The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-p...Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
Nitrogen doping in chemical vapor deposition-derived ultrananocrystalline diamond(UNCD)films in-creases the electronic conductivity,yet its microstructural effects on electron transport are insufficiently understood.W...Nitrogen doping in chemical vapor deposition-derived ultrananocrystalline diamond(UNCD)films in-creases the electronic conductivity,yet its microstructural effects on electron transport are insufficiently understood.We investigated the formation of nitrogen-induced diaph-ite structures(hybrid diamond-graphite phases)and their role in changing the conductivity.Nitrogen doping in a hy-drogen-rich plasma environment promotes the emergence of unique sp^(3)-sp^(2)bonding interfaces,where diamond grains are covalently integrated with graphitic domains,facilitating a structure-driven electronic transition.High-resolution transmis-sion electron microscopy and selected area electron diffraction reveal five-fold,six-fold and twelve-fold symmetries,along with an atypical{200}crystallographic reflection,confirming diaphite formation in 5%and 10%N-doped UNCD films,while high-er doping levels(15%and 20%)result in extensive graphitization.Raman spectroscopy tracks the evolution of sp^(2)bonding with increasing nitrogen content,while atomic force microscopy and X-ray diffraction indicate a consistent diamond grain size of~8 nm.Cryogenic electronic transport measurements reveal a conductivity increase from 8.72 to 708 S/cm as the nitrogen dop-ing level increases from 5%to 20%,which is attributed to defect-mediated carrier transport and 3D weak localization.The res-ulting conductivity is three orders of magnitude higher than previously reported.These findings establish a direct correlation between diaphite structural polymorphism and tunable electronic properties in nitrogen-doped UNCD films,offering new ways for defect-engineering diamond-based electronic materials.展开更多
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.C...We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.Compared with single N-doped BCDs(N-BCDs) and Pr-doped BCDs(Pr-BCDs),Pr/N-BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%.More importantly,under certain conditions,Pr/N-BCDs and 2,4-dinitrophenylhydrazide(2,4-DNPH) had significant fluorescence internal filtration effect(IFE) and dynamic quenching effect,and in the concentration range of0.50-20 μmol·L^(-1),the concentration of 2,4-DNPH had a good linear relationship with the fluorescence quenching signal,and the detection limit was as low as 2.1 nmol·L^(-1).展开更多
The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy beco...The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy becomes defect dipole,which prevents the domain rotation.In this field,a serious problem is that generally,Qm decreases as the temperature(T)increases,since the oxygen vacancies are decoupled from the defect dipoles.In this work,Q_(m) of Pb_(0.95)Sr_(0.05)(Zr_(0.53)Ti_(0.47))O_(3)(PSZT)ceramics doped by 0.40%Fe_(2)O_(3)(in mole)abnormally increases as T increases,of which the Qm and piezoelectric coefficient(d_(33))at room temperature and Curie temperature(TC)are 507,292 pC/N,and 345℃,respectively.The maximum Qm of 824 was achieved in the range of 120–160℃,which is 62.52%higher than that at room temperature,while the dynamic piezoelectric constant(d_(31))was just slightly decreased by 3.85%.X-ray diffraction(XRD)and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases,and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240℃.It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240℃,which pins domain rotation,resulting in the enhanced Q_(m) with the increasing temperature.These results give a potential path to design high Q_(m) at high temperature.展开更多
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.展开更多
In a high heat flux ablative environment,the surface temperature of aircraft rises rapidly,leading to traditional high thermal conductivity materials being ineffective at protecting internal metal components.In this s...In a high heat flux ablative environment,the surface temperature of aircraft rises rapidly,leading to traditional high thermal conductivity materials being ineffective at protecting internal metal components.In this study,continuous carbon fiber reinforced Li_(2)O-Al_(2)O_(3)-SiO_(2)(C_(f)/LAS)glass ceramic composites doped with SiC particles(SiC_(p))were prepared by slurry immersion winding and hot pressing sintering.Effect of matrix crystallinity on ablative properties of the composites under ultra-high heat flux was investigated.By utilizing heat absorption and low thermal conductivity characteristics associated with SiO_(2)gasification within composite materials,both surface and internal temperatures of these materials are effectively reduced,thereby ensuring the safe operation of aircraft and electronic devices.Results indicate that the average linear ablation rate of composites doped with 10%(in mass)of SiC_(p)significantly decreases at a heat flux of 20 MW/m^(2).Transmission electron microscope observation reveals that the doped glass matrix exhibits increased crystallinity,reduced internal stress,and minimized lattice distortion,thereby enhancing the composites’high-temperature performance.However,excessive SiC_(p)doping leads to reduced crystallinity and deteriorated ablation performance.Ultimately,the average linear ablation rate of C_(f)/LAS composites with 10%(in mass)SiC_(p)at 20 MW/m^(2)heat flux is comparable to that of commercial carbon/carbon composites,accompanied by providing lower thermal conductivity and higher bending strength.This novel high-performance C_(f)/LAS composite is cost-effective,short-cycled,and suitable for mass production,offering promising potential for widespread application in ablation-resistant components of hypersonic vehicles.展开更多
Al-doped manganese dioxide(MnO_(2))was synthesized by simple hydrothermal method,and a controllable phase transition of the MnO_(2)crystal phase fromβtoδwas achieved.The effects of Al doping concentration on the str...Al-doped manganese dioxide(MnO_(2))was synthesized by simple hydrothermal method,and a controllable phase transition of the MnO_(2)crystal phase fromβtoδwas achieved.The effects of Al doping concentration on the structure and electrochemical properties of electrode materials were studied in detail.The results show that the controlled synthesis requires a synergy between KMnO_(4),MnCl_(2)and AlCl_(3),and that Al^(3+)plays an important role.Compared with the pure phase MnO_(2),the crystallinity of Al-doped MnO_(2)decreases and the specific surface area increases,which provides more active sites for the electrode material.When 3 mmol Al^(3+)is added,the prepared MnO_(2)-3 has the largest specific capacitance and the highest rate performance.The energy density of the asymmetric supercapacitor(ASC)with MnO_(2)-3 as the positive electrode and activated carbon(AC)as the negative electrode can reach 18.4 W·h/kg at the power density of 400 W/kg,and the capacity can maintain 90%of the initial value after 20000 cycles,indicating that Al-doped MnO_(2)has certain practical application value.This study provides favorable guidance for MnO_(2)as a high performance electrode material.展开更多
Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for...Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for further investigation,and the specifically exposed crystal faces of CeO_(2)may have an impact on the performance of nitrogen doped CeO_(2).Herein,nitrogen-doped CeO_(2)with different morphologies and exposed crystal faces was prepared,and its performances in the photocatalytic degradation of tetracycline(TC)or hydrogen production via water splitting were evaluated.Density functional theory(DFT)was used to simulate the band structures,density of states,and oxygen defect properties of different CeO_(2)structures.It was found that nitrogen doping and OVs synergistically promoted the catalytic activity of nitrogen-doped CeO_(2).In addition,the exposed crystal faces of CeO_(2)have significant effects on the introduction of nitrogen and the ease of OV generation,as well as the synergistic effect of nitrogen doping with OVs.Among them,the rod-like nitrogen-doped CeO_(2)with exposed(110)face(R-CeO_(2)-NH_(3))showed a photocatalytic degradation ratio of 73.59%for TC and hydrogen production of 156.89μmol/g,outperforming other prepared photocatalysts.展开更多
Y_(3)Al_(2)Ga_(3)O_(12):Ce^(3+),Cr^(3+)(YAGG:Ce^(3+),Cr^(3+)),as a persistent luminescent material,has advantages of high initial luminescence intensity and long persistent time,which is promising in persistent lumine...Y_(3)Al_(2)Ga_(3)O_(12):Ce^(3+),Cr^(3+)(YAGG:Ce^(3+),Cr^(3+)),as a persistent luminescent material,has advantages of high initial luminescence intensity and long persistent time,which is promising in persistent luminescent material applications.At present,YAGG:Ce^(3+),Cr^(3+)powders exhibit good persistent performance,but their persistent performance of ceramics still needs to be further improved to meet the new requirements.In this work,(Y_(0.998)Ce_(0.002))_(3)(Al_(1-x)Cr_(x))_(2)Ga_(3)O_(12) ceramics with different Cr^(3+)doping concentrations were prepared by solid-state reaction,including air pre-sintering,hot isostatic pressing(HIP)post-treatment and air annealing,to investigate the effects of Cr^(3+)doping concentration on the microstructure,optical properties and persistent performance of the ceramics.The results showed that as the doping concentration of Cr^(3+)increased from 0.025%to 0.2%(in atom),no significant effect of Cr^(3+)concentration on the morphology of pre-sintered ceramics or HIP post-treatment ceramics was observed,but the in-line transmittance gradually increased while the persistent performance gradually decreased.Among them,YAGG:Ce^(3+),Cr^(3+)ceramics doped with 0.025%Cr^(3+)showed the strongest initial luminescence intensity exceeding 6055 mcd/m^(2) and a persistent time of 1030 min after air pre-sintering combined with HIP post-treatment and air annealing.By optimizing the Cr^(3+)doping concentration and the fabrication process,the persistent luminescence(PersL)performance of the YAGG:Ce^(3+),Cr^(3+)ceramics was obviously improved.展开更多
Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluoresc...Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eul-xLx（TTA）3Phen complex system are identical with that of EuTTA3Phen, which indicates that the complexes (Eul-xLx（TTA）3Phen) are similar in structure to （Eu （TTA）3Phen.） For the above doping elements, co-fluorescence enhancement has the following order: Gd3+>Y3+>La3+, and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+, Y3+, La3+. Among all the complexes, Eu0.6Gd0.4（TTA）3Phen complex has the strongest fluorescent intensity. Applying Eu0.6Gd0.4（TTA）3Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1%（mass fraction）.展开更多
In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological charact...In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction(XRD),N_(2)-physisorption for BET surface area measurements,scanning and transmission electronic microscopies(SEM and TEM),UV-Vis diffuse spectroscopy(DRS)and X-ray photoelectron spectroscopy(XPS),in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation.Results have shown important differences among the catalysts depending on the metal added.Sulphated TiO_(2)/Cu(1%Cu)was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min.The appropriate physico-chemical features of this photocatalyst,given by the addition of combined copper and sulphate ions,explain its excellence in photocatalytic reaction.展开更多
In order to investigate whether endohedral He-doping is possible or not in CL-20,a density functional treatment has been carried out at the levels of B3LYP/6-31++G(d,p)and B3PW91/6-31++G(d,p).Some physicochemical and ...In order to investigate whether endohedral He-doping is possible or not in CL-20,a density functional treatment has been carried out at the levels of B3LYP/6-31++G(d,p)and B3PW91/6-31++G(d,p).Some physicochemical and quantum chemical properties of the helium-doped CL-20 (He@CL-20)are compared with the respective values of the parent explosive CL-20.The helium doping caused swelling of CL-20cage but no bond rupture occurred.Doped helium acquired some positive charge.展开更多
W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and m...W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and morphology of Li4Ti4.psW0.05Ol2. W-doping does not change the phase composition and particle morphology, while remarkably improves its cycling stability at high charge/discharge rate. Li4Ti4.95W0.05O12 exhibits an excellent rate capability with a reversible capacity of 131.2 mA.h/g at 10C and even 118.6 mA.h/g at 20C. The substitution of W for Ti site can enhance the electronic conductivity of Li4TisO12 via the generation of mixing Ti4＋/Ti3＋, which indicates that Li4Ti4.psW0.05O12 is promising as a high rate anode for the lithium-ion batteries.展开更多
The effects of CaO content in the range from 0 to 4.0%, and sintering temperature on the phase composition, relative density and electrical conductivity of 10NiO-NiFe2O4 composites doped with CaO were studied. The res...The effects of CaO content in the range from 0 to 4.0%, and sintering temperature on the phase composition, relative density and electrical conductivity of 10NiO-NiFe2O4 composites doped with CaO were studied. The results show that there is no change of structure for NiO or NiFe2O4; there is apparent oxygen absorbing and releasing behavior during the heating process in air for 10NiO-NiFe2O4 composites. Introduction of CaO can accelerate the densification of 10NiO-NiFe2O4 composites. The maximum value of relative density is 98.75% for composite doped with 2.0% CaO and sintered at 1 200 ℃, which is beyond about 20% for the undoped composites. The sintering activated energy of sample containing 2% CaO decreases by 15.87 kJ/mol, compared with that of the undoped sample.展开更多
Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response me...Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.展开更多
A new anodic material of ternary Pb-0.8%Ag-(0-5.0%)Bi alloy for zinc electrowinning was obtained by doping Bi.The anodic oxygen evolution potential,corrosion rate,surface products after polarization,and microstructure...A new anodic material of ternary Pb-0.8%Ag-(0-5.0%)Bi alloy for zinc electrowinning was obtained by doping Bi.The anodic oxygen evolution potential,corrosion rate,surface products after polarization,and microstructures before and after polarization were studied and compared with those of Pb-0.8%Ag anode used in industry.The results show the anodic overpotential decreases with the increase of Bi content in the alloys.When the content of Bi is 1.0%(mass fraction),the anodic overpotential is 40-50 mV lower than that of Pb-0.8%Ag anode.While the corrosion rate decreases and then increases with the increase of Bi content.The Pb-0.8%Ag-0.1%Bi anode has the lowest corrosion rate(0.090 6 mg/(h·cm2).Doping Bi influences the structure of the anodic layer,but does not change the phase.The Pb-0.8%Ag-1.0%Bi anode layer is of a more fine-grained structure compared with Pb-0.8%Ag anode.展开更多
Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon e...Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon electrode were fabricated and compared with the redox type capacitors （PLi/PLi） based on two uniformly Li-doping polyaniline electrodes. The electrochemical performances of the two types of supercapacitors were characterized in non-aqueous electrolyte. PLi/C supercapacitors have a wider effective energy storage potential range and a higher upper potential. At the same time, the PLi/C supercapacitor exhibits a specific capacity of 120.93 F/g at initial discharge and retains 80% after 500 cycles. The ohmic internal resistance （REs） of PLi/C supercapacitor is 5.0 Ω, which is smaller than that of PLi/PLi capacitor （5.5 Ω）. Moreover, it can be seen that EtgNBF4 organic solution is more suitable for using as organic electrolyte of PLi/C capacitor compared with organic solution containing LiPFr.展开更多
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金supported by National Key R&D Program of China(2021YFB4001401)National Natural Science Foundation of China(52272190,22178023).
文摘Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
文摘Nitrogen doping in chemical vapor deposition-derived ultrananocrystalline diamond(UNCD)films in-creases the electronic conductivity,yet its microstructural effects on electron transport are insufficiently understood.We investigated the formation of nitrogen-induced diaph-ite structures(hybrid diamond-graphite phases)and their role in changing the conductivity.Nitrogen doping in a hy-drogen-rich plasma environment promotes the emergence of unique sp^(3)-sp^(2)bonding interfaces,where diamond grains are covalently integrated with graphitic domains,facilitating a structure-driven electronic transition.High-resolution transmis-sion electron microscopy and selected area electron diffraction reveal five-fold,six-fold and twelve-fold symmetries,along with an atypical{200}crystallographic reflection,confirming diaphite formation in 5%and 10%N-doped UNCD films,while high-er doping levels(15%and 20%)result in extensive graphitization.Raman spectroscopy tracks the evolution of sp^(2)bonding with increasing nitrogen content,while atomic force microscopy and X-ray diffraction indicate a consistent diamond grain size of~8 nm.Cryogenic electronic transport measurements reveal a conductivity increase from 8.72 to 708 S/cm as the nitrogen dop-ing level increases from 5%to 20%,which is attributed to defect-mediated carrier transport and 3D weak localization.The res-ulting conductivity is three orders of magnitude higher than previously reported.These findings establish a direct correlation between diaphite structural polymorphism and tunable electronic properties in nitrogen-doped UNCD films,offering new ways for defect-engineering diamond-based electronic materials.
基金supported by the National Natural Science Foundation of China (Grant No.22063010)the Natural Science Foundation of Shaanxi Province (Grant No.2022QFY07-05)Yan'an Science and Technology Plan Project (Grants No.2022SLJBZ-002, 2023-CYL-193)。
文摘We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.Compared with single N-doped BCDs(N-BCDs) and Pr-doped BCDs(Pr-BCDs),Pr/N-BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%.More importantly,under certain conditions,Pr/N-BCDs and 2,4-dinitrophenylhydrazide(2,4-DNPH) had significant fluorescence internal filtration effect(IFE) and dynamic quenching effect,and in the concentration range of0.50-20 μmol·L^(-1),the concentration of 2,4-DNPH had a good linear relationship with the fluorescence quenching signal,and the detection limit was as low as 2.1 nmol·L^(-1).
基金National Natural Science Foundation of China(U2241242)National Key R&D Program of China(2023YFB3812000,2021YFA0716502)。
文摘The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy becomes defect dipole,which prevents the domain rotation.In this field,a serious problem is that generally,Qm decreases as the temperature(T)increases,since the oxygen vacancies are decoupled from the defect dipoles.In this work,Q_(m) of Pb_(0.95)Sr_(0.05)(Zr_(0.53)Ti_(0.47))O_(3)(PSZT)ceramics doped by 0.40%Fe_(2)O_(3)(in mole)abnormally increases as T increases,of which the Qm and piezoelectric coefficient(d_(33))at room temperature and Curie temperature(TC)are 507,292 pC/N,and 345℃,respectively.The maximum Qm of 824 was achieved in the range of 120–160℃,which is 62.52%higher than that at room temperature,while the dynamic piezoelectric constant(d_(31))was just slightly decreased by 3.85%.X-ray diffraction(XRD)and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases,and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240℃.It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240℃,which pins domain rotation,resulting in the enhanced Q_(m) with the increasing temperature.These results give a potential path to design high Q_(m) at high temperature.
基金the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
基金National Natural Science Foundation of China(U23A6014,52103357)。
文摘In a high heat flux ablative environment,the surface temperature of aircraft rises rapidly,leading to traditional high thermal conductivity materials being ineffective at protecting internal metal components.In this study,continuous carbon fiber reinforced Li_(2)O-Al_(2)O_(3)-SiO_(2)(C_(f)/LAS)glass ceramic composites doped with SiC particles(SiC_(p))were prepared by slurry immersion winding and hot pressing sintering.Effect of matrix crystallinity on ablative properties of the composites under ultra-high heat flux was investigated.By utilizing heat absorption and low thermal conductivity characteristics associated with SiO_(2)gasification within composite materials,both surface and internal temperatures of these materials are effectively reduced,thereby ensuring the safe operation of aircraft and electronic devices.Results indicate that the average linear ablation rate of composites doped with 10%(in mass)of SiC_(p)significantly decreases at a heat flux of 20 MW/m^(2).Transmission electron microscope observation reveals that the doped glass matrix exhibits increased crystallinity,reduced internal stress,and minimized lattice distortion,thereby enhancing the composites’high-temperature performance.However,excessive SiC_(p)doping leads to reduced crystallinity and deteriorated ablation performance.Ultimately,the average linear ablation rate of C_(f)/LAS composites with 10%(in mass)SiC_(p)at 20 MW/m^(2)heat flux is comparable to that of commercial carbon/carbon composites,accompanied by providing lower thermal conductivity and higher bending strength.This novel high-performance C_(f)/LAS composite is cost-effective,short-cycled,and suitable for mass production,offering promising potential for widespread application in ablation-resistant components of hypersonic vehicles.
基金Project(202203021221138)supported by the Collaborative Innovation Center for Shanxi Advanced Permanent Materials and Technologythe 1331 Engineering of Shanxi ProvinceFundamental Research Program of Shanxi Province,China。
文摘Al-doped manganese dioxide(MnO_(2))was synthesized by simple hydrothermal method,and a controllable phase transition of the MnO_(2)crystal phase fromβtoδwas achieved.The effects of Al doping concentration on the structure and electrochemical properties of electrode materials were studied in detail.The results show that the controlled synthesis requires a synergy between KMnO_(4),MnCl_(2)and AlCl_(3),and that Al^(3+)plays an important role.Compared with the pure phase MnO_(2),the crystallinity of Al-doped MnO_(2)decreases and the specific surface area increases,which provides more active sites for the electrode material.When 3 mmol Al^(3+)is added,the prepared MnO_(2)-3 has the largest specific capacitance and the highest rate performance.The energy density of the asymmetric supercapacitor(ASC)with MnO_(2)-3 as the positive electrode and activated carbon(AC)as the negative electrode can reach 18.4 W·h/kg at the power density of 400 W/kg,and the capacity can maintain 90%of the initial value after 20000 cycles,indicating that Al-doped MnO_(2)has certain practical application value.This study provides favorable guidance for MnO_(2)as a high performance electrode material.
基金Project(52164025)supported by the National Natural Science Foundation of ChinaProject([2020]1Y219)supported by the Basic Research Program from the Science&Technology Department of Guizhou Province,China+2 种基金Project([2019]30)supported by the Training Project from Guizhou University,ChinaProject([2023]04)supported by the Guizhou University Innovation Talent Team Project,ChinaProject([2022]041)supported by the Natural Science Research Project of Guizhou Provincial Department of Education,China。
文摘Nitrogen doping has significant effects on the photocatalytic performance of ceria(CeO_(2)),and the possible synergistic effect with the inevitably introduced abundant oxygen vacancies(OVs)is of great significance for further investigation,and the specifically exposed crystal faces of CeO_(2)may have an impact on the performance of nitrogen doped CeO_(2).Herein,nitrogen-doped CeO_(2)with different morphologies and exposed crystal faces was prepared,and its performances in the photocatalytic degradation of tetracycline(TC)or hydrogen production via water splitting were evaluated.Density functional theory(DFT)was used to simulate the band structures,density of states,and oxygen defect properties of different CeO_(2)structures.It was found that nitrogen doping and OVs synergistically promoted the catalytic activity of nitrogen-doped CeO_(2).In addition,the exposed crystal faces of CeO_(2)have significant effects on the introduction of nitrogen and the ease of OV generation,as well as the synergistic effect of nitrogen doping with OVs.Among them,the rod-like nitrogen-doped CeO_(2)with exposed(110)face(R-CeO_(2)-NH_(3))showed a photocatalytic degradation ratio of 73.59%for TC and hydrogen production of 156.89μmol/g,outperforming other prepared photocatalysts.
基金National Key R&D Program of China(2023YFB3506600)。
文摘Y_(3)Al_(2)Ga_(3)O_(12):Ce^(3+),Cr^(3+)(YAGG:Ce^(3+),Cr^(3+)),as a persistent luminescent material,has advantages of high initial luminescence intensity and long persistent time,which is promising in persistent luminescent material applications.At present,YAGG:Ce^(3+),Cr^(3+)powders exhibit good persistent performance,but their persistent performance of ceramics still needs to be further improved to meet the new requirements.In this work,(Y_(0.998)Ce_(0.002))_(3)(Al_(1-x)Cr_(x))_(2)Ga_(3)O_(12) ceramics with different Cr^(3+)doping concentrations were prepared by solid-state reaction,including air pre-sintering,hot isostatic pressing(HIP)post-treatment and air annealing,to investigate the effects of Cr^(3+)doping concentration on the microstructure,optical properties and persistent performance of the ceramics.The results showed that as the doping concentration of Cr^(3+)increased from 0.025%to 0.2%(in atom),no significant effect of Cr^(3+)concentration on the morphology of pre-sintered ceramics or HIP post-treatment ceramics was observed,but the in-line transmittance gradually increased while the persistent performance gradually decreased.Among them,YAGG:Ce^(3+),Cr^(3+)ceramics doped with 0.025%Cr^(3+)showed the strongest initial luminescence intensity exceeding 6055 mcd/m^(2) and a persistent time of 1030 min after air pre-sintering combined with HIP post-treatment and air annealing.By optimizing the Cr^(3+)doping concentration and the fabrication process,the persistent luminescence(PersL)performance of the YAGG:Ce^(3+),Cr^(3+)ceramics was obviously improved.
文摘Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eul-xLx（TTA）3Phen complex system are identical with that of EuTTA3Phen, which indicates that the complexes (Eul-xLx（TTA）3Phen) are similar in structure to （Eu （TTA）3Phen.） For the above doping elements, co-fluorescence enhancement has the following order: Gd3+>Y3+>La3+, and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+, Y3+, La3+. Among all the complexes, Eu0.6Gd0.4（TTA）3Phen complex has the strongest fluorescent intensity. Applying Eu0.6Gd0.4（TTA）3Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1%（mass fraction）.
文摘In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction(XRD),N_(2)-physisorption for BET surface area measurements,scanning and transmission electronic microscopies(SEM and TEM),UV-Vis diffuse spectroscopy(DRS)and X-ray photoelectron spectroscopy(XPS),in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation.Results have shown important differences among the catalysts depending on the metal added.Sulphated TiO_(2)/Cu(1%Cu)was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min.The appropriate physico-chemical features of this photocatalyst,given by the addition of combined copper and sulphate ions,explain its excellence in photocatalytic reaction.
文摘In order to investigate whether endohedral He-doping is possible or not in CL-20,a density functional treatment has been carried out at the levels of B3LYP/6-31++G(d,p)and B3PW91/6-31++G(d,p).Some physicochemical and quantum chemical properties of the helium-doped CL-20 (He@CL-20)are compared with the respective values of the parent explosive CL-20.The helium doping caused swelling of CL-20cage but no bond rupture occurred.Doped helium acquired some positive charge.
文摘W-doped Li4TisO12 in the form of Li4Ti4.95W0.osO12 was firstly synthesized via solid state reaction. X-ray diffraction （XRD） and scanning electron microscope （gEM） were employed to characterize the structure and morphology of Li4Ti4.psW0.05Ol2. W-doping does not change the phase composition and particle morphology, while remarkably improves its cycling stability at high charge/discharge rate. Li4Ti4.95W0.05O12 exhibits an excellent rate capability with a reversible capacity of 131.2 mA.h/g at 10C and even 118.6 mA.h/g at 20C. The substitution of W for Ti site can enhance the electronic conductivity of Li4TisO12 via the generation of mixing Ti4＋/Ti3＋, which indicates that Li4Ti4.psW0.05O12 is promising as a high rate anode for the lithium-ion batteries.
基金Project (2005CB623703) supported by the National Key Fundamental Research and Development Program of ChinaProject (50474051) supported by the National Natural Science Foundation of ChinaProject (03JJY3080) supported by the Natural Science Foundation of Hunan Province, China
文摘The effects of CaO content in the range from 0 to 4.0%, and sintering temperature on the phase composition, relative density and electrical conductivity of 10NiO-NiFe2O4 composites doped with CaO were studied. The results show that there is no change of structure for NiO or NiFe2O4; there is apparent oxygen absorbing and releasing behavior during the heating process in air for 10NiO-NiFe2O4 composites. Introduction of CaO can accelerate the densification of 10NiO-NiFe2O4 composites. The maximum value of relative density is 98.75% for composite doped with 2.0% CaO and sintered at 1 200 ℃, which is beyond about 20% for the undoped composites. The sintering activated energy of sample containing 2% CaO decreases by 15.87 kJ/mol, compared with that of the undoped sample.
文摘Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.
基金Project(2007SK2009)supported by the Science and Technology Research Project of Hunan Province,China
文摘A new anodic material of ternary Pb-0.8%Ag-(0-5.0%)Bi alloy for zinc electrowinning was obtained by doping Bi.The anodic oxygen evolution potential,corrosion rate,surface products after polarization,and microstructures before and after polarization were studied and compared with those of Pb-0.8%Ag anode used in industry.The results show the anodic overpotential decreases with the increase of Bi content in the alloys.When the content of Bi is 1.0%(mass fraction),the anodic overpotential is 40-50 mV lower than that of Pb-0.8%Ag anode.While the corrosion rate decreases and then increases with the increase of Bi content.The Pb-0.8%Ag-0.1%Bi anode has the lowest corrosion rate(0.090 6 mg/(h·cm2).Doping Bi influences the structure of the anodic layer,but does not change the phase.The Pb-0.8%Ag-1.0%Bi anode layer is of a more fine-grained structure compared with Pb-0.8%Ag anode.
基金Project(2008AA03Z207) supported by the National High-Tech Research and Development Program of China
文摘Polyaniline（PANI） nanofiber was synthesized by interfacial polymerization utilizing the interface between HC1 and CCl4. The hybrid type supercapacitors （PLi/C） based on Li-doping polyaniline and activated carbon electrode were fabricated and compared with the redox type capacitors （PLi/PLi） based on two uniformly Li-doping polyaniline electrodes. The electrochemical performances of the two types of supercapacitors were characterized in non-aqueous electrolyte. PLi/C supercapacitors have a wider effective energy storage potential range and a higher upper potential. At the same time, the PLi/C supercapacitor exhibits a specific capacity of 120.93 F/g at initial discharge and retains 80% after 500 cycles. The ohmic internal resistance （REs） of PLi/C supercapacitor is 5.0 Ω, which is smaller than that of PLi/PLi capacitor （5.5 Ω）. Moreover, it can be seen that EtgNBF4 organic solution is more suitable for using as organic electrolyte of PLi/C capacitor compared with organic solution containing LiPFr.
