylic acid(FDCA),is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics.The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions,fast reaction rate,and high selectivity.The theoretical potential of the HMF electrooxidation reaction(HMFOR,0.3 V vs.reversible hydrogen electrode,RHE)is also lower than that of the oxygen evolution reaction(OER,1.23 V vs.RHE).Coupling anodic HMFOR with cathodic hydrogen evolution reaction(HER)is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen(H2)evolution.However,the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging.In this study,Co-doped Ni-Mo-O porous nanorods grown on a nickel foam(Co-NiMoO/NF)is prepared by simple hydrothermal and calcination methods for both HMFOR and HER.Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR(E10/100=1.31/1.37 V vs.RHE)and HER(E−10/−100=−35/−123 mV vs.RHE)and shows durable HMFOR/HER stability.In particular,Co-NiMoO/NF maintains high FDCA selectivity(~99.2%)and Faradaic efficiency(~95.7%)for 40 successive cycles at 1.36 V vs.RHE for HMFOR.Conversely,Co-NiMoO/NF maintains stable operation at−200 mA∙cm^(−2)for 50 h with no significant activity attenuation for HER.When coupled as a bifunctional electrode for overall HMF splitting,Co-NiMoO/NF reaches an electric flux of 50 mA∙cm^(−2)at 1.48 V,which is 290 mV lower than that of the overall water splitting.This confirms that the HMFOR-assisted H2 production over Co-NiMoO/NF significantly reduces the energy consumption.Moreover,the two-electrode system maintains good FDCA selectivity(97.6%)for 10 cycles at 1.45 V,implying good stability of HMFOR-assisted H2 evolution.The remarkable catalytic performance of Co-NiMoO/NF could be due to the introduction of Co,which optimizes the electronic structure of Ni-Mo-O and adsorption behaviors of the reactants,thereby enhancing the intrinsic activity and stability of the catalyst.Meanwhile,the porous nanorod structure enhanced the mass transport of substrates and desorption of bubbles,thereby elevating the HMFOR/HER kinetics.This study provides useful insights for designing efficient and durable bifunctional catalysts for HMFOR and HER.
基金Project(22078368)supported by the National Natural Science Foundation of China。
文摘The utilization of solar energy for hydrogen production via water splitting has garnered considerable attention in the realm of renewable energy.Si nanowires photocathodes own the advantages of effective photon absorption,non toxicity and industrial applicability.Nevertheless,the photoelectrocatalytic(PEC)performance of Si nanowires photocathodes is still limited by ineffective or deficient active sites on their surfaces.Here,we develop an efficient Si based photocathode modified with Al-porphyrin-based MOF(Al-PMOF),consisted of an earth-abundant metal containing Al(OH)O_(4) cluster bridged by 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin.The assembled Al-PMOF significantly enhances the photocurrent density of bare Si nanowires photocathodes,resulting in a twofold increase under equivalent conditions,alongside a positive shift of 200 mV in the onset potential of the Si/Al-PMOF photocathode.The improved PEC hydrogen evolution performance is ascribed to accelerate surface charge transfer of Si photocathode and provision of favorable active site for the hydrogen evolution reaction.This work provides insights into the fabrication of semiconductor/molecule catalyst hybrid photocathodes,thus facilitating the realization of high-efficiency PEC water splitting.
基金Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652B004,2024RC13)Special Basic Cooperative Research Programs of Yunnan Provincial Undergraduate Universities Association(202101BA070001-085)。
文摘Transition metal dichalcogenides(TMDs)recently attracted widespread attention due to their potential application to the electrocatalysis of the hydrogen evolution reaction(HER).However,their HER performance is far inferior to that of platinum(Pt)metal.Preparation of multi-elemental alloy and construction of heterostructure are considered as highly effective methods to enhance hydrogen production activity.Herein,a novel quaternary CoMoSSe alloy with heterostructure was synthesized on the surface of carbon black(CB)particles(CoMoSSe@CB)by a simple Sol-Gel process and thereafter served as HER catalyst.Compared to CoSe@CB and MoS2@CB electrocatalysts,CoMoSSe@CB exhibits superior HER activity with a low overpotential of 190 mV at-10 mA·cm^(-2) and a Tafel slope of 62 mV·dec^(-1).This improvement is attributed to the alloying effects among Co,Mo,S and Se,as well as the heterogeneous structure in the composite material,which regulate the electronic structure and intermediate free energy,thereby increasing the number of active sites and enhancing charge-transfer ability.This work can provide new ideas and concepts for designing novel and efficient TMD electrocatalysts.
文摘MoS_(2)/CuS composite catalysts were successfully synthesized using a one-step hydrothermal method with sodium molybdate dihydrate,thiourea,oxalic acid,and copper nitrate trihydrate as raw materials.The hydrogen pro-duction performance of MoS_(2)/CuS prepared with different molar ratios of Mo to Cu precursors(n_(Mo)∶n_(Cu))as cathodic catalysts was investigated in the two-chamber microbial electrolytic cell(MEC).X-ray diffraction(XRD),X-ray pho-toelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscope(TEM),linear scanning voltammetry(LSV),electrochemical impedance analysis(EIS),and cyclic voltammetry(CV)were used to characterize the synthesized catalysts for testing and analyzing the hydrogen-producing performance.The results showed that the hydrogen evolution performance of MoS_(2)/CuS-20%(nMo∶nCu=5∶1)was better than that of platinum(Pt)mesh,and the hydrogen production rate of MoS_(2)/CuS-20%as a cathode in MEC was(0.2031±0.0237)m^(3)_(H_(2))·m^(-3)·d^(-1) for 72 h at an applied voltage of 0.8 V,which was slightly higher than that of Pt mesh of(0.1886±0.0134)m^(3)_(H_(2))·m^(-3)·d^(-1).The addition of a certain amount of CuS not only regulates the electron transfer ability of MoS_(2) but also increases the density of active sites.
文摘Iron(Fe)nanoparticles and graphite(Gr)with different masses of bismuth trisulfide(Bi_(2)S_(3))were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi_(2)S_(3)@Fe-Gr.The hydrogen evolution reaction and iron passivation process on these iron electrodes were investigated in alkaline and neutral solutions.The iron electrode Bi_(2)S_(3)-3@Fe-Gr(The additional amount of Bi_(2)S_(3)was 3 mg)revealed the strongest ability to inhibit hydrogen evolution among the iron electrodes of the present investigation,while the Bi_(2)S_(3)-6@Fe-Gr electrode(The additional amount of Bi_(2)S_(3)was 6 mg)delivered significant performance in inhibiting anodic passivation.This is because the high-energy ball milling process leads to the well-dispersion of Bi_(2)S_(3)and the changes in the surface of Fe nanoparticles,thereby slowing down the passivation of the iron electrode surface.
基金supported by the National Key R&D Program of China(2018YFA0702001)National Natural Science Foundation of China(22371268,22301287)+3 种基金Fundamental Research Funds for the Central Universities(WK2060000016)Anhui Provincial Natural Science Foundation(2208085J09,2208085QB33)Collaborative Innovation Program of Hefei Science Center,CAS(2022HSC-CIP020)Youth Innovation Promotion Association of the Chinese Academy of Science(2018494)and USTC Tang Scholar.
文摘The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.
基金Project(145209113)supported by the Basic Research Expenses of Department of Education of Heilongjiang Province,China。
文摘Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic element atoms,we prepared four different NiX(X=Cl_(2),(CH_(3)COO)_(2),(NO_(3))2,SO_(4))@CNT catalysts.Additionally,by adjusting the temperature,these four materials were expanded into twelve catalyst materials for comparative optimization of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activity.Ultimately,Ni(NO_(3))2@CNT-900 typically exhibits superior OER and HER activity.In 1 mol/L KOH solution with a current density of 10 mA/cm^(2),the overpotentials of HER and OER of Ni(NO_(3))2@CNT-900 are only 145 mV and 300 mV,respectively.Furthermore,the Ni(NO_(3))2@CNT-900 shows excellent durability in both HER and OER.
文摘Owing to the growing consumption of non-renewable resources and increased environmental pollution,significant attention has been directed toward developing renewable and environmentally friendly energy sources.Hydrogen has emerged as a clean energy carrier and is considered an ideal chemical for power generation via fuel cells.Using renewable energy to power hydrogen production is an attractive prospect,and hydrogen production through photoelectrochemical water splitting is considered a promising area of interest;consequently,significant research is being conducted on rationally designed photoelectrodes.Generally,a photocathode for hydrogen evolution must have a conduction band that is more negative than the reduction potential of hydrogen.Numerous photocathode materials have been developed based on this premise;these include p-Si,InP,and GaN.Compared with other photocathode materials,Cu-based compounds are advantageous owing to their low preparation costs and diverse chemical states.For example,Cu_(2)O is a non-toxic p-type metal oxide semiconductor material with an appropriate band structure for water splitting and a direct band gap of 1.9-2.2 eV.Furthermore,the production of Cu_(2)O is facile,and the required materials are abundant;thus,it has attracted significant interest as a material for photocathodes.However,Cu_(2)O suffers from rapid recombination of photogenerated carriers and severe photo-corrosion,leading to unsatisfactory efficiency and poor stability.Intrinsically,the poor photo-stability of Cu_(2)O can be attributed to the location of the redox potential of Cu_(2)O within its bandgap,owing to which photoelectrons tend to preferentially reduce Cu_(2)O to Cu rather than reduce water to reduction.Therefore,Cu_(2)O itself is not an ideal hydrogen evolution catalyst.Thus,co-catalysts are necessary to improve its hydrogen evolution activity and photostability.In addition to co-catalysts,combining Cu_(2)O with tailored n-type semiconductors to generate built-in electric fields of p-n junctions has attracted extensive attention owing to its ability of increasing the separation of photogenerated carriers.Similarly,applying a hole transfer layer on the substrate can promote photocarrier separation.Furthermore,considering that water is indispensable for Cu_(2)O reduction,one effective approach to improve the stability of Cu_(2)O is the addition of a protective/passivation layer to isolate Cu_(2)O from water in aqueous electrolytes.In this review,we provide a brief overview of the mechanism of photoelectrochemical water splitting and the band structure of Cu_(2)O ;preparation methods of Cu_(2)O photocathodes;strategies to improve the efficiency and stability of Cu_(2)O photocathodes,including the construction of p-n junctions,integration with co-catalysts,and modifications using hole transport layers;advanced photoelectrochemical characterization techniques;and a discussion regarding the direction of future photocathode research.
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011).
文摘Exploiting highly active and non-noble metal bifunctional catalysts at large current density is significant for the advancement of water electrolysis.In this work,CeO_(2)electronically structure modulated FeNi bimetallic composite porous nanosheets in-situ grown on nickel foam(NiFe_(2)O_(4)-Fe_(24)N_(10)-CeO_(2)/NF)is synthesized.Electrochemical experiments show that the NiFe_(2)O_(4)-Fe_(24)N_(10)-CeO_(2)/NF exhibited the outstanding activities toward both oxygen and hydrogen evolution reactions(OER and HER)(η1000=352 mV andη1000=429 mV,respectively).When assembled into a two-electrode system for overall water splitting(OWS),it only needs a low cell voltage of 1.81 V to drive 100 mA·cm^(-2).And it can operate stably at±500 mA·cm^(-2)over 30 h toward OER,HER and OWS without significant activity changes.The reason could be assigned to the electronic modulating of CeO_(2)on FeNi composite,which can boost the intrinsic activity and optimize the adsorption of reaction intermediates.Moreover,the porous nanosheets insitu grown on NF could enhance the contact of active site with electrolyte and facilitate the gas release,thus improving its chemical and mechanical stabilities.This study highlights a novel approach to design bifunctional non-noble metal catalysts for water splitting at large current density.
基金Project(21905232) supported by the National Natural Science Foundation of China。
文摘Non-precious electro catalysts with high-efficiency, cheapness and stablility are of great significance to replace noble metal electro catalysts in the hydrogen evolution reaction(HER) and oxygen evolution reaction(OER). In this work, triangular Cu@CuO nanorods on Cu nanosheets were fabricated by a novel in-situ oxidation approach using Cu nanosheets as self-template and conductive nano-substrate in an aqueous solution of NaOH/H2O2, and then by lowtemperature phosphorization treatments. The experimental results show that the phosphating temperature has a significant effect on the morphology, composition and number of active sites of Cu@Cu_(3)P nanorods. The Cu@Cu_(3)P-280 electrode exhibits a good HER catalytic activity of achieving a current density of 10 mA/cm^(2) at 252 mV in acid electrolyte. After catalysis for 14 h, the current density can still reach 72% of the initial value. Moreover, the Cu@Cu_(3)P-280 electrode also shows an excellent OER catalytic activity in basic electrolyte, reaching a current density of 10 mA/cm^(2) at the overpotential value of 200 mV. After catalysis for 12 h, the current density remained more than 93% of the initial value. This work provides a theoretical basis for the directional design and preparation of sustainable, low-cost, bifunctional electrocatalytic materials.
文摘Continued growth in energy demand and increased environmental pollution constitute major challenges that need to be addressed urgently.The development and utilization of renewable,sustainable,and clean energy sources,such as wind and solar,are crucial.However,the instability of these intermittent energy sources makes the need for energy storage systems increasingly urgent.Aqueous zinc-ion batteries(AZIBs)have received widespread attention due to their unique advantages,such as high energy density,cost-effectiveness,environmental friendliness,and safety.However,AZIBs face significant challenges,mainly the formation of zinc dendrites that seriously affect the stability and lifetime of the batteries,leading to battery failure.Therefore,reducing the formation of zinc dendrites is crucial for improving the performance of AZIBs.This review systematically and comprehensively comprehends the current strategies and advances in inhibiting the formation of zinc dendrites.By comprehensively analyzing the latest developments in zinc anode,electrolyte,separator design and modification,as well as other novel mechanisms,it provides researchers with a thorough understanding to guide future research and advance the development of AZIBs.
基金supported by the Dean/Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2023K001)Taishan Scholars Foundation of Shandong province(TSQN201909058).
文摘Heterojunction catalysts composed of transition metal sulfides exhibited excellent potentials in electrocatalytic water splitting.Herein,we have designed a FeS/Co_(3)S_(4) heterojunction catalyst for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline water/seawater solution.Three-dimensional nanoarrays were grown on nickel foam,and the successful synthesis of heterojunction endowed excellent activity to the catalyst.In alkaline water/seawater solution,the low overpotentials(at current density of 10 mA/cm^(2))of HER were 120.3 and 135.6 mV and the low overpotentials of OER were 212 and 232 mV,respectively.This work provided an effective method for highly-efficiently electrocatalytic splitting of water via fabrication of heterojunction.
