Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promisin...Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.展开更多
Owing to their unique optical properties and nontoxicity,lead-free halide double perovskite nanocrystals are of interest for widespread applications.Herein,the colloid synthesis and photoluminescenc e property of Ag^(...Owing to their unique optical properties and nontoxicity,lead-free halide double perovskite nanocrystals are of interest for widespread applications.Herein,the colloid synthesis and photoluminescenc e property of Ag^(+)-Eu^(3+)codoped Cs_(2)NaInCl_(6)nanocrystals were investigated.The pe rovskite nanocrystals exhibit a broad warm-white photo luminescence with correlated color temperature(CCT)of 3447 K and color rendering index(CRI)of 90.2,and the means of codoping would improve its optical performance.A fast energy transfer and a long-lived self-trapped excitons state are unveiled by the femtosecond transient absorption spectra.The fast energy transfer from the self-trapped excitons of host nanocrystals to the Eu^(3+)ions is helpful to achieve a broad photoluminescence,and the quantum yield of Cs_(2)NaInCl_(6):0.05Ag^(+)-Eu^(3+)anocrystals can be enha nced to 69.5%.There is a large exciton binding energy and strong electron-phonon interaction in the codoped perovskite nanocrystals.The efficient and excellent air-stable double perovskite nanocrystals would be considered as a single-component phosphor for warm-white lighting.展开更多
In this study, we have performed first-principles screened exchanged hybrid density function theory with the HSE06 function calculations of the C-Mo, C-W, N-Nb and N-Ta codoped anatase TiO2 systems to investigate the ...In this study, we have performed first-principles screened exchanged hybrid density function theory with the HSE06 function calculations of the C-Mo, C-W, N-Nb and N-Ta codoped anatase TiO2 systems to investigate the effect of codoping on the electronic structure of TiO2. The calculated results demonstrate that （W（s）＋C（s）） codoped TiO2 narrows the band gap significantly, and have little influence on the position of conduction band edges, therefore, enhances the efficiency of the photocatalytic hydrogen generation from water and the photodegradation of organic pollutants. Moreover, the proper oxygen pressure and temperature are two key factors during synthesis which should be carefully under control so that the desired （W（s）＋C（s）） codoped TiO2 can be obtained.展开更多
Diamond crystals were synthesized with different doping proportions of N-H-O at 5.5 GPa-7.1 GPa and 1370℃-1450℃. With the increase in the N-H-O doping ratio, the crystal growth rate decreased, the temperature and pr...Diamond crystals were synthesized with different doping proportions of N-H-O at 5.5 GPa-7.1 GPa and 1370℃-1450℃. With the increase in the N-H-O doping ratio, the crystal growth rate decreased, the temperature and pressure conditions required for diamond nucleation became increasingly stringent, and the diamond crystallization process was affected. [111] became the dominant plane of diamonds;surface morphology became block-like;and growth texture,stacking faults, and etch pits increased. The diamond crystals had a two-dimensional growth habit. Increasing the doping concentration also increased the amount of N that entered the diamond crystals as confirmed via Fourier transform infrared spectroscopy. However, crystal quality gradually deteriorated as verified by the red-shifting of Raman peak positions and the widening of the Raman full width at half maximum. With the increase in the doping ratio, the photoluminescence property of the diamond crystals also drastically changed. The intensity of the N vacancy center of the diamond crystals changed, and several Ni-related defect centers, such as the NE1 and NE3 centers, appeared. Diamond synthesis in N-H-O-bearing fluid provides important information for deepening our understanding of the growth characteristics of diamonds in complex systems and the formation mechanism of natural diamonds, which are almost always N-rich and full of various defect centers. Meanwhile, this study proved that the type of defect centers in diamond crystals could be regulated by controlling the N-H-O impurity contents of the synthesis system.展开更多
N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The syn...N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The synthesized photocatalysts were investigated by X- ray diffraction （XRD）,X-ray photoelectron spectroscopy （XPS）,ultraviolet-visible diffuse reflectance spectroscopy （UV-Vis DRS） and photodegradation reaction tests of 4-chlorophenol under visible light irradiation to understand the relationship between the structure of NFTO catalyst and corresponding photocatalytic activity.The crystal phase and particle size of catalysts were found to be largely affected by the calcination temperature.In addition,N-F-codoping could inhibit phase transition of TiO2 from anatase to rutile.The presence of N and F atoms in the lattice of TiO2 is responsible for the visible light catalytic activity.In UV-Vis DRS tests,the spectrum of NFTO exhibited red shift compared with Degussa P25 and the band gap was reduced to around 2.92 eV.Under optimal calcination temperature and dopant concentration conditions,the NFTO photocatalyst exhibited the highest activity in the photodegradation reaction tests of 4-chlorophenol under visible light irradiation with a degradation rate of 75.84%.Besides,the 5-recycle test showed that NFTO photocatalyst could be reused and its activity kept stable under visible light irradiation.展开更多
Carbon-based materials have become a research hotspot in the field of energy storage devices in recent years due to their abundant resources,low cost,and environmental friendliness.However,the low capacity and poor hi...Carbon-based materials have become a research hotspot in the field of energy storage devices in recent years due to their abundant resources,low cost,and environmental friendliness.However,the low capacity and poor high rate performance still constitute great challenges.Metal organic framework-derived carbon has been widely researched because of its high porosity,tunable structure,and good conductivity.In this work,N/S codoped hierarchical porous carbon microspheres were prepared by a high-temperature heat treatment and atomic doping process using a zinc-based organic framework as the precursor.When used as a potassium-ion battery anode,it has a high reversible specific capacity(435.7 mAh g^(-1)),good rate performance(133.5 mAh g^(-1)at 10,000 m A g^(-1)),and long-term cycling stability(73.2%capacity retention after the 2500th cycle).The potassium storage mechanism of the derived carbon was explained by various electrochemical analysis methods and microstructure characterization techniques,and the relationship between the structural characteristics and electrochemical properties was researched.In a supercapacitor,the porous carbon material exhibits a specific capacitance of 307.2 F g^(-1)at a current density of 0.2 A g^(-1)in a KOH aqueous solution and achieves a retention rate of 99.88%after 10,000 cycles.The assembled symmetric supercapacitor device delivers a high energy density of 6.69 Wh kg^(-1),with a corresponding power density of 2500 W kg^(-1).In addition,density functional theory calculations further confirmed that N/S codoping can improve the adsorption capacities of potassium and hydroxyl ions in the derived carbon.展开更多
In the iron-based high-To bulk superconductors, Tc above 50 K was only observed in the electron-doped 1111-type compounds. Here we revisit the electron-doped SmFeAsO polycrystals to make a further investigation for th...In the iron-based high-To bulk superconductors, Tc above 50 K was only observed in the electron-doped 1111-type compounds. Here we revisit the electron-doped SmFeAsO polycrystals to make a further investigation for the highest Tc in these materials. To introduce more electron carriers and less crystal lattice distortions, we study the Th and F eodoping effects into the Sm-O layers with heavy electron doping. Dozens of Sm1-xThx FeAsO1-yFy samples are synthesized through the solid state reaction method, and these samples are carefully characterized by the structural, resistive, and magnetic measurements. We find that the codoping of Th and F clearly enhances the superconducting Tc more than the Th or F single-doped samples, with the highest record Tc up to 58.6K when x = 0.2 and y=0.225. Further element doping causes more impurities and lattice distortions in the samples with a weakened superconductivity.展开更多
Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg...Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg_(3)Sb_(2)remains lower than 1,which is mainly attributed to its inferior electrical properties.Herein,we synergistically optimize the thermoelectric properties of p-type Mg_(3)Sb_(2)materials via codoping of Cd and Ag,which were synthesized by high-energy ball milling combined with hot pressing.It is found that Cd doping not only increases the carrier mobility of p-type Mg_(3)Sb_(2),but also diminishes its thermal conductivity(κ_(tot)),with Mg_(2.85)Cd_(0.5)Sb_(2)achieving a lowκtot value of∼0.67 W m^(−1)K^(−1)at room temperature.Further Ag doping elevates the carrier concentration,so that the power factor is optimized over the entire temperature range.Eventually,a peak zT of∼0.75 at 773 K and an excellent average zT of∼0.41 over 300−773 K are obtained in Mg_(2.82)Ag_(0.03)Cd_(0.5)Sb_(2),which are∼240%and∼490%higher than those of pristine Mg_(3.4)Sb_(2),respectively.This study provides an effective pathway to synergistically improve the thermoelectric performance of p-type Mg_(3)Sb_(2)by codoping Cd and Ag,which is beneficial to the future applications of Mg_(3)Sb_(2)-based thermoelectric materials.展开更多
In this work, a simple method to modulate the crystal phase and morphology with a large amount of K＋ions codoping is proposed. The phase changes to the mixture of β-Na YF4 and β-KYF4 with increasing the content of...In this work, a simple method to modulate the crystal phase and morphology with a large amount of K＋ions codoping is proposed. The phase changes to the mixture of β-Na YF4 and β-KYF4 with increasing the content of K^＋ions to 80 mol%.When it exceeds 80 mol%, β-Na YF4 disappears gradually and β-KYF4 dominates with a poor crystalline. In addition, the morphology changes from nanosphere to nanoplate, and then to nanoprism, which indicates that a higher content of K^＋ions favors the growth rates along [0001] than the [10-10] of the nanocrystals. Additionally, the upconversion（UC） luminescence properties and the ratio of red/green（R/G） UC intensity of samples with different phases and morphologies are detected,which makes it possible to tune the UC fluorescence by varying the concentration of K^＋ions.展开更多
In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4＋ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a h...In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4＋ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a hydrothermal method increased to the maximum, about seven times of the non-Zr^4＋ sample when the Zr^4＋ codoping concentration rose to 6 mol%, while the luminescence lifetime was also prolonged by Zr^4＋ codoping. To explore the relationships between the microstructure and upconversion properties, X-ray powder diffraction, field emission scanning electron microscope, electron energy-dispersive spectroscopy and upconversion emission spectroscopy were employed. From these characterizations, we found that the codoping of Zr^4＋ could modulate the crystal microstructure of NaYF_4 for higher upconversion luminescence intensity and longer lifetime. This study may be helpful for the design and synthesis of high-performance upconversion materials.展开更多
The structural,electronic properties and formation energies of sulfur and alkaline earth codoped delafossite CuAlO_2 have been investigated using the first-principles density functional theory calculations.Our results...The structural,electronic properties and formation energies of sulfur and alkaline earth codoped delafossite CuAlO_2 have been investigated using the first-principles density functional theory calculations.Our results reveal that the volume of codoping systems increases with the increasing atomic radius of metal atoms.The formation energies under different growth conditions have been calculated,showing that the codoping systems are formed easily under O-rich growth conditions.Electronic band structures and density of states have been obtained.The decreased bandgaps,enhanced covalence and appearance of electron acceptors after codoping are all good for p-type conductivity.展开更多
The solid acid catalyst, N-F codoped Ti O2/Si O2 composite oxide was prepared by a sol-gel method using NH4 F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction（XRD）, sca...The solid acid catalyst, N-F codoped Ti O2/Si O2 composite oxide was prepared by a sol-gel method using NH4 F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, X-ray photoelectron spectroscopy（XPS）, UV-Visible diffuse reflectance spectroscopy（UV-Vis）,ammonia adsorption and temperature-programmed desorption（NH3-TPD）, in situ Fourier transform infrared spectroscopy（FT-IR） and N2 physical adsorption isotherm. The photocatalytic activity of the catalyst for acrylonitrile degradation was investigated under simulant solar irradiation. The results showed that strong Lewis and Brnsted acid sites appear on the surface of the sample after N-F doping. Systematic investigation showed that the highest photocatalytic activity for acrylonitrile degradation was obtained for samples calcined at 450°C with molar ratio（NH4F to Ti） of 0.8. The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min irradiation, demonstrating the effectiveness of photocatalytic degradation of acrylonitrile with N-F codoped Ti O2/Si O2 composite oxide. The photocatalyst is promising for application under solar light irradiation.Moreover, the intermediates generated after irradiation were verified by gas chromatography-mass spectrometry（GC-MS） analysis and UV-Vis spectroscopy to be simple organic acids with lower toxicity, and the degradation pathway was also proposed for acrylonitrile degradation with the prepared catalyst.展开更多
Co-V-Ga-based shape memory alloys have shown great potential in the field of solid-state elastocaloric refrigeration due to their low stress hysteresis(Δσ_(hys)) and excellent superelasticity.However,large applied s...Co-V-Ga-based shape memory alloys have shown great potential in the field of solid-state elastocaloric refrigeration due to their low stress hysteresis(Δσ_(hys)) and excellent superelasticity.However,large applied stress and low adiabatic temperature change(ΔT_(ad)) greatly limit the application of Co-V-Ga-based alloys as elastocaloric materials.Here,we have successfully achieved a breakthrough in material properties by innovatively introducing the co-doping strategy of Mn and Ti elements.It was found that the synergistic effect of Mn and Ti significantly enhanced the mechanical properties of the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy through solid solution strengthening,fine grain strengthening,and precipitation strengthening mechanisms.A large ΔT_(ad) of-11 K was obtained for the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) bulk poly crystalline alloy under a very low applied stress of 380 MPa.This is mainly due to the strong texture of <001>A.Texture strengthening is the key factor to improve the elastocaloric effect of alloys.At the same time,the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy still maintains a ΔT_(ad) of -4 K without an obvious attenuation trend after 350 elastocaloric cycles under the applied stress of 300 MPa.In addition,due to the low energy dissipation(ΔW),the energy conversion efficiency of the elastocaloric response is greatly improved,so that the coefficient of performance(COP) of the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy material is as high as 28.9,far exceeding most of the current shape memory alloy elastocaloric materials.As a result,the co-doping of Mn and Ti elements makes it possible to prepare an elastocaloric refrigeration alloy with low applied stress and a large elastocaloric effect.展开更多
Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure C...Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure CeO2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD,SEM,EDS,BET,Raman,H2-TPR,XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity.The doped samples maintain the cubic fluorite structure of CeO2 with high crystallinity and small crystallite size,forming Ce-based solid solutions.The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm.The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids.The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies,pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst,thereby enhancing the catalytic activity for CO oxidation.Besides,the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.展开更多
A series of La/Ce-codoped Bi2O3 composite photocatalysts were fabricated via hydrothermal–calcination process. The as-prepared products were intensively characterized by some physicochemical characterizations like N2...A series of La/Ce-codoped Bi2O3 composite photocatalysts were fabricated via hydrothermal–calcination process. The as-prepared products were intensively characterized by some physicochemical characterizations like N2 physical adsorption, X-ray powder diffraction（XRD）, scanning electron microscope（SEM）, transmission electron microscope（TEM）, UV–Vis diffuse reflectance（UV–Vis DRS）, Fourier transform infrared spectroscopy（FT-IR）,photoelectrochemical measurements, and photoluminescence（PL） spectroscopy. The characterization results indicated that La and Ce doping induced obvious crystal phase transformation in Bi2O3, from monoclinic to tetragonal phase. La and Ce codoping also gave rise to the obvious synergetic effects, e.g., the lattice contraction of Bi2O3, the decrease of crystal size and the increase of surface area. The photocatalytic performance of the prepared catalysts was evaluated by removal of dye acid orange II with high concentration under visible light irradiation. Results showed that La/Ce-codoped Bi2O3 displayed much higher photocatalytic performance than that of bare Bi2O3, single La or Ce doped Bi2O3 samples. The superior photocatalytic activity was mainly attributed to the improved texture and surface properties and the synergistic effects of La and Ce codoping on suppressing the recombination of photo-generated electrons（e^-） and holes（h~＋）.展开更多
First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. T...First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.展开更多
基金Key Research and Development Program of Zhejiang,Grant/Award Number:2021C03022National Natural Science Foundation of China,Grant/Award Numbers:22002104,22272115,22202145,22202146,22102112,22202147。
文摘Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.
基金Project supported by the National Natural Science Foundation of China(61805134,11974229,22303044)Fundamental Research Program of Shanxi Province(202203021221121)+3 种基金China Postdoctoral Science Foundation(2022M711898)Natural Science Fo undation of Shandong Province(ZR2023QB135)Postdoctoral Innovation Project of Shandong Province(SDCX-ZG-202201004)Graduate Innovation Project in Shanxi Province(2024KY450)。
文摘Owing to their unique optical properties and nontoxicity,lead-free halide double perovskite nanocrystals are of interest for widespread applications.Herein,the colloid synthesis and photoluminescenc e property of Ag^(+)-Eu^(3+)codoped Cs_(2)NaInCl_(6)nanocrystals were investigated.The pe rovskite nanocrystals exhibit a broad warm-white photo luminescence with correlated color temperature(CCT)of 3447 K and color rendering index(CRI)of 90.2,and the means of codoping would improve its optical performance.A fast energy transfer and a long-lived self-trapped excitons state are unveiled by the femtosecond transient absorption spectra.The fast energy transfer from the self-trapped excitons of host nanocrystals to the Eu^(3+)ions is helpful to achieve a broad photoluminescence,and the quantum yield of Cs_(2)NaInCl_(6):0.05Ag^(+)-Eu^(3+)anocrystals can be enha nced to 69.5%.There is a large exciton binding energy and strong electron-phonon interaction in the codoped perovskite nanocrystals.The efficient and excellent air-stable double perovskite nanocrystals would be considered as a single-component phosphor for warm-white lighting.
基金supported by the NKBRSF (2007CB815202)NKBRSF (No. 2009CB220010)+2 种基金NSFC (20833008)NSFC (No. 20973168)the Solar Energy Initiative of the Knowledge Innovation Program of the Chinese Academy of Science (No. KGCX2-YW-394-2)
文摘In this study, we have performed first-principles screened exchanged hybrid density function theory with the HSE06 function calculations of the C-Mo, C-W, N-Nb and N-Ta codoped anatase TiO2 systems to investigate the effect of codoping on the electronic structure of TiO2. The calculated results demonstrate that （W（s）＋C（s）） codoped TiO2 narrows the band gap significantly, and have little influence on the position of conduction band edges, therefore, enhances the efficiency of the photocatalytic hydrogen generation from water and the photodegradation of organic pollutants. Moreover, the proper oxygen pressure and temperature are two key factors during synthesis which should be carefully under control so that the desired （W（s）＋C（s）） codoped TiO2 can be obtained.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 51772120, 11604246, 51872112, and 11804305)the Project of Jilin Science and Technology Development Plan (Grant No. 20180201079GX)+1 种基金the Fundamental Research Funds for the Central Universities, the Natural Science Foundation of Chongqing, China (Grant No. cstc2019jcyj-msxm X0391)the Science and Technology Research Program of Chongqing Municipal Education Commission (Grant No. KJQN201901405)。
文摘Diamond crystals were synthesized with different doping proportions of N-H-O at 5.5 GPa-7.1 GPa and 1370℃-1450℃. With the increase in the N-H-O doping ratio, the crystal growth rate decreased, the temperature and pressure conditions required for diamond nucleation became increasingly stringent, and the diamond crystallization process was affected. [111] became the dominant plane of diamonds;surface morphology became block-like;and growth texture,stacking faults, and etch pits increased. The diamond crystals had a two-dimensional growth habit. Increasing the doping concentration also increased the amount of N that entered the diamond crystals as confirmed via Fourier transform infrared spectroscopy. However, crystal quality gradually deteriorated as verified by the red-shifting of Raman peak positions and the widening of the Raman full width at half maximum. With the increase in the doping ratio, the photoluminescence property of the diamond crystals also drastically changed. The intensity of the N vacancy center of the diamond crystals changed, and several Ni-related defect centers, such as the NE1 and NE3 centers, appeared. Diamond synthesis in N-H-O-bearing fluid provides important information for deepening our understanding of the growth characteristics of diamonds in complex systems and the formation mechanism of natural diamonds, which are almost always N-rich and full of various defect centers. Meanwhile, this study proved that the type of defect centers in diamond crystals could be regulated by controlling the N-H-O impurity contents of the synthesis system.
基金supported by the Scienceand Technology Project of Education Commission of Chongqing of China(No.KJ110709)the Key Science Project of Ministry of Education of China(No.2008119)+1 种基金the Colleges and Universities Innovation Team Project of Chongqing of China(No.KJTD201020)the Scienceand Technology Project of Engineering Research Centre for Waste Oil,Ministry of Education of China(No.FYKJ2009012)
文摘N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The synthesized photocatalysts were investigated by X- ray diffraction （XRD）,X-ray photoelectron spectroscopy （XPS）,ultraviolet-visible diffuse reflectance spectroscopy （UV-Vis DRS） and photodegradation reaction tests of 4-chlorophenol under visible light irradiation to understand the relationship between the structure of NFTO catalyst and corresponding photocatalytic activity.The crystal phase and particle size of catalysts were found to be largely affected by the calcination temperature.In addition,N-F-codoping could inhibit phase transition of TiO2 from anatase to rutile.The presence of N and F atoms in the lattice of TiO2 is responsible for the visible light catalytic activity.In UV-Vis DRS tests,the spectrum of NFTO exhibited red shift compared with Degussa P25 and the band gap was reduced to around 2.92 eV.Under optimal calcination temperature and dopant concentration conditions,the NFTO photocatalyst exhibited the highest activity in the photodegradation reaction tests of 4-chlorophenol under visible light irradiation with a degradation rate of 75.84%.Besides,the 5-recycle test showed that NFTO photocatalyst could be reused and its activity kept stable under visible light irradiation.
基金supported by the National Natural Science Foundation of China (51764029, 52004116)the National Key Research and Development Program of China (2019YFC1803501)+1 种基金the Applied Basic Research Plan of Yunnan Province(202001AU070039, 2018FB087)the Science Research Foundation of Yunnan Provincial Department of Education (2020J0070)
文摘Carbon-based materials have become a research hotspot in the field of energy storage devices in recent years due to their abundant resources,low cost,and environmental friendliness.However,the low capacity and poor high rate performance still constitute great challenges.Metal organic framework-derived carbon has been widely researched because of its high porosity,tunable structure,and good conductivity.In this work,N/S codoped hierarchical porous carbon microspheres were prepared by a high-temperature heat treatment and atomic doping process using a zinc-based organic framework as the precursor.When used as a potassium-ion battery anode,it has a high reversible specific capacity(435.7 mAh g^(-1)),good rate performance(133.5 mAh g^(-1)at 10,000 m A g^(-1)),and long-term cycling stability(73.2%capacity retention after the 2500th cycle).The potassium storage mechanism of the derived carbon was explained by various electrochemical analysis methods and microstructure characterization techniques,and the relationship between the structural characteristics and electrochemical properties was researched.In a supercapacitor,the porous carbon material exhibits a specific capacitance of 307.2 F g^(-1)at a current density of 0.2 A g^(-1)in a KOH aqueous solution and achieves a retention rate of 99.88%after 10,000 cycles.The assembled symmetric supercapacitor device delivers a high energy density of 6.69 Wh kg^(-1),with a corresponding power density of 2500 W kg^(-1).In addition,density functional theory calculations further confirmed that N/S codoping can improve the adsorption capacities of potassium and hydroxyl ions in the derived carbon.
基金Supported by the National Natural Science Foundation of China under Grant No 11474339the National Basic Research Program of China under Grant No 2016YFA0300301the Youth Innovation Promotion Association of the Chinese Academy of Sciences
文摘In the iron-based high-To bulk superconductors, Tc above 50 K was only observed in the electron-doped 1111-type compounds. Here we revisit the electron-doped SmFeAsO polycrystals to make a further investigation for the highest Tc in these materials. To introduce more electron carriers and less crystal lattice distortions, we study the Th and F eodoping effects into the Sm-O layers with heavy electron doping. Dozens of Sm1-xThx FeAsO1-yFy samples are synthesized through the solid state reaction method, and these samples are carefully characterized by the structural, resistive, and magnetic measurements. We find that the codoping of Th and F clearly enhances the superconducting Tc more than the Th or F single-doped samples, with the highest record Tc up to 58.6K when x = 0.2 and y=0.225. Further element doping causes more impurities and lattice distortions in the samples with a weakened superconductivity.
基金financially supported by the National Natural Science Foundation of China (Grant No. 52071041, 11874356, 51802034)supported by the Key Research Program of Frontier Sciences, CAS (Grant No.QYZDB-SSW-SLH016)
文摘Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg_(3)Sb_(2)remains lower than 1,which is mainly attributed to its inferior electrical properties.Herein,we synergistically optimize the thermoelectric properties of p-type Mg_(3)Sb_(2)materials via codoping of Cd and Ag,which were synthesized by high-energy ball milling combined with hot pressing.It is found that Cd doping not only increases the carrier mobility of p-type Mg_(3)Sb_(2),but also diminishes its thermal conductivity(κ_(tot)),with Mg_(2.85)Cd_(0.5)Sb_(2)achieving a lowκtot value of∼0.67 W m^(−1)K^(−1)at room temperature.Further Ag doping elevates the carrier concentration,so that the power factor is optimized over the entire temperature range.Eventually,a peak zT of∼0.75 at 773 K and an excellent average zT of∼0.41 over 300−773 K are obtained in Mg_(2.82)Ag_(0.03)Cd_(0.5)Sb_(2),which are∼240%and∼490%higher than those of pristine Mg_(3.4)Sb_(2),respectively.This study provides an effective pathway to synergistically improve the thermoelectric performance of p-type Mg_(3)Sb_(2)by codoping Cd and Ag,which is beneficial to the future applications of Mg_(3)Sb_(2)-based thermoelectric materials.
基金supported by the National High Technology Research and Development Program of China(Grant No.2013AA032205)the National Natural Science Foundation of China(Grant No.51272022)the Fundamental Research Funds for the Central Universities,China(Grant No.2012JBZ001)
文摘In this work, a simple method to modulate the crystal phase and morphology with a large amount of K＋ions codoping is proposed. The phase changes to the mixture of β-Na YF4 and β-KYF4 with increasing the content of K^＋ions to 80 mol%.When it exceeds 80 mol%, β-Na YF4 disappears gradually and β-KYF4 dominates with a poor crystalline. In addition, the morphology changes from nanosphere to nanoplate, and then to nanoprism, which indicates that a higher content of K^＋ions favors the growth rates along [0001] than the [10-10] of the nanocrystals. Additionally, the upconversion（UC） luminescence properties and the ratio of red/green（R/G） UC intensity of samples with different phases and morphologies are detected,which makes it possible to tune the UC fluorescence by varying the concentration of K^＋ions.
基金supported by the National Natural Science Foundation of China(No.51102047,51472050)State Key Laboratory of Photocatalysis on Energy and Environment Open Project
文摘In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4＋ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a hydrothermal method increased to the maximum, about seven times of the non-Zr^4＋ sample when the Zr^4＋ codoping concentration rose to 6 mol%, while the luminescence lifetime was also prolonged by Zr^4＋ codoping. To explore the relationships between the microstructure and upconversion properties, X-ray powder diffraction, field emission scanning electron microscope, electron energy-dispersive spectroscopy and upconversion emission spectroscopy were employed. From these characterizations, we found that the codoping of Zr^4＋ could modulate the crystal microstructure of NaYF_4 for higher upconversion luminescence intensity and longer lifetime. This study may be helpful for the design and synthesis of high-performance upconversion materials.
基金Supported by the National Natural Science Foundation of China under Grant Nos.11347199,51402244,and 11547311the Specialized Research Fund for Doctoral Program of Higher Education of China under Grant No.20130184120028+2 种基金the Fundamental Research Fund for the Central UniversitiesChina under Grant Nos.2682014CX084,2682014ZT30,and 2682014ZT31the fund of the State Key Laboratory of Solidification Processing in NWPU under Grant No.SKLSP201511
文摘The structural,electronic properties and formation energies of sulfur and alkaline earth codoped delafossite CuAlO_2 have been investigated using the first-principles density functional theory calculations.Our results reveal that the volume of codoping systems increases with the increasing atomic radius of metal atoms.The formation energies under different growth conditions have been calculated,showing that the codoping systems are formed easily under O-rich growth conditions.Electronic band structures and density of states have been obtained.The decreased bandgaps,enhanced covalence and appearance of electron acceptors after codoping are all good for p-type conductivity.
基金This work was supported by the National Natural Science Foundation of China （ No.：60671010, 20775045 ） and Natural Science Foundation of Shandong Province （Y2006B29）. The authors wish to thank Prof. D.R. Chen and Mr. H.F. Shao for the help in measurements of XRD and XPS, respectively.
基金financially supported by the Science and Technology Innovation Commission of Shenzhen Municipality, China (No. JCYJ20120613154128107)
文摘The solid acid catalyst, N-F codoped Ti O2/Si O2 composite oxide was prepared by a sol-gel method using NH4 F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, X-ray photoelectron spectroscopy（XPS）, UV-Visible diffuse reflectance spectroscopy（UV-Vis）,ammonia adsorption and temperature-programmed desorption（NH3-TPD）, in situ Fourier transform infrared spectroscopy（FT-IR） and N2 physical adsorption isotherm. The photocatalytic activity of the catalyst for acrylonitrile degradation was investigated under simulant solar irradiation. The results showed that strong Lewis and Brnsted acid sites appear on the surface of the sample after N-F doping. Systematic investigation showed that the highest photocatalytic activity for acrylonitrile degradation was obtained for samples calcined at 450°C with molar ratio（NH4F to Ti） of 0.8. The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min irradiation, demonstrating the effectiveness of photocatalytic degradation of acrylonitrile with N-F codoped Ti O2/Si O2 composite oxide. The photocatalyst is promising for application under solar light irradiation.Moreover, the intermediates generated after irradiation were verified by gas chromatography-mass spectrometry（GC-MS） analysis and UV-Vis spectroscopy to be simple organic acids with lower toxicity, and the degradation pathway was also proposed for acrylonitrile degradation with the prepared catalyst.
基金financially supported by the National Natural Science Foundation of China(Nos.52271172 and 51971085)Heilongjiang Provincial Natural Science Foundation of China(No.LH2024E075)
文摘Co-V-Ga-based shape memory alloys have shown great potential in the field of solid-state elastocaloric refrigeration due to their low stress hysteresis(Δσ_(hys)) and excellent superelasticity.However,large applied stress and low adiabatic temperature change(ΔT_(ad)) greatly limit the application of Co-V-Ga-based alloys as elastocaloric materials.Here,we have successfully achieved a breakthrough in material properties by innovatively introducing the co-doping strategy of Mn and Ti elements.It was found that the synergistic effect of Mn and Ti significantly enhanced the mechanical properties of the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy through solid solution strengthening,fine grain strengthening,and precipitation strengthening mechanisms.A large ΔT_(ad) of-11 K was obtained for the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) bulk poly crystalline alloy under a very low applied stress of 380 MPa.This is mainly due to the strong texture of <001>A.Texture strengthening is the key factor to improve the elastocaloric effect of alloys.At the same time,the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy still maintains a ΔT_(ad) of -4 K without an obvious attenuation trend after 350 elastocaloric cycles under the applied stress of 300 MPa.In addition,due to the low energy dissipation(ΔW),the energy conversion efficiency of the elastocaloric response is greatly improved,so that the coefficient of performance(COP) of the Co_(52)V_(31)Ga_(14)Mn_(1)Ti_(2) alloy material is as high as 28.9,far exceeding most of the current shape memory alloy elastocaloric materials.As a result,the co-doping of Mn and Ti elements makes it possible to prepare an elastocaloric refrigeration alloy with low applied stress and a large elastocaloric effect.
基金Project supported by the National Natural Science Foundation of China(21777055)Shandong Provincial Natural Science Foundation(ZR2017BB004)+1 种基金Shandong Province Key Research and Development Plan(2017GGX202004)Shandong Province Major Science and Technology Innovation Project(2017CXGC1004)
文摘Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure CeO2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD,SEM,EDS,BET,Raman,H2-TPR,XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity.The doped samples maintain the cubic fluorite structure of CeO2 with high crystallinity and small crystallite size,forming Ce-based solid solutions.The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm.The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids.The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies,pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst,thereby enhancing the catalytic activity for CO oxidation.Besides,the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.
基金supported by the National Natural Science Foundation of China (Nos. 21567008, 21607064, 21263005)the Natural Science Foundation of Jiangxi Province (No. 20161BAB203090)the Program of Qingjiang Excellent Young Talents, Jiangxi University of Science and Technology,the Landing Project of Science and Technology of Colleges and Universities in Jiangxi Province China (No. KJLD14046)
文摘A series of La/Ce-codoped Bi2O3 composite photocatalysts were fabricated via hydrothermal–calcination process. The as-prepared products were intensively characterized by some physicochemical characterizations like N2 physical adsorption, X-ray powder diffraction（XRD）, scanning electron microscope（SEM）, transmission electron microscope（TEM）, UV–Vis diffuse reflectance（UV–Vis DRS）, Fourier transform infrared spectroscopy（FT-IR）,photoelectrochemical measurements, and photoluminescence（PL） spectroscopy. The characterization results indicated that La and Ce doping induced obvious crystal phase transformation in Bi2O3, from monoclinic to tetragonal phase. La and Ce codoping also gave rise to the obvious synergetic effects, e.g., the lattice contraction of Bi2O3, the decrease of crystal size and the increase of surface area. The photocatalytic performance of the prepared catalysts was evaluated by removal of dye acid orange II with high concentration under visible light irradiation. Results showed that La/Ce-codoped Bi2O3 displayed much higher photocatalytic performance than that of bare Bi2O3, single La or Ce doped Bi2O3 samples. The superior photocatalytic activity was mainly attributed to the improved texture and surface properties and the synergistic effects of La and Ce codoping on suppressing the recombination of photo-generated electrons（e^-） and holes（h~＋）.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10647008, 50971099, and 21176199)the Research Fund for the Doctoral Program of Higher Education, China (Grant Nos. 20096101110017 and 20096101110013)+1 种基金the Key Project of the Natural Science Foundation of Shaanxi Province, China (Grant Nos. 2010JZ002 and 2011JM1001)the Graduate Innovation Fund of Northwest University, China (Grant No. 10YZZ38)
文摘First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, for- mation energies, and electronic and optical properties of Y-doped, N-doped, and （Y, N）-codoped Ti02. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.
