Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selectiv...Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.展开更多
Decarbonization and decontamination of the iron and steel industry(ISI),which contributes up to 15%to anthropogenic CO_(2) emissions(or carbon emissions)and significant proportions of air and water pollutant emissions...Decarbonization and decontamination of the iron and steel industry(ISI),which contributes up to 15%to anthropogenic CO_(2) emissions(or carbon emissions)and significant proportions of air and water pollutant emissions in China,are challenged by the huge demand for steel.Carbon and pollutants often share common emission sources,indicating that emission reduction could be achieved synergistically.Here,we explored the inherent potential of measures to adjust feedstock composition and technological structure and to control the size of the ISI to achieve carbon emission reduction(CER)and pollution emission reduction(PER).We investigated five typical pollutants in this study,namely,petroleum hydrocarbon pollutants and chemical oxygen demand in wastewater,particulate matter,SO_(2),and NO_(x) in off gases,and examined synergies between CER and PER by employing cross elasticity for the period between 2022 and 2035.The results suggest that a reduction of 8.7%-11.7%in carbon emissions and 20%-31%in pollution emissions(except for particulate matter emissions)could be achieved by 2025 under a high steel scrap ratio(SSR)scenario.Here,the SSR and electric arc furnace(EAF)ratio serve critical roles in enhancing synergies between CER and PER(which vary with the type of pollutant).However,subject to a limited volume of steel scrap,a focused increase in the EAF ratio with neglection of the available supply of steel scrap to EAF facilities would lead to an increase carbon and pollution emissions.Although CER can be achieved through SSR and EAF ratio optimization,only when the crude steel production growth rate remains below 2.2%can these optimization measures maintain the emissions in 2030 at a similar level to that in 2021.Therefore,the synergistic effects between PER and CER should be considered when formulating a development route for the ISI in the future.展开更多
Intrinsic topological defect engineering has been proven as a promising strategy to elevate the electrocatalytic activity of carbon materials.However,the controllable construction of high-density and specific topologi...Intrinsic topological defect engineering has been proven as a promising strategy to elevate the electrocatalytic activity of carbon materials.However,the controllable construction of high-density and specific topological defects in carbon frameworks to reveal the relationship between reactivity and defect structure remains a challenging task.Herein,the intrinsic pentagon carbon sites that can favor electron overflow and enhance their binding affinity towards the intermediates of catalytic reaction are firstly presented by the work function and the p-band center calculations.To experimentally verify this,the cage-opening reaction of fullerene is proposed and utilized for synthesizing carbon quantum dots with specific pentagon configuration(CQDs-P),subsequently utilizing CQDs-P to modulate the micro-scale defect density of three-dimensional reduced graphene oxide(rGO)viaπ-πinteractions.The multiple spatial-scale rGO-conjugated CQDs-P structure simultaneously possesses abundant pentagon and edge defects as catalytic active sites and long-range-orderedπelectron delocalization system as conductive network.The defects-rich CQDs-P/rGO-4 all-carbon-based catalyst exhibits superb catalytic activity for triiodide reduction reaction with a high photoelectric conversion efficiency of 8.40%,superior to the Pt reference(7.97%).Theoretical calculations suggest that pentagon defects in the carbon frameworks can promote charge transfer and modulate the adsorption/dissociation behavior of the reaction intermediates,thus enhancing the electrocatalytic activity of the catalyst.This work confirms the role of intrinsic pentagon defects in catalytic reactions and provides a new insight into the synthesis of defects-rich carbon catalysts.展开更多
The industrial sector is the primary source of carbon emissions in China.In pursuit of meeting its carbon reduction targets,China aims to promote resource consumption sustainability,reduce energy consumption,and achie...The industrial sector is the primary source of carbon emissions in China.In pursuit of meeting its carbon reduction targets,China aims to promote resource consumption sustainability,reduce energy consumption,and achieve carbon neutrality within its processing industries.An effective strategy to promote energy savings and carbon reduction throughout the life cycle of materials is by applying life cycle engineering technology.This strategy aims to attain an optimal solution for material performance,resource consumption,and environmental impact.In this study,five types of technologies were considered:raw material replacement,process reengineering,fuel replacement,energy recycling and reutilization,and material recycling and reutilization.The meaning,methodology,and development status of life cycle engineering technology abroad and domestically are discussed in detail.A multidimensional analysis of ecological design was conducted from the perspectives of resource and energy consumption,carbon emissions,product performance,and recycling of secondary resources in a manufacturing process.This coupled with an integrated method to analyze carbon emissions in the entire life cycle of a material process industry was applied to the nonferrous industry,as an example.The results provide effective ideas and solutions for achieving low or zero carbon emission production in the Chinese industry as recycled aluminum and primary aluminum based on advanced technologies had reduced resource consumption and emissions as compared to primary aluminum production.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
The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetal...The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.展开更多
Since the carbon neutrality target was proposed,many countries have been facing severe challenges to carbon emission reduction sustainably.This study is conducted using a tripartite evolutionary game model to explore ...Since the carbon neutrality target was proposed,many countries have been facing severe challenges to carbon emission reduction sustainably.This study is conducted using a tripartite evolutionary game model to explore the impact of the central environmental protection inspection(CEPI)on driving carbon emission reduction,and to study what factors influence the strategic choices of each party and how they interact with each other.The research results suggest that local governments and manufacturing enterprises would choose strategies that are beneficial to carbon reduction when CEPI increases.When the initial willingness of all parties increases 20%,50%—80%,the time spent for the whole system to achieve stability decreases from 100%,60%—30%.The evolutionary result of“thorough inspection,regulation implementation,low-carbon management”is the best strategy for the tripartite evolutionary game.Moreover,the smaller the cost and the larger the benefit,the greater the likelihood of the three-party game stability strategy appears.This study has important guiding significance for other developing countries to promote carbon emission reduction by environmental policy.展开更多
Photocatalysis has emerged as a promising alternative for converting and utilizing CO_(2).Polymeric carbon nitride(PCN),typically synthesized through the one-step thermal polycondensation of nitrogen-rich precursors,h...Photocatalysis has emerged as a promising alternative for converting and utilizing CO_(2).Polymeric carbon nitride(PCN),typically synthesized through the one-step thermal polycondensation of nitrogen-rich precursors,has shown considerable promise due to its adjustable band structure and inherent safety.Over the past five years,significant literature in this field has identified five primary methods for modifying PCN:morphology modulation,element doping,defect induction,co-catalyst loading,and heterojunction construction.A detailed discussion on how each modification method influences light absorption,charge separation,and surface reaction efficiencies in photocatalysis is provided.Based on these findings,several future directions for the development of PCN-based materials are proposed,such as designing tailored PCN structures for specific photocatalytic reactions and using theoretical calculations to verify and correct results from current characterization methods.Despite the challenges associated with the large-scale synthesis of PCN materials with controllable structures and satisfactory performance,this work offers valuable insights for advancing photocatalytic PCN-based systems for large-scale solar fuel production.展开更多
Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily a...Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.展开更多
In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream proces...In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream processes.This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO_(3).Firstly,a mass and energy balance of the coupled process was established in Aspen Plus.Following this,process optimization and energy integration were implemented to provide optimized operation conditions.Lastly,a life cycle assessment was carried out to assess the carbon footprint of the coupled process.Results reveal that the decomposition temperature of CaCO_(3)in an H_(2)atmosphere can be reduced to 780℃(generally around 900℃),and the conversion of CO_(2)from CaCO_(3)decomposition reached 81.33%with an H2:CO ratio of 2.49 in gaseous products.By optimizing systemic energy through heat integration,an energy efficiency of 86.30%was achieved.Additionally,the carbon footprint analysis revealed that the process with energy integration had a low global warming potential(GWP)of-2.624 kg·kg^(-1)(CO_(2)/CaO).Conclusively,this work performed a systematic analysis of introducing biomass-derived H_(2)into CaCO_(3)calcination and demonstrated the positive role of reductive calcination using green H_(2)in mitigating CO_(2)emissions within the carbonate industry.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dime...Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.展开更多
As the most significant green ecological resource in densely populated and economically developed areas,urban landscaping plays a pivotal role in carbon sink value and multiple ecosystem service functions.It is a cruc...As the most significant green ecological resource in densely populated and economically developed areas,urban landscaping plays a pivotal role in carbon sink value and multiple ecosystem service functions.It is a crucial element in the advancement of green and low-carbon initiatives in China’s major cities and the realization of a carbon-neutral vision.By analyzing the relationship between carbon emission reduction and urban landscaping,the paper sorts out and summarizes the basic principles of urban landscaping design,proposes the role of landscape design in urban landscaping,and plans countermeasures for carbon reduction in urban landscaping,with a view to optimizing the construction and management of urban landscaping.展开更多
Under the background of"dual-carbon",green finance is an important way to promote carbon emission reduction and realize the development of a low-carbon economy.Using provincial panel data from 2000 to 2020,t...Under the background of"dual-carbon",green finance is an important way to promote carbon emission reduction and realize the development of a low-carbon economy.Using provincial panel data from 2000 to 2020,this paper constructs a basic regression model to study the"carbon reduction"effect,mechanism of action,and heterogeneity of green finance.The study finds that:the development of green finance significantly inhibits carbon emissions and has an obvious"carbon reduction"effect;green technology innovation has a mediating effect on the carbon emission reduction effect of green finance;in regions with a high level of economic development or a high degree of marketization,the"carbon reduction"effect of green finance is significant.展开更多
Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we...Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we prepared mesoporous carbon nanofibers(mCNFs)functionalized with ordered PtFe alloys(O-PtFe-mCNFs)by a composite micelle interface-induced co-assembly method using poly(ethylene oxide)-block-polystyrene(PEO-b-PS)as a template.When employed as electrocatalysts,O-PtFe-mCNFs exhibited superior electrocatalytic performance for the NO_(3RR)compared to the mCNFs functionalized with disordered PtFe alloys(D-PtFe-mCNFs).Notably,the NH_(3)production performance was particularly outstanding,with a maximum NH_(3)yield of up to 959.6μmol/(h·cm~2).Furthermore,the Faraday efficiency(FE)was even 88.0%at-0.4 V vs.reversible hydrogen electrode(RHE).This finding provides compelling evidence of the potential of ordered PtFe alloy catalysts for the electrocatalytic NO_(3)RR.展开更多
The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases ...The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.展开更多
The ambient electrical conductivity (AEC) of carbon cathode materials was investigated in respect to their open porosity, crystal structure and graphite content using hydrostatic method, four-probe technique and X-ray...The ambient electrical conductivity (AEC) of carbon cathode materials was investigated in respect to their open porosity, crystal structure and graphite content using hydrostatic method, four-probe technique and X-ray diffraction (XRD), respectively. The AEC is proportional to the specific conductivity (σ0) and the exponential of (1?ε) (ε is porosity) by a quasi-uniform formula based on the percolation theory. Theσ0 can reflect the intrinsic conductivity of the carbon cathodes free of pores, and it depends on the mean crystallite size parallel to the layer (002). The exponentn is dependent on the materials nature of the cathode aggregates, while an averaged value, 4.65, can practically work well with 5 types of cathode materials. The calculation ofσ0 can be extended to the graphitic cathodes containing different aggregates using the simple rule of mixture.展开更多
Noble metals, such as platinum, ruthenium and iridium‐group metals, are often used as oxygen reduction or evolution reaction (ORR/OER) electrocatalysts. To reduce the cost and provide an application of bifunctional...Noble metals, such as platinum, ruthenium and iridium‐group metals, are often used as oxygen reduction or evolution reaction (ORR/OER) electrocatalysts. To reduce the cost and provide an application of bifunctional catalysis, in this work, cobalt oxide supported on nitrogen and phospho‐rus co‐doped carbon (Co3O4/NPC) was fabricated and examined as a bifunctional electrocatalyst for OER and ORR. To prepare Co3O4/NPC, NPC was pyrolyzed from melamine and phytic acid support‐ed on carbon, followed by the solvothermal synthesis of Co3O4 on NPC. Linear sweep voltammetry was used to evaluate the activity for OER and ORR. For OER, Co3O4/NPC showed an onset potential of 0.54 V (versus the saturated calomel electrode) and a current density of 21.95 mA/cm2 at 0.80 V, which was better than both Co3O4/C and NPC. The high activity of Co3O4/NPC was attributed to a synergistic effect of the N, P co‐dopants and Co3O4. For ORR, Co3O4/NPC exhibited an activity close to commercial Pt/C in terms of the diffusion limited current density (–4.49 vs–4.76 mA/cm2 at–0.80 V), and Co3O4 played the key role for the catalysis. Chronoamperometry (current versus time) was used to evaluate the stability, which showed that Co3O4/NPC maintained 46%current after the chronoamperometry test for OER and 95% current for ORR. Overall, Co3O4/NPC exhibited high activity and improved stability for both OER and ORR.展开更多
The oxygen reduction reaction (ORR) is traditionally performed using noble‐metals catalysts, e.g. Pt. However, these metal‐based catalysts have the drawbacks of high costs, low selectivity, poor stabili‐ties, and...The oxygen reduction reaction (ORR) is traditionally performed using noble‐metals catalysts, e.g. Pt. However, these metal‐based catalysts have the drawbacks of high costs, low selectivity, poor stabili‐ties, and detrimental environmental effects. Here, we describe metal‐free nitrogen‐doped carbon nanoblocks (NCNBs) with high nitrogen contents (4.11%), which have good electrocatalytic proper‐ties for ORRs. This material was fabricated using a scalable, one‐step process involving the pyrolysis of tris(hydroxymethyl)aminomethane (Tris) at 800℃. Rotating ring disk electrode measurements show that the NCNBs give a high electrocatalytic performance and have good stability in ORRs. The onset potential of the catalyst for the ORR is-0.05 V (vs Ag/AgCl), the ORR reduction peak potential is-0.20 V (vs Ag/AgCl), and the electron transfer number is 3.4. The NCNBs showed pronounced electrocatalytic activity, improved long‐term stability, and better tolerance of the methanol crosso‐ver effect compared with a commercial 20 wt%Pt/C catalyst. The composition and structure of, and nitrogen species in, the NCNBs were investigated using Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction. The pyroly‐sis of Tris at high temperature increases the number of active nitrogen sites, especially pyridinic nitrogen, which creates a net positive charge on adjacent carbon atoms, and the high positive charge promotes oxygen adsorption and reduction. The results show that NCNBs prepared by pyrolysis of Tris as nitrogen and carbon sources are a promising ORR catalyst for fuel cells.展开更多
Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)...Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.展开更多
基金the Science and Technology Key Project of Anhui Province,China(No.2022e03020004).
文摘Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.
基金supported by the National Key Research and Development Program of China(2019YFC1904800)the National Natural Science Foundation of China(72274105).
文摘Decarbonization and decontamination of the iron and steel industry(ISI),which contributes up to 15%to anthropogenic CO_(2) emissions(or carbon emissions)and significant proportions of air and water pollutant emissions in China,are challenged by the huge demand for steel.Carbon and pollutants often share common emission sources,indicating that emission reduction could be achieved synergistically.Here,we explored the inherent potential of measures to adjust feedstock composition and technological structure and to control the size of the ISI to achieve carbon emission reduction(CER)and pollution emission reduction(PER).We investigated five typical pollutants in this study,namely,petroleum hydrocarbon pollutants and chemical oxygen demand in wastewater,particulate matter,SO_(2),and NO_(x) in off gases,and examined synergies between CER and PER by employing cross elasticity for the period between 2022 and 2035.The results suggest that a reduction of 8.7%-11.7%in carbon emissions and 20%-31%in pollution emissions(except for particulate matter emissions)could be achieved by 2025 under a high steel scrap ratio(SSR)scenario.Here,the SSR and electric arc furnace(EAF)ratio serve critical roles in enhancing synergies between CER and PER(which vary with the type of pollutant).However,subject to a limited volume of steel scrap,a focused increase in the EAF ratio with neglection of the available supply of steel scrap to EAF facilities would lead to an increase carbon and pollution emissions.Although CER can be achieved through SSR and EAF ratio optimization,only when the crude steel production growth rate remains below 2.2%can these optimization measures maintain the emissions in 2030 at a similar level to that in 2021.Therefore,the synergistic effects between PER and CER should be considered when formulating a development route for the ISI in the future.
基金partly supported by the National Natural Science Foundation of China(22078052)the National Key R&D Program of China(2022YFB4101602)the Fundamental Research Funds for the Central Universities(DUT22LAB612)。
文摘Intrinsic topological defect engineering has been proven as a promising strategy to elevate the electrocatalytic activity of carbon materials.However,the controllable construction of high-density and specific topological defects in carbon frameworks to reveal the relationship between reactivity and defect structure remains a challenging task.Herein,the intrinsic pentagon carbon sites that can favor electron overflow and enhance their binding affinity towards the intermediates of catalytic reaction are firstly presented by the work function and the p-band center calculations.To experimentally verify this,the cage-opening reaction of fullerene is proposed and utilized for synthesizing carbon quantum dots with specific pentagon configuration(CQDs-P),subsequently utilizing CQDs-P to modulate the micro-scale defect density of three-dimensional reduced graphene oxide(rGO)viaπ-πinteractions.The multiple spatial-scale rGO-conjugated CQDs-P structure simultaneously possesses abundant pentagon and edge defects as catalytic active sites and long-range-orderedπelectron delocalization system as conductive network.The defects-rich CQDs-P/rGO-4 all-carbon-based catalyst exhibits superb catalytic activity for triiodide reduction reaction with a high photoelectric conversion efficiency of 8.40%,superior to the Pt reference(7.97%).Theoretical calculations suggest that pentagon defects in the carbon frameworks can promote charge transfer and modulate the adsorption/dissociation behavior of the reaction intermediates,thus enhancing the electrocatalytic activity of the catalyst.This work confirms the role of intrinsic pentagon defects in catalytic reactions and provides a new insight into the synthesis of defects-rich carbon catalysts.
基金supported by the National Key Research and Development Programs(2021YFB3704201 and 2021YFB3700902).
文摘The industrial sector is the primary source of carbon emissions in China.In pursuit of meeting its carbon reduction targets,China aims to promote resource consumption sustainability,reduce energy consumption,and achieve carbon neutrality within its processing industries.An effective strategy to promote energy savings and carbon reduction throughout the life cycle of materials is by applying life cycle engineering technology.This strategy aims to attain an optimal solution for material performance,resource consumption,and environmental impact.In this study,five types of technologies were considered:raw material replacement,process reengineering,fuel replacement,energy recycling and reutilization,and material recycling and reutilization.The meaning,methodology,and development status of life cycle engineering technology abroad and domestically are discussed in detail.A multidimensional analysis of ecological design was conducted from the perspectives of resource and energy consumption,carbon emissions,product performance,and recycling of secondary resources in a manufacturing process.This coupled with an integrated method to analyze carbon emissions in the entire life cycle of a material process industry was applied to the nonferrous industry,as an example.The results provide effective ideas and solutions for achieving low or zero carbon emission production in the Chinese industry as recycled aluminum and primary aluminum based on advanced technologies had reduced resource consumption and emissions as compared to primary aluminum production.
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.
基金Natural Science Foundation of Jiangsu Province (BK20210735)National Natural Science Foundation of China (52201269, 52302296)+4 种基金Collaborative Innovation Center of Suzhou Nano Science and Technologythe 111 Projectthe Suzhou Key Laboratory of Functional Nano and Soft MaterialsJiangsu Key Laboratory for Carbon-Based Functional Materials & Devicesthe funding from the Gusu leading talent plan for scientific and technological innovation and entrepreneurship (ZXL2022487)。
文摘The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.
基金the financial support from the Postdoctoral Science Foundation of China(2022M720131)Spring Sunshine Collaborative Research Project of the Ministry of Education(202201660)+3 种基金Youth Project of Gansu Natural Science Foundation(22JR5RA542)General Project of Gansu Philosophy and Social Science Foundation(2022YB014)National Natural Science Foundation of China(72034003,72243006,and 71874074)Fundamental Research Funds for the Central Universities(2023lzdxjbkyzx008,lzujbky-2021-sp72)。
文摘Since the carbon neutrality target was proposed,many countries have been facing severe challenges to carbon emission reduction sustainably.This study is conducted using a tripartite evolutionary game model to explore the impact of the central environmental protection inspection(CEPI)on driving carbon emission reduction,and to study what factors influence the strategic choices of each party and how they interact with each other.The research results suggest that local governments and manufacturing enterprises would choose strategies that are beneficial to carbon reduction when CEPI increases.When the initial willingness of all parties increases 20%,50%—80%,the time spent for the whole system to achieve stability decreases from 100%,60%—30%.The evolutionary result of“thorough inspection,regulation implementation,low-carbon management”is the best strategy for the tripartite evolutionary game.Moreover,the smaller the cost and the larger the benefit,the greater the likelihood of the three-party game stability strategy appears.This study has important guiding significance for other developing countries to promote carbon emission reduction by environmental policy.
基金the National Natural Science Foundation of China(22209207)the National Key Research and Development Program of China(2022YFB4002400).
文摘Photocatalysis has emerged as a promising alternative for converting and utilizing CO_(2).Polymeric carbon nitride(PCN),typically synthesized through the one-step thermal polycondensation of nitrogen-rich precursors,has shown considerable promise due to its adjustable band structure and inherent safety.Over the past five years,significant literature in this field has identified five primary methods for modifying PCN:morphology modulation,element doping,defect induction,co-catalyst loading,and heterojunction construction.A detailed discussion on how each modification method influences light absorption,charge separation,and surface reaction efficiencies in photocatalysis is provided.Based on these findings,several future directions for the development of PCN-based materials are proposed,such as designing tailored PCN structures for specific photocatalytic reactions and using theoretical calculations to verify and correct results from current characterization methods.Despite the challenges associated with the large-scale synthesis of PCN materials with controllable structures and satisfactory performance,this work offers valuable insights for advancing photocatalytic PCN-based systems for large-scale solar fuel production.
文摘Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.
基金support from the National Natural Science Foundation of China(21978128,91934302)partial support from the State Key Laboratory of Materials-oriented Chemical Engineering(ZK202006)also acknowledged.Additionallysupported by the“Cultivation Program for The Excellent Doctoral Dissertation of Nanjing Tech University(3800124701)”.
文摘In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream processes.This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO_(3).Firstly,a mass and energy balance of the coupled process was established in Aspen Plus.Following this,process optimization and energy integration were implemented to provide optimized operation conditions.Lastly,a life cycle assessment was carried out to assess the carbon footprint of the coupled process.Results reveal that the decomposition temperature of CaCO_(3)in an H_(2)atmosphere can be reduced to 780℃(generally around 900℃),and the conversion of CO_(2)from CaCO_(3)decomposition reached 81.33%with an H2:CO ratio of 2.49 in gaseous products.By optimizing systemic energy through heat integration,an energy efficiency of 86.30%was achieved.Additionally,the carbon footprint analysis revealed that the process with energy integration had a low global warming potential(GWP)of-2.624 kg·kg^(-1)(CO_(2)/CaO).Conclusively,this work performed a systematic analysis of introducing biomass-derived H_(2)into CaCO_(3)calcination and demonstrated the positive role of reductive calcination using green H_(2)in mitigating CO_(2)emissions within the carbonate industry.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
基金National Natural Science Foundation of China,Grant/Award Numbers:51873085,52071171,52202248The Australian Government through the Cooperative Research Centres Projects,Grant/Award Number:CRCPⅩⅢ000077+10 种基金Linkage Project,Grant/Award Numbers:LP210100467,LP210200345,LP210200504,LP220100088Natural Science Foundation of Liaoning Province‐Outstanding Youth Foundation,Grant/Award Number:2022‐YQ‐14Discovery Project,Grant/Award Number:DP220100603China Scholarship Council(CSC Scholarship),Grant/Award Number:202006800009Liaoning Revitalization Talents Program,Grant/Award Number:XLYC2007056Australian Research Council(ARC)through Future Fellowship,Grant/Award Numbers:FT210100298,FT210100806Shenyang Science and Technology Project,Grant/Award Number:21‐108‐9‐04Industrial Transformation Training Centre schemes,Grant/Award Number:IC180100005Natural Science Foundation of Liaoning Province,Grant/Award Number:2020‐MS‐137Key Research Project of Department of Education of Liaoning Province,Grant/Award Number:LJKZZ20220015Liaoning BaiQianWan Talents Program,Grant/Award Number:LNBQW2018B0048。
文摘Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.
文摘As the most significant green ecological resource in densely populated and economically developed areas,urban landscaping plays a pivotal role in carbon sink value and multiple ecosystem service functions.It is a crucial element in the advancement of green and low-carbon initiatives in China’s major cities and the realization of a carbon-neutral vision.By analyzing the relationship between carbon emission reduction and urban landscaping,the paper sorts out and summarizes the basic principles of urban landscaping design,proposes the role of landscape design in urban landscaping,and plans countermeasures for carbon reduction in urban landscaping,with a view to optimizing the construction and management of urban landscaping.
文摘Under the background of"dual-carbon",green finance is an important way to promote carbon emission reduction and realize the development of a low-carbon economy.Using provincial panel data from 2000 to 2020,this paper constructs a basic regression model to study the"carbon reduction"effect,mechanism of action,and heterogeneity of green finance.The study finds that:the development of green finance significantly inhibits carbon emissions and has an obvious"carbon reduction"effect;green technology innovation has a mediating effect on the carbon emission reduction effect of green finance;in regions with a high level of economic development or a high degree of marketization,the"carbon reduction"effect of green finance is significant.
基金National Natural Science Foundation of China(Nos.52225204,52173233 and 52202085)Innovation Program of Shanghai Municipal Education Commission,China(No.2021-01-07-00-03-E00109)+3 种基金Natural Science Foundation of Shanghai,China(No.23ZR1479200)“Shuguang Program”Supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission,China(No.20SG33)Fundamental Research Funds for the Central Universities,China(No.2232024Y-01)DHU Distinguished Young Professor Program,China(Nos.LZA2022001 and LZB2023002)。
文摘Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we prepared mesoporous carbon nanofibers(mCNFs)functionalized with ordered PtFe alloys(O-PtFe-mCNFs)by a composite micelle interface-induced co-assembly method using poly(ethylene oxide)-block-polystyrene(PEO-b-PS)as a template.When employed as electrocatalysts,O-PtFe-mCNFs exhibited superior electrocatalytic performance for the NO_(3RR)compared to the mCNFs functionalized with disordered PtFe alloys(D-PtFe-mCNFs).Notably,the NH_(3)production performance was particularly outstanding,with a maximum NH_(3)yield of up to 959.6μmol/(h·cm~2).Furthermore,the Faraday efficiency(FE)was even 88.0%at-0.4 V vs.reversible hydrogen electrode(RHE).This finding provides compelling evidence of the potential of ordered PtFe alloy catalysts for the electrocatalytic NO_(3)RR.
基金Projects(51304091,U1302274)supported by the National Natural Science Foundation of ChinaProjects(2013FD009,2013FZ007)supported by Applied Basic Research Program of Yunnan Province,ChinaProject(2012HB009)supported by the Candidate Talents Training Fund of Yunnan Province,China
文摘The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.
基金Project(20110006110003)supported by the Research Fund for the Doctoral Program of Higher Education of ChinaProject(51434005)supported by the National Natural Science Foundation of China
文摘The ambient electrical conductivity (AEC) of carbon cathode materials was investigated in respect to their open porosity, crystal structure and graphite content using hydrostatic method, four-probe technique and X-ray diffraction (XRD), respectively. The AEC is proportional to the specific conductivity (σ0) and the exponential of (1?ε) (ε is porosity) by a quasi-uniform formula based on the percolation theory. Theσ0 can reflect the intrinsic conductivity of the carbon cathodes free of pores, and it depends on the mean crystallite size parallel to the layer (002). The exponentn is dependent on the materials nature of the cathode aggregates, while an averaged value, 4.65, can practically work well with 5 types of cathode materials. The calculation ofσ0 can be extended to the graphitic cathodes containing different aggregates using the simple rule of mixture.
基金supported by the National Natural Science Foundation of China (21375016,20475022 and 21505019)~~
文摘Noble metals, such as platinum, ruthenium and iridium‐group metals, are often used as oxygen reduction or evolution reaction (ORR/OER) electrocatalysts. To reduce the cost and provide an application of bifunctional catalysis, in this work, cobalt oxide supported on nitrogen and phospho‐rus co‐doped carbon (Co3O4/NPC) was fabricated and examined as a bifunctional electrocatalyst for OER and ORR. To prepare Co3O4/NPC, NPC was pyrolyzed from melamine and phytic acid support‐ed on carbon, followed by the solvothermal synthesis of Co3O4 on NPC. Linear sweep voltammetry was used to evaluate the activity for OER and ORR. For OER, Co3O4/NPC showed an onset potential of 0.54 V (versus the saturated calomel electrode) and a current density of 21.95 mA/cm2 at 0.80 V, which was better than both Co3O4/C and NPC. The high activity of Co3O4/NPC was attributed to a synergistic effect of the N, P co‐dopants and Co3O4. For ORR, Co3O4/NPC exhibited an activity close to commercial Pt/C in terms of the diffusion limited current density (–4.49 vs–4.76 mA/cm2 at–0.80 V), and Co3O4 played the key role for the catalysis. Chronoamperometry (current versus time) was used to evaluate the stability, which showed that Co3O4/NPC maintained 46%current after the chronoamperometry test for OER and 95% current for ORR. Overall, Co3O4/NPC exhibited high activity and improved stability for both OER and ORR.
基金supported by the National Natural Science Foundation of China (21375088,21575090)Scientific Research Project of Beijing Educational Committee (KM201410028006)+1 种基金Scientific Research Base Development Program of the Beijing Municipal Commission of EducationYouth Talent Project of the Beijing Municipal Commission of Education (CIT & TCD201504072)~~
文摘The oxygen reduction reaction (ORR) is traditionally performed using noble‐metals catalysts, e.g. Pt. However, these metal‐based catalysts have the drawbacks of high costs, low selectivity, poor stabili‐ties, and detrimental environmental effects. Here, we describe metal‐free nitrogen‐doped carbon nanoblocks (NCNBs) with high nitrogen contents (4.11%), which have good electrocatalytic proper‐ties for ORRs. This material was fabricated using a scalable, one‐step process involving the pyrolysis of tris(hydroxymethyl)aminomethane (Tris) at 800℃. Rotating ring disk electrode measurements show that the NCNBs give a high electrocatalytic performance and have good stability in ORRs. The onset potential of the catalyst for the ORR is-0.05 V (vs Ag/AgCl), the ORR reduction peak potential is-0.20 V (vs Ag/AgCl), and the electron transfer number is 3.4. The NCNBs showed pronounced electrocatalytic activity, improved long‐term stability, and better tolerance of the methanol crosso‐ver effect compared with a commercial 20 wt%Pt/C catalyst. The composition and structure of, and nitrogen species in, the NCNBs were investigated using Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction. The pyroly‐sis of Tris at high temperature increases the number of active nitrogen sites, especially pyridinic nitrogen, which creates a net positive charge on adjacent carbon atoms, and the high positive charge promotes oxygen adsorption and reduction. The results show that NCNBs prepared by pyrolysis of Tris as nitrogen and carbon sources are a promising ORR catalyst for fuel cells.
基金financial support from the National Natural Science Foundation of China(No.22272038)the Science and Technology Planning Project of Guangzhou City(No.2023A03J0026)。
文摘Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.