Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru ...Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.展开更多
Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising...Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.展开更多
Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free he...Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free heteroatoms to obtain the best electrocatalytic performance through three types of dual-doped carbon,including XC-N(first X doping then N doping),NC-X(first N doping then X doping) and NXC(N and X doping)(X=P,S and F).XC-N has more defect than the other two indicated by Raman spectra.X-ray photoelectron spectrom(XPS) measurements indicate that N and X have been dual-doped into the carbon matrix with different doping contents and modes,Electrocatalytic results,including the potential of ORR peak(Ep),the half-wave potential,the diffusion-limiting current density mainly follows the order of XC-N>NC-X> NXC,Furthermore,the synergistic effect of second atom doping are also compared with the single doped carbon(NC,PC,SC and FC).The differences in electronegativity and atomic radius of these metal-free heteroatoms can affect the defect degree,the doping content and mode of hete roatoms on carbon matrix,induce polarization effect and space effect to affect O2 adsorption and product desorption,ultimately to the ORR electrocatalytic performance.展开更多
Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains cha...Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains challenging.Here,for the first time,we use the stronger electronegativity of a rare‐Earth yttrium ion(Y^(3+))to induce in situ NiCo‐layered double‐hydroxide nanosheets from NiCo foam(NCF)treated by a dielectric barrier discharge plasma NCF(PNCF),and then obtain nitrogen‐doped YNiCo phosphide(N‐YNiCoP/PNCF)after the phosphating process using radiofrequency plasma in nitrogen.The obtained NYNiCoP/PNCF has a large specific surface area,rich heterointerfaces,and an optimized electronic structure,inducing high electrocatalytic activity in HER(331mV vs.2000mA cm^(−2))and OER(464mV vs.2000mA cm^(−2))reactions in 1MKOH electrolyte.X‐ray absorption spectroscopy and density functional theory quantum chemistry calculations reveal that the coordination number of CoNi decreased with the incorporation of Y atoms,which induce much shorter bonds of Ni and Co ions and promote long‐term stability of N‐YNiCoP in HER and OER under the simulated industrial conditions.Meanwhile,the CoN‐YP_(5) heterointerface formed by plasma N‐doping is the active center for overall water splitting.This work expands the applications of rare‐Earth elements in engineering bifunctional electrocatalysts and provides a new avenue for designing highperformance transition‐metal‐based catalysts in the renewable energy field.展开更多
Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation o...Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.展开更多
Recently electrochemical synthesis of H_(2)O_(2)through oxygen reduction reaction(ORR)via 2e^(-)pathway is considered as a green and on-site route.However,it still remains a big challenge for fabricating novel metal-f...Recently electrochemical synthesis of H_(2)O_(2)through oxygen reduction reaction(ORR)via 2e^(-)pathway is considered as a green and on-site route.However,it still remains a big challenge for fabricating novel metal-free catalysts under acidic solutions,since it suffers from high overpotential due to the intrinsically week*OOH adsorption.Herein,a co-doped carbon nanosheet(O/N–C)catalyst toward regulating O and N content was synthesized for improving the selectivity and activity of H_(2)O_(2)electrosynthesis process.The O/N–C exhibits outstanding 2e-ORR performance with low onset potential of 0.4 V(vs.RHE)and a selectivity of 92.4%in 0.1 mol/L HClO_(4)solutions.The in situ electrochemical impedance spectroscopy(EIS)tests reveals that the N incorporation contributes to the fast ORR kinetics.The density functional theory(DFT)calculations demonstrate that the binding strength of*OOH was optimized by the co-doping of oxygen and nitrogen at certain content,and the O/N–C–COOH site exhibits a lower theoretical overpotential for H_(2)O_(2)formation than O–C–COOH site.Furthermore,the promoted kinetics for typical organic dye degradation in simultaneous electron-Fenton process on O/N–C catalyst was demonstrated particularly for broadening its environmental application.展开更多
The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appr...The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appropriate n-type semiconductor were innovatively and reasonably selected to enhance the photocatalytic performance of pristine p-type cuprous oxide(Cu_(2)O).In this study,the defect regula-tion of N doping(1)achieved the small-size effect of Cu_(2)O,(2)optimized the electron features,and(3)improved the kinetics of reactive oxygen species.The p-n heterojunction with PDINH was developed to sharply improve the light utilization of Cu_(2)O,from the UV region to the near-infrared region.As expected,the optimized Cu_(2)N_(x)O_(1–x)/PDINH(x=0.02)exhibited excellent long-term photocatalytic antibacterial ac-tivities,with antibacterial rates exceeding 91%against Staphylococcus aureus and Pseudomonas aeruginosa.Defect regulation and p-n heterojunction of Cu_(2)O-based composites thus provide a great deal of potential for future advancements in photocatalysis.展开更多
A novel three-dimensional (3D) layered MoS2@graphene functionalized with nitrogen-doped graphene quantum dots (MoS2@N-GQDs-GR) composites as an enhanced electrochemical hydrogen evolution catalyst. The few layered MoS...A novel three-dimensional (3D) layered MoS2@graphene functionalized with nitrogen-doped graphene quantum dots (MoS2@N-GQDs-GR) composites as an enhanced electrochemical hydrogen evolution catalyst. The few layered MoS2 nanoflowers supported on N-GQDs-GR surface were elaborately fabricated by one-pot hydrothermal method, which MoS2 and N-GQDs-GR exist in a bonding manner of Mo-N. In addition, due to the layered MoS2 sheet edge exposes more hydrogen evolution active sites and N-GQDs-GR have high conductivity, the composites exhibit prominent electrocatalytic activity with a low overpotential 99 mV, a small Tafel slope 49.3 mV/dec. Therefore, that the current work will develop HER catalysts may replace Pt.展开更多
Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their ou...Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their outstanding electrical conductivity, hierarchical porous structure, intrinsic heteroatom doping, and environmental friendliness. Here, we investigate the potential of hierarchical N-doped porous carbon (NPC) derived from jackfruit rags through a facile pyrolysis as an anode material for SIBs. The cycling performance of NPC at 1 A/g for 2000 cycles featured a stable reversible capacity of 122.3 mA h/g with an outstanding capacity retention of 99.1%. These excellent electrochemical properties can be attributed to the unique structure of NPC;it features hierarchical porosity with abundant carbon edge defects and large speci c surface areas. These results illuminate the potential application of jackfruit rags-derived porous carbon in SIBs.展开更多
Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated g...Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.展开更多
Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-do...Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-doping and oxygen vacancies by etching Co3O4 nanosheets with NH3 plasma. Comparing with the pristine Co3O4 nanosheets(1.79 V), the porous CoxOy nanosheets with N-doping and oxygen vacancies have a much lower potential of 1.51 V versus RHE to reach the current density of 10 mA cm-2. The obtained sample has a lower Tafel slope of 68 m V dec-1 than the pristine Co3O4 nanosheets(234 mV dec-1).The disclosed Co^2+, which is responsible for the formation of active sites(CoOOH), N-doping and oxygen vacancies, gives rise to better performance of OER.展开更多
This report describes an equivalent doping profile transformation method with which the avalanche breakdown voltage of the asymmetric linearly graded junction was analytically predicted.The maximum breakdown voltage a...This report describes an equivalent doping profile transformation method with which the avalanche breakdown voltage of the asymmetric linearly graded junction was analytically predicted.The maximum breakdown voltage and the different depletion layer extension on the diffused side and substrate side are demonstrated in the report.The report shows the equivalent doping profile method is valid to predict the breakdown voltage of the complex P N junction.The analytical results agree with the experimental breakdown voltage in comparison with the abrupt junction and symmetric linearly graded junction approximations.展开更多
Heteroatoms doped Carbon materials have been proved as promising catalyst support material for oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC). In this paper, nitrogen-doped porous nanofi...Heteroatoms doped Carbon materials have been proved as promising catalyst support material for oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC). In this paper, nitrogen-doped porous nanofibers (N-PCNF) were fabricated via cost effective electrospinning technique by blending the PI and PAN as precursors, followed by heat treatment procedures. The N-PCNFs were used as support to prepare platinum (Pt) catalyst (Pt/N-PCNFs). SEM figure indicated that the porous structures not only existed on the surface but also in the cross session of the fibers. XPS and TEM displayed that with the help of heteroatoms nitrogen, the fiber had rougher surface and more defective structure, contributing to the dispersion of Pt nanoparticles. The catalytic performance for ORR was evaluated by cyclic voltammetry (CV) and liner sweep voltammetry (LSV) with a rotating disk electrode (RDE). According to the results, Pt/N-PCNF exhibited superior property (more positive onset potential and half-wave potential) than that of JM20. The excellent ORR activity of Pt/N-PCNF was attributed to the enriched nitrogen heteroatoms coordinated within the microstructure which increased the exposure of more active sites and dispersion of Pt nanoparticles.展开更多
Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity i...Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.展开更多
The transformation of Li_(2)S_(2)-Li_(2)S is indubitably the most crucial and labored rate-limiting step among the sophisticated reactions for the lithium-sulfur batteries(LSBs),the adjustment of which is anticipated ...The transformation of Li_(2)S_(2)-Li_(2)S is indubitably the most crucial and labored rate-limiting step among the sophisticated reactions for the lithium-sulfur batteries(LSBs),the adjustment of which is anticipated to impede the shuttle effect.Herein,a N,Se dual-doped carbon nanocages embedded by Co-CoSe_(2)nanoparticles(Co-CoSe_(2)@NSeC)is employed as a functional coating layer on commercial separator to improve the performance of LSBs.The well-designed N,Se co-doped nanostructures endow the modified layer with a satisfactory capacity for blocking polysulfides.Both calculations and experiments jointly disclose that the Li_(2)S_(2)to Li_(2)S reaction,including the liquid-solid conversion,was prominently expedited both thermodynamically and electrodynamically.Consequently,the batteries fabricated with Co-CoSe_(2)@NSeC modified separator can deliver a favorable 764.2 mAh g^(−1)with 8.0 C,accompanied by a salient long cycling lifespan(only 0.066%at 1 C and 0.061%under 2 C after 1000 and 2000 cycles),and a desired anode protection.In addition,despite a raised areal loading of 7.53 mg cm^(−2)was introduced,the cells assembled by Co-CoSe_(2)@NSeC@PP are allowed to produce an outstanding initial behavior of 8.71 mAh cm^(−2)under 0.2 C.This work may reinforce further explorations and serve with valuable insights into N,Se dual-doping materials for high-performance LSBs.展开更多
The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most sta...The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most stable structure for the smallest formation energy.After N-doping,the charge density distribution significantly changes,and the acceptor impurity level is introduced above the valence band and intersects with the Fermi level.The impurity absorption edges appear to shift toward longer wavelengths with an increase in N-doping concentration.The complex refractive index shows metallic characteristics in the N-doped β-Ga2O3.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 conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient...The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.展开更多
Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only sh...Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.展开更多
基金supported by the Development Project of Youth Innovation Team in Shandong Colleges and Universities(No.2019KJC031)the Natural Science Foundation of Shandong Province(Nos.ZR2019MB064,ZR2021MB122 and ZR2022MB137)the Doctoral Program of Liaocheng University(No.318051608).
文摘Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.
基金supported by the National Natural Science Foundation of China(21421001 , 21573115)the 111 project (B12015)+1 种基金the Fundamental Research Funds for the Central Universities(63185015)the Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2017-K13)
文摘Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.
基金the financial support of this work by the National Natural Science Foundation of China (No.21406139)the Development Project of University of Shanghai for Science and Technology (No.2019KJFZ019)+1 种基金the Scientific Research Innovation Project of Shanghai Education Commission (No.2019-01-07-0007-E00015)the Basic Research Project (No.19JC1410402)。
文摘Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free heteroatoms to obtain the best electrocatalytic performance through three types of dual-doped carbon,including XC-N(first X doping then N doping),NC-X(first N doping then X doping) and NXC(N and X doping)(X=P,S and F).XC-N has more defect than the other two indicated by Raman spectra.X-ray photoelectron spectrom(XPS) measurements indicate that N and X have been dual-doped into the carbon matrix with different doping contents and modes,Electrocatalytic results,including the potential of ORR peak(Ep),the half-wave potential,the diffusion-limiting current density mainly follows the order of XC-N>NC-X> NXC,Furthermore,the synergistic effect of second atom doping are also compared with the single doped carbon(NC,PC,SC and FC).The differences in electronegativity and atomic radius of these metal-free heteroatoms can affect the defect degree,the doping content and mode of hete roatoms on carbon matrix,induce polarization effect and space effect to affect O2 adsorption and product desorption,ultimately to the ORR electrocatalytic performance.
基金National Natural Science Foundation of China,Grant/Award Number:52177162the Natural Science Foundation of Zhejiang Province,Grant/Award Numbers:LZ22E070003,LQ22E020006+1 种基金the Funding Project for Academic/Technical Leaders of Jiangxi Province,Grant/Award Number:20225BCJ22003the Natural Science Foundation of Jiangxi Province,Grant/Award Number:20212ACB211001。
文摘Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains challenging.Here,for the first time,we use the stronger electronegativity of a rare‐Earth yttrium ion(Y^(3+))to induce in situ NiCo‐layered double‐hydroxide nanosheets from NiCo foam(NCF)treated by a dielectric barrier discharge plasma NCF(PNCF),and then obtain nitrogen‐doped YNiCo phosphide(N‐YNiCoP/PNCF)after the phosphating process using radiofrequency plasma in nitrogen.The obtained NYNiCoP/PNCF has a large specific surface area,rich heterointerfaces,and an optimized electronic structure,inducing high electrocatalytic activity in HER(331mV vs.2000mA cm^(−2))and OER(464mV vs.2000mA cm^(−2))reactions in 1MKOH electrolyte.X‐ray absorption spectroscopy and density functional theory quantum chemistry calculations reveal that the coordination number of CoNi decreased with the incorporation of Y atoms,which induce much shorter bonds of Ni and Co ions and promote long‐term stability of N‐YNiCoP in HER and OER under the simulated industrial conditions.Meanwhile,the CoN‐YP_(5) heterointerface formed by plasma N‐doping is the active center for overall water splitting.This work expands the applications of rare‐Earth elements in engineering bifunctional electrocatalysts and provides a new avenue for designing highperformance transition‐metal‐based catalysts in the renewable energy field.
文摘Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.
基金supported by the National Natural Science Foundation of China(Nos.U22A20432,22278364,22211530045,22178308)the Fundamental Research Funds for the Central Universities(Nos.226-2022-00044,226-2022-00055)+6 种基金the Research Funds of Institute of Zhejiang University-Quzhou(No.IZQ2021KJ2003)National Key Research and Development Program of China(No.2022YFB4002100)the development project of Zhejiang Province's"Jianbing"and"Lingyan"(No.2023C01226)the Startup Foundation for Hundred-Talent Program of Zhejiang Universitythe Science Foundation of Donghai Laboratory(No.DH_(2)022ZY0009)Zhejiang University Global Partnership Fundthe China Postdoctoral Science Foundation(No.2021M702813)。
文摘Recently electrochemical synthesis of H_(2)O_(2)through oxygen reduction reaction(ORR)via 2e^(-)pathway is considered as a green and on-site route.However,it still remains a big challenge for fabricating novel metal-free catalysts under acidic solutions,since it suffers from high overpotential due to the intrinsically week*OOH adsorption.Herein,a co-doped carbon nanosheet(O/N–C)catalyst toward regulating O and N content was synthesized for improving the selectivity and activity of H_(2)O_(2)electrosynthesis process.The O/N–C exhibits outstanding 2e-ORR performance with low onset potential of 0.4 V(vs.RHE)and a selectivity of 92.4%in 0.1 mol/L HClO_(4)solutions.The in situ electrochemical impedance spectroscopy(EIS)tests reveals that the N incorporation contributes to the fast ORR kinetics.The density functional theory(DFT)calculations demonstrate that the binding strength of*OOH was optimized by the co-doping of oxygen and nitrogen at certain content,and the O/N–C–COOH site exhibits a lower theoretical overpotential for H_(2)O_(2)formation than O–C–COOH site.Furthermore,the promoted kinetics for typical organic dye degradation in simultaneous electron-Fenton process on O/N–C catalyst was demonstrated particularly for broadening its environmental application.
基金supported by the National Natural Science Foundation Joint Fund(Nos.U1806223 and U2106226)the National Natural Science Foundation of China(No.52371081)the Key Technology Research and Development Program of Shandong Province(No.2020CXGC010703).
文摘The defect regulation and p-n heterojunction of composites have gained significant attention due to their potential applications.Nitrogen(N)as doping heteroatoms and perylene-3,4,9,10-tetracarboximide(PDINH)as an appropriate n-type semiconductor were innovatively and reasonably selected to enhance the photocatalytic performance of pristine p-type cuprous oxide(Cu_(2)O).In this study,the defect regula-tion of N doping(1)achieved the small-size effect of Cu_(2)O,(2)optimized the electron features,and(3)improved the kinetics of reactive oxygen species.The p-n heterojunction with PDINH was developed to sharply improve the light utilization of Cu_(2)O,from the UV region to the near-infrared region.As expected,the optimized Cu_(2)N_(x)O_(1–x)/PDINH(x=0.02)exhibited excellent long-term photocatalytic antibacterial ac-tivities,with antibacterial rates exceeding 91%against Staphylococcus aureus and Pseudomonas aeruginosa.Defect regulation and p-n heterojunction of Cu_(2)O-based composites thus provide a great deal of potential for future advancements in photocatalysis.
基金financially supported by the National Natural Science Foundation of China(Nos. 21165016, 21175108, 21265018)the Science and Technology Support Projects of Gansu Province (Nos. 1011GKCA025, 090GKCA036,1208RJZM289)
文摘A novel three-dimensional (3D) layered MoS2@graphene functionalized with nitrogen-doped graphene quantum dots (MoS2@N-GQDs-GR) composites as an enhanced electrochemical hydrogen evolution catalyst. The few layered MoS2 nanoflowers supported on N-GQDs-GR surface were elaborately fabricated by one-pot hydrothermal method, which MoS2 and N-GQDs-GR exist in a bonding manner of Mo-N. In addition, due to the layered MoS2 sheet edge exposes more hydrogen evolution active sites and N-GQDs-GR have high conductivity, the composites exhibit prominent electrocatalytic activity with a low overpotential 99 mV, a small Tafel slope 49.3 mV/dec. Therefore, that the current work will develop HER catalysts may replace Pt.
基金financially supported by National Natural Science Foundation of China (Nos. 21875253, 21703249)the 1000 Plan Professorship for Young Talents
文摘Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their outstanding electrical conductivity, hierarchical porous structure, intrinsic heteroatom doping, and environmental friendliness. Here, we investigate the potential of hierarchical N-doped porous carbon (NPC) derived from jackfruit rags through a facile pyrolysis as an anode material for SIBs. The cycling performance of NPC at 1 A/g for 2000 cycles featured a stable reversible capacity of 122.3 mA h/g with an outstanding capacity retention of 99.1%. These excellent electrochemical properties can be attributed to the unique structure of NPC;it features hierarchical porosity with abundant carbon edge defects and large speci c surface areas. These results illuminate the potential application of jackfruit rags-derived porous carbon in SIBs.
基金Y.Hou expresses appreciation of the assistance of the NSFC 51702284 and 21878270Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Startup Foundation for Hundred-Talent Program of Zhejiang University(112100-193820101/001/022).
文摘Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.
基金supported by the National Natural Science Foundation of China(Grant Nos.:51402100,21573066)
文摘Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-doping and oxygen vacancies by etching Co3O4 nanosheets with NH3 plasma. Comparing with the pristine Co3O4 nanosheets(1.79 V), the porous CoxOy nanosheets with N-doping and oxygen vacancies have a much lower potential of 1.51 V versus RHE to reach the current density of 10 mA cm-2. The obtained sample has a lower Tafel slope of 68 m V dec-1 than the pristine Co3O4 nanosheets(234 mV dec-1).The disclosed Co^2+, which is responsible for the formation of active sites(CoOOH), N-doping and oxygen vacancies, gives rise to better performance of OER.
文摘This report describes an equivalent doping profile transformation method with which the avalanche breakdown voltage of the asymmetric linearly graded junction was analytically predicted.The maximum breakdown voltage and the different depletion layer extension on the diffused side and substrate side are demonstrated in the report.The report shows the equivalent doping profile method is valid to predict the breakdown voltage of the complex P N junction.The analytical results agree with the experimental breakdown voltage in comparison with the abrupt junction and symmetric linearly graded junction approximations.
文摘Heteroatoms doped Carbon materials have been proved as promising catalyst support material for oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC). In this paper, nitrogen-doped porous nanofibers (N-PCNF) were fabricated via cost effective electrospinning technique by blending the PI and PAN as precursors, followed by heat treatment procedures. The N-PCNFs were used as support to prepare platinum (Pt) catalyst (Pt/N-PCNFs). SEM figure indicated that the porous structures not only existed on the surface but also in the cross session of the fibers. XPS and TEM displayed that with the help of heteroatoms nitrogen, the fiber had rougher surface and more defective structure, contributing to the dispersion of Pt nanoparticles. The catalytic performance for ORR was evaluated by cyclic voltammetry (CV) and liner sweep voltammetry (LSV) with a rotating disk electrode (RDE). According to the results, Pt/N-PCNF exhibited superior property (more positive onset potential and half-wave potential) than that of JM20. The excellent ORR activity of Pt/N-PCNF was attributed to the enriched nitrogen heteroatoms coordinated within the microstructure which increased the exposure of more active sites and dispersion of Pt nanoparticles.
基金supported by the National Natural Science Foundation of China(22171266)the FJIRSM&IUE Joint Research Fund(RHZX-2019-002)+2 种基金the STS Project(KFJ-STS-QYZD-2021-09002)the National Key Basic Research Program of China(2017YFA0403402)the Project of the National Natural Science Foundation of China(U1932119)。
文摘Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.
基金supported by the National Natural Science Foundation of China(No.21875039)the Project on the Integration of Industry-Education-Research of Fujian Province(No.2021H6020).
文摘The transformation of Li_(2)S_(2)-Li_(2)S is indubitably the most crucial and labored rate-limiting step among the sophisticated reactions for the lithium-sulfur batteries(LSBs),the adjustment of which is anticipated to impede the shuttle effect.Herein,a N,Se dual-doped carbon nanocages embedded by Co-CoSe_(2)nanoparticles(Co-CoSe_(2)@NSeC)is employed as a functional coating layer on commercial separator to improve the performance of LSBs.The well-designed N,Se co-doped nanostructures endow the modified layer with a satisfactory capacity for blocking polysulfides.Both calculations and experiments jointly disclose that the Li_(2)S_(2)to Li_(2)S reaction,including the liquid-solid conversion,was prominently expedited both thermodynamically and electrodynamically.Consequently,the batteries fabricated with Co-CoSe_(2)@NSeC modified separator can deliver a favorable 764.2 mAh g^(−1)with 8.0 C,accompanied by a salient long cycling lifespan(only 0.066%at 1 C and 0.061%under 2 C after 1000 and 2000 cycles),and a desired anode protection.In addition,despite a raised areal loading of 7.53 mg cm^(−2)was introduced,the cells assembled by Co-CoSe_(2)@NSeC@PP are allowed to produce an outstanding initial behavior of 8.71 mAh cm^(−2)under 0.2 C.This work may reinforce further explorations and serve with valuable insights into N,Se dual-doping materials for high-performance LSBs.
基金Project supported by the National Natural Science Foundation of China (Grant No. 10974077)the Natural Science Foundation of Shandong Province,China (Grant No. 2009ZRB01702)the Shandong Provincial Higher Educational Science and Technology Program,China (Grant No. J10LA08)
文摘The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most stable structure for the smallest formation energy.After N-doping,the charge density distribution significantly changes,and the acceptor impurity level is introduced above the valence band and intersects with the Fermi level.The impurity absorption edges appear to shift toward longer wavelengths with an increase in N-doping concentration.The complex refractive index shows metallic characteristics in the N-doped β-Ga2O3.
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financially supported by Guangdong Province Science and Technology Plan Project for Public Welfare Fund and Ability Construction Project(JCYJ20180301171324915)the National Natural Science Foundation of China(No.21503116)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn20161004)the Youth 1000 Talent Program of China。
文摘The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.
基金financial support by the National Natural Science Foundation of China (Grant: 51333008)Young Teacher Training Program of Sun Yat-sen University (Grant: 17lgpy86)
文摘Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.
