A low-grade nickel laterite ore was reduced at different reduction temperatures. The morphology of metallic particles was investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS)...A low-grade nickel laterite ore was reduced at different reduction temperatures. The morphology of metallic particles was investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Experimental results indicate that the metallic nickel and iron gradually assemble and grow into larger spherical particles with increasing temperature and prolonging time. After reduction, the nickel laterite ore obviously changes into two parts of Fe-Ni metallic particles and slag matrix. An obvious relationship is found between the reduction of iron magnesium olivine and its crystal chemical properties. The nickel and iron oxides are reduced to metallic by reductant, and the lattice of olivine is destroyed. The entire reduction process is comprised of oxide reduction and metallic phase growth.展开更多
In order to ascertain the reaction behavior of rare earth minerals in coal-based reduction, X-ray diffraction(XRD), scanning electron microscopy(SEM), and energy dispersive spectroscopy(EDS) analyses were applie...In order to ascertain the reaction behavior of rare earth minerals in coal-based reduction, X-ray diffraction(XRD), scanning electron microscopy(SEM), and energy dispersive spectroscopy(EDS) analyses were applied to investigate the rare earth minerals in Bayan Obo.The occurrence state and regularity of rare earth elements were analyzed under different reduction time. The results reveal that rare earth elements in rare earth minerals exist in RE(CO3)F(bastnaesite) and REPO4(monazite). In this research, at 1,498 K with a C/O molar ratio(i.e., molar ratio of fixed carbon in the coal to reducible oxygen in the ore) of2.5, rare earth minerals primarily decompose into RE2O3at5 min. When the time is extended to 10 min, solid-phase reactions occur among RE2O3, CaO, and SiO2, and the resultant is cerium wollastonite(CaO·2RE2O3·3SiO2). At reaction time 〉20 min, rare earth elements mainly exist in cerium wollastonite(CaO·2RE2O3·3SiO2), and the grain size varies in the range of 10–30 μm. The results show that coal-based reduction is efficient to recover rare earth minerals in reduced materials.展开更多
The application of coal-based reduction in the efficient recovery of iron from refractory iron-bearing resources is comprehensively reviewed.Currently,the development and beneficiation of refractory iron-bearing resou...The application of coal-based reduction in the efficient recovery of iron from refractory iron-bearing resources is comprehensively reviewed.Currently,the development and beneficiation of refractory iron-bearing resources have attracted increasing attention.However,the effect of iron recovery by traditional beneficiation methods is unacceptable.Coal-based reduction followed by magnetic separation is proposed,which adopts coal as the reductant to reduce iron oxides to metallic iron below the melting temperature.The metallic iron particles aggregate and grow,and the particle size continuously increases to be suitable for magnetic separation.The optimization and application of coal-based reduction have been abundantly researched.A detailed literature study on coal-based reduction is performed from the perspectives of thermodynamics,reduction kinetics,growth of metallic iron particles,additives,and application.The coal-based reduction industrial equipment can be developed based on the existing pyrometallurgical equipments,rotary hearth furnace and rotary kiln,which are introduced briefly.However,coal-based reduction currently mainly adopts coal as a reductant and fuel,which may result in high levels of carbon dioxide emissions,energy consumption,and pollution.Technological innovation aiming at decreasing carbon dioxide emissions is a new trend of green and sustainable development of the steel industry.Therefore,the substitution of coal with clean energy(hydrogen,biomass,etc.)for iron oxide reduction shows promise in the future.展开更多
To understand the migration mechanisms of phosphorus(P)during coal-based reduction,a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions.The migration characteristics and kinetic...To understand the migration mechanisms of phosphorus(P)during coal-based reduction,a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions.The migration characteristics and kinetics of P were investigated by a field-emission electron probe microanalyzer(FE-EPMA)and using the basic principle of solid phase mass transfer,respectively.Experimental results showed that the P transferred from the slag to the metallic phase during reduction,and the migration process could be divided into three stages:phosphorus diffusing from the slag to the metallic interface,the formation of Fe P compounds at the slag metal interface and P diffusing from the slag metal interface to the metallic interior.The reduction time and temperature significantly influenced the phosphorus content of the metallic and slag phases.The P content of the metallic phase increased with increasing reduction time and temperature,while that of the slag phase gradually decreased.The P diffusion constant and activation energy were determined and a migration kinetics model of P in coal-based reduction was proposed.P diffusion in the metallic phase was the controlling step of the P migration.展开更多
Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reducti...Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.展开更多
This study focuses on the reduction of phosphorus from high-phosphorus-content oolitic iron ore via coal-based reduction. The distribution behavior of phosphorus (i.e., the phosphorus content and the phosphorus distr...This study focuses on the reduction of phosphorus from high-phosphorus-content oolitic iron ore via coal-based reduction. The distribution behavior of phosphorus (i.e., the phosphorus content and the phosphorus distribution ratio in the metal, slag, and gas phases) during reduction was investigated in detail. Experimental results showed that the distribution behavior of phosphorus was strongly influenced by the reduction temperature, the reduction time, and the C/O molar ratio. A higher temperature and a longer reaction time were more favor-able for phosphorus reduction and enrichment in the metal phase. An increase in the C/O ratio improved phosphorus reduction but also hin-dered the mass transfer of the reduced phosphorus when the C/O ratio exceeded 2.0. According to scanning electron microscopy analysis, the iron ore was transformed from an integral structure to metal and slag fractions during the reduction process. Apatite in the ore was reduced to P, and the reduced P was mainly enriched in the metal phase. These results suggest that the proposed method may enable utilization of high-phosphorus-content oolitic iron ore resources.展开更多
To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure...To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the re- duced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumula- tive frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol^-1, and 922.05, respec- tively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.展开更多
The sticking phenomenon between molten slag and refractory is one of the crucial problems when preparing ferronickel from laterite ore using rotary hearth fulnace or rotary kiln processes. This study aims to ameliorat...The sticking phenomenon between molten slag and refractory is one of the crucial problems when preparing ferronickel from laterite ore using rotary hearth fulnace or rotary kiln processes. This study aims to ameliorate sticking problems by using silicon dioxide (SiO2) to adjust the melting degree of file briquette during reduction roasting. Thermodynamic analysis indicates that the melting temperature of the slag gradually increases with an increase in the SiO2 proportion (SiO2/(SiO2 + A1203 + MgO) mass ratio). Experimental validations also prove that the briquette retains its original shape when the SiO2 proportion is greater than 75wt%, and sticking problems axe avoided during reduction. A ferronickel product with 8.33wt% Ni and 84.71wt% Fe was prepared via reductive roasting at 1500~C for 90 min with a SiO2 proportion of 75wt% and a C/O molar ratio of 1.0 followed by dry magnetic separation; the corresponding recoveries of Ni and Fe reached 75.70% and 77.97%, respectively. The micro stxucture and phase txmlsformation of reduced briquette reveals that the aggregation and growth of ferroinckel particles were not significantly affected after adding SiO2 to the reduction process.展开更多
A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V-Ti-Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio (η), ...A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V-Ti-Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio (η), S removal ratio (Rs), and P removal ratio (Rp) were studied and analyzed on the basis of chemical composition determined via inductively coupled plasma optical emission spectroscopy. The metallic iron particle size and the element distribution of Fe, V, Cr, and Ti in a reduced briquette after water cooling treatment at 1350℃ were determined and observed via scanning electron microscopy. The results show that the water cooling treatment improved the η, Rs, and Rp in the coal-based reduction of V-Ti-Cr iron ore compared to those obtained with a furnace cooling treatment. Meanwhile, the particle size of metallic iron obtained via the water cooling treatment was smaller than that of metallic iron obtained via the furnace cooling treatment; however, the particle size reached 70 μm at 1350℃, which is substantially larger than the minimum particle size required (20 μm) for magnetic separation. Therefore, the water cooling treatment described in this work is a good method for improving the quality of metallic iron in coal-based reduction and it could be applied in the coal-based reduction of V-Ti-Cr iron ore followed by magnetic separation.展开更多
An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio...An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.展开更多
The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The ef...The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.展开更多
Coal-based soild wastes(CBSWs)are industrial byproducts that can be harmful to the environment.The exploitation and utilization of CBsWs offer societal advantages such as resource conservation,pollution reduction,and ...Coal-based soild wastes(CBSWs)are industrial byproducts that can be harmful to the environment.The exploitation and utilization of CBsWs offer societal advantages such as resource conservation,pollution reduction,and cost-effective production.However,environmentally sustainable management remains a worldwide challenge due to the substantial production volume and limited disposal capacity of CBSWs.The physicochemical properties and utilization of CBSWs are summarized,including fly ash,coal gangue and coal gasification slag.It also presents the current global applications status of CBSWs resources and examines market supply and demand.Subsequently,the paper provides an overview of studies on ways to utilise CBSWs,highlighting the primary avenues of CBSWs resource utilization which are mainly from the fields of chemical materials,metallurgy and agriculture.Furthermore,a comparative evaluation of the various methods for CBSWs resource recovery is conducted,outlining their respective advantages and disadvantages.The future development of CBSWs recycling processes is also discussed.The review concludes that while there is a growing need for attention in CBSWs recycling,its utilization will involve a combination of both large-scale treatment and refinement processes.The paper aims to offer references and insights for the effective utilization and environmental protection of CBSWs.Future direction will focus on the collaborative utilization of CBSWs,emphasizing on the combination of large-scale and high-value utilization.In addition,there is a need to establish a comprehensive database based on on-site production practices,explore on-site solutions to reduce transportation costs,and improve physicochemical properties during the production process.展开更多
Aiming at mitigating the high risks associated with conventional explosive blasting,this study developed a safe directional fracturing technique,i.e.instantaneous expansion with a single fracture(IESF),using a coal-ba...Aiming at mitigating the high risks associated with conventional explosive blasting,this study developed a safe directional fracturing technique,i.e.instantaneous expansion with a single fracture(IESF),using a coal-based solid waste expanding agent.First,the mechanism of directional fracturing blasting by the IESF was analyzed,and the criterion of directional crack initiation was established.On this basis,laboratory experiments and numerical simulations were conducted to systematically evaluate the directional fracturing blasting performance of the IESF.The results indicate that the IESF presents an excellent directional fracturing effect,with average surface undulation differences ranging from 8.1 mm to 22.7 mm on the fracture surfaces.Moreover,during concrete fracturing tests,the stresses and strains in the fracturing direction are measured to be 2.16-3.71 times and 8 times larger than those in the nonfracturing direction,respectively.Finally,the IESF technique was implemented for no-pillar mining with gob-side entry retaining through roof cutting and pressure relief in an underground coal mine.The IESF technique effectively created directional cracks in the roof without causing severe roadway deformation,achieving an average cutting rate and maximum roadway deformation of 94%and 197 mm,respectively.These on-site test results verified its excellent directional rock fracturing performance.The IESF technique,which is safe,efficient,and green,has considerable application prospects in the field of rock mechanics and engineering.展开更多
The application of liquid core reduction(LCR)technology in thin slab continuous casting can refine the internal microstruc-tures of slabs and improve their production efficiency.To avoid crack risks caused by large de...The application of liquid core reduction(LCR)technology in thin slab continuous casting can refine the internal microstruc-tures of slabs and improve their production efficiency.To avoid crack risks caused by large deformation during the LCR process and to minimize the thickness of the slab in bending segments,the maximum theoretical reduction amount and the corresponding reduction scheme for the LCR process must be determined.With SPA-H weathering steel as a specific research steel grade,the distributions of tem-perature and deformation fields of a slab with the LCR process were analyzed using a three-dimensional thermal-mechanical finite ele-ment model.High-temperature tensile tests were designed to determine the critical strain of corner crack propagation and intermediate crack initiation with various strain rates and temperatures,and a prediction model of the critical strain for two typical cracks,combining the effects of strain rate and temperature,was proposed by incorporating the Zener-Hollomon parameter.The crack risks with different LCR schemes were calculated using the crack risk prediction model,and the maximum theoretical reduction amount for the SPA-H slab with a transverse section of 145 mm×1600 mm was 41.8 mm,with corresponding reduction amounts for Segment 0 to Segment 4 of 15.8,7.3,6.5,6.4,and 5.8 mm,respectively.展开更多
Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-perform...Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.展开更多
Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This ...Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This study aims to elucidate the response patterns of nitrogen-cycling microorganisms under long-term heavy metal(loids)exposure.The results showed that the diversity and abundance of nitrogen-cyclingmicroorganisms showed negative feedback to heavy metal(loids)concentrations.Denitrifying microorganisms were shown to be the dominant microorganisms with over 60%of relative abundance and a complex community structure including 27 phyla.Further,the key bacterial species in the denitrification process were calculated using a random forest model,where the top three key species(Pseudomonas stutzei,Sphingobium japonicum and Leifsonia rubra)were found to play a prominent role in nitrite reduction.Functional gene analysis and qPCR revealed that nirK,which is involved in nitrite reduction,significantly accumulated in the most metal-rich soil with the increase of absolute abundance of 63.86%.The experimental results confirmed that the activity of nitrite reductase(Nir)encoded by nirK in the soil was increased at high concentrations of heavy metal(loids).Partial least squares-path model identified three potential modes of nitrite reduction processes being stimulated by heavy metal(loids),the most prominent of which contributed to enhanced nirK abundance and soil Nir activity through positive stimulation of key species.The results provide new insights and preliminary evidence on the stimulation of nitrite reduction processes by heavy metal(loids).展开更多
Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange...Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells.For fundamental understanding,clearly identifying the metalsupport effect on enhancement mechanisms of ORR electrocatalysis is definitely needed.In this work,the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations,electrochemical measurements and theoretical DFT-calculations/AIMD-simulations.The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H_(2)-O_(2)fuel cell.Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles,which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.展开更多
Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2)...Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.展开更多
The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-bas...The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-based catalyst PrO_(x)-NC,and optimized the calcination temperature and proportion.The PrO_(x)-NC-900 catalyst has high durability and activity and exhibits superior ORR performance in alkaline electrolytes with an onset potential(E_(0))of 0.96 V and a half-wave potential(E_(1/2))of 0.85 V.The research results indicate that the ORR performance of rare earth oxide composite carbon catalysts can be improved by adjusting oxygen vacancies(Ov).In addition,high specific surface area,N rich defect carbon.increased oxygen vacancies,and the synergistic effect of oxygen vacancies and N-doped carbon interfacial layer play a significant part in the enhancement of ORR.The performance of the zinc air battery assembled with PrO_(x)-NC-900 is significantly improved,and rare earth oxides and carbon frameworks originating from metal organic frameworks(MOFs)contribute to the oxygen electrocatalyst and electron transfer rate of the zinc air battery.This catalyst provides promising information for the development of rare earth metal oxide nanostructures as potential candidate materials for ORR in alkaline media.展开更多
A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for ...A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.展开更多
基金Project(51134002)supported by the National Natural Science Foundation of ChinaProject(2012BAB14B02)supported by the Ministry of Science and Technology of ChinaProject(12120113086600)supported by Ministry of Land and Resources of China
文摘A low-grade nickel laterite ore was reduced at different reduction temperatures. The morphology of metallic particles was investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Experimental results indicate that the metallic nickel and iron gradually assemble and grow into larger spherical particles with increasing temperature and prolonging time. After reduction, the nickel laterite ore obviously changes into two parts of Fe-Ni metallic particles and slag matrix. An obvious relationship is found between the reduction of iron magnesium olivine and its crystal chemical properties. The nickel and iron oxides are reduced to metallic by reductant, and the lattice of olivine is destroyed. The entire reduction process is comprised of oxide reduction and metallic phase growth.
基金financially supported by the National Natural Science Foundation of China (Nos. 51204033 and 51134002)
文摘In order to ascertain the reaction behavior of rare earth minerals in coal-based reduction, X-ray diffraction(XRD), scanning electron microscopy(SEM), and energy dispersive spectroscopy(EDS) analyses were applied to investigate the rare earth minerals in Bayan Obo.The occurrence state and regularity of rare earth elements were analyzed under different reduction time. The results reveal that rare earth elements in rare earth minerals exist in RE(CO3)F(bastnaesite) and REPO4(monazite). In this research, at 1,498 K with a C/O molar ratio(i.e., molar ratio of fixed carbon in the coal to reducible oxygen in the ore) of2.5, rare earth minerals primarily decompose into RE2O3at5 min. When the time is extended to 10 min, solid-phase reactions occur among RE2O3, CaO, and SiO2, and the resultant is cerium wollastonite(CaO·2RE2O3·3SiO2). At reaction time 〉20 min, rare earth elements mainly exist in cerium wollastonite(CaO·2RE2O3·3SiO2), and the grain size varies in the range of 10–30 μm. The results show that coal-based reduction is efficient to recover rare earth minerals in reduced materials.
基金financially supported by the National Natural Science Foundation of China (No. 52022019)the National Key R&D Program of China (No. 2021YFC2901000)the Fok Ying Tung Education Foundation (No. 161045)
文摘The application of coal-based reduction in the efficient recovery of iron from refractory iron-bearing resources is comprehensively reviewed.Currently,the development and beneficiation of refractory iron-bearing resources have attracted increasing attention.However,the effect of iron recovery by traditional beneficiation methods is unacceptable.Coal-based reduction followed by magnetic separation is proposed,which adopts coal as the reductant to reduce iron oxides to metallic iron below the melting temperature.The metallic iron particles aggregate and grow,and the particle size continuously increases to be suitable for magnetic separation.The optimization and application of coal-based reduction have been abundantly researched.A detailed literature study on coal-based reduction is performed from the perspectives of thermodynamics,reduction kinetics,growth of metallic iron particles,additives,and application.The coal-based reduction industrial equipment can be developed based on the existing pyrometallurgical equipments,rotary hearth furnace and rotary kiln,which are introduced briefly.However,coal-based reduction currently mainly adopts coal as a reductant and fuel,which may result in high levels of carbon dioxide emissions,energy consumption,and pollution.Technological innovation aiming at decreasing carbon dioxide emissions is a new trend of green and sustainable development of the steel industry.Therefore,the substitution of coal with clean energy(hydrogen,biomass,etc.)for iron oxide reduction shows promise in the future.
基金financially supported by the National Natural Science Foundation of China (No.51604063)
文摘To understand the migration mechanisms of phosphorus(P)during coal-based reduction,a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions.The migration characteristics and kinetics of P were investigated by a field-emission electron probe microanalyzer(FE-EPMA)and using the basic principle of solid phase mass transfer,respectively.Experimental results showed that the P transferred from the slag to the metallic phase during reduction,and the migration process could be divided into three stages:phosphorus diffusing from the slag to the metallic interface,the formation of Fe P compounds at the slag metal interface and P diffusing from the slag metal interface to the metallic interior.The reduction time and temperature significantly influenced the phosphorus content of the metallic and slag phases.The P content of the metallic phase increased with increasing reduction time and temperature,while that of the slag phase gradually decreased.The P diffusion constant and activation energy were determined and a migration kinetics model of P in coal-based reduction was proposed.P diffusion in the metallic phase was the controlling step of the P migration.
基金supported by the National Natural Science Foundation of China(Nos.51134002 and 51074036)
文摘Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.
基金financially supported by the National Natural Science Foundation of China(No.51134002)the Fundamental Research Funds for the Central Universi-ties of China(No.N120601004)
文摘This study focuses on the reduction of phosphorus from high-phosphorus-content oolitic iron ore via coal-based reduction. The distribution behavior of phosphorus (i.e., the phosphorus content and the phosphorus distribution ratio in the metal, slag, and gas phases) during reduction was investigated in detail. Experimental results showed that the distribution behavior of phosphorus was strongly influenced by the reduction temperature, the reduction time, and the C/O molar ratio. A higher temperature and a longer reaction time were more favor-able for phosphorus reduction and enrichment in the metal phase. An increase in the C/O ratio improved phosphorus reduction but also hin-dered the mass transfer of the reduced phosphorus when the C/O ratio exceeded 2.0. According to scanning electron microscopy analysis, the iron ore was transformed from an integral structure to metal and slag fractions during the reduction process. Apatite in the ore was reduced to P, and the reduced P was mainly enriched in the metal phase. These results suggest that the proposed method may enable utilization of high-phosphorus-content oolitic iron ore resources.
基金financially supported by the National Natural Science Foundation of China(Nos.51134002 and 51604063)the Fundamental Research Funds for the Central Universities(No.N140108001)
文摘To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the re- duced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumula- tive frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol^-1, and 922.05, respec- tively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.
基金the National Natural Science Foundation of China(No.51234010)the Fundamental Research Funds for Central Universities(No.106112017CDJXY130001)for the financial support provided for this research
文摘The sticking phenomenon between molten slag and refractory is one of the crucial problems when preparing ferronickel from laterite ore using rotary hearth fulnace or rotary kiln processes. This study aims to ameliorate sticking problems by using silicon dioxide (SiO2) to adjust the melting degree of file briquette during reduction roasting. Thermodynamic analysis indicates that the melting temperature of the slag gradually increases with an increase in the SiO2 proportion (SiO2/(SiO2 + A1203 + MgO) mass ratio). Experimental validations also prove that the briquette retains its original shape when the SiO2 proportion is greater than 75wt%, and sticking problems axe avoided during reduction. A ferronickel product with 8.33wt% Ni and 84.71wt% Fe was prepared via reductive roasting at 1500~C for 90 min with a SiO2 proportion of 75wt% and a C/O molar ratio of 1.0 followed by dry magnetic separation; the corresponding recoveries of Ni and Fe reached 75.70% and 77.97%, respectively. The micro stxucture and phase txmlsformation of reduced briquette reveals that the aggregation and growth of ferroinckel particles were not significantly affected after adding SiO2 to the reduction process.
基金financially supported by the Programs of the National Natural Science Foundation of China(Nos.51604065,51090384,51674084,51174051,and 51574082)the National Basic Research Program of China(No.2013CB632603)+1 种基金the Fundamental Funds for the Central Universities(Nos.150203003 and 150202001)the National Key Technology Research and development Program(No.2015BAB19B02)
文摘A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V-Ti-Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio (η), S removal ratio (Rs), and P removal ratio (Rp) were studied and analyzed on the basis of chemical composition determined via inductively coupled plasma optical emission spectroscopy. The metallic iron particle size and the element distribution of Fe, V, Cr, and Ti in a reduced briquette after water cooling treatment at 1350℃ were determined and observed via scanning electron microscopy. The results show that the water cooling treatment improved the η, Rs, and Rp in the coal-based reduction of V-Ti-Cr iron ore compared to those obtained with a furnace cooling treatment. Meanwhile, the particle size of metallic iron obtained via the water cooling treatment was smaller than that of metallic iron obtained via the furnace cooling treatment; however, the particle size reached 70 μm at 1350℃, which is substantially larger than the minimum particle size required (20 μm) for magnetic separation. Therefore, the water cooling treatment described in this work is a good method for improving the quality of metallic iron in coal-based reduction and it could be applied in the coal-based reduction of V-Ti-Cr iron ore followed by magnetic separation.
基金funded by the National Natural Science Foundation of China(Nos.U20A20145,51774205)the Open Project from Engineering Research Center of the Ministry of Education,Sichuan University,China.
文摘An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.
基金Projects(2013CB632601,2013CB632604)supported by the National Basic Research Program of ChinaProject(51125018)supported by the National Science Foundation for Distinguished Young Scholars of China+1 种基金Project(KGZD-EW-201-2)supported by the Key Research Program of the Chinese Academy of SciencesProjects(51374191,21106167,51104139)supported by the National Natural Science Foundation of China
文摘The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.
基金supported by the following:“National Natural Science Foundation of China”(22478231)“Natural Science Foundation of Henan”(242300421449)“Fundamental Research Program of Shanxi Province”(202403021221011).
文摘Coal-based soild wastes(CBSWs)are industrial byproducts that can be harmful to the environment.The exploitation and utilization of CBsWs offer societal advantages such as resource conservation,pollution reduction,and cost-effective production.However,environmentally sustainable management remains a worldwide challenge due to the substantial production volume and limited disposal capacity of CBSWs.The physicochemical properties and utilization of CBSWs are summarized,including fly ash,coal gangue and coal gasification slag.It also presents the current global applications status of CBSWs resources and examines market supply and demand.Subsequently,the paper provides an overview of studies on ways to utilise CBSWs,highlighting the primary avenues of CBSWs resource utilization which are mainly from the fields of chemical materials,metallurgy and agriculture.Furthermore,a comparative evaluation of the various methods for CBSWs resource recovery is conducted,outlining their respective advantages and disadvantages.The future development of CBSWs recycling processes is also discussed.The review concludes that while there is a growing need for attention in CBSWs recycling,its utilization will involve a combination of both large-scale treatment and refinement processes.The paper aims to offer references and insights for the effective utilization and environmental protection of CBSWs.Future direction will focus on the collaborative utilization of CBSWs,emphasizing on the combination of large-scale and high-value utilization.In addition,there is a need to establish a comprehensive database based on on-site production practices,explore on-site solutions to reduce transportation costs,and improve physicochemical properties during the production process.
基金supported by the National Natural Science Foundation of China(Grant No.52404155)State Key Laboratory of Mining Disaster Prevention and Control(Shandong University of Science and Technology)+1 种基金Ministry of Education(Grant No.JMDPC202402)supported by the opening project of State Key Laboratory of Explosion Science and Safety Protection(Beijing Institute of Technology).The opening project number is KFJJ24-20M.
文摘Aiming at mitigating the high risks associated with conventional explosive blasting,this study developed a safe directional fracturing technique,i.e.instantaneous expansion with a single fracture(IESF),using a coal-based solid waste expanding agent.First,the mechanism of directional fracturing blasting by the IESF was analyzed,and the criterion of directional crack initiation was established.On this basis,laboratory experiments and numerical simulations were conducted to systematically evaluate the directional fracturing blasting performance of the IESF.The results indicate that the IESF presents an excellent directional fracturing effect,with average surface undulation differences ranging from 8.1 mm to 22.7 mm on the fracture surfaces.Moreover,during concrete fracturing tests,the stresses and strains in the fracturing direction are measured to be 2.16-3.71 times and 8 times larger than those in the nonfracturing direction,respectively.Finally,the IESF technique was implemented for no-pillar mining with gob-side entry retaining through roof cutting and pressure relief in an underground coal mine.The IESF technique effectively created directional cracks in the roof without causing severe roadway deformation,achieving an average cutting rate and maximum roadway deformation of 94%and 197 mm,respectively.These on-site test results verified its excellent directional rock fracturing performance.The IESF technique,which is safe,efficient,and green,has considerable application prospects in the field of rock mechanics and engineering.
基金supported by the National Natural Science Foundation of China(No.52474355)the Liaoning Province Science and Technology Plan Joint Program(Key Research and Development Program Project),China(Nos.2022JH25/10200003 and 2023JH2/101800058).
文摘The application of liquid core reduction(LCR)technology in thin slab continuous casting can refine the internal microstruc-tures of slabs and improve their production efficiency.To avoid crack risks caused by large deformation during the LCR process and to minimize the thickness of the slab in bending segments,the maximum theoretical reduction amount and the corresponding reduction scheme for the LCR process must be determined.With SPA-H weathering steel as a specific research steel grade,the distributions of tem-perature and deformation fields of a slab with the LCR process were analyzed using a three-dimensional thermal-mechanical finite ele-ment model.High-temperature tensile tests were designed to determine the critical strain of corner crack propagation and intermediate crack initiation with various strain rates and temperatures,and a prediction model of the critical strain for two typical cracks,combining the effects of strain rate and temperature,was proposed by incorporating the Zener-Hollomon parameter.The crack risks with different LCR schemes were calculated using the crack risk prediction model,and the maximum theoretical reduction amount for the SPA-H slab with a transverse section of 145 mm×1600 mm was 41.8 mm,with corresponding reduction amounts for Segment 0 to Segment 4 of 15.8,7.3,6.5,6.4,and 5.8 mm,respectively.
基金supported by the National Natural Science Foundation of China(No.21571062)the Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher Learning to JGL,and the Fundamental Research Funds for the Central Universities(No.222201717003)。
文摘Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.
基金supported by the National Natural Science Foundation of China(No.41977029).
文摘Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This study aims to elucidate the response patterns of nitrogen-cycling microorganisms under long-term heavy metal(loids)exposure.The results showed that the diversity and abundance of nitrogen-cyclingmicroorganisms showed negative feedback to heavy metal(loids)concentrations.Denitrifying microorganisms were shown to be the dominant microorganisms with over 60%of relative abundance and a complex community structure including 27 phyla.Further,the key bacterial species in the denitrification process were calculated using a random forest model,where the top three key species(Pseudomonas stutzei,Sphingobium japonicum and Leifsonia rubra)were found to play a prominent role in nitrite reduction.Functional gene analysis and qPCR revealed that nirK,which is involved in nitrite reduction,significantly accumulated in the most metal-rich soil with the increase of absolute abundance of 63.86%.The experimental results confirmed that the activity of nitrite reductase(Nir)encoded by nirK in the soil was increased at high concentrations of heavy metal(loids).Partial least squares-path model identified three potential modes of nitrite reduction processes being stimulated by heavy metal(loids),the most prominent of which contributed to enhanced nirK abundance and soil Nir activity through positive stimulation of key species.The results provide new insights and preliminary evidence on the stimulation of nitrite reduction processes by heavy metal(loids).
基金supported by the National Natural Science Foundation of China(Nos.22272105 and 22002110)Natural Science Foundation of Shanghai(No.23ZR1423900)。
文摘Nitrogen-doping of carbon support(N-C)for platinum(Pt)nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells.For fundamental understanding,clearly identifying the metalsupport effect on enhancement mechanisms of ORR electrocatalysis is definitely needed.In this work,the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations,electrochemical measurements and theoretical DFT-calculations/AIMD-simulations.The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H_(2)-O_(2)fuel cell.Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles,which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.
基金supported by the National Natural Science Foundation of China(Nos.22106105 and 22201180)the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-E00015)+2 种基金Shanghai Science and Technology Innovation Program(No.21DZ1206300)the Central Local Science and Technology Development Guidance Fund(No.YDZX20213100003002)Shanghai Science and Technology Commission Program(No.20060502200).
文摘Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.
基金Project supported by the National Natural Science Foundation of China(22062019)the Natural Science Foundation of Inner Mongolia of China(2022QN02002)Science and Technology Program of Inner Mongolia Autonomous Region,China(2020PT0003)。
文摘The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-based catalyst PrO_(x)-NC,and optimized the calcination temperature and proportion.The PrO_(x)-NC-900 catalyst has high durability and activity and exhibits superior ORR performance in alkaline electrolytes with an onset potential(E_(0))of 0.96 V and a half-wave potential(E_(1/2))of 0.85 V.The research results indicate that the ORR performance of rare earth oxide composite carbon catalysts can be improved by adjusting oxygen vacancies(Ov).In addition,high specific surface area,N rich defect carbon.increased oxygen vacancies,and the synergistic effect of oxygen vacancies and N-doped carbon interfacial layer play a significant part in the enhancement of ORR.The performance of the zinc air battery assembled with PrO_(x)-NC-900 is significantly improved,and rare earth oxides and carbon frameworks originating from metal organic frameworks(MOFs)contribute to the oxygen electrocatalyst and electron transfer rate of the zinc air battery.This catalyst provides promising information for the development of rare earth metal oxide nanostructures as potential candidate materials for ORR in alkaline media.
基金supported by the National Natural Science Foundation of China(No.U2067212)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.