Perovskite-like oxide La2-xSrxCuO4 （x = 0, 1） single crystallites with microrod-like morphologies and tetragonal crystal structures were prepared hydrothermally at 240 ℃ with poly（ethylene glycol） （PEG） or hexa...Perovskite-like oxide La2-xSrxCuO4 （x = 0, 1） single crystallites with microrod-like morphologies and tetragonal crystal structures were prepared hydrothermally at 240 ℃ with poly（ethylene glycol） （PEG） or hexadecyltrimethyl ammonium bromide （CTAB） as a surfactant and after calcination at 850 ℃. The physicochemical properties of the materials were characterized by means of XRD, BET, SEM, TEM/SAED （selected-area electron diffraction）, XPS and H2-TPR techniques. It is found that doping Sr2＋ to La2CuO4 lattice enhanced the catalytic activity for methane combustion and the LaSrCuO4 catalyst derived from PEG is the best among the tested ones. It is concluded that factors, such as adsorbed oxygen species concentration, reducibility and surface area, determined the catalytic performance of such single-crystalline materials.展开更多
Since 1986,the donor-acceptor (D:A) heterojunction has been regarded a necessity for high-efficiency organic photovoltaics (OPVs),due to its unique advantage in compensating the intrinsic limitations of organic semico...Since 1986,the donor-acceptor (D:A) heterojunction has been regarded a necessity for high-efficiency organic photovoltaics (OPVs),due to its unique advantage in compensating the intrinsic limitations of organic semiconductors,such as high exciton binding energy and poor ambipolar charge mobility. While this adversely causes tremendous non-radiative charge recombination and instability issues,which currently become the most critical limits for commercialization of OPVs. Here,we present a concept-to-proof study on the potential of D:A heterojunction free OPV by taking advantage of recent progress of non-fullerene acceptors. First,we demonstrate that the “free carriers” can be spontaneously generated upon illumination in an NFA,i.e.,the 6TIC-4F single layer. Second,the 6TIC-4F layer also exhibits good ambipolar charge transporting property. These exceptional characteristics distinguish it from the traditional organic semiconductors,and relieve it from the reliance of D:A heterojunction to independently work as active layer. As a result,the subsequent OPV by simply sandwiching the 6TIC-4F layer between the cathode and anode yields a considerably high power conversion efficiency ~1%. Moreover,we find the D:A heterojunction free device exhibits two order of magnitude higher electroluminescence quantum efficiency and significantly reduced VOC loss by 0.16 eV compared to those of the D:A BHJ structure,validating its promise for higher efficiency in the future. Therefore,our work demonstrates the possibility of using D:A heterojunction-free device structure for high performance,that can potentially become the next game changer of OPV.展开更多
A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ （x： 0–0.4） with oxygen excess were prepared using ultrasound-assisted citric ac...A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ （x： 0–0.4） with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption （NO-TPD）. The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1？x Co x O 4-δ ones possessed excessive oxygen （i.e., over-stoichiometric oxygen）; with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 〉 NdSrCu 0.8 Co 0.2 O 3.736 〉 NdSrCu 0.6 Co 0.4 O 3.789 〉 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 〉 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 〉 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3＋ /Cu 2＋ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.展开更多
Both bismuth and copper are non-toxic and earth-abundant elements suitable for lead-free halide perovskite-like photovoltaic devices. Here, we report a highly facile route for in-situ producing copper-bismuth-iodide(C...Both bismuth and copper are non-toxic and earth-abundant elements suitable for lead-free halide perovskite-like photovoltaic devices. Here, we report a highly facile route for in-situ producing copper-bismuth-iodide(CuBiI4) thin films directly on ITO substrate at room temperature, by utilizing a Bi-Cu alloy layer as precursor. X-ray diffraction and transmission electron microscopy(TEM) results verified the formation of well crystallized CuBiI4 thin films with [222] orientation. The transient photovoltage(TPV) analysis revealed that the CuBiI4 is an n-type semiconductor with a suitable band gap of ~1.81 eV, preferable to photoelectric conversion compared with CH3NH3PbI3. It is very interesting that the subsequent spin-coating process of the classical Spiro-MeOTAD organic solution with TBP and acetonitrile resulted in a dense and smooth CuBiI4:SpiroMeOTAD bulk-heterojunction film. The preliminarily fabricated simple sandwich structures of ITO/CuBiI4:Spiro-MeOTAD/Au hybrid solar cell devices displayed efficient photovoltaic performance with the PCE up to 1.119% of the best sample. The room temperature direct metal surface elemental reaction(DMSER) method may provide a new insight for all-inorganic lead free perovskite-like AaBbXx compounds and high performance photovoltaic devices.展开更多
The experimental and calculated data on the existence of complex oxides in solid state with the octahedral structures of four families,namely perovskites,Bi-containing layered perovskite-like ones,tetragonal tungsten ...The experimental and calculated data on the existence of complex oxides in solid state with the octahedral structures of four families,namely perovskites,Bi-containing layered perovskite-like ones,tetragonal tungsten bronzes and pyrochlores,and about their phase transitions are systematized and summarized on the basis of the quasi-elastic or geometric models of these structures.It has been established that similar existence areas and similar correlations between the interatomic bond strains in their structures,on the one hand,and the temperatures of their ferroelectric or antiferroelectric phase transitions,on the other hand,are observed for all of them,despite the differences in the compositions and structures of these oxides,but taking into account their similar parameters.展开更多
Nanosized La2-xKxNiMnO6 catalysts with ABO3 type perovskite-like structure were prepared by auto-combustion method using citric acid as a ligand to control particle size and morphology.The structures and properties of...Nanosized La2-xKxNiMnO6 catalysts with ABO3 type perovskite-like structure were prepared by auto-combustion method using citric acid as a ligand to control particle size and morphology.The structures and properties of these perovskite-like oxides were investigated by X-ray powder diffraction（XRD）and temperature-programmed reduction（TPR）.The catalytic activities for soot combustion were evaluated by temperature- programmed oxidation（TPO）with pure O2 and O2/NOx as oxidant,respectively.In the La2-xKxNiMnO6 catalysts,the partial substitution of K at A-site leads to an increase of the concentrations of high valence cation and oxygen vacancy,which enhance the catalytic activity for soot combustion.The optimal substitution amount of K was equal to x=0.4 among these samples.Tp（peak temperature）in O2-TPO profile was 420-C and Tp in O2/NOx-TPO profile was 370-C over La1.6K0.4NiMnO6 catalyst for soot particulates combustion under loose contact conditions between catalyst and soot.展开更多
A series of oxides(La_(2-x)Ce_xCoO_(4±y)) with perovskite-like structure were prepared by the Pechini sol–gel method for dry reforming of methane reaction(DRM). The prepared catalysts were characterized by BET, ...A series of oxides(La_(2-x)Ce_xCoO_(4±y)) with perovskite-like structure were prepared by the Pechini sol–gel method for dry reforming of methane reaction(DRM). The prepared catalysts were characterized by BET, XRD,TGA, H_2-TPR and SEM. Experimental results indicate that the addition of Ce can impact both sample morphology and catalytic performance significantly compared with La_2CoO_4 catalyst, and LaCeCoO_4 presented the highest catalytic ability among all the samples. The Ce addition tends to increase the specific surface area of La_(2-x)Ce_xCoO_(4±y)from 0.2 to 8.5 m^2·g^(-1), suggesting that LaCeCoO_4 catalyst contained more well-dispersed active sites and more space to reaction. Moreover, the catalytic performance and anti-coking ability were substantially improved after Ce addition during DRM, which may be attributed to the decrease of LaCoO_3 particle size and growth of oxygen storage capacity, respectively.展开更多
基金supported by the National Natural Science Foundation of China (No. 20973017 and 21077007)the Creative Research Foundation of Beijing University Technology (No. 00500054R4003)the Creative Research Team of Beijing Municipality (No. PHR201007105)
文摘Perovskite-like oxide La2-xSrxCuO4 （x = 0, 1） single crystallites with microrod-like morphologies and tetragonal crystal structures were prepared hydrothermally at 240 ℃ with poly（ethylene glycol） （PEG） or hexadecyltrimethyl ammonium bromide （CTAB） as a surfactant and after calcination at 850 ℃. The physicochemical properties of the materials were characterized by means of XRD, BET, SEM, TEM/SAED （selected-area electron diffraction）, XPS and H2-TPR techniques. It is found that doping Sr2＋ to La2CuO4 lattice enhanced the catalytic activity for methane combustion and the LaSrCuO4 catalyst derived from PEG is the best among the tested ones. It is concluded that factors, such as adsorbed oxygen species concentration, reducibility and surface area, determined the catalytic performance of such single-crystalline materials.
基金supported by the National Key Research and Development Program of China(No.2022YFB4200600)the National Natural Science Foundation of China(Nos.52173185 and 52127806)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.226-2022-00133 and 226-2022-00209)L.Z.thanks the research start-up fund from Zhejiang University.
文摘Since 1986,the donor-acceptor (D:A) heterojunction has been regarded a necessity for high-efficiency organic photovoltaics (OPVs),due to its unique advantage in compensating the intrinsic limitations of organic semiconductors,such as high exciton binding energy and poor ambipolar charge mobility. While this adversely causes tremendous non-radiative charge recombination and instability issues,which currently become the most critical limits for commercialization of OPVs. Here,we present a concept-to-proof study on the potential of D:A heterojunction free OPV by taking advantage of recent progress of non-fullerene acceptors. First,we demonstrate that the “free carriers” can be spontaneously generated upon illumination in an NFA,i.e.,the 6TIC-4F single layer. Second,the 6TIC-4F layer also exhibits good ambipolar charge transporting property. These exceptional characteristics distinguish it from the traditional organic semiconductors,and relieve it from the reliance of D:A heterojunction to independently work as active layer. As a result,the subsequent OPV by simply sandwiching the 6TIC-4F layer between the cathode and anode yields a considerably high power conversion efficiency ~1%. Moreover,we find the D:A heterojunction free device exhibits two order of magnitude higher electroluminescence quantum efficiency and significantly reduced VOC loss by 0.16 eV compared to those of the D:A BHJ structure,validating its promise for higher efficiency in the future. Therefore,our work demonstrates the possibility of using D:A heterojunction-free device structure for high performance,that can potentially become the next game changer of OPV.
基金Supported by the National Natural Science Foundation of China(2027101920876034)the Science and Technology Foundation of Office of Education of Heilongjiang Province(11531z11)
基金supported by the Natural Science Foundation of Beijing Municipality Key Class B Project (No.KZ200610005004)the Beijing Municipal Commission of Education (No. PHR200907105)the Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(PHR (IHLB))
文摘A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ （x： 0–0.4） with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption （NO-TPD）. The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1？x Co x O 4-δ ones possessed excessive oxygen （i.e., over-stoichiometric oxygen）; with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 〉 NdSrCu 0.8 Co 0.2 O 3.736 〉 NdSrCu 0.6 Co 0.4 O 3.789 〉 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 〉 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 〉 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3＋ /Cu 2＋ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.
基金supported by the National Natural Science Foundation of China (21673200, 61504117 and U1604121)the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (144200510014)
文摘Both bismuth and copper are non-toxic and earth-abundant elements suitable for lead-free halide perovskite-like photovoltaic devices. Here, we report a highly facile route for in-situ producing copper-bismuth-iodide(CuBiI4) thin films directly on ITO substrate at room temperature, by utilizing a Bi-Cu alloy layer as precursor. X-ray diffraction and transmission electron microscopy(TEM) results verified the formation of well crystallized CuBiI4 thin films with [222] orientation. The transient photovoltage(TPV) analysis revealed that the CuBiI4 is an n-type semiconductor with a suitable band gap of ~1.81 eV, preferable to photoelectric conversion compared with CH3NH3PbI3. It is very interesting that the subsequent spin-coating process of the classical Spiro-MeOTAD organic solution with TBP and acetonitrile resulted in a dense and smooth CuBiI4:SpiroMeOTAD bulk-heterojunction film. The preliminarily fabricated simple sandwich structures of ITO/CuBiI4:Spiro-MeOTAD/Au hybrid solar cell devices displayed efficient photovoltaic performance with the PCE up to 1.119% of the best sample. The room temperature direct metal surface elemental reaction(DMSER) method may provide a new insight for all-inorganic lead free perovskite-like AaBbXx compounds and high performance photovoltaic devices.
基金Research was financially supported by the Ministry of Science and Higher Education of the Russian Federation(State assignment in the field of scientific activity,Southern Federal University,2020).
文摘The experimental and calculated data on the existence of complex oxides in solid state with the octahedral structures of four families,namely perovskites,Bi-containing layered perovskite-like ones,tetragonal tungsten bronzes and pyrochlores,and about their phase transitions are systematized and summarized on the basis of the quasi-elastic or geometric models of these structures.It has been established that similar existence areas and similar correlations between the interatomic bond strains in their structures,on the one hand,and the temperatures of their ferroelectric or antiferroelectric phase transitions,on the other hand,are observed for all of them,despite the differences in the compositions and structures of these oxides,but taking into account their similar parameters.
基金supported by the National Natural Science Foundation of China(No.20603016)the Liaoning Provincial Science&Technology Project of China(No.20071074)
文摘Nanosized La2-xKxNiMnO6 catalysts with ABO3 type perovskite-like structure were prepared by auto-combustion method using citric acid as a ligand to control particle size and morphology.The structures and properties of these perovskite-like oxides were investigated by X-ray powder diffraction（XRD）and temperature-programmed reduction（TPR）.The catalytic activities for soot combustion were evaluated by temperature- programmed oxidation（TPO）with pure O2 and O2/NOx as oxidant,respectively.In the La2-xKxNiMnO6 catalysts,the partial substitution of K at A-site leads to an increase of the concentrations of high valence cation and oxygen vacancy,which enhance the catalytic activity for soot combustion.The optimal substitution amount of K was equal to x=0.4 among these samples.Tp（peak temperature）in O2-TPO profile was 420-C and Tp in O2/NOx-TPO profile was 370-C over La1.6K0.4NiMnO6 catalyst for soot particulates combustion under loose contact conditions between catalyst and soot.
基金supported by the National Natural Science Foundation of China (52192610 and 62274127)the National Key Research and Development Program of China (2021YFA0715600, 2021YFA0717700 and 2018YFB2202900)+1 种基金Wuhu and Xidian University Special Fund for Industry-University Research Cooperationthe Fundamental Research Funds for the Central Universities。
文摘低维非铅金属卤化物材料因其优异的光电特性在可见光盲紫外探测领域具有很大的潜力.本文通过吡啶添加剂辅助一步溶液法成功制备了高质量类钙钛矿CsAg_(2)I_(3)薄膜,该薄膜展示出p型及202 meV低激子结合能(Eb).其Eb甚至和2D铅卤钙钛矿相当,有利于光生载流子分离.此外,探索了基于type-Ⅱ型n-p异质结SnO_(2)/CsAg_(2)I_(3)的自驱动紫外探测器,其中4.13 eV宽带隙、0.214 eV低Urbach能量的SnO_(2)的引入抑制了持续光电导效应.所制备的探测器件具有高灵敏特性及在可见光盲紫外探测器中超快的响应时间(47/74μs),大致快于当前CsAg_(2)I_(3)探测器数值的两个数量级.其响应度和探测率分别高达0.032 A W^(-1)和1.2×10^(11)Jones.此外,异质结>90%高可见光透光性展现出优越的可见光盲特性.这种优异的器件性能、可溶液法制备及长期稳定性为未来可见光盲、自驱动、稳定、环保的商用紫外探测器的制备提供了新思路.
基金Supported by the National Natural Science Foundation of China(21276209)the Natural Science Foundation of Shaanxi Province(2017JM2033)the Local Service Fund of Education Department of Shaanxi Province(18JF031)
文摘A series of oxides(La_(2-x)Ce_xCoO_(4±y)) with perovskite-like structure were prepared by the Pechini sol–gel method for dry reforming of methane reaction(DRM). The prepared catalysts were characterized by BET, XRD,TGA, H_2-TPR and SEM. Experimental results indicate that the addition of Ce can impact both sample morphology and catalytic performance significantly compared with La_2CoO_4 catalyst, and LaCeCoO_4 presented the highest catalytic ability among all the samples. The Ce addition tends to increase the specific surface area of La_(2-x)Ce_xCoO_(4±y)from 0.2 to 8.5 m^2·g^(-1), suggesting that LaCeCoO_4 catalyst contained more well-dispersed active sites and more space to reaction. Moreover, the catalytic performance and anti-coking ability were substantially improved after Ce addition during DRM, which may be attributed to the decrease of LaCoO_3 particle size and growth of oxygen storage capacity, respectively.
