Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,...Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.展开更多
Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocat...Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.展开更多
The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)...The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles...Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.展开更多
The direct reduction process is an important development direction of low-carbon ironmaking and efficient comprehensive utilization of poly-metallic iron ore,such as titanomagnetite.However,the defluidization of reduc...The direct reduction process is an important development direction of low-carbon ironmaking and efficient comprehensive utilization of poly-metallic iron ore,such as titanomagnetite.However,the defluidization of reduced iron particles with a high metallization degree at a high temperature will seriously affect the operation of fluidized bed reduction.Coupling the pre-oxidation enhancing reduction and the particle surface modification of titanomagnetite,the behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized bed reduction of titanomagnetite are systematically studied in this paper.Pre-oxidation treatment of titanomagnetite can significantly lower the critical stable reduction fluidization gas velocity to 0.17 m/s,which is reduced by 56%compared to that of titanomagnetite reduction without pre-oxidation,while achieving a metallization degree of>90%,Corresponding to the different reduction fluidization behaviors,three pre-oxidation operation regions have been divided,taking oxidation degrees of 26%and 86%as the boundaries.Focusing on the particle surface morphology evolution in the pre-oxidation-reduction process,the relationship between the surface morphology of pre-oxidized ore and the reduced iron with fluidization properties is built.The improving method of pre-oxidation on the reduction fluidization provides a novel approach to prevent defluidization by particle surface modification,especially for the fluidized bed reduction of poly-metallic iron ore.展开更多
The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction ...The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction treatment and mechanical activation significantly accelerate the extraction of Fe,Ca and Mg from Panxi ilmenite concentration;however,the CaO and MgO contents of the calcined residues obtained from oxidized-reduced ilmenite concentration are higher than the standard values required by chlorination process.The Ca and Mg in oxidized-reduced ilmenite concentration can be leached much faster after mechanical activation,yielding a synthetic rutile which meets the requirements of chlorination process containing 90.50% TiO2 and 1.37% total iron as well as combined CaO and MgO of 1.00%.The optimum oxidation and reduction conditions are as follows：oxidization at 900 ℃ in the presence of oxygen for 15 min and reduction at 750 ℃ by hydrogen for 30 min.展开更多
Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. ...Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction （ORR） in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has ...Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.展开更多
Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0...Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0919),a self-developed antidepressant with selective sigma-1 receptor agonist properties,and its associated mechanisms and targets in traumatic brain injury.Behavioral experiments to assess functional deficits were followed by assessment of neuronal damage through histological analyses and examination of blood-brain barrier permeability and brain edema.Next,we investigated the antioxidative effects of YL-0919 by assessing the levels of traditional markers of oxidative stress in vivo in mice and in vitro in HT22 cells.Finally,the targeted action of YL-0919 was verified by employing a sigma-1 receptor antagonist(BD-1047).Our findings demonstrated that YL-0919 markedly improved deficits in motor function and spatial cognition on day 3 post traumatic brain injury,while also decreasing neuronal mortality and reversing blood-brain barrier disruption and brain edema.Furthermore,YL-0919 effectively combated oxidative stress both in vivo and in vitro.The protective effects of YL-0919 were partially inhibited by BD-1047.These results indicated that YL-0919 relieved impairments in motor and spatial cognition by restraining oxidative stress,a neuroprotective effect that was partially reversed by the sigma-1 receptor antagonist BD-1047.YL-0919 may have potential as a new treatment for traumatic brain injury.展开更多
We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) change...We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.展开更多
In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low...In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.展开更多
The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge...The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge challenge.Herein,a recyclable carbon fiber cloth-supported porous CdS nanorod photocatalyst was fabricated by a two-step hydrothermal treatment using AgVO_(3) nanowires as templates.The results indicated that under visible-light illumination,the carbon cloth-supported porous CdS nanorods showed improved photocatalytic activity for the reduction of Cr(Ⅵ),with an apparent rate constant exceeding that of carbon cloth-supported CdS nanospheres by a factor of 1.65 times.Moreover,the carbon cloth-supported porous CdS nanorods can be easily separated and be reused.This brings a new perspective for developing photocatalysts with high efficiency and recyclability for wastewater treatment.展开更多
A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with ...A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.展开更多
The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can in...Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can influence the permeability of burden due to the fine particle size of dust,which results in incomplete reduction reactions during the smelting process.In this paper,silicomanganese dust,graphite powder,and other additives were pressed to form carbon-containing dust briquettes,and the self-reduction process of the dust briquettes was investigated through the isothermal thermogravimetric method with different carbon–oxygen (C/O) molar ratios,contents of fluxing agents,and reduction temperatures.Various reduction kinetic models for dust briquettes at different temperatures were established.The results show that the reaction fraction of the dust briquettes was about 90%at a C/O molar ratio of 1.2 with optimal reduction efficiency.The addition of CaF_(2)contributed to the decrease in the melting point and viscosity of dust briquettes,which increased their reduction rate.As the reduction temperature increased,the reduction rate of dust briquettes increased.The reduction reaction rate of dust briquettes was controlled through gas-phase diffusion.Meanwhile,their reduction process was analyzed kinetically,with the reaction time of 5 min as the dividing line.The apparent activation energies for the two diffusion stages were 56.10 and 100.52 kJ/mol,respectively.The kinetic equations are expressed as[1-(1-f)^(1/3)]^(2)=0.69e^(-56100/(RT))t and [1-(1-f)^(1/3)]^(2)=2.06e^(-100520/(RT))t.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
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)...Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.展开更多
基金supported by the National Science and Technology Major Project(No.2016ZX05011-003)The Certificate of China Postdoctoral Science Foundation(No.2016M592241).
文摘Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.
文摘Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.
基金supported by the National Projects of the National Research Foundation(NRF)funded by Republic of Korea(#2022R1F1A1072739 and#2022R1A2C1004392)Prof.Nashrah is also grateful for financial supports by the YU Infra-Project in conjunction with BK21 FOUR National Program(#222A251009)by the Nano-Fab-NRF grant funded by Republic of Korea(#2009-0082580).
文摘The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
文摘Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.
基金grateful for financial support from the National Natural Science Foundation of China(Nos.22378405 and 51974287)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA29040100)the National Key Research and Development Program of China(No.2023YFC2908002).
文摘The direct reduction process is an important development direction of low-carbon ironmaking and efficient comprehensive utilization of poly-metallic iron ore,such as titanomagnetite.However,the defluidization of reduced iron particles with a high metallization degree at a high temperature will seriously affect the operation of fluidized bed reduction.Coupling the pre-oxidation enhancing reduction and the particle surface modification of titanomagnetite,the behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized bed reduction of titanomagnetite are systematically studied in this paper.Pre-oxidation treatment of titanomagnetite can significantly lower the critical stable reduction fluidization gas velocity to 0.17 m/s,which is reduced by 56%compared to that of titanomagnetite reduction without pre-oxidation,while achieving a metallization degree of>90%,Corresponding to the different reduction fluidization behaviors,three pre-oxidation operation regions have been divided,taking oxidation degrees of 26%and 86%as the boundaries.Focusing on the particle surface morphology evolution in the pre-oxidation-reduction process,the relationship between the surface morphology of pre-oxidized ore and the reduced iron with fluidization properties is built.The improving method of pre-oxidation on the reduction fluidization provides a novel approach to prevent defluidization by particle surface modification,especially for the fluidized bed reduction of poly-metallic iron ore.
基金Project(2009FJ3082)supported by Research Project of Science and Technology in Hunan Province,ChinaProject(2007CB613606)supported by the National Basic Research Program of China
文摘The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction treatment and mechanical activation significantly accelerate the extraction of Fe,Ca and Mg from Panxi ilmenite concentration;however,the CaO and MgO contents of the calcined residues obtained from oxidized-reduced ilmenite concentration are higher than the standard values required by chlorination process.The Ca and Mg in oxidized-reduced ilmenite concentration can be leached much faster after mechanical activation,yielding a synthetic rutile which meets the requirements of chlorination process containing 90.50% TiO2 and 1.37% total iron as well as combined CaO and MgO of 1.00%.The optimum oxidation and reduction conditions are as follows：oxidization at 900 ℃ in the presence of oxygen for 15 min and reduction at 750 ℃ by hydrogen for 30 min.
基金Project(10JJ9003) supported by Hunan Provincial Natural Science Foundation and Xiangtan Natural Science United Foundation,China Project(11K023) supported by Scientific Research Fund of Hunan Provincial Education Department,China
文摘Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction （ORR） in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金funded by the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China(No.22471103,22425105,22201111,21931001,22221001,and 22271124)+5 种基金Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04)the 111 Project(B20027)as well as the National Natural Science Foundation of Gansu Province(22JR5RA470)the Fundamental Research Funds for the Central Universities(lzujbky-2023-eyt03)supported by the Agency for Science,Technology and Research(A*STAR)MTC Individual Research Grants(IRG)M22K2c0078.
文摘Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.
基金supported by the National Natural Science Foundation of China,Nos.82204360(to HM)and 82270411(to GW)National Science and Technology Innovation 2030 Major Program,No.2021ZD0200900(to YL)。
文摘Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0919),a self-developed antidepressant with selective sigma-1 receptor agonist properties,and its associated mechanisms and targets in traumatic brain injury.Behavioral experiments to assess functional deficits were followed by assessment of neuronal damage through histological analyses and examination of blood-brain barrier permeability and brain edema.Next,we investigated the antioxidative effects of YL-0919 by assessing the levels of traditional markers of oxidative stress in vivo in mice and in vitro in HT22 cells.Finally,the targeted action of YL-0919 was verified by employing a sigma-1 receptor antagonist(BD-1047).Our findings demonstrated that YL-0919 markedly improved deficits in motor function and spatial cognition on day 3 post traumatic brain injury,while also decreasing neuronal mortality and reversing blood-brain barrier disruption and brain edema.Furthermore,YL-0919 effectively combated oxidative stress both in vivo and in vitro.The protective effects of YL-0919 were partially inhibited by BD-1047.These results indicated that YL-0919 relieved impairments in motor and spatial cognition by restraining oxidative stress,a neuroprotective effect that was partially reversed by the sigma-1 receptor antagonist BD-1047.YL-0919 may have potential as a new treatment for traumatic brain injury.
基金Funded by Scientific and Technological Innovation Project of Carbon Emission Peak and Carbon Neutrality of Jiangsu Province(No.BE2022028-4)。
文摘We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.
基金supported by Taishan Scholars Foundation of Shandong province(tsqn 201909058)。
文摘In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.
文摘The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge challenge.Herein,a recyclable carbon fiber cloth-supported porous CdS nanorod photocatalyst was fabricated by a two-step hydrothermal treatment using AgVO_(3) nanowires as templates.The results indicated that under visible-light illumination,the carbon cloth-supported porous CdS nanorods showed improved photocatalytic activity for the reduction of Cr(Ⅵ),with an apparent rate constant exceeding that of carbon cloth-supported CdS nanospheres by a factor of 1.65 times.Moreover,the carbon cloth-supported porous CdS nanorods can be easily separated and be reused.This brings a new perspective for developing photocatalysts with high efficiency and recyclability for wastewater treatment.
文摘A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
基金financially supported by the Hubei Provincial Key Laboratory for New Processes of Ironmaking and Steelmaking (No. KF-20-3)Shandong Postdoctoral Science Foundation, China (No. SDCX-ZG-202301014)。
文摘Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can influence the permeability of burden due to the fine particle size of dust,which results in incomplete reduction reactions during the smelting process.In this paper,silicomanganese dust,graphite powder,and other additives were pressed to form carbon-containing dust briquettes,and the self-reduction process of the dust briquettes was investigated through the isothermal thermogravimetric method with different carbon–oxygen (C/O) molar ratios,contents of fluxing agents,and reduction temperatures.Various reduction kinetic models for dust briquettes at different temperatures were established.The results show that the reaction fraction of the dust briquettes was about 90%at a C/O molar ratio of 1.2 with optimal reduction efficiency.The addition of CaF_(2)contributed to the decrease in the melting point and viscosity of dust briquettes,which increased their reduction rate.As the reduction temperature increased,the reduction rate of dust briquettes increased.The reduction reaction rate of dust briquettes was controlled through gas-phase diffusion.Meanwhile,their reduction process was analyzed kinetically,with the reaction time of 5 min as the dividing line.The apparent activation energies for the two diffusion stages were 56.10 and 100.52 kJ/mol,respectively.The kinetic equations are expressed as[1-(1-f)^(1/3)]^(2)=0.69e^(-56100/(RT))t and [1-(1-f)^(1/3)]^(2)=2.06e^(-100520/(RT))t.
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 Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
基金supported by the National Natural Science Foundation of China(22279025,21773048)the Natural Science Foundation of Heilongjiang Province(LH2021A013)+1 种基金the Sichuan Science and Technology Program(2021YFSY0022)the Fundamental Research Funds for the Central Universities(2023FRFK06005,HIT.NSRIF202204)。
文摘Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.
