Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then...Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).展开更多
Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled elec...The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled electron transfer(PCET)hinders the overall OER efficiency.Herein,we report an ionic liquid(IL)modified CoSn(OH)_(6)nanocubes(denoted as CoS-n(OH)_(6)-IL),which could be prepared through a facile strategy.The modified IL would not change the structural character-istics of CoSn(OH)_(6),but could effectively regulate the local proton activity near the active sites.The CoSn(OH)_(6)-IL exhibited higher intrinsic OER performances than the pristine CoSn(OH)_(6)in neutral media.For example,the current density of CoS-n(OH)_(6)-IL at 1.8 V versus reversible hydrogen electrode(RHE)was about 4 times higher than that of CoSn(OH)_(6).According to the pH-dependent kinetic investigations,operando electrochemical impedance spectroscopic,chemical probe tests,and deuterium kinetic isotope effects,the interfacial layer of IL could be utilized as a proton transfer mediator to promote the proton transfer,which enhances the surface coverage of OER intermediates and reduces the activation barrier.Consequent-ly,the sluggish OER kinetics would be efficiently accelerated.This study provides a facile and effective strategy to facilitate the PCET processes and is beneficial to guide the rational design of OER electrocatalysts.展开更多
Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face o...Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face of nickel foam(NF).The specific structure of the as-prepared FeOOH@CoMoO_(4)/NF-400s provided pronounced porosity and extensive surface area,enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions.Furthermore,the introduction of FeOOH,which induces electron transfer from FeOOH to CoMoO_(4),confirms their strong electronic interaction,thereby leading to an accelerated surface catalytic reaction.Consequently,the constructed FeOOH@CoMoO_(4)/NF-400s heterostructure demonstrated exceptional oxygen evolu-tion reaction(OER)activity,requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm^(-2),cou-pled with the superior Tafel slope value of 49.56 mV·dec^(-1)and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm^(-2).展开更多
Recovering valuable metals from spent lithium-ion batteries(LIBs)for high value-added application is beneficial for global energy cycling and environmental protection.In this work,we obtain the high-performance N-dope...Recovering valuable metals from spent lithium-ion batteries(LIBs)for high value-added application is beneficial for global energy cycling and environmental protection.In this work,we obtain the high-performance N-doped Ni-Co-Mn(N-NCM)electrocatalyst from waste LIBs,for robust oxygen evolution application.Lithium-rich solution and NCM oxides are effectively separated from ternary cathode materials by sulfation roasting and low-temperature water leaching approach,in which the recovery efficiency of Li metal reaches nearly 100%.By facile NH_(3)treatment,the incorporation of N into NCM significantly increases the ratio of low-valence state Co^(2+)and Mn^(2+),and the formed Mn-N bond benefits the surface catalytic kinetics.Meanwhile,the N doping induces lattice expansion of the NCM,triggering tensile stress to favor the adsorption of the reactant.Thus,the optimized N-NCM electrocatalyst exhibits the superior overpotentials of 256 and 453 mV to achieve the current density of 10 and 100 mA/cm^(2),respectively,with a low Tafel slope of 37.3 mV/dec.This work provides a fresh avenue for recycling spent LIBs in the future to achieve sustainable development.展开更多
Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hin...Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Several tritylodontid taxa have been reported from the Upper Jurassic of the Wucaiwan area in the Junggar Basin of Xinjiang,northwestern China,including Yuanotherium minor.The original study described the partially pr...Several tritylodontid taxa have been reported from the Upper Jurassic of the Wucaiwan area in the Junggar Basin of Xinjiang,northwestern China,including Yuanotherium minor.The original study described the partially preserved postcanine teeth in the middle of the left upper maxilla.After detailed re-examination of the specimen and by CT scanning,3D reconstruction,and scanning electron microscopy observations,we provided a more detailed description of the osteology,neurosensory,and tooth wear pattern for all the bones preserved in this specimen and clarified some characters.Based on new information about the cusp wear pattern,the chewing movement pattern of the dentition and detailed cusp morphology,we discussed the cuspal homology of upper cheek teeth of tritylodontids and postulate a standardized method for cusp identification.We hypothesize that the unique maxilla characteristics furnish the evidence for transitional stages about the evolution of the upper jaw-palate structure in tritylodontids.展开更多
The performance of a material is directly affected by its microstructural development during the solidification phase. Discrete cellular automaton (CA) models are widelyused in materials science to simulate and predic...The performance of a material is directly affected by its microstructural development during the solidification phase. Discrete cellular automaton (CA) models are widelyused in materials science to simulate and predict microstructural growth. This review comprehensively explains the developments and applications of CA in solidification structure simulation, including the theoretical underpinnings, computational procedures, software development, and recent advances. Summarizes the potential and limitations of cellular automata in understanding microstructure evolution during solidification, explores the evolution of microstructures during solidification, and adds to our existing knowledge of cellular automaton theory. Finally, the research trend in simulating the evolution of the solidification microstructure using cellular automaton theory is explored.展开更多
The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea o...The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea oxidation reaction(UOR).Herein,we report the loosely porous CoOOH nano-architecture(CoOOH LPNAs)with hydrophilic surface and abundant oxygen vacancies(Ov)on carbon fiber paper(CFP)by electrochemical reconstruction of the CoP nanoneedles precursor.The resulting three-dimensional electrode exhibited an impressively low potential of 1.38 V at 1000 mA·cm^(−2) and excellent durability for UOR.Furthermore,when tested in an anion exchange membrane(AEM)electrolyzer,it required only 1.53 V at 1000 mA·cm^(−2) for industrial urea-assisted water splitting and operated stably for 100 h without degrada-tion.Experimental and theoretical investigations revealed that rich oxygen vacancies effectively modulate the electronic structure of the CoOOH while creating unique Co3-triangle sites with Co atoms close together.As a result,the adsorption and desorption processes of reactants and intermediates in UOR could be finely tuned,thereby significantly reducing ther-modynamic barriers.Additionally,the superhydrophilic self-supported nanoarray structure facilitated rapid gas bubble release,improving the overall efficiency of the reaction and preventing potential catalyst detachment caused by bubble accumulation,thereby improving both catalytic activity and stability at high current densities.展开更多
Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometri...Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms,thus exhibiting superior electrocata-lytic activity and durability.However,quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging.Herein,a series of ternary Pt_(2)NiCo interme-tallic catalysts(o-Pt_(2)NiCo)with different ordering degree were synthesized by annealing temperature modulation.Among them,the o-Pt_(2)NiCo which annealed at 800℃for two hours exhibits the highest ordering degree and the optimal ORR ac-tivity,which the mass activity of o-Pt_(2)NiCo is 1.8 times and 2.8 times higher than that of disordered Pt_(2)NiCo alloy and Pt/C.Furthermore,the o-Pt_(2)NiCo still maintains 70.8%mass activity after 30,000 potential cycles.Additionally,the ORR activity test results for Pt_(2)NiCo IMC with different ordering degree also provide a positive correlation between the ordering degree and ORR activity.This work provides a prospective design direction for ternary Pt-based electrocatalysts.展开更多
With the urgent need to resolve complex behaviors in nonlinear evolution equations,this study makes a contribution by establishing the local existence of solutions for Cauchy problems associated with equations of mixe...With the urgent need to resolve complex behaviors in nonlinear evolution equations,this study makes a contribution by establishing the local existence of solutions for Cauchy problems associated with equations of mixed types.Our primary contribution is the establishment of solution existence,illuminating the dynamics of these complex equations.To tackle this challenging problem,we construct an approximate solution sequence and apply the contraction mapping principle to rigorously prove local solution existence.Our results significantly advance the understanding of nonlinear evolution equations of mixed types.Furthermore,they provide a versatile,powerful approach for tackling analogous challenges across physics,engineering,and applied mathematics,making this work a valuable reference for researchers in these fields.展开更多
An evolution inequality of Sobolev type involving a nonlinear convolution term is considered.By using the nonlinear capacity method and the contradiction argument,the non-existence of the nontrivial local weak solutio...An evolution inequality of Sobolev type involving a nonlinear convolution term is considered.By using the nonlinear capacity method and the contradiction argument,the non-existence of the nontrivial local weak solution is proved.展开更多
The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).展开更多
The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed t...The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.展开更多
The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their pot...The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.展开更多
On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil ...On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.展开更多
Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces great...Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.展开更多
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
文摘Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
基金supported by the National Natural Science Foundation of China(22209040,22202063).
文摘The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled electron transfer(PCET)hinders the overall OER efficiency.Herein,we report an ionic liquid(IL)modified CoSn(OH)_(6)nanocubes(denoted as CoS-n(OH)_(6)-IL),which could be prepared through a facile strategy.The modified IL would not change the structural character-istics of CoSn(OH)_(6),but could effectively regulate the local proton activity near the active sites.The CoSn(OH)_(6)-IL exhibited higher intrinsic OER performances than the pristine CoSn(OH)_(6)in neutral media.For example,the current density of CoS-n(OH)_(6)-IL at 1.8 V versus reversible hydrogen electrode(RHE)was about 4 times higher than that of CoSn(OH)_(6).According to the pH-dependent kinetic investigations,operando electrochemical impedance spectroscopic,chemical probe tests,and deuterium kinetic isotope effects,the interfacial layer of IL could be utilized as a proton transfer mediator to promote the proton transfer,which enhances the surface coverage of OER intermediates and reduces the activation barrier.Consequent-ly,the sluggish OER kinetics would be efficiently accelerated.This study provides a facile and effective strategy to facilitate the PCET processes and is beneficial to guide the rational design of OER electrocatalysts.
文摘Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face of nickel foam(NF).The specific structure of the as-prepared FeOOH@CoMoO_(4)/NF-400s provided pronounced porosity and extensive surface area,enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions.Furthermore,the introduction of FeOOH,which induces electron transfer from FeOOH to CoMoO_(4),confirms their strong electronic interaction,thereby leading to an accelerated surface catalytic reaction.Consequently,the constructed FeOOH@CoMoO_(4)/NF-400s heterostructure demonstrated exceptional oxygen evolu-tion reaction(OER)activity,requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm^(-2),cou-pled with the superior Tafel slope value of 49.56 mV·dec^(-1)and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm^(-2).
基金Project(2022YFC3900804)supported by the National Key Research and Development Program,ChinaProjects(2021JJ10058,2022JJ10074)supported by the Natural Science Foundation of Hunan Province of China。
文摘Recovering valuable metals from spent lithium-ion batteries(LIBs)for high value-added application is beneficial for global energy cycling and environmental protection.In this work,we obtain the high-performance N-doped Ni-Co-Mn(N-NCM)electrocatalyst from waste LIBs,for robust oxygen evolution application.Lithium-rich solution and NCM oxides are effectively separated from ternary cathode materials by sulfation roasting and low-temperature water leaching approach,in which the recovery efficiency of Li metal reaches nearly 100%.By facile NH_(3)treatment,the incorporation of N into NCM significantly increases the ratio of low-valence state Co^(2+)and Mn^(2+),and the formed Mn-N bond benefits the surface catalytic kinetics.Meanwhile,the N doping induces lattice expansion of the NCM,triggering tensile stress to favor the adsorption of the reactant.Thus,the optimized N-NCM electrocatalyst exhibits the superior overpotentials of 256 and 453 mV to achieve the current density of 10 and 100 mA/cm^(2),respectively,with a low Tafel slope of 37.3 mV/dec.This work provides a fresh avenue for recycling spent LIBs in the future to achieve sustainable development.
文摘Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
文摘Several tritylodontid taxa have been reported from the Upper Jurassic of the Wucaiwan area in the Junggar Basin of Xinjiang,northwestern China,including Yuanotherium minor.The original study described the partially preserved postcanine teeth in the middle of the left upper maxilla.After detailed re-examination of the specimen and by CT scanning,3D reconstruction,and scanning electron microscopy observations,we provided a more detailed description of the osteology,neurosensory,and tooth wear pattern for all the bones preserved in this specimen and clarified some characters.Based on new information about the cusp wear pattern,the chewing movement pattern of the dentition and detailed cusp morphology,we discussed the cuspal homology of upper cheek teeth of tritylodontids and postulate a standardized method for cusp identification.We hypothesize that the unique maxilla characteristics furnish the evidence for transitional stages about the evolution of the upper jaw-palate structure in tritylodontids.
文摘The performance of a material is directly affected by its microstructural development during the solidification phase. Discrete cellular automaton (CA) models are widelyused in materials science to simulate and predict microstructural growth. This review comprehensively explains the developments and applications of CA in solidification structure simulation, including the theoretical underpinnings, computational procedures, software development, and recent advances. Summarizes the potential and limitations of cellular automata in understanding microstructure evolution during solidification, explores the evolution of microstructures during solidification, and adds to our existing knowledge of cellular automaton theory. Finally, the research trend in simulating the evolution of the solidification microstructure using cellular automaton theory is explored.
基金supported by the Applied Basic Research Program of Yunnan Province(202101BE070001-032)Yunnan Major Scientific and Technological Projects(No.202202AG050001).
文摘The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea oxidation reaction(UOR).Herein,we report the loosely porous CoOOH nano-architecture(CoOOH LPNAs)with hydrophilic surface and abundant oxygen vacancies(Ov)on carbon fiber paper(CFP)by electrochemical reconstruction of the CoP nanoneedles precursor.The resulting three-dimensional electrode exhibited an impressively low potential of 1.38 V at 1000 mA·cm^(−2) and excellent durability for UOR.Furthermore,when tested in an anion exchange membrane(AEM)electrolyzer,it required only 1.53 V at 1000 mA·cm^(−2) for industrial urea-assisted water splitting and operated stably for 100 h without degrada-tion.Experimental and theoretical investigations revealed that rich oxygen vacancies effectively modulate the electronic structure of the CoOOH while creating unique Co3-triangle sites with Co atoms close together.As a result,the adsorption and desorption processes of reactants and intermediates in UOR could be finely tuned,thereby significantly reducing ther-modynamic barriers.Additionally,the superhydrophilic self-supported nanoarray structure facilitated rapid gas bubble release,improving the overall efficiency of the reaction and preventing potential catalyst detachment caused by bubble accumulation,thereby improving both catalytic activity and stability at high current densities.
基金supported by the National Natural Science Foundation(22279036)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003).
文摘Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms,thus exhibiting superior electrocata-lytic activity and durability.However,quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging.Herein,a series of ternary Pt_(2)NiCo interme-tallic catalysts(o-Pt_(2)NiCo)with different ordering degree were synthesized by annealing temperature modulation.Among them,the o-Pt_(2)NiCo which annealed at 800℃for two hours exhibits the highest ordering degree and the optimal ORR ac-tivity,which the mass activity of o-Pt_(2)NiCo is 1.8 times and 2.8 times higher than that of disordered Pt_(2)NiCo alloy and Pt/C.Furthermore,the o-Pt_(2)NiCo still maintains 70.8%mass activity after 30,000 potential cycles.Additionally,the ORR activity test results for Pt_(2)NiCo IMC with different ordering degree also provide a positive correlation between the ordering degree and ORR activity.This work provides a prospective design direction for ternary Pt-based electrocatalysts.
基金Supported by the National Natural Science Foundation of China(12201368,62376252)Key Project of Natural Science Foundation of Zhejiang Province(LZ22F030003)Zhejiang Province Leading Geese Plan(2024C02G1123882,2024C01SA100795).
文摘With the urgent need to resolve complex behaviors in nonlinear evolution equations,this study makes a contribution by establishing the local existence of solutions for Cauchy problems associated with equations of mixed types.Our primary contribution is the establishment of solution existence,illuminating the dynamics of these complex equations.To tackle this challenging problem,we construct an approximate solution sequence and apply the contraction mapping principle to rigorously prove local solution existence.Our results significantly advance the understanding of nonlinear evolution equations of mixed types.Furthermore,they provide a versatile,powerful approach for tackling analogous challenges across physics,engineering,and applied mathematics,making this work a valuable reference for researchers in these fields.
基金Supported by Scientific Research Fund of Hunan Provincial Education Departmen(t23A0361)。
文摘An evolution inequality of Sobolev type involving a nonlinear convolution term is considered.By using the nonlinear capacity method and the contradiction argument,the non-existence of the nontrivial local weak solution is proved.
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
基金supported by National Natural Science Foundation of China(22379059)Applied Basic Research Program Project of Liaoning Province(2023JH2/101300224)+4 种基金Service Local Project of the Education Department of Liaoning Province(Enlisting and Leading)(LJKFZ20220201)General Project of the Educational Department of Liaoning Province(LJKMZ20220728)supported by Talent Scientific Research Fund of Liaoning Petrochemical University(2019-XJJL-028)Collaborative Innovation Project of Beijing-Tianjin-Hebei(Tianjin)(22PTXTHZ00020)Basic scientific research project of Liaoning Provincial Department of Education(LJ212410148019)。
文摘The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.
基金supported by the National Natural Science Foundation of China(22179138).
文摘The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.
基金National Key Research and Development Program of China(2020YFA0710302)The Major Research Plan of the National Natural Science Foundation of China(91963206)+2 种基金The National Natural Science Foundation of China(52072169,51972164,51972167,22279053)The Fundamental Research Funds for the Central Universities(14380193)The Program for Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101).
文摘On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.
基金supported by the National Natural Science Foundation of China(52376080 and 52306122)the Anhui Provincial Natural Science Foundation(2308085QE174)+3 种基金the China Postdoctoral Science Foundation(2023TQ0346)the Postdoctoral Fellowship Program of CPSF(GZC20232522)the Fundamental Research Funds for the Central Universities(WK2090000057)the Students’Innovation and Entrepreneurship Foundation of USTC(CY2023C008).
文摘Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.
