The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries（NIBs） due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective...The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries（NIBs） due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective because it needs to be sintered under oxygen atmosphere at high temperature and followed by a quenching procedure. Here we first report that the pure β phase can be stabilized by Cu-doping and easily synthesized by replacing a proportion of Mn with Cu via a simplified process including sintering in air and cooling to room temperature naturally. Based on the first-principle calculations, the band gap decreases from 0.7 eV to 0.3 eV, which indicates that the electronic conductivity can be improved by Cu-doping. The designed -NaCu（0.1）Mn（0.9）O2 is applied as cathode in NIBs, exhibiting an energy density of 419 Wh/kg and better performance in terms of rate capability and cycling stability than those in the undoped case.展开更多
ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO：Cu film can be enhanced by a moderate level ...ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO：Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO：Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.展开更多
Cu doped Mg(OH)_(2) nanoparticles were synthesized with varying concentrations from 0 to 10%by a chemical synthesis technique of coprecipitation.X-rays diffraction (XRD) of the samples confirms that all the samples ac...Cu doped Mg(OH)_(2) nanoparticles were synthesized with varying concentrations from 0 to 10%by a chemical synthesis technique of coprecipitation.X-rays diffraction (XRD) of the samples confirms that all the samples acquire the hexagonal crystal structure.XRD results indicated the solubility limit of dopant in the host material and the secondary phase of CuO was observed beyond 3%Cu doping in Mg(OH)_(2).The reduction in the size of nanoparticles was observed from 166 to 103 nm for Mg(OH)_(2) and 10% Cu doped Mg(OH)_(2)samples,respectively.The shift in absorption spectra exhibited the systematical enhancement in optical bandgap from 5.25 to 6.085 eV.A good correlation was observed between the bandgap energy and crystallite size of the nanocrystals which confirmed the size induced effect in the nanoparticles.The transformation in the sample morphology was observed from irregular spherical particles to sepals like shapes with increasing the Cu concentration in the host material.The energy dispersive X-Ray (EDX) analysis confirmed the purity of mass percentage composition of the elements present in the samples.展开更多
Semiconductor-based photocatalysis by utilizing solar energy for sustainable organic pollutant elimination has been a promising tactic to alleviate environmental issues.Nevertheless,the development of robust and effic...Semiconductor-based photocatalysis by utilizing solar energy for sustainable organic pollutant elimination has been a promising tactic to alleviate environmental issues.Nevertheless,the development of robust and efficient photocatalysts to degrade organic pollutants still faces major challenges because of insufficient charge separation.Here we design and fabricate a heterojunction consisting of copper,carbon-modified TiO_(2),and sulfur-doped g-C_(3)N_(4)nanosheets(i.e.,S-C_(3)N_(4)/Cu/C-TiO_(2)).The heterostructure affords a remarkable synergistic photocatalysis for tetracycline hydrochloride degradation,achieving an 82.6%removal efficiency within 30 min under visible light irradiation,about 15.4 and 7.3 times higher than that of S-C_(3)N_(4)and C-TiO_(2),respectively.The superior performance is attributed to the synergy between Cu doping and the Z-scheme heterojunction,which not only enhances the interfacial electric field effect,facilitating charge separation,but also boosts the redox capability.The charge carrier transfer between Cu/C-TiO_(2)and S-C_(3)N_(4)follows a Z-scheme,as verified by trapping experiments,electron spin-resonance spectroscopy,and density functional theory calculations.Furthermore,the tetracycline hydrochloride degradation pathways are enunciated by liquid chromatograph mass spectrometry analysis.This work provides an effective approach for constructing high-performance photocatalysts that have potential in environmental remediation.展开更多
Due to their high capacity,the P2-type layered oxide cathodes containing oxygen redox reaction processes have attracted wide attention for sodium-ion batteries.However,these materials usually exhibit poor electro-chem...Due to their high capacity,the P2-type layered oxide cathodes containing oxygen redox reaction processes have attracted wide attention for sodium-ion batteries.However,these materials usually exhibit poor electro-chemical properties,resulting from irreversible oxygen redox reactions and phase transition processes at high voltages,and thus hinder their large-scale application.This work reveals the mechanism for the significantly improved cycle stability and rate performance of Co/Ni-free Na_(0.7)5Li_(0.25-2/3x)CuxMn_(0.75-1/3x)O_(2)via Cu doping.Ex-situ XPS demonstrates that Cu doping reduces the amount of Mn^(3+)that triggers the Jahn-Teller effect during the cycling.In addition,the electron enrichment of oxygen around Cu can alleviate the irreversible oxidation of oxygen,and thus suppressing the phase transition originates from the rapid weakening of the electrostatic repulsion between O-O.Meanwhile,in-situ XRD results verify that the Na_(0.7)5Li_(0.19)Cu_(0.09)Mn_(0.7)2O_(2)maintains the P2 phase structure during charging and discharging,resulting in a near-zero strain characteristic of 1.9%.Therefore,the optimized cathode delivers a high reversible capacity of 194.9 mAh g−1 at 0.1 C and excellent capacity retention of 88.6%after 100 cycles at 5 C.The full cell paired with commercial hard carbon anode delivers energy density of 240 Wh kg−1.Our research provides an idea for designing a new type of intercalated cathode for sodium-ion batteries with low cost and high energy density.展开更多
Large Seebeck coefficients induced by high degeneracy of conduction band minimum,and low intrinsic lattice thermal conductivity originated from large lattice vibrational anharmonicity render Mg_(3)Sb_(2)as a promising...Large Seebeck coefficients induced by high degeneracy of conduction band minimum,and low intrinsic lattice thermal conductivity originated from large lattice vibrational anharmonicity render Mg_(3)Sb_(2)as a promising n-type thermoelectric material.Herein,we demonstrated unique concentration-dependent occupation behaviors of Cu in Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)matrix,evidenced by structural characterization and transport property measurements.It is found that Cu atoms prefer to enter the interstitial lattice sites in Mg_(3)Sb_(2)host with low doping level(Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+x%Cu,x<0.3%),acting as donors for providing additional electrons without deteriorating the carrier mobility.When x is larger than 0.3%,the excessive Cu atoms are inclined to substitute Mg atoms,yielding acceptors to decrease the electron concentration.As a result,the electrical conductivity of the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+0.3%Cu sample reaches 2.3×10^(4)S/m at 300 K,increasing by 300%compared with that of the pristine sample.The figure of merit zT values in the whole measured temperature range are significantly improved by the synergetic improvement of power factor and reduction of thermal conductivity.An average zT∼1.07 from 323 K to 773 K has been achieved for the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+0.3%Cu sample,which is about 30%higher than that of the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01) sample.展开更多
Electron transfer is an important way to activate persulfate.Currently,the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself,which can lead to selective activation o...Electron transfer is an important way to activate persulfate.Currently,the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself,which can lead to selective activation of persulfate or oxidation of the catalyst,respectively,and thus become a bottleneck restricting its application.In this work,Cu−doped FeVO_(4)(Cu−FVO)was prepared,and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate(PMS)activation.The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light.This system manifested a broad applicability to various organic contaminants even with complex matrix.Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO.Furthermore,Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS,through which photogenerated electrons achieved an efficient PMS activation.Meanwhile,holes were consumed by organic contaminants to avoid the oxidation of catalyst.These collectively enhanced the photocatalytic activity and stability of Cu−FVO,which also maintained high catalytic activity even after 20 cycling degradation reactions.展开更多
Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have receive...Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have received considerable attention in ADMFCs among non-platinum catalysts due to their high activity and tolerance against CO poisoning,which is strongly determined by their composition and structure.Herein,a one-spot hydrothermal method to synthesize Cu-doped Pd_(7)Te_(3)ultrathin nanowires was proposed.The density functional theory calculations show that the Cu doping simultaneously facilitates the desorption of CO^(*)and adsorption of OH,which refreshes the active sites quickly and thus enhances the electroactivity for MOR.Benefiting from their ultrathin architecture and the modified bonding and anti-bonding d states of Pd,Cu-doped Pd_(7)Te_(3)nanowires show about twofold and threefold mass activity promotion and enhanced durability for MOR when compared to the pure Pd_(7)Te_(3)nanowires and commercial Pd/C catalysts.This work not only provides a simple one-step synthesis strategy for Pd-based nanowire catalysts,but also helps to inspire the catalyst design in ADMFC.展开更多
A series of copper-doped Ti-Ce-O_x complex oxide catalysts were synthesized by sol-gel method and evaluated for selective catalytic reduction of NO by NH_3 at low temperature. The promotional effect of copper doping o...A series of copper-doped Ti-Ce-O_x complex oxide catalysts were synthesized by sol-gel method and evaluated for selective catalytic reduction of NO by NH_3 at low temperature. The promotional effect of copper doping on their structure, acidity and catalytic activity were investigated by means of Brumauer-Emmett-Teller（BET）, temperature-programmed reduction（H_2-TPR）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, temperature programmed desorption（NH_3-TPD） and pyridine adsorption infrared spectrum（Py-IR） technologies. Results showed that the copper additives could improve the low temperature catalytic performance for selective catalytic reduction of Ti-Ce-O_x catalyst and the NO conversion efficiency of Ti-Cu-Ce-O_x catalyst reached above 90% at 150-250 oC（Ti/Cu=4）. The introduction of copper could enhance the redox property of the Ti-Ce-O_x complex oxide catalyst, refine the particle size caused by lattice distortion and oxygen vacancy defect and enhance the acid amount of the Lewis acid site. Moreover, Ti-Cu-Ce-O_x complex oxide catalyst also had good anti-sulfur ability and anti-water influence, when injecting 300 ppm SO_2 and 10 vol.%H_2O, the NO conversion efficiency of Ti-Cu-Ce-O_x catalyst reached 80%.展开更多
We reported an effective method to synthesize In2S3 and Cu-doped In2S3 two-dimensional ultrathin nanoflakes by the hydrothermal method through tuning the Cu/In molar ratio. The transmission electron microscope images ...We reported an effective method to synthesize In2S3 and Cu-doped In2S3 two-dimensional ultrathin nanoflakes by the hydrothermal method through tuning the Cu/In molar ratio. The transmission electron microscope images showed that the products had ultrathin flake-like shape with wrinkling and rolling. The X-ray diffraction patterns indicated the crystal phase of nanoflakes was varied from β-In2S3 to tetragonal-Cu InS2 as the Cu/In molar ratio was increased. The In2S3 nanoflakes exhibited absorption band at 450 nm, while new absorption peaks in turn appeared at 550 nm and 670 nm as the Cu/In molar ratio was increased. In addition, the two-dimensional ultrathin nanoflakes exhibited intense photocurrent response.展开更多
The La_(2/3)Ca_(1/3)Mn_(1- x )Cu_ x O_3 (0≤ x <6%) samples were prepared by sol-gel method. Transport properties, conductive mechanism and low-field magnetoresistance ( MR _0) were investigated. It is found that c...The La_(2/3)Ca_(1/3)Mn_(1- x )Cu_ x O_3 (0≤ x <6%) samples were prepared by sol-gel method. Transport properties, conductive mechanism and low-field magnetoresistance ( MR _0) were investigated. It is found that conductive mechanism is described by Mott′s variable-range hopping and the MR _0 near the insulator-metal transition temperature ( T _p) increases from 2% to 80% with x from 0 to 4% for a low field of 0.3 T. The experiment also shows that the intergrain magnetoresistance is largely improved. The results indicate that a proper amount of Cu doping can substantially improve magnetoresistance effects.展开更多
The sol-gel method was adopted to prepare series of La2/3Cal/3Mn0.98Cu0.02O3 samples sintered at different temperatures, and the structure of samples, high-temperature electrical conductive mechanism and electronic tr...The sol-gel method was adopted to prepare series of La2/3Cal/3Mn0.98Cu0.02O3 samples sintered at different temperatures, and the structure of samples, high-temperature electrical conductive mechanism and electronic transport properties of double-peak resistance were investigated. X-ray diffraction pattern indicates that the samples are in perovskite structures and obey the Vari- able-Rang Hopping Mechanism of p = p 0exp[（T0/T）^1/4] under high temperatures during the electrical conduction. In addition, based on the polycrystalline granular system surface and image, the reasonable explanation was given for the double-peak resistance phemomenon.展开更多
The influence of Cu dopant (x) and sintering temperature (T s) on the transport properties of La 2/3Ca 1/3Mn 1-xCu xO 3 series samples prepared by Sol-Gel technique was investigated.X-ray diffraction patte...The influence of Cu dopant (x) and sintering temperature (T s) on the transport properties of La 2/3Ca 1/3Mn 1-xCu xO 3 series samples prepared by Sol-Gel technique was investigated.X-ray diffraction patterns show that all the samples with different Cu dopant and sintering temperatures (T s) are of single phase without obvious lattice distortion.Experimental results indicate that the insulator-metal transition temperature is directly related to the sintering temperature and Cu dopant x.It is interesting to observe that a proper amount of Cu dopant can substantially improve magnetoresistance effects.展开更多
The as-cast Cu-doped Fe_(83)Ga_(17)alloys were prepared by arc-melting.The microstructures and magnetostrictions of(Fe_(83)Ga_(17))_(100-x)Cu_(x)(x=0,3,6,9,12,15)alloys were investigated by X-ray diffraction,scanning ...The as-cast Cu-doped Fe_(83)Ga_(17)alloys were prepared by arc-melting.The microstructures and magnetostrictions of(Fe_(83)Ga_(17))_(100-x)Cu_(x)(x=0,3,6,9,12,15)alloys were investigated by X-ray diffraction,scanning electron microscopy,energy dispersive spectroscopy and strain gauge magnetostriction measurement.Vibrating sample magnetometer was employed to investigate the magnetic properties of(Fe_(83)Ga_(17))_(100-x)Cu_(x)(x=0,3,6,9,12,15).First-principal calculation was employed to make lattice structure and energy simulation.The results indicate that Cu dopants dissolve into A2 lattice by interstitial doping,which induces tetragonal-like distortion of A2 lattice.And the magnetostriction for Cu-doped Fe_(83)Ga_(17)alloys is lower than that of Fe_(83)Ga_(17)alloy.The reduction of magnetostriction is attribute to the increase of Young’s modulus caused by Cu dopants dissolve into A2 lattice by interstitial doping and the decrease of magnetoelastic coupling coefficient for Cu-doped Fe_(83)Ga_(17)alloys caused by Cu dopants dissolve into A2 lattice.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
Here, undoped and Cu doped ZnO nanoparticles(NPs) have been prepared by chemical co-precipitation technique. X-ray diffraction(XRD) results reveal that Cu ions are successfully doped into ZnO matrix without altering i...Here, undoped and Cu doped ZnO nanoparticles(NPs) have been prepared by chemical co-precipitation technique. X-ray diffraction(XRD) results reveal that Cu ions are successfully doped into ZnO matrix without altering its wurtzite phase. The single wurtzite phase of ZnO is retained even for 10 wt% Cu doped ZnO sample. It is observed from the electron microscopy results that higher level of Cu doping varies the morphology of ZnO NPs from spherical to flat NPs. Moreover, the particle size is found to increase with the increase in Cu doping level. Raman spectroscopy results further confirm that Cu dopant has not altered the wurtzite structure of ZnO. Impedance spectroscopy results reveal that the dielectric constant and dielectric loss have increasing trend with Cu doping. Cu doping has been found to slightly decrease the bactericidal potency of ZnO nanoparticles.展开更多
Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaC...Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaCl flux method.The solubility of Cd in Cu2Se at room temperature was less than 6%,and a second phase of CdSe was found in the samples with large initial Cd content(x=0.01 and 0.02).Field-emission scanning electron microscopic image showed that the arranged lamellae formed a large-scale layered structure with an average thickness of approximately 100 nm.Transmission electron microscopy demonstrated that doping of Cd atoms did not destroy the crystal integrity of Cu2Se.A small amount of Cd in Cu2Se could reduce the electrical and thermal conductivities of the material,thus significantly enhancing its thermoelectric performance.With the increase in Cd content in the sample,the carrier concentration decreased and the mobility increased gradually.Thermogravimetric differential thermal analysis showed that no weight loss occurred below the melting point.Excessive Cd doping led to the emergence of the second phase of CdSe in the sample,thus significantly increasing the thermal conductivity of the material.A maximum ZT value of 1.67 at 700 K was obtained in the Cu1.9925SeCd0.0075 sample.展开更多
Ga doped ZnO （OZO）/Cu grid/GZO transparent conductive electrode （TCE） structures were fabricated at room temperature （RT） by using electron beam evaporation （EBE） for the Cu grids and RF magnetron sputtering f...Ga doped ZnO （OZO）/Cu grid/GZO transparent conductive electrode （TCE） structures were fabricated at room temperature （RT） by using electron beam evaporation （EBE） for the Cu grids and RF magnetron sputtering for the GZO layers. In this work, we investigated the electrical and optical characteristics of GZO/Cu grid/GZO multilayer electrode for thin film solar cells by using evaporated Cu grid and sputtered GZO thin films to enhance the optical transparency without significantly affecting their conductivity. The optical transmittance and sheet resistance of GZO/Cu grid/GZO multilayer are higher than those of GZO/Cu film/GZO multilayer independent of Cu grid separation distance and increase with increasing Cu grid separation distances. The calculation of both transmittance and sheet resistance of GZO/Cu grid] GZO multilayer was based on Cu filling factor correlated with the geometry of Cu grid. The calculated values for the transmittance and sheet resistance of the GZO/Cu grid/GZO multilayer were similar to the experimentally observed ones. The highest figure of merit ФTc is 5.18× 10^-3Ω^-1 for the GZO/Cu grid] GZO multilayer with Cu grid separation distance of 1 mm was obtained, in this case, the transmittance and resistivity were 82.72% and 2.17 × 10 ^-4Ωcm, respectively. The transmittance and resistivity are accentahle for nractical thin film snlar cell annlicatinn~展开更多
Via the first principles calculations, we predict that Cu doped graphene oxide （GO） is a much better nanocatalyst in terms of activity and feasibility. The high activity of Cu doped graphene oxides may be attributed...Via the first principles calculations, we predict that Cu doped graphene oxide （GO） is a much better nanocatalyst in terms of activity and feasibility. The high activity of Cu doped graphene oxides may be attributed to the charge transfer between the GO and Cu atom, resulting in an activated Cu atom. In the ER mechanism, the CO molecules directly react with the activated O2, then forming a metastable carbonate-like intermediate state （OOCO）. The reaction may proceed via two reaction paths of OOCO → CO2 ＋ O and CO ＋ OOCO → 2CO2, respectively. The calculated results show that the latter path is relatively more thermodynamically favorable with a modest energy barrier, so it should be more preferred. We expect our theoretical predictions to open a new avenue to fabricate carbon-based catalysts for CO oxidation with lower cost and higher activity.展开更多
Low cost co-precipitation method was used to synthesize Cu(0-0.05)doped MgO samples with fixed concertation of Zn=0.01.X-ray diffraction(XRD)spectra confirmed the phase purity of the samples for 0≤Cu≤0.03 doping con...Low cost co-precipitation method was used to synthesize Cu(0-0.05)doped MgO samples with fixed concertation of Zn=0.01.X-ray diffraction(XRD)spectra confirmed the phase purity of the samples for 0≤Cu≤0.03 doping concentration.The secondary phase for 0.04≤Cu≤0.05 exhibited the formation of mixed metal oxides.The crystallite size was found to increase from 17.5 to 23.5 nm for 0≤Cu≤0.03 and then decreased from 22 to 18.5 nm for 0.04≤Cu≤0.05.The estimated bandgap first reduced from 5.48 to 4.88 eV and then increased from 5.21 to 5.36 eV.The morphology of the samples transformed from spheroidal shape to star-like shape.The obtained results reveal that the structural and optical property are in good agreement with the morphological transition.The peak shifting towards the lower values of vibrational frequency from 694 to 579 cm^(-1) confirms the incorporation of Cu/Zn in Mg-O lattice.The tuning of optical bandgap and structural properties with varying dopant concentration in MgO nanomaterials can be used for multifunctional modern energy storage and optoelectronic devices.展开更多
基金Supported by the National Key Technologies R&D Program of China under Grant No 2016YFB0901500the National Nature Science Foundation of China under Grant Nos 51725206 and 51421002
文摘The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries（NIBs） due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective because it needs to be sintered under oxygen atmosphere at high temperature and followed by a quenching procedure. Here we first report that the pure β phase can be stabilized by Cu-doping and easily synthesized by replacing a proportion of Mn with Cu via a simplified process including sintering in air and cooling to room temperature naturally. Based on the first-principle calculations, the band gap decreases from 0.7 eV to 0.3 eV, which indicates that the electronic conductivity can be improved by Cu-doping. The designed -NaCu（0.1）Mn（0.9）O2 is applied as cathode in NIBs, exhibiting an energy density of 419 Wh/kg and better performance in terms of rate capability and cycling stability than those in the undoped case.
基金Project supported by the Natural Science Foundation of Gansu Province, China (Grant No. 0803RJZA008)the Fundamental Research Funds for the Central Universities, China (Grant No. zyz2012057)+1 种基金the National Natural Science Foundation of China (Grant No. 11004141)the Program for New Century Excellent Talents in University, China (Grant No. 11-0351)
文摘ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO：Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO：Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.
文摘Cu doped Mg(OH)_(2) nanoparticles were synthesized with varying concentrations from 0 to 10%by a chemical synthesis technique of coprecipitation.X-rays diffraction (XRD) of the samples confirms that all the samples acquire the hexagonal crystal structure.XRD results indicated the solubility limit of dopant in the host material and the secondary phase of CuO was observed beyond 3%Cu doping in Mg(OH)_(2).The reduction in the size of nanoparticles was observed from 166 to 103 nm for Mg(OH)_(2) and 10% Cu doped Mg(OH)_(2)samples,respectively.The shift in absorption spectra exhibited the systematical enhancement in optical bandgap from 5.25 to 6.085 eV.A good correlation was observed between the bandgap energy and crystallite size of the nanocrystals which confirmed the size induced effect in the nanoparticles.The transformation in the sample morphology was observed from irregular spherical particles to sepals like shapes with increasing the Cu concentration in the host material.The energy dispersive X-Ray (EDX) analysis confirmed the purity of mass percentage composition of the elements present in the samples.
基金supported by the National Natural Science Foundation of China(No.21972010)the National Key Research and Development Program of China(No.2022YFC2105900).
文摘Semiconductor-based photocatalysis by utilizing solar energy for sustainable organic pollutant elimination has been a promising tactic to alleviate environmental issues.Nevertheless,the development of robust and efficient photocatalysts to degrade organic pollutants still faces major challenges because of insufficient charge separation.Here we design and fabricate a heterojunction consisting of copper,carbon-modified TiO_(2),and sulfur-doped g-C_(3)N_(4)nanosheets(i.e.,S-C_(3)N_(4)/Cu/C-TiO_(2)).The heterostructure affords a remarkable synergistic photocatalysis for tetracycline hydrochloride degradation,achieving an 82.6%removal efficiency within 30 min under visible light irradiation,about 15.4 and 7.3 times higher than that of S-C_(3)N_(4)and C-TiO_(2),respectively.The superior performance is attributed to the synergy between Cu doping and the Z-scheme heterojunction,which not only enhances the interfacial electric field effect,facilitating charge separation,but also boosts the redox capability.The charge carrier transfer between Cu/C-TiO_(2)and S-C_(3)N_(4)follows a Z-scheme,as verified by trapping experiments,electron spin-resonance spectroscopy,and density functional theory calculations.Furthermore,the tetracycline hydrochloride degradation pathways are enunciated by liquid chromatograph mass spectrometry analysis.This work provides an effective approach for constructing high-performance photocatalysts that have potential in environmental remediation.
基金financially supported by the National Natural Science Foundation of China(22271211)the Natural Science Foundation of Shanxi Province(20210302123107 and 202202060301018)。
文摘Due to their high capacity,the P2-type layered oxide cathodes containing oxygen redox reaction processes have attracted wide attention for sodium-ion batteries.However,these materials usually exhibit poor electro-chemical properties,resulting from irreversible oxygen redox reactions and phase transition processes at high voltages,and thus hinder their large-scale application.This work reveals the mechanism for the significantly improved cycle stability and rate performance of Co/Ni-free Na_(0.7)5Li_(0.25-2/3x)CuxMn_(0.75-1/3x)O_(2)via Cu doping.Ex-situ XPS demonstrates that Cu doping reduces the amount of Mn^(3+)that triggers the Jahn-Teller effect during the cycling.In addition,the electron enrichment of oxygen around Cu can alleviate the irreversible oxidation of oxygen,and thus suppressing the phase transition originates from the rapid weakening of the electrostatic repulsion between O-O.Meanwhile,in-situ XRD results verify that the Na_(0.7)5Li_(0.19)Cu_(0.09)Mn_(0.7)2O_(2)maintains the P2 phase structure during charging and discharging,resulting in a near-zero strain characteristic of 1.9%.Therefore,the optimized cathode delivers a high reversible capacity of 194.9 mAh g−1 at 0.1 C and excellent capacity retention of 88.6%after 100 cycles at 5 C.The full cell paired with commercial hard carbon anode delivers energy density of 240 Wh kg−1.Our research provides an idea for designing a new type of intercalated cathode for sodium-ion batteries with low cost and high energy density.
基金supported by the National Key Research and Development Program of China(Nos.2018YFA0702100 and 2019YFA0210001)National Natural Science Foundation of China(No.U21A2054 and 52072234)K.Guo acknowledges the support from Key Discipline of Materials Science and Engineering,Bureau of Education of Guangzhou(No.202255464)。
文摘Large Seebeck coefficients induced by high degeneracy of conduction band minimum,and low intrinsic lattice thermal conductivity originated from large lattice vibrational anharmonicity render Mg_(3)Sb_(2)as a promising n-type thermoelectric material.Herein,we demonstrated unique concentration-dependent occupation behaviors of Cu in Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)matrix,evidenced by structural characterization and transport property measurements.It is found that Cu atoms prefer to enter the interstitial lattice sites in Mg_(3)Sb_(2)host with low doping level(Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+x%Cu,x<0.3%),acting as donors for providing additional electrons without deteriorating the carrier mobility.When x is larger than 0.3%,the excessive Cu atoms are inclined to substitute Mg atoms,yielding acceptors to decrease the electron concentration.As a result,the electrical conductivity of the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+0.3%Cu sample reaches 2.3×10^(4)S/m at 300 K,increasing by 300%compared with that of the pristine sample.The figure of merit zT values in the whole measured temperature range are significantly improved by the synergetic improvement of power factor and reduction of thermal conductivity.An average zT∼1.07 from 323 K to 773 K has been achieved for the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01)+0.3%Cu sample,which is about 30%higher than that of the Mg_(3.4)Sb_(1.5)Bi_(0.49)Te_(0.01) sample.
基金Z.Z.acknowledges the financial support by the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(Grant No.SKLPEE-KF202403)Fuzhou University,and the Natural Science Foundation of Fujian Province(Grant No.2021J05029)J.L.is grateful for the financial support from National Natural Science Foundation of China(NSFC,Grant No.22371042).
文摘Electron transfer is an important way to activate persulfate.Currently,the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself,which can lead to selective activation of persulfate or oxidation of the catalyst,respectively,and thus become a bottleneck restricting its application.In this work,Cu−doped FeVO_(4)(Cu−FVO)was prepared,and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate(PMS)activation.The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light.This system manifested a broad applicability to various organic contaminants even with complex matrix.Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO.Furthermore,Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS,through which photogenerated electrons achieved an efficient PMS activation.Meanwhile,holes were consumed by organic contaminants to avoid the oxidation of catalyst.These collectively enhanced the photocatalytic activity and stability of Cu−FVO,which also maintained high catalytic activity even after 20 cycling degradation reactions.
基金supported by the National Natural Science Foundation of China(Nos.22275178 and 22005285)the Fundamental Research Funds for the Central Universities(Nos.JUSRP123013 and JUSRP123015)+1 种基金performed on Hefei advanced computing centerSupercomputing USTC and National Supercomputing Center in Shenzhen are acknowledged for computational support.
文摘Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have received considerable attention in ADMFCs among non-platinum catalysts due to their high activity and tolerance against CO poisoning,which is strongly determined by their composition and structure.Herein,a one-spot hydrothermal method to synthesize Cu-doped Pd_(7)Te_(3)ultrathin nanowires was proposed.The density functional theory calculations show that the Cu doping simultaneously facilitates the desorption of CO^(*)and adsorption of OH,which refreshes the active sites quickly and thus enhances the electroactivity for MOR.Benefiting from their ultrathin architecture and the modified bonding and anti-bonding d states of Pd,Cu-doped Pd_(7)Te_(3)nanowires show about twofold and threefold mass activity promotion and enhanced durability for MOR when compared to the pure Pd_(7)Te_(3)nanowires and commercial Pd/C catalysts.This work not only provides a simple one-step synthesis strategy for Pd-based nanowire catalysts,but also helps to inspire the catalyst design in ADMFC.
基金supported by the National Natural Science Foundation of China(51272105)the National Key Technology R&D Program of China(2012BAE01B03)+1 种基金the Research Subject of Environmental Protection Department of Jiangsu Province of China(2013006)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘A series of copper-doped Ti-Ce-O_x complex oxide catalysts were synthesized by sol-gel method and evaluated for selective catalytic reduction of NO by NH_3 at low temperature. The promotional effect of copper doping on their structure, acidity and catalytic activity were investigated by means of Brumauer-Emmett-Teller（BET）, temperature-programmed reduction（H_2-TPR）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, temperature programmed desorption（NH_3-TPD） and pyridine adsorption infrared spectrum（Py-IR） technologies. Results showed that the copper additives could improve the low temperature catalytic performance for selective catalytic reduction of Ti-Ce-O_x catalyst and the NO conversion efficiency of Ti-Cu-Ce-O_x catalyst reached above 90% at 150-250 oC（Ti/Cu=4）. The introduction of copper could enhance the redox property of the Ti-Ce-O_x complex oxide catalyst, refine the particle size caused by lattice distortion and oxygen vacancy defect and enhance the acid amount of the Lewis acid site. Moreover, Ti-Cu-Ce-O_x complex oxide catalyst also had good anti-sulfur ability and anti-water influence, when injecting 300 ppm SO_2 and 10 vol.%H_2O, the NO conversion efficiency of Ti-Cu-Ce-O_x catalyst reached 80%.
基金Supported by the National Key Research&Development Program of China(2017YFA0303402)the Large-Scale Instrument and Equipment Sharing Foundation of Wuhan University
文摘We reported an effective method to synthesize In2S3 and Cu-doped In2S3 two-dimensional ultrathin nanoflakes by the hydrothermal method through tuning the Cu/In molar ratio. The transmission electron microscope images showed that the products had ultrathin flake-like shape with wrinkling and rolling. The X-ray diffraction patterns indicated the crystal phase of nanoflakes was varied from β-In2S3 to tetragonal-Cu InS2 as the Cu/In molar ratio was increased. The In2S3 nanoflakes exhibited absorption band at 450 nm, while new absorption peaks in turn appeared at 550 nm and 670 nm as the Cu/In molar ratio was increased. In addition, the two-dimensional ultrathin nanoflakes exhibited intense photocurrent response.
文摘The La_(2/3)Ca_(1/3)Mn_(1- x )Cu_ x O_3 (0≤ x <6%) samples were prepared by sol-gel method. Transport properties, conductive mechanism and low-field magnetoresistance ( MR _0) were investigated. It is found that conductive mechanism is described by Mott′s variable-range hopping and the MR _0 near the insulator-metal transition temperature ( T _p) increases from 2% to 80% with x from 0 to 4% for a low field of 0.3 T. The experiment also shows that the intergrain magnetoresistance is largely improved. The results indicate that a proper amount of Cu doping can substantially improve magnetoresistance effects.
基金Funded by the National Natural Science Foundation of China (No.60471024)
文摘The sol-gel method was adopted to prepare series of La2/3Cal/3Mn0.98Cu0.02O3 samples sintered at different temperatures, and the structure of samples, high-temperature electrical conductive mechanism and electronic transport properties of double-peak resistance were investigated. X-ray diffraction pattern indicates that the samples are in perovskite structures and obey the Vari- able-Rang Hopping Mechanism of p = p 0exp[（T0/T）^1/4] under high temperatures during the electrical conduction. In addition, based on the polycrystalline granular system surface and image, the reasonable explanation was given for the double-peak resistance phemomenon.
文摘The influence of Cu dopant (x) and sintering temperature (T s) on the transport properties of La 2/3Ca 1/3Mn 1-xCu xO 3 series samples prepared by Sol-Gel technique was investigated.X-ray diffraction patterns show that all the samples with different Cu dopant and sintering temperatures (T s) are of single phase without obvious lattice distortion.Experimental results indicate that the insulator-metal transition temperature is directly related to the sintering temperature and Cu dopant x.It is interesting to observe that a proper amount of Cu dopant can substantially improve magnetoresistance effects.
基金the National Natural Science Foundation of China(No.51661027)the Natural Science Foundation of Inner Mongolia(No.2019MS05002)。
文摘The as-cast Cu-doped Fe_(83)Ga_(17)alloys were prepared by arc-melting.The microstructures and magnetostrictions of(Fe_(83)Ga_(17))_(100-x)Cu_(x)(x=0,3,6,9,12,15)alloys were investigated by X-ray diffraction,scanning electron microscopy,energy dispersive spectroscopy and strain gauge magnetostriction measurement.Vibrating sample magnetometer was employed to investigate the magnetic properties of(Fe_(83)Ga_(17))_(100-x)Cu_(x)(x=0,3,6,9,12,15).First-principal calculation was employed to make lattice structure and energy simulation.The results indicate that Cu dopants dissolve into A2 lattice by interstitial doping,which induces tetragonal-like distortion of A2 lattice.And the magnetostriction for Cu-doped Fe_(83)Ga_(17)alloys is lower than that of Fe_(83)Ga_(17)alloy.The reduction of magnetostriction is attribute to the increase of Young’s modulus caused by Cu dopants dissolve into A2 lattice by interstitial doping and the decrease of magnetoelastic coupling coefficient for Cu-doped Fe_(83)Ga_(17)alloys caused by Cu dopants dissolve into A2 lattice.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金funded by the Higher Education Commission, Pakistan (HEC) IPFP (Grant No. PM-IPFP/HRD/HEC/2011/3386)funding for HEC Ph.D. Scholar (Tariq Jan)
文摘Here, undoped and Cu doped ZnO nanoparticles(NPs) have been prepared by chemical co-precipitation technique. X-ray diffraction(XRD) results reveal that Cu ions are successfully doped into ZnO matrix without altering its wurtzite phase. The single wurtzite phase of ZnO is retained even for 10 wt% Cu doped ZnO sample. It is observed from the electron microscopy results that higher level of Cu doping varies the morphology of ZnO NPs from spherical to flat NPs. Moreover, the particle size is found to increase with the increase in Cu doping level. Raman spectroscopy results further confirm that Cu dopant has not altered the wurtzite structure of ZnO. Impedance spectroscopy results reveal that the dielectric constant and dielectric loss have increasing trend with Cu doping. Cu doping has been found to slightly decrease the bactericidal potency of ZnO nanoparticles.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61864012 and 21701140)the Program for Innovative Research Team(in Science and Technology)in University of Yunnan Province,China.
文摘Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaCl flux method.The solubility of Cd in Cu2Se at room temperature was less than 6%,and a second phase of CdSe was found in the samples with large initial Cd content(x=0.01 and 0.02).Field-emission scanning electron microscopic image showed that the arranged lamellae formed a large-scale layered structure with an average thickness of approximately 100 nm.Transmission electron microscopy demonstrated that doping of Cd atoms did not destroy the crystal integrity of Cu2Se.A small amount of Cd in Cu2Se could reduce the electrical and thermal conductivities of the material,thus significantly enhancing its thermoelectric performance.With the increase in Cd content in the sample,the carrier concentration decreased and the mobility increased gradually.Thermogravimetric differential thermal analysis showed that no weight loss occurred below the melting point.Excessive Cd doping led to the emergence of the second phase of CdSe in the sample,thus significantly increasing the thermal conductivity of the material.A maximum ZT value of 1.67 at 700 K was obtained in the Cu1.9925SeCd0.0075 sample.
基金support of the key project of the National Natural Science Foundation of China under Grant Nos.91333203 and 51172204the Program for Innovative Research Team in University of Ministry of Education of China under Grant No.IRT13037the Zhejiang Provincial Department of Science and Technology of China under Grant No.2010R50020
文摘Ga doped ZnO （OZO）/Cu grid/GZO transparent conductive electrode （TCE） structures were fabricated at room temperature （RT） by using electron beam evaporation （EBE） for the Cu grids and RF magnetron sputtering for the GZO layers. In this work, we investigated the electrical and optical characteristics of GZO/Cu grid/GZO multilayer electrode for thin film solar cells by using evaporated Cu grid and sputtered GZO thin films to enhance the optical transparency without significantly affecting their conductivity. The optical transmittance and sheet resistance of GZO/Cu grid/GZO multilayer are higher than those of GZO/Cu film/GZO multilayer independent of Cu grid separation distance and increase with increasing Cu grid separation distances. The calculation of both transmittance and sheet resistance of GZO/Cu grid] GZO multilayer was based on Cu filling factor correlated with the geometry of Cu grid. The calculated values for the transmittance and sheet resistance of the GZO/Cu grid/GZO multilayer were similar to the experimentally observed ones. The highest figure of merit ФTc is 5.18× 10^-3Ω^-1 for the GZO/Cu grid] GZO multilayer with Cu grid separation distance of 1 mm was obtained, in this case, the transmittance and resistivity were 82.72% and 2.17 × 10 ^-4Ωcm, respectively. The transmittance and resistivity are accentahle for nractical thin film snlar cell annlicatinn~
基金supported by the National Natural Science Foundation of China(No.21004009)the Foundation of Jiangxi Educational Committee(No.GJJ14485)
文摘Via the first principles calculations, we predict that Cu doped graphene oxide （GO） is a much better nanocatalyst in terms of activity and feasibility. The high activity of Cu doped graphene oxides may be attributed to the charge transfer between the GO and Cu atom, resulting in an activated Cu atom. In the ER mechanism, the CO molecules directly react with the activated O2, then forming a metastable carbonate-like intermediate state （OOCO）. The reaction may proceed via two reaction paths of OOCO → CO2 ＋ O and CO ＋ OOCO → 2CO2, respectively. The calculated results show that the latter path is relatively more thermodynamically favorable with a modest energy barrier, so it should be more preferred. We expect our theoretical predictions to open a new avenue to fabricate carbon-based catalysts for CO oxidation with lower cost and higher activity.
文摘Low cost co-precipitation method was used to synthesize Cu(0-0.05)doped MgO samples with fixed concertation of Zn=0.01.X-ray diffraction(XRD)spectra confirmed the phase purity of the samples for 0≤Cu≤0.03 doping concentration.The secondary phase for 0.04≤Cu≤0.05 exhibited the formation of mixed metal oxides.The crystallite size was found to increase from 17.5 to 23.5 nm for 0≤Cu≤0.03 and then decreased from 22 to 18.5 nm for 0.04≤Cu≤0.05.The estimated bandgap first reduced from 5.48 to 4.88 eV and then increased from 5.21 to 5.36 eV.The morphology of the samples transformed from spheroidal shape to star-like shape.The obtained results reveal that the structural and optical property are in good agreement with the morphological transition.The peak shifting towards the lower values of vibrational frequency from 694 to 579 cm^(-1) confirms the incorporation of Cu/Zn in Mg-O lattice.The tuning of optical bandgap and structural properties with varying dopant concentration in MgO nanomaterials can be used for multifunctional modern energy storage and optoelectronic devices.
