Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.展开更多
Breakthroughs in energy storage and conversion devices depend heavily on the exploration of low-cost and high-performance materials.Carbon-supported electrocatalysts with dimensional varieties have recently attracted ...Breakthroughs in energy storage and conversion devices depend heavily on the exploration of low-cost and high-performance materials.Carbon-supported electrocatalysts with dimensional varieties have recently attracted significant attention due to their strong structural flexibility and easy accessibility.Nevertheless,understanding the connection between their electronic,structural properties,and catalytic performance must remain a top priority.Synchrotron radiation(SR)X-ray absorption spectroscopy(XAS)techniques,including hard XAS and soft XAS,are recognized as efficient and comprehensive platforms for probing the surface,interface,and bulk electronic structure of elements of interest in the materials community.In the past decade,the flourishing development of materials science and advanced characterization technologies have led to a deeper understanding at different temporal,longitudinal,and spatial scales.In this review,we briefly describe the concept of XAS techniques and summarize their recent progress in addressing scientific questions on carbon-supported electrocatalysts through the development of advanced instruments and experimental methods.We then discuss the remaining challenges and potential research directions in nextgeneration materials frontiers,and suggest challenges and perspectives for shedding light on the structure–activity relationship.展开更多
Rational synthesis of a new class of electrocatalysts with high-performance and low-cost is of great significance for future fuel cell devices. Herein, we demonstrate a general one-step simultaneous reduction method t...Rational synthesis of a new class of electrocatalysts with high-performance and low-cost is of great significance for future fuel cell devices. Herein, we demonstrate a general one-step simultaneous reduction method to prepare carbon-supported Pd M（M = Co, Fe, Ni） alloyed nanodendrites with the assistance of oleylamine and octadecylene. The morphology, structure and composition of the obtained Pd M nanodendrites/C catalysts have been fully characterized. The combination of the dendritic structural feature and alloyed synergy offer higher atomic utilization efficiency, excellent catalytic activity and enhanced stability for the formic acid oxidation reaction（FAOR）. Strikingly, the as-synthesized Pd Co nanodendrites/C catalyst could afford a mass current density of 2467.7 A g, which is almost 3.53 and 10.4 times higher than those of lab-made Pd/C sample(698.3 A g) and commercial Pd/C catalyst(237.6 A g), respectively. Furthermore, the PdC o nanodendrites/C catalyst also exhibit superior stability relative to the Pd/C catalysts, make it a promising anodic electrocatalyst in practical fuel cells in the future. Additionally, the present feasible synthetic approach is anticipated to provide a versatile strategy toward the preparation of other metal alloy nanodendrites/carbon nanohybrids.展开更多
This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess a...This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.展开更多
Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt...Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.展开更多
Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen ba...Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.展开更多
The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluate...The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli.The key factors affecting the inactivation effciency were investigated,including electric power of lamp, temperature,and pH values.The results show that the TiO2/AC composites have high inactivation properties of E.coli in compari...展开更多
As a main oxidizer in solid composite propellants,ammonium perchlorate(AP)plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid composite propellants....As a main oxidizer in solid composite propellants,ammonium perchlorate(AP)plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid composite propellants.To improve the performance of solid composite propellant,it is necessary to take measures to modify the thermal decomposition behavior of AP.In recent years,transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraordinary catalytic activity.In this review,we highlight strategies to enhance the thermal decomposition of AP by tuning morphology,varying the types of metal ion,and coupling with carbon analogue.The enhanced catalytic performance can be ascribed to synergistic effect,increased surface area,more exposed active sites,and accelerated electron transportation and so on.The mechanism of AP decomposition mixed with catalyst has also been briefly summarized.Finally,a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.展开更多
Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and wer...Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.展开更多
Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HD...Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.展开更多
By evaluating the SEM images,specific surface area,and the catalytic synthesis reaction conditions of an activated carbon-supported p-toluenesulfonic acid catalyst,and comparing the physical and chemical properties,in...By evaluating the SEM images,specific surface area,and the catalytic synthesis reaction conditions of an activated carbon-supported p-toluenesulfonic acid catalyst,and comparing the physical and chemical properties,infrared spectra,nuclear magnetic resonance spectra,oxidation stability,thermal stability,hydrolytic stability,and extreme pressure anti-wear performance of the synthesized trihydroxymethylpropyl trioleate with imported reference esters,the feasibility of its application as a substitute was investigated.The results indicated that the activated carbon-supported p-toluenesulfonic acid catalyst exhibited loose porosity,high specific surface area,and high esterification efficiency.When synthesized under optimal conditions,the yield rate of trihydroxymethylpropyl trioleate reached 99.3%,with a simple separation process that did not require additional steps such as neutralization and washing and generated minimal wastewater.The physical and chemical properties of the synthesized trihydroxymethylpropyl trioleate were comparable to those of the reference ester in terms of color,viscosity,viscosity index,flash point,and pour point.Moreover,the peak position and peak height in the infrared and nuclear magnetic carbon spectra were essentially the same.Through comprehensive evaluations and comparisons of various properties,it was determined that the performance of trihydroxymethylpropyl trioleate was comparable to that of the imported reference esters.展开更多
Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a...Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.展开更多
Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to thei...Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.展开更多
Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of elect...Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of electro-deposition and hydrothermal reaction.Systematic investigation of Ru doping in the NiMnB matrix revealed significant improvements in electrocatalytic performance.The Ru/NiMnB SCPs demonstrate superior OER/HER activity with low overpotentials of 150 and 103 mV at 50mA/cm^(2)in 1 M KOH,making them highly competitive with state-of-the-art electrocatalysts.Remarkably,the Ru/NiMnB SCPs exhibit a low 2-E cell voltage of 2.80 V at ultra-high current density of 2,000 m A/cm^(2)in 1 M KOH,outperforming the standard benchmark electrodes of RuO_(2)||Pt/C,thereby positioning Ru/NiMnB as one of the best bifunctional electrocatalysts.These SCPs exhibit exceptional high-current characteristics,stability and corrosion resistance,as evidenced by continuous operation at 1,000 mA/cm^(2)high-current density for over 150 h in 6 M KOH at elevated temperatures under harsh industrial conditions.Only a small amount of Ru incorporation significantly enhances the electrocatalytic performances of NiMnB,attributed to increased active sites and improved intrinsic properties such as conductivity,adsorption/desorption capability and reaction rates.Consequently,Ru/NiMnB SCPs present a promising bi-functional electrode concept for efficient green H_(2)production.展开更多
The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplore...The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.展开更多
Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree c...Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.展开更多
High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.展开更多
Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quant...Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quantum confinement of anionicelectrons leads to many interesting phenomena,but a severe chemical instability due to their open structures is one of the majordisadvantages for practical applications.Here we report that one-dimensional(1D)dititanium sulfide electride exhibits an ex-traordinary stability originating from the surface self-passivation and consequent durability in bifunctional electrocatalytic activity.Theoretical calculations identify the uniqueness of the 1D[Ti_(2)S]^(2+)·2e^(−)electride,where multiple cavities form two distinct channelstructures of anionic electrons.Combined surface structure analysis and in-situ work function measurement indicate that thenatural formation of amorphous titanium oxide surface layer in air is responsible for the remarkable inertness in water and pH-varied solutions.This makes the[Ti_(2)S]^(2+)·2e^(−)electride an ideal support for a heterogenous metal-electride hybrid catalyst,demonstrating the enhanced efficiency and superior durability in both the hydrogen evolution and oxygen reduction reactionscompared to commercial Pt/C catalysts.This study will stimulate further exploratory research for developing a chemically stableelectride in reactive conditions,evoking a strategy for a practical electrocatalyst for industrial energy conversions.展开更多
Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM&...Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.展开更多
Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimat...Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.展开更多
基金the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
基金supported in part by the National Key R&D Program of China(Nos.2020YFA0405800,2022YFA1504104,and 2022YFA1605400)the National Natural Science Foundation of China(Nos.12225508,12322515,U1932201,U2032113,and 22075264)+5 种基金the Youth Innovation Promotion Association of CAS(No.2022457)the Institute of Energy,Hefei Comprehensive National Science Center,University Synergy Innovation Program of Anhui Province(No.GXXT-2020-002)and the CAS Iterdisciplinary Innovation Team.We thank the Shanghai Synchrotron Radiation Facility(BL14W1,BL14B1,and SSRF)the Beijing Synchrotron Radiation Facility(1W1B,4B7A,and BSRF)the Hefei Synchrotron Radiation Facility(Infrared Spectroscopy and Microspectroscopy,MCD-A and MCD-B Soochow Beamline for Energy Materials at NSRL)and the USTC Center for Micro and Nanoscale Research and Fabrication for helps in characterizations.
文摘Breakthroughs in energy storage and conversion devices depend heavily on the exploration of low-cost and high-performance materials.Carbon-supported electrocatalysts with dimensional varieties have recently attracted significant attention due to their strong structural flexibility and easy accessibility.Nevertheless,understanding the connection between their electronic,structural properties,and catalytic performance must remain a top priority.Synchrotron radiation(SR)X-ray absorption spectroscopy(XAS)techniques,including hard XAS and soft XAS,are recognized as efficient and comprehensive platforms for probing the surface,interface,and bulk electronic structure of elements of interest in the materials community.In the past decade,the flourishing development of materials science and advanced characterization technologies have led to a deeper understanding at different temporal,longitudinal,and spatial scales.In this review,we briefly describe the concept of XAS techniques and summarize their recent progress in addressing scientific questions on carbon-supported electrocatalysts through the development of advanced instruments and experimental methods.We then discuss the remaining challenges and potential research directions in nextgeneration materials frontiers,and suggest challenges and perspectives for shedding light on the structure–activity relationship.
基金financial supports from NSFC(no.21576139,21503111 and 21376122)Natural Science Foundation of Jiangsu Province(BK20171473)+2 种基金Natural Science Foundation of Jiangsu Higher Education Institutions of China(16KJB150020)National and Local Joint Engineering Research Center of Biomedical Functional Materialsa project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Rational synthesis of a new class of electrocatalysts with high-performance and low-cost is of great significance for future fuel cell devices. Herein, we demonstrate a general one-step simultaneous reduction method to prepare carbon-supported Pd M（M = Co, Fe, Ni） alloyed nanodendrites with the assistance of oleylamine and octadecylene. The morphology, structure and composition of the obtained Pd M nanodendrites/C catalysts have been fully characterized. The combination of the dendritic structural feature and alloyed synergy offer higher atomic utilization efficiency, excellent catalytic activity and enhanced stability for the formic acid oxidation reaction（FAOR）. Strikingly, the as-synthesized Pd Co nanodendrites/C catalyst could afford a mass current density of 2467.7 A g, which is almost 3.53 and 10.4 times higher than those of lab-made Pd/C sample(698.3 A g) and commercial Pd/C catalyst(237.6 A g), respectively. Furthermore, the PdC o nanodendrites/C catalyst also exhibit superior stability relative to the Pd/C catalysts, make it a promising anodic electrocatalyst in practical fuel cells in the future. Additionally, the present feasible synthetic approach is anticipated to provide a versatile strategy toward the preparation of other metal alloy nanodendrites/carbon nanohybrids.
基金supported by the Russian Science Foundation(project No.24-43-00215,http://rscf.ru/project/24-43-00215/).
文摘This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.
基金supported by the National Natural Science Foundation of China(Grant Nos.:21825201,52401244 and 52201227)Henan Province Key Research and Development and Promotion Program(Scientific and Technological Breakthrough Project:232102240088 and 252102230078)+3 种基金the Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(252102230078)Doctoral Research Startup Fund Project of Henan Open University(BSJH-2025-04)Zhejiang Provincial Natural Science Foundation of China(LQ24B020005,LQ23B030001)China Postdoctoral Science Foundation(2024M762442).
文摘Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.
基金financially supported by the National Natural Science Foundation of China(U21A20311,U24A2040,52171141,52272117)the Natural Science Foundation of Shandong Province(ZR2022JQ19)+3 种基金the Key Technology Research Project of Shandong Province(2023CXGC010202)the Taishan Industrial Experts Program(TSCX202306142)the Core Facility Sharing Platform of Shandong Universitythe Foundation of Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University。
文摘Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.
基金supported by the Educational and Tech-nological Department of Hunan Province(No.08B063)the Natural Science Foundation of Science and Technology Department of Hunan Government(No.2007GK3060)the Doctor Foundation of Jishou University(No.JSDXKYZZ200648).
文摘The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli.The key factors affecting the inactivation effciency were investigated,including electric power of lamp, temperature,and pH values.The results show that the TiO2/AC composites have high inactivation properties of E.coli in compari...
基金This work was financially supported by the Science and Technology project of Jiangsu province(BN2015021,XZ-SZ201819).
文摘As a main oxidizer in solid composite propellants,ammonium perchlorate(AP)plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid composite propellants.To improve the performance of solid composite propellant,it is necessary to take measures to modify the thermal decomposition behavior of AP.In recent years,transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraordinary catalytic activity.In this review,we highlight strategies to enhance the thermal decomposition of AP by tuning morphology,varying the types of metal ion,and coupling with carbon analogue.The enhanced catalytic performance can be ascribed to synergistic effect,increased surface area,more exposed active sites,and accelerated electron transportation and so on.The mechanism of AP decomposition mixed with catalyst has also been briefly summarized.Finally,a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.
基金supported by the Natural Science Foundation of China(91645115 and 21473003)High-level talents funding project of Hebei(CL201601,E2016100015)science technology research and development guidance program project of Baoding City(No.16ZF027)
文摘Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.
基金financial support from the Nankai UniversityNational Science Foundation of China(No.21875119)+1 种基金Natural Science Foundation of Tianjin(19JCYBJC17500)the open fund of the key laboratory of advanced functional polymer materials,the ministry of education(Nankai University,KLFPM202001)。
文摘Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.
文摘By evaluating the SEM images,specific surface area,and the catalytic synthesis reaction conditions of an activated carbon-supported p-toluenesulfonic acid catalyst,and comparing the physical and chemical properties,infrared spectra,nuclear magnetic resonance spectra,oxidation stability,thermal stability,hydrolytic stability,and extreme pressure anti-wear performance of the synthesized trihydroxymethylpropyl trioleate with imported reference esters,the feasibility of its application as a substitute was investigated.The results indicated that the activated carbon-supported p-toluenesulfonic acid catalyst exhibited loose porosity,high specific surface area,and high esterification efficiency.When synthesized under optimal conditions,the yield rate of trihydroxymethylpropyl trioleate reached 99.3%,with a simple separation process that did not require additional steps such as neutralization and washing and generated minimal wastewater.The physical and chemical properties of the synthesized trihydroxymethylpropyl trioleate were comparable to those of the reference ester in terms of color,viscosity,viscosity index,flash point,and pour point.Moreover,the peak position and peak height in the infrared and nuclear magnetic carbon spectra were essentially the same.Through comprehensive evaluations and comparisons of various properties,it was determined that the performance of trihydroxymethylpropyl trioleate was comparable to that of the imported reference esters.
基金supported by Research Grants of the NRF(2023R1A2C2003823,RS-2024-00405818)funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea。
文摘Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.
基金financial support by the National Natural Science Foundation of China(No.52102241)Doctor of Suzhou University Scientific Research Foundation(Nos.2022BSK019,2020BS015)+2 种基金the Primary Research and Development Program of Anhui Province(No.201904a05020087)the Natural Science Research Project in Universities of Anhui Province in China(Nos.2022AH051386,KJ2021A1114)the Foundation(No.GZKF202211)of State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology。
文摘Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
基金Core Research Institute Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(No.2018R1A6A1A03025242)in part by the research grant of Kwangwoon University in 2024。
文摘Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of electro-deposition and hydrothermal reaction.Systematic investigation of Ru doping in the NiMnB matrix revealed significant improvements in electrocatalytic performance.The Ru/NiMnB SCPs demonstrate superior OER/HER activity with low overpotentials of 150 and 103 mV at 50mA/cm^(2)in 1 M KOH,making them highly competitive with state-of-the-art electrocatalysts.Remarkably,the Ru/NiMnB SCPs exhibit a low 2-E cell voltage of 2.80 V at ultra-high current density of 2,000 m A/cm^(2)in 1 M KOH,outperforming the standard benchmark electrodes of RuO_(2)||Pt/C,thereby positioning Ru/NiMnB as one of the best bifunctional electrocatalysts.These SCPs exhibit exceptional high-current characteristics,stability and corrosion resistance,as evidenced by continuous operation at 1,000 mA/cm^(2)high-current density for over 150 h in 6 M KOH at elevated temperatures under harsh industrial conditions.Only a small amount of Ru incorporation significantly enhances the electrocatalytic performances of NiMnB,attributed to increased active sites and improved intrinsic properties such as conductivity,adsorption/desorption capability and reaction rates.Consequently,Ru/NiMnB SCPs present a promising bi-functional electrode concept for efficient green H_(2)production.
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L574)the Guizhou Provincial Science and Technology Foundation([2024]ZK General 425 and 438)+1 种基金the National Natural Science Foundation of China(22309033)the Academic Young Talent Foundation of Guizhou Normal University([2022]B05 and B06)。
文摘The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
基金financially supported by the National Natural Science Foundation of China(No.22279047)the Instrumental Analysis Center of Jiangsu University of Science and Technology。
文摘Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.
基金supported by the Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2022M3H4A1A01010832 and RS-2024-00449682)the Basic Science Research Program through the NRF funded by the Ministry of Education(2021R1A6A1A03039696)+1 种基金Computer time allocation has been provided by the US DOE INCITE program(DE-AC02-06CH11357)National ScienceFoundation ACCESS program(NSF-2138296)。
文摘Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quantum confinement of anionicelectrons leads to many interesting phenomena,but a severe chemical instability due to their open structures is one of the majordisadvantages for practical applications.Here we report that one-dimensional(1D)dititanium sulfide electride exhibits an ex-traordinary stability originating from the surface self-passivation and consequent durability in bifunctional electrocatalytic activity.Theoretical calculations identify the uniqueness of the 1D[Ti_(2)S]^(2+)·2e^(−)electride,where multiple cavities form two distinct channelstructures of anionic electrons.Combined surface structure analysis and in-situ work function measurement indicate that thenatural formation of amorphous titanium oxide surface layer in air is responsible for the remarkable inertness in water and pH-varied solutions.This makes the[Ti_(2)S]^(2+)·2e^(−)electride an ideal support for a heterogenous metal-electride hybrid catalyst,demonstrating the enhanced efficiency and superior durability in both the hydrogen evolution and oxygen reduction reactionscompared to commercial Pt/C catalysts.This study will stimulate further exploratory research for developing a chemically stableelectride in reactive conditions,evoking a strategy for a practical electrocatalyst for industrial energy conversions.
基金supported by grants from the National Natural Science Foundation of China (22178339)2023 Innovation-driven Development Special Foundation of Guangxi(AA23023021)the Hundred Talents Program (A) of the Chinese Academy of Sciences
文摘Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.
基金supported by the Natural Science Foundation of China(22309179)the Natural Science Foundation of China(12404049)+4 种基金Natural Science Foundation of Ningxia(2023AAC01003)Guangdong Basic and Applied Basic Research Foundation(2021A1515110156,2022A1515010724,2023A1515110521,2023B1515120095,2024A1515011260)Science and Technology Program of Guangzhou(No.2019050001)the Outstanding Youth Project of Guangdong Natural Science Foundation(2021B1515020051)Dalian Revitalization Talents Program(No.2022RG01).
文摘Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.
