Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3...Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.展开更多
The development of high-performance transition metal sulfide(TMS)/carbon composites to replace conventional graphite anode remains a critical challenge for advancing lithium-ion batteries(LIBs).In this study,a facile ...The development of high-performance transition metal sulfide(TMS)/carbon composites to replace conventional graphite anode remains a critical challenge for advancing lithium-ion batteries(LIBs).In this study,a facile self-sacrifice template method is developed to prepare FeS encapsulated into N,S co-doped carbon(FeS/NSC)composite using melamine-cyanuric acid(MCA)supermolecule as a multifunctional template precursor.The function of MCA supermolecule for material synthesis is explored,revealing its special function as a dispersant,dopant and pore-forming agent.Furthermore,the effect of Fe source dosage on the morphology,structure and composition of the final products is explored.The resultant FeS/NSC-0.1(where 0.1 represents the mass of added Fe source)exhibits the most optimal proportion,characterized by a good dispersion status of FeS within the NSC matrix,effective N,S co-doping and ample porosity.Benefiting from these merits,the FeS/NSC-0.1 anode demonstrates significantly improved cycling stability and rate capability when compared to the counterparts.Undoubtedly,this work offers a universal method to produce advanced transition metal sulfide/carbon composite electrodes for energy storage and conversion systems.展开更多
Carbonaceous materials have drawn much attention in potassium-ion batteries (PIBs) due to their low price and superior physicochemical properties. However, the application of carbonaceous materials in PIB anodes is hi...Carbonaceous materials have drawn much attention in potassium-ion batteries (PIBs) due to their low price and superior physicochemical properties. However, the application of carbonaceous materials in PIB anodes is hindered by sluggish kinetics and large volume expansion. Herein, N/S co-doped carbon nanocapsule (NSCN) is constructed for superior K+ storage. The NSCN possesses 3D nanocapsule framework with abundant meso/macropores, which guarantees structural robustness and accelerates ions/electrons transportation. The high-level N/S co-doping in carbon matrix not only generates ample defects and active sites for K+ adsorption, but also expands interlayer distance for facile K+ intercalation/deintercalation. As a result, the NSCN electrode delivers a high reversible capacity (408 mAh g^(−1) at 0.05 A g^(−1)), outstanding rate capability (149 mAh g^(−1) at 5 A g^(−1)) and favorable cycle stability (150m Ah g^(−1) at 2 A g^(−1) after 2000 cycles). Ex situ TEM, Raman and XPS measurements demonstrate the excellent stability and reversibility of NSCN electrode during potassiation/depotassiation process. This work provides inspiration for the optimization of energy storage materials by structure and doping engineering.展开更多
Heteroatom-doped porous carbon materials have been widely studied due to their high specific surface area and high heteroatom content,but it is difficult to achieve high specific surface area and high heteroatom conte...Heteroatom-doped porous carbon materials have been widely studied due to their high specific surface area and high heteroatom content,but it is difficult to achieve high specific surface area and high heteroatom content at the same time.Herein,a simple method is introduced to prepare N/O co-doped hierarchical porous carbon materials(DNZKs).Phthalonitrile resins(DNZs)were prepared by using 1,3-bis(3,4-dicyanophenoxy)benzene as raw material and ZnCl_(2)/urea as composite curing agent,and then using KOH as activator to successfully prepare DNZKs with high specific surface area,developed pores and high N/O content.The porous carbon material(DNZK@400)obtained at a curing temperature of 400℃ has the highest N content(4.97%(mass)),a large specific surface area(2026 m^(2)·g^(-1)),a high micropore proportion(0.9),a high O content(7.53%(mass)),and the best specific capacitance(up to 567 F·g^(-1) at 0.1 A·g^(-1)),which can be attribute to the high temperature resistance of the nitrogencontaining aromatic heterocyclic structure in DNZs.When the mass ratio of resin and KOH is 1:1,the specific capacitance of the sample tested by the acid three-electrode system is obtained,and it is found that the material has high cycling stability(119%specific capacitance retention after 100,000 cycle tests).This work proposes a simple and easy-to-operate method for the preparation of multifunctional porous carbon.展开更多
Exploring inexpensive and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) is critical for rechargeable metal-air batteries. Herein, we report a new 3D hier...Exploring inexpensive and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) is critical for rechargeable metal-air batteries. Herein, we report a new 3D hierarchical sulfur and nitrogen co-doped carbon nanocages(hSNCNC) as a promising bifunctional oxygen electrocatalyst by an in-situ MgO template method with pyridine and thiophene as the mixed precursor. The as-prepared h SNCNC exhibits a positive half-wave potential of 0.792 V(vs. reversible hydrogen electrode, RHE) for ORR, and a low operating potential of 1.640 V at a 10 mA cm-2 current density for OER. The reversible oxygen electrode index is 0.847 V, far superior to commercial Pt/C and IrO2,which reaches the top level of the reported bifunctional catalysts. Consequently, the hSNCNC as air cathodes in an assembled Zn-air battery features low charge/discharge overpotential and long lifetime. The remarkable properties arises from the introduced multiple heteroatom dopants and stable 3D hierarchical structure with multi-scale pores, which provides the abundant uniform high-active S and N species and efficient charge transfer as well as mass transportation. These results demonstrate the potential strategy in developing suitable carbon-based bi-/multi-functional catalysts to enable the next generation of the rechargeable metal-air batteries.展开更多
The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution rea...The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.展开更多
Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples w...Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.展开更多
A new nonporous Zn-based metal-organic framework(NPMOF) synthesized from a high nitrogencontaining rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sourc...A new nonporous Zn-based metal-organic framework(NPMOF) synthesized from a high nitrogencontaining rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sources.A series of NPMOF-derived porous carbons with very high N/O contents(24.1% for NPMOF-700,20.2% for NPMOF-800,15.1% for NPMOF-900) were prepared by adjusting the pyrolysis temperatures.The NPMOF-800 fabrica ted electrode exhibits a high capacitance of220 F/g and extremely large surface area normalized capacitance of 57.7 μF/cm~2 compared to other reported MOF-derived porous carbon electrodes,which could be attributed to the abundant ultramicroporosity and high N/O co-doping.More importantly,symmetric supercapacitor assembled with the MOF-derived carbon manifests prominent stability,i.e.,99.1 % capacitance retention after 10,000 cycles at 1.0 A/g.This simple preparation of MOF-derived porous carbon materials not only finds an application direction for a variety of porous or even nonporous MOFs,but also opens a way for the production of porous carbon materials for superior energy storage.展开更多
Designing highly active and stable electrocata-lysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is a challenge for energy con-version and storage technology.In this work,a S and N co-doped g...Designing highly active and stable electrocata-lysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is a challenge for energy con-version and storage technology.In this work,a S and N co-doped graphene supported cobalt–nickel sulfide composite catalyst(rGO@SN-CoNi_(2)S_(4))was synthesized simply via a one-step hydrothermal method.The as-synthesized CoNi_(2)S_(4)particles grew in a mosaic manner inside GO lamellae and were encapsulated with graphene.As a bifunctional catalyst,the r GO@SN-CoNi_(2)S_(4)exhibits excellent electrocatalytic performance under alkaline con-ditions,which only required the overpotential of 142.6 mV(vs.RHE)and 310 m V(vs.RHE)to deliver a current density of 10 mA·cm^(-2) for HER and OER,respectively.The good hydrophilicity of the r GO@SN,the pure phase of bimetallic structure,and the chemical coupling/interaction between the CoNi_(2)S_(4)and the rGO@SN are attributable to be the possible reasons responsible for the higher HER and OER catalytic activities.Additionally,the rGO@SN-CoNi_(2)S_(4)also shows a great potential for serving as an excellent cathode and anode electrolyzer during the water splitting process.展开更多
Magnetically separated and N, S co-doped mesoporous carbon microspheres （NIS-MCMs/Fe304） are fabricated by encapsulating Si02 nanoparticles within N, S-containing polymer microspheres which were prepared using resor...Magnetically separated and N, S co-doped mesoporous carbon microspheres （NIS-MCMs/Fe304） are fabricated by encapsulating Si02 nanoparticles within N, S-containing polymer microspheres which were prepared using resorcinol/formaldehyde as the carbon source and cysteine as the nitrogen and sulfur co-precursors, followed by the carbonization process, silica template removal, and the introduction of Fe3O4 into the carbon mesopores. N/S-MCMs/Fe3O4 exhibits an enhanced Hg2＋ adsorption capacity of 74.5 rag/g, and the adsorbent can be conveniently and rapidly separated from wastewater using an external magnetic field. This study opens up new opportunities to synthesize well- developed, carbon-based materials as an adsorbent for potential applications in the removal of mercury ions from wastewater.展开更多
Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O c...Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.展开更多
Bisphenol A(BPA)has received increasing attention due to its long-term industrial application and persistence in environmental pollution.Iron-based carbon catalyst activation of peroxymonosulfate(PMS)shows a good pros...Bisphenol A(BPA)has received increasing attention due to its long-term industrial application and persistence in environmental pollution.Iron-based carbon catalyst activation of peroxymonosulfate(PMS)shows a good prospect for effective elimination of recalcitrant contaminants in water.Herein,considering the problem about the leaching of iron ions and the optimization of heteroatoms doping,the iron,nitrogen and sulfur co-doped tremellalike carbon catalyst(Fe-NS@C)was rationally designed using very little iron,S-C_(3)N_(4) and low-cost chitosan(CS)via the impregnation-calcination method.The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA(20 mg/L)by activating PMS with the high kinetic constant(1.492 min^(−1))in 15 min.Besides,the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference,but also maintained an excellent degradation efficiency on different pollutants.Impressively,increased S-C_(3)N_(4) doping amount modulated the contents of different N species in Fe-NS@C,and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing SC_(3)N_(4) contents,verifying pyridine N and Fe-Nx as main active sites in the system.Meanwhile,thiophene sulfur(C-S-C)as active sites played an auxiliary role.Furthermore,quenching experiment,EPR analysis and electrochemical test proved that surface-bound radicals(·OH and SO_(4)^(·−))and non-radical pathways worked in the BPA degradation(the former played a dominant role).Finally,possible BPA degradation route were proposed.This work provided a promising way to synthesize the novel Fe,N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.展开更多
The poor rate capability of battery-type anode is usually the bottleneck of the power-energy outputs of a hybrid alkaline metal ion capacitor.In this work,nitrogen and oxygen co-doped mesoporous carbon spheres with ex...The poor rate capability of battery-type anode is usually the bottleneck of the power-energy outputs of a hybrid alkaline metal ion capacitor.In this work,nitrogen and oxygen co-doped mesoporous carbon spheres with excellent rate performance and cycle stability are used as anode materials of sodium ion capacitors(SICs).The high N and O element doping levels as well as the amorphous and mesoporous structure have enabled prominent capacitive Na ion storage behavior,which in turn match well with the capacitive cathode in the hybrid device.Under optimum conditions,the SIC delivers a high energy density of 103.1 Wh kg^(-1)at a power density of 205.6 W kg^(-1).Even at a high power density of 7520 W kg^(-1),an energy density of 23.5 Wh kg^(-1)is still maintained.Moreover,a robust cycle stability with capacity retention of 84.6%after 2500 cycles at 1 A g^(-1)is maintained.Such excellent electrochemical performances convincingly demonstrate that the all-carbon based SICs with the highly capacitive N and O co-doped mesoporous carbon anode can be promising Na ion-based energy storage devices alternative to their Li ion-based counterparts.展开更多
Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon micros...Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon microspheres (NSCs) were synthesized from the polymerization products during persulfate wet air oxidation of benzothiazole. The contents of doped N and S as well as the structural stability were maneuvered by adjusting the subsequent N_(2)-annealing temperature. Compared with the prevailing single-walled carbon nanotubes, the N_(2)-annealed NSCs demonstrated a higher catalytic ozonation activity for benzimidazole degradation. According to the quantitative structure-activity relationship (QSAR) analysis, the synergistic effect between the graphitic N and the thiophene-S which redistributed the charge distribution of the carbon basal plane contributed to the activity enhancement of the N_(2)-annealed NSCs. Additionally, the hollow structure within the microspheres served as the microreactor to boost the mass transfer and reaction kinetics via the nanoconfinement effects. Quenching and electron paramagnetic resonance (EPR) tests revealed that benzimidazole degradation was dominated by the produced singlet oxygen (^(1)O_(2)) species, while hydroxyl radicals (^(·)OH) were also generated and participated. This study puts forward a novel strategy for synthesis of heteroatom-doped nanocarbons and sheds a light on the relationship between the active sites on the doped nanocarbons and the catalytic performance.展开更多
The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the explorat...The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea(TU) encapsulated in zeolitic imidazolate frameworks(TU@ZIF) composites,which delivered very good oxygen reduction reaction(ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode(RHE), good stability and methanol tolerance. Density functional theory(DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O_(2)adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.展开更多
The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for ...The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for the photocatalytic removal of gaseous formaldehyde(a volatile organic compound).Among the obtained catalysts,the presence of oxygen vacancies restricted photogenerated electron and holes recombination.98.00%removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp.The removal efficiency for formaldehyde was well retained for five cycle experiment.The results from PL,TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes,and the enhanced charge separation led to a significant increase in photocatalytic activity.The photocatalytic oxidation mechanism indicated that the ^(•)OH and ^(•)O_(2)−radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H_(2)O and CO_(2).展开更多
The high cost and complex modification process of carbon felt electrodes limits its further popularization in vanadium redox flow batteries(VFBs).By introducing low-cost melamine foam,nitrogen,phosphorus,and sulfur co...The high cost and complex modification process of carbon felt electrodes limits its further popularization in vanadium redox flow batteries(VFBs).By introducing low-cost melamine foam,nitrogen,phosphorus,and sulfur co-doped carbon nanotubes/melamine foam composite electrode(NPS-CNTs-CMF)is designed and fabricated via immersing melamine foam in a solution containing N,P,and S co-doped CNTs.The integration of modified CNTs significantly enhances the conductivity and hydrophilicity of the electrode.Moreover,the composite electrode also demonstrates outstanding electrocatalytic activity owing to the heteroatom doping that further inspired the electrocatalytic activity of CNTs.Density function theory cal-culations further uncover that introducing heteroatoms on CNTs not only promotes the adsorption of vanadium ions but also facilitates the electron transfer between vanadium ions and MF substrate.As a result,the battery loading with NPS-CNTs-CMF exhibits excellent battery performance,achieving energy efficiency of 80.12%at 300 mA cm^(-2).Additionally,the long-term cycling stability is attained over 200 consecutive charge-discharge cycles at 300 mA cm^(−2).This study provides a novel melamine foam mate-rial with low cost and simple modification,and this new composite structure stimulates the development of high-performance electrodes in VFBs.展开更多
基金supported by the National Natural Science Foun-dation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(No.2021CFB133).
文摘Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.
基金supported by the Science Technology Talents Lifting Project of Hunan Province(No.2022TJ-N16)the Natural Science Foundation of Hunan Province(Nos.2024JJ4022,2023JJ30277,2025JJ60382)+3 种基金the China Postdoctoral Fellowship Program(GZC20233205)the Scientifc Research Fund of Hunan Provincial Education Department,China(No.24B0270)the National Natural Science Foundation of China(No.32201646)the Key Project of Jiangxi Provincial Research and Development Program(No.20243BBI91001).
文摘The development of high-performance transition metal sulfide(TMS)/carbon composites to replace conventional graphite anode remains a critical challenge for advancing lithium-ion batteries(LIBs).In this study,a facile self-sacrifice template method is developed to prepare FeS encapsulated into N,S co-doped carbon(FeS/NSC)composite using melamine-cyanuric acid(MCA)supermolecule as a multifunctional template precursor.The function of MCA supermolecule for material synthesis is explored,revealing its special function as a dispersant,dopant and pore-forming agent.Furthermore,the effect of Fe source dosage on the morphology,structure and composition of the final products is explored.The resultant FeS/NSC-0.1(where 0.1 represents the mass of added Fe source)exhibits the most optimal proportion,characterized by a good dispersion status of FeS within the NSC matrix,effective N,S co-doping and ample porosity.Benefiting from these merits,the FeS/NSC-0.1 anode demonstrates significantly improved cycling stability and rate capability when compared to the counterparts.Undoubtedly,this work offers a universal method to produce advanced transition metal sulfide/carbon composite electrodes for energy storage and conversion systems.
基金the financial supports from the National Natural Science Foundation of China(Grant Nos.51872005,U1508201,52072002)。
文摘Carbonaceous materials have drawn much attention in potassium-ion batteries (PIBs) due to their low price and superior physicochemical properties. However, the application of carbonaceous materials in PIB anodes is hindered by sluggish kinetics and large volume expansion. Herein, N/S co-doped carbon nanocapsule (NSCN) is constructed for superior K+ storage. The NSCN possesses 3D nanocapsule framework with abundant meso/macropores, which guarantees structural robustness and accelerates ions/electrons transportation. The high-level N/S co-doping in carbon matrix not only generates ample defects and active sites for K+ adsorption, but also expands interlayer distance for facile K+ intercalation/deintercalation. As a result, the NSCN electrode delivers a high reversible capacity (408 mAh g^(−1) at 0.05 A g^(−1)), outstanding rate capability (149 mAh g^(−1) at 5 A g^(−1)) and favorable cycle stability (150m Ah g^(−1) at 2 A g^(−1) after 2000 cycles). Ex situ TEM, Raman and XPS measurements demonstrate the excellent stability and reversibility of NSCN electrode during potassiation/depotassiation process. This work provides inspiration for the optimization of energy storage materials by structure and doping engineering.
基金supported by the National Natural Science Foundation of China(51673033 and 52073038)the Fundamental Research Funds for the Central Universities(DUT22LAB605).
文摘Heteroatom-doped porous carbon materials have been widely studied due to their high specific surface area and high heteroatom content,but it is difficult to achieve high specific surface area and high heteroatom content at the same time.Herein,a simple method is introduced to prepare N/O co-doped hierarchical porous carbon materials(DNZKs).Phthalonitrile resins(DNZs)were prepared by using 1,3-bis(3,4-dicyanophenoxy)benzene as raw material and ZnCl_(2)/urea as composite curing agent,and then using KOH as activator to successfully prepare DNZKs with high specific surface area,developed pores and high N/O content.The porous carbon material(DNZK@400)obtained at a curing temperature of 400℃ has the highest N content(4.97%(mass)),a large specific surface area(2026 m^(2)·g^(-1)),a high micropore proportion(0.9),a high O content(7.53%(mass)),and the best specific capacitance(up to 567 F·g^(-1) at 0.1 A·g^(-1)),which can be attribute to the high temperature resistance of the nitrogencontaining aromatic heterocyclic structure in DNZs.When the mass ratio of resin and KOH is 1:1,the specific capacitance of the sample tested by the acid three-electrode system is obtained,and it is found that the material has high cycling stability(119%specific capacitance retention after 100,000 cycle tests).This work proposes a simple and easy-to-operate method for the preparation of multifunctional porous carbon.
基金financial support from the National Natural Science Foundation of China (21773111, 21473089, 21573107 and 51571110)the National Key Research and Development Program of China (2017YFA0206503, 2018YFA0209103)+1 种基金Priority Academic Program Development of Jiangsu Higher Education Institutions, Fundamental Research Funds for the Central Universitiesthe program B for outstanding PhD candidate of Nanjing University (201702B049)
文摘Exploring inexpensive and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) is critical for rechargeable metal-air batteries. Herein, we report a new 3D hierarchical sulfur and nitrogen co-doped carbon nanocages(hSNCNC) as a promising bifunctional oxygen electrocatalyst by an in-situ MgO template method with pyridine and thiophene as the mixed precursor. The as-prepared h SNCNC exhibits a positive half-wave potential of 0.792 V(vs. reversible hydrogen electrode, RHE) for ORR, and a low operating potential of 1.640 V at a 10 mA cm-2 current density for OER. The reversible oxygen electrode index is 0.847 V, far superior to commercial Pt/C and IrO2,which reaches the top level of the reported bifunctional catalysts. Consequently, the hSNCNC as air cathodes in an assembled Zn-air battery features low charge/discharge overpotential and long lifetime. The remarkable properties arises from the introduced multiple heteroatom dopants and stable 3D hierarchical structure with multi-scale pores, which provides the abundant uniform high-active S and N species and efficient charge transfer as well as mass transportation. These results demonstrate the potential strategy in developing suitable carbon-based bi-/multi-functional catalysts to enable the next generation of the rechargeable metal-air batteries.
基金Collaborative Innovation Center of Suzhou Nano Science and TechnologyNational Natural Science Foundation of China,Grant/Award Numbers:21773163,22271203+3 种基金EPSRC for an Overseas Travel Grant,Grant/Award Number:EP/R023816/1State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry,Grant/Award Number:KF2021005Priority Academic Program Development of Jiangsu Higher Education InstitutionsProject of Scientific and Technologic Infrastructure of Suzhou,Grant/Award Number:SZS201905。
文摘The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.
文摘Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.
基金financially supported by the National Natural Science Foundation of China (Nos.21501135,21875165)the Fundamental Research Funds for the Central Universitiesthe Recruitment Program of Global Experts of China。
文摘A new nonporous Zn-based metal-organic framework(NPMOF) synthesized from a high nitrogencontaining rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sources.A series of NPMOF-derived porous carbons with very high N/O contents(24.1% for NPMOF-700,20.2% for NPMOF-800,15.1% for NPMOF-900) were prepared by adjusting the pyrolysis temperatures.The NPMOF-800 fabrica ted electrode exhibits a high capacitance of220 F/g and extremely large surface area normalized capacitance of 57.7 μF/cm~2 compared to other reported MOF-derived porous carbon electrodes,which could be attributed to the abundant ultramicroporosity and high N/O co-doping.More importantly,symmetric supercapacitor assembled with the MOF-derived carbon manifests prominent stability,i.e.,99.1 % capacitance retention after 10,000 cycles at 1.0 A/g.This simple preparation of MOF-derived porous carbon materials not only finds an application direction for a variety of porous or even nonporous MOFs,but also opens a way for the production of porous carbon materials for superior energy storage.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation (Nos. 2020A1515110473 and 2019A1515110528)。
文摘Designing highly active and stable electrocata-lysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is a challenge for energy con-version and storage technology.In this work,a S and N co-doped graphene supported cobalt–nickel sulfide composite catalyst(rGO@SN-CoNi_(2)S_(4))was synthesized simply via a one-step hydrothermal method.The as-synthesized CoNi_(2)S_(4)particles grew in a mosaic manner inside GO lamellae and were encapsulated with graphene.As a bifunctional catalyst,the r GO@SN-CoNi_(2)S_(4)exhibits excellent electrocatalytic performance under alkaline con-ditions,which only required the overpotential of 142.6 mV(vs.RHE)and 310 m V(vs.RHE)to deliver a current density of 10 mA·cm^(-2) for HER and OER,respectively.The good hydrophilicity of the r GO@SN,the pure phase of bimetallic structure,and the chemical coupling/interaction between the CoNi_(2)S_(4)and the rGO@SN are attributable to be the possible reasons responsible for the higher HER and OER catalytic activities.Additionally,the rGO@SN-CoNi_(2)S_(4)also shows a great potential for serving as an excellent cathode and anode electrolyzer during the water splitting process.
基金financially supported by the National Natural Science Foundation of China (Nos. 21207099, 21273162, and 21473122)the Science and Technology Commission of Shanghai Municipality, China (No. 14DZ2261100)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Large Equipment Test Foundation of Tongji University
文摘Magnetically separated and N, S co-doped mesoporous carbon microspheres （NIS-MCMs/Fe304） are fabricated by encapsulating Si02 nanoparticles within N, S-containing polymer microspheres which were prepared using resorcinol/formaldehyde as the carbon source and cysteine as the nitrogen and sulfur co-precursors, followed by the carbonization process, silica template removal, and the introduction of Fe3O4 into the carbon mesopores. N/S-MCMs/Fe3O4 exhibits an enhanced Hg2＋ adsorption capacity of 74.5 rag/g, and the adsorbent can be conveniently and rapidly separated from wastewater using an external magnetic field. This study opens up new opportunities to synthesize well- developed, carbon-based materials as an adsorbent for potential applications in the removal of mercury ions from wastewater.
基金supported by the National Key R&D Program of China(2021YFC2103704)the National Natural Science Foundation of China(22022812,21978259)+1 种基金Key R&D Program of Zhejiang(2022C01208)Institute of Zhejiang University-Quzhou S&T Planed Projects(IZQ2021KJ1001)。
文摘Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.
基金This work was supported by the Major special projects of Science and Technology Department of Sichuan Province(No.2020ZDZX0020).
文摘Bisphenol A(BPA)has received increasing attention due to its long-term industrial application and persistence in environmental pollution.Iron-based carbon catalyst activation of peroxymonosulfate(PMS)shows a good prospect for effective elimination of recalcitrant contaminants in water.Herein,considering the problem about the leaching of iron ions and the optimization of heteroatoms doping,the iron,nitrogen and sulfur co-doped tremellalike carbon catalyst(Fe-NS@C)was rationally designed using very little iron,S-C_(3)N_(4) and low-cost chitosan(CS)via the impregnation-calcination method.The as-prepared Fe-NS@C exhibited excellent performance for complete removal of BPA(20 mg/L)by activating PMS with the high kinetic constant(1.492 min^(−1))in 15 min.Besides,the Fe-NS@C/PMS system not only possessed wide pH adaptation and high resistance to environmental interference,but also maintained an excellent degradation efficiency on different pollutants.Impressively,increased S-C_(3)N_(4) doping amount modulated the contents of different N species in Fe-NS@C,and the catalytic activity of Fe-NS@C-1-x was visibly enhanced with increasing SC_(3)N_(4) contents,verifying pyridine N and Fe-Nx as main active sites in the system.Meanwhile,thiophene sulfur(C-S-C)as active sites played an auxiliary role.Furthermore,quenching experiment,EPR analysis and electrochemical test proved that surface-bound radicals(·OH and SO_(4)^(·−))and non-radical pathways worked in the BPA degradation(the former played a dominant role).Finally,possible BPA degradation route were proposed.This work provided a promising way to synthesize the novel Fe,N and S co-doping carbon catalyst for degrading organic pollutants with low metal leaching and high catalytic ability.
基金financially supported by the Natural Science Foundation projects(No.2020J01287)Guidance Project(No.2020H0024)of Fujian Provincethe Program for Innovative Research Team in Science and Technology in Fujian Province University。
文摘The poor rate capability of battery-type anode is usually the bottleneck of the power-energy outputs of a hybrid alkaline metal ion capacitor.In this work,nitrogen and oxygen co-doped mesoporous carbon spheres with excellent rate performance and cycle stability are used as anode materials of sodium ion capacitors(SICs).The high N and O element doping levels as well as the amorphous and mesoporous structure have enabled prominent capacitive Na ion storage behavior,which in turn match well with the capacitive cathode in the hybrid device.Under optimum conditions,the SIC delivers a high energy density of 103.1 Wh kg^(-1)at a power density of 205.6 W kg^(-1).Even at a high power density of 7520 W kg^(-1),an energy density of 23.5 Wh kg^(-1)is still maintained.Moreover,a robust cycle stability with capacity retention of 84.6%after 2500 cycles at 1 A g^(-1)is maintained.Such excellent electrochemical performances convincingly demonstrate that the all-carbon based SICs with the highly capacitive N and O co-doped mesoporous carbon anode can be promising Na ion-based energy storage devices alternative to their Li ion-based counterparts.
基金financial supports from the National Natural Science Foundation of China (No21978324)Tianjin Municipal Science and Technology Bureau (No.18YFYSZ00170)+1 种基金Beijing Natural Science Foundation (No. 8192039)Science Foundation of China University of Petroleum,Beijing(No. 2462020YXZZ034)。
文摘Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon microspheres (NSCs) were synthesized from the polymerization products during persulfate wet air oxidation of benzothiazole. The contents of doped N and S as well as the structural stability were maneuvered by adjusting the subsequent N_(2)-annealing temperature. Compared with the prevailing single-walled carbon nanotubes, the N_(2)-annealed NSCs demonstrated a higher catalytic ozonation activity for benzimidazole degradation. According to the quantitative structure-activity relationship (QSAR) analysis, the synergistic effect between the graphitic N and the thiophene-S which redistributed the charge distribution of the carbon basal plane contributed to the activity enhancement of the N_(2)-annealed NSCs. Additionally, the hollow structure within the microspheres served as the microreactor to boost the mass transfer and reaction kinetics via the nanoconfinement effects. Quenching and electron paramagnetic resonance (EPR) tests revealed that benzimidazole degradation was dominated by the produced singlet oxygen (^(1)O_(2)) species, while hydroxyl radicals (^(·)OH) were also generated and participated. This study puts forward a novel strategy for synthesis of heteroatom-doped nanocarbons and sheds a light on the relationship between the active sites on the doped nanocarbons and the catalytic performance.
基金supported financially by the National Natural Science Foundation of China (No. 21905271)Liaoning Natural Science Foundation (No. 20180510029)the Dalian National Laboratory for Clean Energy (DNL), DNL Cooperation Fund, Chinese Academy of Sciences (No. DNL180402)。
文摘The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea(TU) encapsulated in zeolitic imidazolate frameworks(TU@ZIF) composites,which delivered very good oxygen reduction reaction(ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode(RHE), good stability and methanol tolerance. Density functional theory(DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O_(2)adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.21876008 and 22276009).
文摘The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for the photocatalytic removal of gaseous formaldehyde(a volatile organic compound).Among the obtained catalysts,the presence of oxygen vacancies restricted photogenerated electron and holes recombination.98.00%removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp.The removal efficiency for formaldehyde was well retained for five cycle experiment.The results from PL,TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes,and the enhanced charge separation led to a significant increase in photocatalytic activity.The photocatalytic oxidation mechanism indicated that the ^(•)OH and ^(•)O_(2)−radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H_(2)O and CO_(2).
基金supported by the National Key R&D Program of China(Grant No.2022YFB2404901)the National Natural Science Foundation of China(Grant No.21975267)the Central Guidance on Local Science and Technology Development Fund of Liaoning Province(No.2022JH6/100100001).
文摘The high cost and complex modification process of carbon felt electrodes limits its further popularization in vanadium redox flow batteries(VFBs).By introducing low-cost melamine foam,nitrogen,phosphorus,and sulfur co-doped carbon nanotubes/melamine foam composite electrode(NPS-CNTs-CMF)is designed and fabricated via immersing melamine foam in a solution containing N,P,and S co-doped CNTs.The integration of modified CNTs significantly enhances the conductivity and hydrophilicity of the electrode.Moreover,the composite electrode also demonstrates outstanding electrocatalytic activity owing to the heteroatom doping that further inspired the electrocatalytic activity of CNTs.Density function theory cal-culations further uncover that introducing heteroatoms on CNTs not only promotes the adsorption of vanadium ions but also facilitates the electron transfer between vanadium ions and MF substrate.As a result,the battery loading with NPS-CNTs-CMF exhibits excellent battery performance,achieving energy efficiency of 80.12%at 300 mA cm^(-2).Additionally,the long-term cycling stability is attained over 200 consecutive charge-discharge cycles at 300 mA cm^(−2).This study provides a novel melamine foam mate-rial with low cost and simple modification,and this new composite structure stimulates the development of high-performance electrodes in VFBs.
