Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to st...Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+) exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+) displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G) to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+ )was greatly boosted because there was energy transfer and co-emission between Mn^(2+) and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+) emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+ and a blue chip.At a warm white-light corresponding color temperature(3009 K) with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+) would have great application potential as a red-emitting phosphor for white LEDs.展开更多
Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high curr...Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.展开更多
By using an improved Bridgman method,0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/y mol%Eu^(3+)(y=0,0.4,0.6,0.8)doped Na_(5)Y_(9)F_(32)single crystals were prepared.The x-ray diffraction,excitation spectra,emission spectra and flu...By using an improved Bridgman method,0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/y mol%Eu^(3+)(y=0,0.4,0.6,0.8)doped Na_(5)Y_(9)F_(32)single crystals were prepared.The x-ray diffraction,excitation spectra,emission spectra and fluorescence decay curves were used to explore the crystal structure and optical performance of the obtained samples.When excited by 362 nm light,the cool white emission was realized by Na_(5)Y_(9)F_(32)single crystal triply-doped with 0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/0.8 mol%Eu^(3+),in which the Commission Internationale de l’Eclairage(CIE)chromaticity coordinate was(0.2995,0.3298)and the correlated color temperature(CCT)was 6586 K.The integrated normalized emission intensity of the tridoped single crystal at 448 K could keep 62%of that at 298 K.The internal quantum yield(QY)was calculated to be~15.16%by integrating spheres.These results suggested that the single crystals tri-doped with Tm^(3+),Tb^(3+)and Eu^(3+)ions have a promising potential application for white light-emitting diodes(w-LEDs).展开更多
A series of SrIn2 O4 ：Eu^3＋ phosphors are synthesized by a high temperature solid-state method, and their luminescent properties are investigated. They can be excited by 395-nm radiation, and produce red emission （...A series of SrIn2 O4 ：Eu^3＋ phosphors are synthesized by a high temperature solid-state method, and their luminescent properties are investigated. They can be excited by 395-nm radiation, and produce red emission （619 nm）; however, they have a low absorption of near-ultraviolet light with the wavelength of 400nm–405 nm. When co-doped with A^＋ （A=Li, Na, K）, the emission intensity of SrIn2O4 ：Eu^3＋ is significantly enhanced, but its emission and excitation spectral profile is unchanged. With co-doping Sm^3＋ , not only is the emission intensity of SrIn2 O4 ：Eu^3＋ enhanced, but also the absorption is broadened and strengthened in the range of 400 nm–405nm. The effect of Sm^3＋ -doped content on the emission intensity of SrIn2O4 ：Eu^3＋ , Sm^3＋ is investigated, and the optimal Sm^3＋ content is 0.02 mol.展开更多
Pure WOand Yb:WOthin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-r...Pure WOand Yb:WOthin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-ray diffraction analysis shows that all thin films are polycrystalline nature and exhibit monoclinic crystal structure. The 3 at% Yb:WOfilm shows superior photoelectrochemical（PEC） performance than that of pure WOfilm and it shows maximum photocurrent density（Iph= 1090 μA/cm） having onset potentials around +0.3 V/SCE in 0.01 M HClO. The photoelectrocatalytic process is more effective than that of the photocatalytic process for degradation of methyl orange（MO） dye. Yb doping in WOphotocatalyst is greatly effective to degrade MO dye. The enhancement in photoelectrocatalytic activity is mainly due to the suppressing the recombination rate of photogenerated electron-hole pairs. The mineralization of MO dye in aqueous solution is studied by measuring chemical oxygen demand（COD） values.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
Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) a...Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) and Zn-air batteries. Herein, a trifunctional electrocatalyst of urchin-like Al,P-codoped Co3O4 microspheres supported on Ni foam(denoted as AP-CONPs/NF) was fabricated via a hydrothermal process and subsequent low-temperature annealing and phosphorization, exhibiting enhanced OER, HER and ORR activities compared with single-doped and undoped samples. Their surface self-organized microstructure and excellent "superaerophobic" feature make a high bubble repellency, which boost diffusion of reactants and electrolyte-electrode intimate contact. The codoping of Al and P elements into Co3O4 betters right the balance among surface chemical state, the increased oxygen vacancies and the promoted charge transfer. Encouraged by these synergistic advantages, the AP-CONPs/NF was further employed as excellent bifunctional electrodes for the OWS(low cell voltage of 1.57 V at 10 mA cm-2) and as air cathode for rechargeable Zn-air batteries(high power density of 89.1 mW cm-2), which demonstrates a great feasibility for practical applications.展开更多
文摘Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+) exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+) displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G) to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+ )was greatly boosted because there was energy transfer and co-emission between Mn^(2+) and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+) emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+ and a blue chip.At a warm white-light corresponding color temperature(3009 K) with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+) would have great application potential as a red-emitting phosphor for white LEDs.
基金National Natural Science Foundation of China(No.22272149,22062025)Yunnan University’s Research Innovation Fund for Graduate Students(No.KC-23234085)+1 种基金Workstation of Academician Chen Jing of Yunnan Province(No.202105AF150012)Free Exploration Fund for Academician(No.202405AA350001)。
文摘Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.
基金Project supported by the National Natural Science Foundation of China(Grant No.62275133)the Natural Science Foundation of Zhejiang Province of China(Grant No.LY22E020002)+1 种基金the Natural Science Foundation of Ningbo(Grant Nos.2021J077 and 202003N4099)K.C.Wong Magna Fund in Ningbo University
文摘By using an improved Bridgman method,0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/y mol%Eu^(3+)(y=0,0.4,0.6,0.8)doped Na_(5)Y_(9)F_(32)single crystals were prepared.The x-ray diffraction,excitation spectra,emission spectra and fluorescence decay curves were used to explore the crystal structure and optical performance of the obtained samples.When excited by 362 nm light,the cool white emission was realized by Na_(5)Y_(9)F_(32)single crystal triply-doped with 0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/0.8 mol%Eu^(3+),in which the Commission Internationale de l’Eclairage(CIE)chromaticity coordinate was(0.2995,0.3298)and the correlated color temperature(CCT)was 6586 K.The integrated normalized emission intensity of the tridoped single crystal at 448 K could keep 62%of that at 298 K.The internal quantum yield(QY)was calculated to be~15.16%by integrating spheres.These results suggested that the single crystals tri-doped with Tm^(3+),Tb^(3+)and Eu^(3+)ions have a promising potential application for white light-emitting diodes(w-LEDs).
基金Project supported by the National Natural Science Foundation of China (Grant No. 50902042)the Natural Science Foundation of Hebei Province, China(Grant Nos. E2009000209 and E2010000283)+1 种基金the Education Bureau Foundation of Hebei Province, China (Grant No. 2009313)the Key Laboratory of Luminescence and Optical Information, Beijing Jiaotong University, Ministry of Education, China (Grant No. 2010LOI12)
文摘A series of SrIn2 O4 ：Eu^3＋ phosphors are synthesized by a high temperature solid-state method, and their luminescent properties are investigated. They can be excited by 395-nm radiation, and produce red emission （619 nm）; however, they have a low absorption of near-ultraviolet light with the wavelength of 400nm–405 nm. When co-doped with A^＋ （A=Li, Na, K）, the emission intensity of SrIn2O4 ：Eu^3＋ is significantly enhanced, but its emission and excitation spectral profile is unchanged. With co-doping Sm^3＋ , not only is the emission intensity of SrIn2 O4 ：Eu^3＋ enhanced, but also the absorption is broadened and strengthened in the range of 400 nm–405nm. The effect of Sm^3＋ -doped content on the emission intensity of SrIn2O4 ：Eu^3＋ , Sm^3＋ is investigated, and the optimal Sm^3＋ content is 0.02 mol.
基金University Grants Commission(UGC),New Delhi,for the financial support through the project No.‘‘41-869/2012(SR)’’
文摘Pure WOand Yb:WOthin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-ray diffraction analysis shows that all thin films are polycrystalline nature and exhibit monoclinic crystal structure. The 3 at% Yb:WOfilm shows superior photoelectrochemical（PEC） performance than that of pure WOfilm and it shows maximum photocurrent density（Iph= 1090 μA/cm） having onset potentials around +0.3 V/SCE in 0.01 M HClO. The photoelectrocatalytic process is more effective than that of the photocatalytic process for degradation of methyl orange（MO） dye. Yb doping in WOphotocatalyst is greatly effective to degrade MO dye. The enhancement in photoelectrocatalytic activity is mainly due to the suppressing the recombination rate of photogenerated electron-hole pairs. The mineralization of MO dye in aqueous solution is studied by measuring chemical oxygen demand（COD） values.
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the National Natural Science Foundation of China(21421001,21573115,21875118)the Natural Science Foundation of Tianjin(17JCYBJC17100,19JCZDJC37700)。
文摘Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) and Zn-air batteries. Herein, a trifunctional electrocatalyst of urchin-like Al,P-codoped Co3O4 microspheres supported on Ni foam(denoted as AP-CONPs/NF) was fabricated via a hydrothermal process and subsequent low-temperature annealing and phosphorization, exhibiting enhanced OER, HER and ORR activities compared with single-doped and undoped samples. Their surface self-organized microstructure and excellent "superaerophobic" feature make a high bubble repellency, which boost diffusion of reactants and electrolyte-electrode intimate contact. The codoping of Al and P elements into Co3O4 betters right the balance among surface chemical state, the increased oxygen vacancies and the promoted charge transfer. Encouraged by these synergistic advantages, the AP-CONPs/NF was further employed as excellent bifunctional electrodes for the OWS(low cell voltage of 1.57 V at 10 mA cm-2) and as air cathode for rechargeable Zn-air batteries(high power density of 89.1 mW cm-2), which demonstrates a great feasibility for practical applications.
