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
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
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
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
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
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
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
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.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
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
Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field c...Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.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
Building a lunar human base is one of the important goals of human lunar exploration.This paper proposes a method for the production of oxygen by combining photothermal synergistic water decomposition with high-temper...Building a lunar human base is one of the important goals of human lunar exploration.This paper proposes a method for the production of oxygen by combining photothermal synergistic water decomposition with high-temperature carbon dioxide electrolysis,utilizing the full solar spectrum.The optimal oxygen production rates under different solid oxide electrolysis cell inlet temperatures T_(e),ultraviolet(UV)separation wavelengths λ_(2),infrared(IR)separation wavelengths,and photovoltaic cell materials were explored.The results indicate that the inlet temperature of the solid oxide electrolysis cell should be as high as possible so that more carbon dioxide can be converted into carbon monoxide and oxygen.Furthermore,when the ultraviolet separation wavelength is approximately 385 nm,the proportion of solar energy allocated to the photoreaction and electrolysis cell is optimal,and the oxygen production rate is highest at 2.754×10^(-4) mol/s.Moreover,the infrared separation wavelength should be increased as much as possible within the allowable range to increase the amount of solar radiation allocated to the electrolysis cell to improve the rate of oxygen generation.In addition,copper indium gallium selenide(CIGS)has a relatively large separation wavelength,which can result in a high oxygen production rate of 3.560×10^(-4) mol/s.The proposed integrated oxygen production method can provide a feasible solution for supplying oxygen to a lunar human base.展开更多
Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and exp...Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.展开更多
Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for...Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for further investigation,and the specifically exposed crystal faces of CeO_(2)may have an impact on the performance of nitrogen doped CeO_(2).Herein,nitrogen-doped CeO_(2)with different morphologies and exposed crystal faces was prepared,and its performances in the photocatalytic degradation of tetracycline(TC)or hydrogen production via water splitting were evaluated.Density functional theory(DFT)was used to simulate the band structures,density of states,and oxygen defect properties of different CeO_(2)structures.It was found that nitrogen doping and OVs synergistically promoted the catalytic activity of nitrogen-doped CeO_(2).In addition,the exposed crystal faces of CeO_(2)have significant effects on the introduction of nitrogen and the ease of OV generation,as well as the synergistic effect of nitrogen doping with OVs.Among them,the rod-like nitrogen-doped CeO_(2)with exposed(110)face(R-CeO_(2)-NH_(3))showed a photocatalytic degradation ratio of 73.59%for TC and hydrogen production of 156.89μmol/g,outperforming other prepared photocatalysts.展开更多
The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosi...The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosite(Pb-J)were 130℃,30 g/L H_(2)SO_(4),15 g/L Fe^(3+),and an oxygen partial pressure of 0.4 MPa.Furthermore,increased Fe^(3+)concentration and oxygen partial pressure did not enhance jarosite formation.Conversely,lowering the temperature and increasing the H_(2)SO_(4) concentration facilitated PbSO_(4) formation and inhibited its further conversion to Pb-J.Additionally,the effects of potassium sulfate,sodium sulfate,and high concentrations of zinc sulfate on the phase transformation of galena were examined through leaching tests,XRD,SEM-EDS,and FT-IR analyses.All three sulfates inhibited the conversion of galena to Pb-J.Among these,potassium sulfate prevented Pb-J formation and converted it more thoroughly into potassium jarosite.However,high concentrations of zinc sulfate facilitated the crystallization of both PbSO_(4) and Pb-J,which altered the morphology of the product.Zinc ions coprecipitated with Pb-J,thereby integrating into the product.展开更多
Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involv...Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.展开更多
The melt stirring in a large copper smelting oxygen bottom-blown furnace is caused by the large amount of gas movement blown in by two rows of oxygen lances.At present,the two rows of oxygen lances provide oxygen of e...The melt stirring in a large copper smelting oxygen bottom-blown furnace is caused by the large amount of gas movement blown in by two rows of oxygen lances.At present,the two rows of oxygen lances provide oxygen of equal strength,and the stirring in the central area of the melt is insufficient,which restricts the efficient progress of the smelting reaction.This study proposes a strong-weak coupling oxygen supply method and establishes an equivalent model based on a large bottom-blown furnace(LBBF)of an enterprise to simulate the bubble characteristics and flow characteristics of the molten pool.The results show that adjusting the flow ratio between the two rows of oxygen lances can create a“strong”and a“weak”coexisting source of disturbance in an LBBF.It is worth noting that when the flow rate ratio of the two rows of oxygen lances is 1.6,the peak velocity generated by the“strong”distur bance source in the molten pool increases by 18.92%,and the disturbance range increases.This method effectively strengthens the stirring in the central area of the molten pool,improves smelting efficiency,and does not produce harmful melt splashes.It provides important guidance for optimizing production practice.展开更多
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).
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.
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.
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(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.
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the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
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.
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(52164028,52274297)the Start-up Research Foundation of Hainan University(KYQD(ZR)20008,KYQD(ZR)21125,KYQD(ZR)23169))+1 种基金Collaborative Innovation Center of Marine Science and Technology of Hainan University(XTCX2022HYC14)Innovative Research Project for Postgraduate Students in Hainan Province(Qhyb2024-95).
文摘Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
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.
基金supported by the National Natural Science Foundation of China(52106276 and 52130601).
文摘Building a lunar human base is one of the important goals of human lunar exploration.This paper proposes a method for the production of oxygen by combining photothermal synergistic water decomposition with high-temperature carbon dioxide electrolysis,utilizing the full solar spectrum.The optimal oxygen production rates under different solid oxide electrolysis cell inlet temperatures T_(e),ultraviolet(UV)separation wavelengths λ_(2),infrared(IR)separation wavelengths,and photovoltaic cell materials were explored.The results indicate that the inlet temperature of the solid oxide electrolysis cell should be as high as possible so that more carbon dioxide can be converted into carbon monoxide and oxygen.Furthermore,when the ultraviolet separation wavelength is approximately 385 nm,the proportion of solar energy allocated to the photoreaction and electrolysis cell is optimal,and the oxygen production rate is highest at 2.754×10^(-4) mol/s.Moreover,the infrared separation wavelength should be increased as much as possible within the allowable range to increase the amount of solar radiation allocated to the electrolysis cell to improve the rate of oxygen generation.In addition,copper indium gallium selenide(CIGS)has a relatively large separation wavelength,which can result in a high oxygen production rate of 3.560×10^(-4) mol/s.The proposed integrated oxygen production method can provide a feasible solution for supplying oxygen to a lunar human base.
基金Project(52174338)supported by the National Natural Science Foundation of ChinaProjects(2022JJ20086,2021JJ30796)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(2023CXQD005)supported by the Central South University Innovation-Driven Research Programme,ChinaProject(23B0841)supported by the Education Department of Hunan Provincial Government,China。
文摘Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.
基金Project(52164025)supported by the National Natural Science Foundation of ChinaProject([2020]1Y219)supported by the Basic Research Program from the Science&Technology Department of Guizhou Province,China+2 种基金Project([2019]30)supported by the Training Project from Guizhou University,ChinaProject([2023]04)supported by the Guizhou University Innovation Talent Team Project,ChinaProject([2022]041)supported by the Natural Science Research Project of Guizhou Provincial Department of Education,China。
文摘Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for further investigation,and the specifically exposed crystal faces of CeO_(2)may have an impact on the performance of nitrogen doped CeO_(2).Herein,nitrogen-doped CeO_(2)with different morphologies and exposed crystal faces was prepared,and its performances in the photocatalytic degradation of tetracycline(TC)or hydrogen production via water splitting were evaluated.Density functional theory(DFT)was used to simulate the band structures,density of states,and oxygen defect properties of different CeO_(2)structures.It was found that nitrogen doping and OVs synergistically promoted the catalytic activity of nitrogen-doped CeO_(2).In addition,the exposed crystal faces of CeO_(2)have significant effects on the introduction of nitrogen and the ease of OV generation,as well as the synergistic effect of nitrogen doping with OVs.Among them,the rod-like nitrogen-doped CeO_(2)with exposed(110)face(R-CeO_(2)-NH_(3))showed a photocatalytic degradation ratio of 73.59%for TC and hydrogen production of 156.89μmol/g,outperforming other prepared photocatalysts.
基金Projects(2023AG05008,202302AB080012)supported by the Yunnan Major Scientific and Technological Program,ChinaProject(202405AC350015)supported by the Science and Technology Talent Programme of Yunnan Province,China。
文摘The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosite(Pb-J)were 130℃,30 g/L H_(2)SO_(4),15 g/L Fe^(3+),and an oxygen partial pressure of 0.4 MPa.Furthermore,increased Fe^(3+)concentration and oxygen partial pressure did not enhance jarosite formation.Conversely,lowering the temperature and increasing the H_(2)SO_(4) concentration facilitated PbSO_(4) formation and inhibited its further conversion to Pb-J.Additionally,the effects of potassium sulfate,sodium sulfate,and high concentrations of zinc sulfate on the phase transformation of galena were examined through leaching tests,XRD,SEM-EDS,and FT-IR analyses.All three sulfates inhibited the conversion of galena to Pb-J.Among these,potassium sulfate prevented Pb-J formation and converted it more thoroughly into potassium jarosite.However,high concentrations of zinc sulfate facilitated the crystallization of both PbSO_(4) and Pb-J,which altered the morphology of the product.Zinc ions coprecipitated with Pb-J,thereby integrating into the product.
基金supported by the National Natural Science Foundation of China(No.22375021,22235003,22261132516&22205021)the BIT Research and Innovation 265 Promoting Project(Grant No.2023YCXZ017)。
文摘Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.
基金Project(2022YFC3901501)supported by the National Key R&D Program of ChinaProject(U20A20273)supported by the National Natural Science Foundation of China+1 种基金Project(2022JJ10078)supported by the Natural Science Foundation for Distinguished Young Scholars of Hunan Province,ChinaProject(2021RC3005)supported by the Science and Technology Innovation Program of Hunan Province,China。
文摘The melt stirring in a large copper smelting oxygen bottom-blown furnace is caused by the large amount of gas movement blown in by two rows of oxygen lances.At present,the two rows of oxygen lances provide oxygen of equal strength,and the stirring in the central area of the melt is insufficient,which restricts the efficient progress of the smelting reaction.This study proposes a strong-weak coupling oxygen supply method and establishes an equivalent model based on a large bottom-blown furnace(LBBF)of an enterprise to simulate the bubble characteristics and flow characteristics of the molten pool.The results show that adjusting the flow ratio between the two rows of oxygen lances can create a“strong”and a“weak”coexisting source of disturbance in an LBBF.It is worth noting that when the flow rate ratio of the two rows of oxygen lances is 1.6,the peak velocity generated by the“strong”distur bance source in the molten pool increases by 18.92%,and the disturbance range increases.This method effectively strengthens the stirring in the central area of the molten pool,improves smelting efficiency,and does not produce harmful melt splashes.It provides important guidance for optimizing production practice.
