Design and fabrication of framework-structured porous precursors have been regarded as a prospective albeit challenging strategy to obtain bimetal/NC-enriched bifunctional elecrocatalysts. In this work, an effective b...Design and fabrication of framework-structured porous precursors have been regarded as a prospective albeit challenging strategy to obtain bimetal/NC-enriched bifunctional elecrocatalysts. In this work, an effective bottom-up approach involving solution-based self-assembly and a post-annealing process was developed to confine (Co, Zn)-N-C active sites into N-enriched graphitic carbon nanocages. This novel architecture containing N-doped-C stabilized bimetallic nanoparticles derived from ZIF precursors was well-studied by a series of characterization and analysis techniques. Details were given that these well-dispersed (Co, Zn) nanoparticles were encapsulated into the pyridinic-N-dominated graphitic carbon nanocage with a total metal loading of approximately 7.4 at.%. This favorable hierarchical structure not only enhances the electron conductivity, but also owns a sufficient BET surface area facilitating the gas-liquid-solid triphase reaction and producing more space to store discharge products. Importantly, results infer that the interesting nanoframes manifests a satisfying ORR/OER activity and enhanced cell performance whether liquid or solid-state electrolytes are used. As such, our work rationalizes that this type of cage-shaped bimetal-N-C material is promising for high-performance Li-O2 batteries.展开更多
The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system...The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.展开更多
Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements hav...Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.展开更多
The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-ass...The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.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
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparti...Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.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
There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNT...There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.展开更多
The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile...The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.展开更多
One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel ...One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel bifunctional layer consisting of vertically aligned carbon nanotubes(VACNTs)and nanoparticles of Pt-Co catalysts(Pt-Co/VACNTs)is reported for highperformance PEMFCs.Readily prepared by a two-step process,the Pt-Co/VACNTs layer with a hydrophilic catalyst-loaded side and a hydrophobic gas diffusion side enables a PTFE-free electrode structure with fully exposed catalyst active sites and superior gas–water diffusion capability.When tested in a PEMFC,the bi-functional Pt-Co/VACNTs layer with ultralow Pt loading(~65μgcathodecm-2)demonstrates a power density of 19.5 kW gPt cathode-1 at 0.6 V,more than seven times that of a cell with commercial Pt/C catalyst(2.7 kW gPt cathode-1 at 0.6 V)at a loading of 400μgcathodecm-2 tested under similar conditions.This remarkable design of VACNTs-based catalyst with dual functionalities enables much lower Pt loading,faster mass transport,and higher electrochemical performance and stability.Further,the preparation procedure can be easily scaled up for low-cost fabrication and commercialization.展开更多
A novel bi-functional photorefractive acrylate polymer with pendant carbazolyl groups and azo derivatives as side chains was synthesized. Photorefractive experiments showed a high two-beam coupling gain coefficient of...A novel bi-functional photorefractive acrylate polymer with pendant carbazolyl groups and azo derivatives as side chains was synthesized. Photorefractive experiments showed a high two-beam coupling gain coefficient of 93 cm(-1), diffraction efficiency of 12% and electro-optic coefficient of 26 pm/V were obtained.展开更多
We report an organic/inorganic hybridized nanocomposite consisting of a bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl serves as a polymeric charge-transporting and second-order nonliner optical matrix, ...We report an organic/inorganic hybridized nanocomposite consisting of a bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl serves as a polymeric charge-transporting and second-order nonliner optical matrix, and CdS nanoparticles as photosensitizers to manifest photorefractive （PR） effect. The unpoled PVNPAK film exhibits a second harmonic generation （SHG） coefficient of 4.7 pm/V due to the possibility of self-alignment of the azo chromophore. Significant enhancement of photoconductivity is noticed with the increase of CdS nanoparticles concentration. The photorefractive property of the polymer nanocomposites were determined by two-beam coupling （TBC） experiment. The TBC gain and diffraction efficiency of 11.89 cm-1 and 3.2% were obtained for PVNPAK/CdS at zero electrical field.展开更多
Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covale...Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.展开更多
The aim of this theoretical investigation is the description of the multicomponent mass transfer process in the Nano- Composites (NC)—novel materials with the bi-functional matrix. The new theoretical NC Model is ass...The aim of this theoretical investigation is the description of the multicomponent mass transfer process in the Nano- Composites (NC)—novel materials with the bi-functional matrix. The new theoretical NC Model is assigned for the modern theoretical investigations of the multicomponent mass transfer kinetics in the bi-functional NC materials. This NC Model for the multicomponent mass transfer in the bi-functional NC matrix includes into the consideration the proposed key conception—two co-existing routes: I—chemical reactions onto the active NC centers-sites, and II—diffusion mass transfer inside the bi-functional NC matrix. All the results are presented in the terms of the additional key concept: propagating multicomponent concentration waves (W+) in the NC matrix. The used W+ concept for the description of the multicomponent NC mass transfer kinetics give the clear interpretation of the computerized results. The mass transfer process in the NC matrix has been described theoretically by computerized simulation. The results of the calculations are new and illustrated by author’s animations showing visually the propagation of the multicomponent concentration waves (W) inside the various NC matrixes: r-beads, cylindrical ro-fibers, or planar L-membranes. Two variants of modeling for mass transfer diffusion kinetics in the bi-functional NC matrixes with one (Variant 1), or two (Variant 2) dissociation-association reactions at the active nano-sites (R0) are considered theoretically.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
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
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
As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind en...As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.展开更多
A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail e...A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles(Co@D-NCNT/CW)to enhance the ORR/OER activity and stability in seawater medium.During the preparation process,the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material,modulating charge distribution and influencing the adsorption and activation processes.The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion.The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in sea water-based alkaline electrolyte.The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm^(-2)and a long-term cycling performance over 500 h.The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm^(-2)and stabilized over 30 h.Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co,optimizing the binding affinity of the Co sites with intermediates and weakening Cl^(-)adsorption.This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures,boosting the development of seawater-based ZABs.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
基金National Basic Research Program of China (No. 2014CB932301)National Natural Science Foundation of China (No. 21473040)Science & Technology Commission of Shanghai Municipality, China (No. 08DZ2270500).
文摘Design and fabrication of framework-structured porous precursors have been regarded as a prospective albeit challenging strategy to obtain bimetal/NC-enriched bifunctional elecrocatalysts. In this work, an effective bottom-up approach involving solution-based self-assembly and a post-annealing process was developed to confine (Co, Zn)-N-C active sites into N-enriched graphitic carbon nanocages. This novel architecture containing N-doped-C stabilized bimetallic nanoparticles derived from ZIF precursors was well-studied by a series of characterization and analysis techniques. Details were given that these well-dispersed (Co, Zn) nanoparticles were encapsulated into the pyridinic-N-dominated graphitic carbon nanocage with a total metal loading of approximately 7.4 at.%. This favorable hierarchical structure not only enhances the electron conductivity, but also owns a sufficient BET surface area facilitating the gas-liquid-solid triphase reaction and producing more space to store discharge products. Importantly, results infer that the interesting nanoframes manifests a satisfying ORR/OER activity and enhanced cell performance whether liquid or solid-state electrolytes are used. As such, our work rationalizes that this type of cage-shaped bimetal-N-C material is promising for high-performance Li-O2 batteries.
基金Project supported by the National Key R&D Program of China(2023YFC3707201)National Natural Science Foundation of China(52200136,52270112,22106172)National Energy-Saving and Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)。
文摘The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.
基金financially supported by the National Natural Science Foundation of China (22350410386,W2412116,22375200,U22A202175,21961142006)。
文摘Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.
基金financial support of the National Natural Science Foundation of China (21875247,21072221, 21172252)the Project of Talent Cultivation for Carbon Peak and Carbon Neutrality of the University of Chinese of Academy of Science
文摘The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.
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supported by the National Natural Science Foundation of China(No.12205165)Hebei Province Innovation Ability Improvement Plan Project(No.225676111H).
文摘Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
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financial support from the National Natural Science Foundation of China (U1510120, 91645110)the Project of Introducing Overseas Intelligence High Education of China (2017-2018)+1 种基金the Graduate Thesis Innovation Foundation of Donghua University (EG2016034)the College of Environmental Science and Engineering, State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University
文摘There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.
基金supported by the National Natural Science Foundation of China (51901083)the Fundamental Research Funds for the Central Universities。
文摘The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.
基金supported by the National Natural Science Foundation of China under(No.21878158,2182880,51678291)Jiangsu Natural Science Foundation for Distinguished Young Scholars(No.BK20170043)+3 种基金the National Key R&D Program of China(2018YFB1502903)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)China Postdoctoral Science Foundation(2019M660112)the Jiangsu Postdoctoral Science Funding Project
文摘One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel bifunctional layer consisting of vertically aligned carbon nanotubes(VACNTs)and nanoparticles of Pt-Co catalysts(Pt-Co/VACNTs)is reported for highperformance PEMFCs.Readily prepared by a two-step process,the Pt-Co/VACNTs layer with a hydrophilic catalyst-loaded side and a hydrophobic gas diffusion side enables a PTFE-free electrode structure with fully exposed catalyst active sites and superior gas–water diffusion capability.When tested in a PEMFC,the bi-functional Pt-Co/VACNTs layer with ultralow Pt loading(~65μgcathodecm-2)demonstrates a power density of 19.5 kW gPt cathode-1 at 0.6 V,more than seven times that of a cell with commercial Pt/C catalyst(2.7 kW gPt cathode-1 at 0.6 V)at a loading of 400μgcathodecm-2 tested under similar conditions.This remarkable design of VACNTs-based catalyst with dual functionalities enables much lower Pt loading,faster mass transport,and higher electrochemical performance and stability.Further,the preparation procedure can be easily scaled up for low-cost fabrication and commercialization.
文摘A novel bi-functional photorefractive acrylate polymer with pendant carbazolyl groups and azo derivatives as side chains was synthesized. Photorefractive experiments showed a high two-beam coupling gain coefficient of 93 cm(-1), diffraction efficiency of 12% and electro-optic coefficient of 26 pm/V were obtained.
基金Funded by the National Natural Science Foundation of China (No.50802069)the Natural Science Foundation of Wuhan University of Tech-nology (471-38650378)
文摘We report an organic/inorganic hybridized nanocomposite consisting of a bi-functional poly（N-vinyl）-3-[p-nitrophenylazo]carbazolyl serves as a polymeric charge-transporting and second-order nonliner optical matrix, and CdS nanoparticles as photosensitizers to manifest photorefractive （PR） effect. The unpoled PVNPAK film exhibits a second harmonic generation （SHG） coefficient of 4.7 pm/V due to the possibility of self-alignment of the azo chromophore. Significant enhancement of photoconductivity is noticed with the increase of CdS nanoparticles concentration. The photorefractive property of the polymer nanocomposites were determined by two-beam coupling （TBC） experiment. The TBC gain and diffraction efficiency of 11.89 cm-1 and 3.2% were obtained for PVNPAK/CdS at zero electrical field.
基金the financially supported from the National Nat-ural Science Foundation of China(Nos.21978178,22008157,and 21776187)the Distinguished Young Scholars for the Natural Science Foundation of Sichuan Province(No.2023NSFSC1915)。
文摘Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.
文摘The aim of this theoretical investigation is the description of the multicomponent mass transfer process in the Nano- Composites (NC)—novel materials with the bi-functional matrix. The new theoretical NC Model is assigned for the modern theoretical investigations of the multicomponent mass transfer kinetics in the bi-functional NC materials. This NC Model for the multicomponent mass transfer in the bi-functional NC matrix includes into the consideration the proposed key conception—two co-existing routes: I—chemical reactions onto the active NC centers-sites, and II—diffusion mass transfer inside the bi-functional NC matrix. All the results are presented in the terms of the additional key concept: propagating multicomponent concentration waves (W+) in the NC matrix. The used W+ concept for the description of the multicomponent NC mass transfer kinetics give the clear interpretation of the computerized results. The mass transfer process in the NC matrix has been described theoretically by computerized simulation. The results of the calculations are new and illustrated by author’s animations showing visually the propagation of the multicomponent concentration waves (W) inside the various NC matrixes: r-beads, cylindrical ro-fibers, or planar L-membranes. Two variants of modeling for mass transfer diffusion kinetics in the bi-functional NC matrixes with one (Variant 1), or two (Variant 2) dissociation-association reactions at the active nano-sites (R0) are considered theoretically.
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 National Natural Science Foundation of China(No.52102470)。
文摘As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.
基金financial support by the Excellent Youth Foundation of Shandong Province(No.ZR2022YQ22)National Natural Science Foundation of China(No.32101451)Youth Innovation Team Project of Shandong Province(No.2022KJ303)。
文摘A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles(Co@D-NCNT/CW)to enhance the ORR/OER activity and stability in seawater medium.During the preparation process,the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material,modulating charge distribution and influencing the adsorption and activation processes.The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion.The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in sea water-based alkaline electrolyte.The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm^(-2)and a long-term cycling performance over 500 h.The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm^(-2)and stabilized over 30 h.Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co,optimizing the binding affinity of the Co sites with intermediates and weakening Cl^(-)adsorption.This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures,boosting the development of seawater-based ZABs.
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.
