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
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
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
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
The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method gr...The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method greatly simplifies the fabrication process of the device,but it is easy to cause lattice damage,introduce crystalline defects,and lead to the increase of the dark current of detectors.Herein,the boron-doped germanium ion implantation process was studied,and the involved lattice damage mechanism was discussed.Experimental conditions involved using 80 keV energy for boron ion implantation,with doses ranging from 1×10^(13)cm^(-2)to 3×10^(15)cm^(-2).After implantation,thermal annealing at 450℃was implemented to optimize dopant activation and mitigate the effects of ion implantation.Various sophisticated characterization techniques,including X-ray dif⁃fraction(XRD),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),and secondary ion mass spec⁃trometry(SIMS)were used to clarify lattice damage.At lower doses,no notable structural alterations were ob⁃served.However,as the dosage increased,specific micro distortions became apparent,which could be attributed to point defects and residual strain.The created lattice damage was recovered by thermal treatment,however,an irreversible strain induced by implantation still existed at heavily dosed samples.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
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
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
Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most...Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most effective strategy to address the above issues.However,the preparation process of carbon-based sulfur hosts is usually complex and costly.Therefore,it is necessary to develop an efficient and cost-effective method to fabricate carbon hosts for high-performance sulfur cathodes.Herein,we reported the fabrication of a bio-derived nitrogen doped porous carbon materials(BNPC)via a molten-salt method for high performance sulfur cathodes.The long-range-ordered honeycomb structure of BNPC is favorable for the trapping of polysulfide(PS)species and accommodates the volumetric variation of sulfur during cycling,while the high graphitization degree of BNPC favors the redox kinetics of sulfur cathodes.Moreover,the nitrogen doping content not only enhances the electrical conductivity of BNPC,but also provides ample anchoring sites for the immobilization of PS,which plays a key role in suppressing the shuttle effect.As a result,the S@BNPC cathode exhibits a high initial specific capacity of 1189.4 mA·h/g at 0.2C.After 300 cycles,S@BNPC still maintains a capacity of 703.2 mA·h/g which corresponds to a fading rate of 0.13%per cycle after the second cycle.This work offers vast opportunities for the large-scale application of high performance carbon-based sulfur hosts.展开更多
Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO...Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO2. Different transformation modes were observed depending on the composition and cooling rate. ZrO2 containing 6% CeO2 showed isothermal transformation behavior, whereas ZrO2 containing 9% and 10% CeO2 showed athermal transformation behavior. However, ZrO2 containing 8% CeO2 showed either isothermal or athermal transformations behavior depending on the cooling rate. A TTT (Time-Temperature-Transformation) diagram was proposed for ZrO2 containing 8% CeO2.展开更多
The un-doped TiO2 and Cs+/Sr2+-doped TiO2 nanometer particles were prepared by sol-gel method using tetrabutyl titanate (Ti(OC4H9)4) as TiO2 precursor,and characterized with X-ray diffraction (XRD) and UV-Vis absorpti...The un-doped TiO2 and Cs+/Sr2+-doped TiO2 nanometer particles were prepared by sol-gel method using tetrabutyl titanate (Ti(OC4H9)4) as TiO2 precursor,and characterized with X-ray diffraction (XRD) and UV-Vis absorption spectra (UV-Vis). The photocatalytic activities of these samples were investigated by the photocatalytic degradation of methyl orange in aqueous suspension under 300 W medium pressure mercury lamp irradiation. The results show that the growth of crystallite size can be controlled effectively for the Cs+/Sr2+-doped TiO2,and crystal phase transformation of nano-sized TiO2 is retarded from anatase structure to rutile structure while using the proper doping concentration of Cs+/Sr2+. It is pure anatase of high photocatalytic activity for Cs+/Sr2+-doped nano-sized TiO2 prepared at 600 ℃ for 2 h. The average crystal sizes of un-doped TiO2,0.1% Cs+-doped TiO2 and 0.3% Sr2+-doped TiO2 are 21.3,13.1 and 10.8 nm,respectively. Moreover,the doping TiO2 can extend the light response to the visible region at 400-600 nm. By measuring their photocatalytic degradation rate of methyl orange solution,the results indicate that Cs+/Sr2+ -doped TiO2 samples are found to improve photocatalytic degradation activity of TiO2 markedly,and the optimal doping concentration is determined to be 0.1% and 0.3% for Cs+ and Sr2+,respectively. Photocatalytic degradation rate of Cs+/Sr2+-doped nano-sized TiO2 can be 15%-25% higher than that of un-doped TiO2 under the same condition.展开更多
The doping reaction of polyaniline with camphor sulfonic acid (CSAH) in different organic solvents was studied by UV Vis spectroscopy. The experimental results show that the polaron band of the species was shifted to ...The doping reaction of polyaniline with camphor sulfonic acid (CSAH) in different organic solvents was studied by UV Vis spectroscopy. The experimental results show that the polaron band of the species was shifted to shorter wavelength when polyaniline was doped with CSAH in N methyl 2 pyrrolidione (NMP) solvent, while the red shift of polaron band was observed when it was in N, N dimethylformamide (DMF). It indicates that the influence of different processing solvents on the doping property of polyaniline is greatly different. N methyl 2 pyrrolidione is a good solvent for polyaniline, polyaniline chain is unfolded in it. The interaction of NMP with CSAH is so strong that the resulting product is apt to dedoping, while the solubility of polyaniline in DMF is relatively low and polyaniline chain is in partly folded state. Thus the doping reaction is kinetically disadvantageous but thermodynamically advantageous.展开更多
A process of preparing ZnO voltage sensitive ceramics doped with some oxides by coprecipitation was described in the paper. The thermal properties of ZnO nanometer powders and the current voltage characteristics of ...A process of preparing ZnO voltage sensitive ceramics doped with some oxides by coprecipitation was described in the paper. The thermal properties of ZnO nanometer powders and the current voltage characteristics of the ceramics have been investigated. The results showed that the six additive ZnO powders with hexagonal system were homogeneous grain size distribution in microstructure, the optimal reaction pH is 6.90±0.05, the temperature for calcining and sintering was at about 500 ℃ and 1100 ℃, respectively. The powders were also examined by SEM, IR and XRD etc, and the effect of doping La 2O 3 on the electrical properties of ZnO varistor was investigated too.展开更多
The meso-macroporous Fe-doped Cu O was prepared by a simple hydrothermal method combined with post-annealing. The samples were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM), Brunaue...The meso-macroporous Fe-doped Cu O was prepared by a simple hydrothermal method combined with post-annealing. The samples were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM), Brunauer-Emmett-Teller N2 adsorption-desorption analyses and UV-vis diffuses reflectance spectroscopy. The Fe-doped Cu O sample shows higher adsorption capacity and photocatalytic activity for xanthate degradation than pure Cu O under visible light irradiation. In addition, the adsorption process is found to fit Langmuir isotherms and pseudo-second-order kinetics. The the first order kinetic Langmuir Hinshelwood model was used to study the reaction kinetics of photocatalytic degradation, and the apparent rate constant( k) was calculated. The value of k for Fe-doped Cu O is 1.5 times that of pure Cu O. The higher photocatalytic activity of Fe-doped Cu O is attributed to higher specific surface area together with stronger visible light absorption.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 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.
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Supported by National Key R&D Program of China(2023YFA1608701)National Natural Science Foundation of China(62274168,11933006,U2141240)Hangzhou Leading Innovation and Entrepreneurship Team(TD2020002)。
文摘The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method greatly simplifies the fabrication process of the device,but it is easy to cause lattice damage,introduce crystalline defects,and lead to the increase of the dark current of detectors.Herein,the boron-doped germanium ion implantation process was studied,and the involved lattice damage mechanism was discussed.Experimental conditions involved using 80 keV energy for boron ion implantation,with doses ranging from 1×10^(13)cm^(-2)to 3×10^(15)cm^(-2).After implantation,thermal annealing at 450℃was implemented to optimize dopant activation and mitigate the effects of ion implantation.Various sophisticated characterization techniques,including X-ray dif⁃fraction(XRD),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),and secondary ion mass spec⁃trometry(SIMS)were used to clarify lattice damage.At lower doses,no notable structural alterations were ob⁃served.However,as the dosage increased,specific micro distortions became apparent,which could be attributed to point defects and residual strain.The created lattice damage was recovered by thermal treatment,however,an irreversible strain induced by implantation still existed at heavily dosed samples.
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.
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.
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.
基金Project(2018YFB0104300)supported by the National Key R&D Program of ChinaProject(51774150)supported by the National Natural Science Foundation of China
文摘Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most effective strategy to address the above issues.However,the preparation process of carbon-based sulfur hosts is usually complex and costly.Therefore,it is necessary to develop an efficient and cost-effective method to fabricate carbon hosts for high-performance sulfur cathodes.Herein,we reported the fabrication of a bio-derived nitrogen doped porous carbon materials(BNPC)via a molten-salt method for high performance sulfur cathodes.The long-range-ordered honeycomb structure of BNPC is favorable for the trapping of polysulfide(PS)species and accommodates the volumetric variation of sulfur during cycling,while the high graphitization degree of BNPC favors the redox kinetics of sulfur cathodes.Moreover,the nitrogen doping content not only enhances the electrical conductivity of BNPC,but also provides ample anchoring sites for the immobilization of PS,which plays a key role in suppressing the shuttle effect.As a result,the S@BNPC cathode exhibits a high initial specific capacity of 1189.4 mA·h/g at 0.2C.After 300 cycles,S@BNPC still maintains a capacity of 703.2 mA·h/g which corresponds to a fading rate of 0.13%per cycle after the second cycle.This work offers vast opportunities for the large-scale application of high performance carbon-based sulfur hosts.
文摘Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO2. Different transformation modes were observed depending on the composition and cooling rate. ZrO2 containing 6% CeO2 showed isothermal transformation behavior, whereas ZrO2 containing 9% and 10% CeO2 showed athermal transformation behavior. However, ZrO2 containing 8% CeO2 showed either isothermal or athermal transformations behavior depending on the cooling rate. A TTT (Time-Temperature-Transformation) diagram was proposed for ZrO2 containing 8% CeO2.
基金Project(09C1014) supported by the Research Foundation of Education Bureau of Hunan Province,ChinaProject(2006180) supported by the Key Discipline (Environmental Sciences) Construction Program of Hunan Province,China
文摘The un-doped TiO2 and Cs+/Sr2+-doped TiO2 nanometer particles were prepared by sol-gel method using tetrabutyl titanate (Ti(OC4H9)4) as TiO2 precursor,and characterized with X-ray diffraction (XRD) and UV-Vis absorption spectra (UV-Vis). The photocatalytic activities of these samples were investigated by the photocatalytic degradation of methyl orange in aqueous suspension under 300 W medium pressure mercury lamp irradiation. The results show that the growth of crystallite size can be controlled effectively for the Cs+/Sr2+-doped TiO2,and crystal phase transformation of nano-sized TiO2 is retarded from anatase structure to rutile structure while using the proper doping concentration of Cs+/Sr2+. It is pure anatase of high photocatalytic activity for Cs+/Sr2+-doped nano-sized TiO2 prepared at 600 ℃ for 2 h. The average crystal sizes of un-doped TiO2,0.1% Cs+-doped TiO2 and 0.3% Sr2+-doped TiO2 are 21.3,13.1 and 10.8 nm,respectively. Moreover,the doping TiO2 can extend the light response to the visible region at 400-600 nm. By measuring their photocatalytic degradation rate of methyl orange solution,the results indicate that Cs+/Sr2+ -doped TiO2 samples are found to improve photocatalytic degradation activity of TiO2 markedly,and the optimal doping concentration is determined to be 0.1% and 0.3% for Cs+ and Sr2+,respectively. Photocatalytic degradation rate of Cs+/Sr2+-doped nano-sized TiO2 can be 15%-25% higher than that of un-doped TiO2 under the same condition.
文摘The doping reaction of polyaniline with camphor sulfonic acid (CSAH) in different organic solvents was studied by UV Vis spectroscopy. The experimental results show that the polaron band of the species was shifted to shorter wavelength when polyaniline was doped with CSAH in N methyl 2 pyrrolidione (NMP) solvent, while the red shift of polaron band was observed when it was in N, N dimethylformamide (DMF). It indicates that the influence of different processing solvents on the doping property of polyaniline is greatly different. N methyl 2 pyrrolidione is a good solvent for polyaniline, polyaniline chain is unfolded in it. The interaction of NMP with CSAH is so strong that the resulting product is apt to dedoping, while the solubility of polyaniline in DMF is relatively low and polyaniline chain is in partly folded state. Thus the doping reaction is kinetically disadvantageous but thermodynamically advantageous.
文摘A process of preparing ZnO voltage sensitive ceramics doped with some oxides by coprecipitation was described in the paper. The thermal properties of ZnO nanometer powders and the current voltage characteristics of the ceramics have been investigated. The results showed that the six additive ZnO powders with hexagonal system were homogeneous grain size distribution in microstructure, the optimal reaction pH is 6.90±0.05, the temperature for calcining and sintering was at about 500 ℃ and 1100 ℃, respectively. The powders were also examined by SEM, IR and XRD etc, and the effect of doping La 2O 3 on the electrical properties of ZnO varistor was investigated too.
基金Project(51102285)supported by the National Natural Science Foundation of China
文摘The meso-macroporous Fe-doped Cu O was prepared by a simple hydrothermal method combined with post-annealing. The samples were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM), Brunauer-Emmett-Teller N2 adsorption-desorption analyses and UV-vis diffuses reflectance spectroscopy. The Fe-doped Cu O sample shows higher adsorption capacity and photocatalytic activity for xanthate degradation than pure Cu O under visible light irradiation. In addition, the adsorption process is found to fit Langmuir isotherms and pseudo-second-order kinetics. The the first order kinetic Langmuir Hinshelwood model was used to study the reaction kinetics of photocatalytic degradation, and the apparent rate constant( k) was calculated. The value of k for Fe-doped Cu O is 1.5 times that of pure Cu O. The higher photocatalytic activity of Fe-doped Cu O is attributed to higher specific surface area together with stronger visible light absorption.
