Energy band structure and interfacial compatibility of heterojunctions are crucial for photocatalysts in promoting photogene rated charge separation and transfer.Here,a combined strategy of vacancy engineering and qua...Energy band structure and interfacial compatibility of heterojunctions are crucial for photocatalysts in promoting photogene rated charge separation and transfer.Here,a combined strategy of vacancy engineering and quantum effect via a facile phosphating process is reported,for the first time,to modulate the energy band structure and the interface of Zn_(x)Cd_(1-x)S/CoP quantum dots(ZCS_(v)/CoP QDs)heterojunction.The combined experimental and theoretical investigation revealed that phosphating process transformed CoO_(x) QDs to CoP QDs,and more importantly,generated considerable amount of sulfur vacancies in ZCS_(v).As a result,a TypeⅡZCS_(v)/CoP QDs heterojunction with compatible interfaces was constructed via in-situ generated P-Zn,P-Cd and S-Co bonds,which facilitated the separation and transfer of the photogenerated charge and thus resulted in a high ability towards hydrogen evolution under visible light(17.53 mmol g^(-1) h^(-1)).This work provides an effective and adaptable strategy to modulate band structure and interfacial compatibility of heterojunctions via vacancy engineering and quantum effect.展开更多
Several samples of manganese oxides La(1-x)2/3Ca1/3MnO3 (V-LCMO) and (La0.7-xY0.3)2/3Ca1/3MnO3 (x<0.15) (V-LYCMO) with vacancies at La-site (La-vacancy) were prepared by solid-state reaction method. The X-ray diffr...Several samples of manganese oxides La(1-x)2/3Ca1/3MnO3 (V-LCMO) and (La0.7-xY0.3)2/3Ca1/3MnO3 (x<0.15) (V-LYCMO) with vacancies at La-site (La-vacancy) were prepared by solid-state reaction method. The X-ray diffraction(XRD) patterns refined by Rietveld confirm that these compounds exhibit single phase structure with orthorhombic symmetry (Pnma). The lattice parameters, Mn—O bond length and Mn—O—Mn bond angle vary with La-vacancy concentration, as an indication of the occurrence of the local Jahn-Teller effect. The measurement result of V-LCMO compounds shows that the maximum magnetoresistance(MR) is about 220% at TIM=268 K and La-vacancy content x=0.04. For V-LYCMO compounds, there exists metal-insulator transition at about 50 K, and a very large MR (over 106%) is observed at the temperature ranging from 40 K to 50 K.展开更多
Samples of manganese oxides La（1-x）2/3Ca1/3MnO3（x 〈 0.10） with Lavacancy were prepared by standard solid-state reaction method. All the samples are single phase, with orthorhombic symmetry （Pnma ）, analyzed by ...Samples of manganese oxides La（1-x）2/3Ca1/3MnO3（x 〈 0.10） with Lavacancy were prepared by standard solid-state reaction method. All the samples are single phase, with orthorhombic symmetry （Pnma ）, analyzed by XRD and with Rietveld Refinement. The effect of different La-site vacancies concentration on electronic transport of La（1-x）2/3Ca1/3MnO3 was investigated. The insulator-metal transition temperature （about 267 K） nearly remains unchanged with the increase of vacancy concentration, which indicates that small La-vacancy does not destroy the double exchange interaction. But the electronic resistance increases and MR value decreases with La-vacancy content x 〉 0.04. The maximum of the MR value （8 T） is about 220% at transition temperature （TMI）.展开更多
Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2（WO3-xQDS/TiO2） were fabricated by solvoth...Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2（WO3-xQDS/TiO2） were fabricated by solvothermal and hydrogen-reduction methods.Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO3-x QDs could be tuned by modulating the addition of the W precursor.Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy（W^5＋/Vo） defects in WO3.These defects led to ohmic contact between WO3-x and TiO2,which altered the charge-transfer pathway from type Ⅱ heterojunction to Z-scheme,and maintained the highly reductive and oxidative ability of TiO2 and WO3-x,respectively.Therefore,the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO2 in hydrogen generation.These results suggest that the formation of W^5＋/Vo defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts.展开更多
基金financially supported by the Taishan Scholar Program of Shandong Province(ts201712046)the Key Research and Development Programme of Shandong Province(2019JZZY010905)+2 种基金the Natural Science Foundation of Shandong Province(ZR2020QB132)the Liaoning BaiQianWan Talents Programthe Royal Society and the Newton Fund(NAF\R1\191294)。
文摘Energy band structure and interfacial compatibility of heterojunctions are crucial for photocatalysts in promoting photogene rated charge separation and transfer.Here,a combined strategy of vacancy engineering and quantum effect via a facile phosphating process is reported,for the first time,to modulate the energy band structure and the interface of Zn_(x)Cd_(1-x)S/CoP quantum dots(ZCS_(v)/CoP QDs)heterojunction.The combined experimental and theoretical investigation revealed that phosphating process transformed CoO_(x) QDs to CoP QDs,and more importantly,generated considerable amount of sulfur vacancies in ZCS_(v).As a result,a TypeⅡZCS_(v)/CoP QDs heterojunction with compatible interfaces was constructed via in-situ generated P-Zn,P-Cd and S-Co bonds,which facilitated the separation and transfer of the photogenerated charge and thus resulted in a high ability towards hydrogen evolution under visible light(17.53 mmol g^(-1) h^(-1)).This work provides an effective and adaptable strategy to modulate band structure and interfacial compatibility of heterojunctions via vacancy engineering and quantum effect.
基金Project(0150014) supported by the Natural Science Foundation of Jiangxi Province, China
文摘Several samples of manganese oxides La(1-x)2/3Ca1/3MnO3 (V-LCMO) and (La0.7-xY0.3)2/3Ca1/3MnO3 (x<0.15) (V-LYCMO) with vacancies at La-site (La-vacancy) were prepared by solid-state reaction method. The X-ray diffraction(XRD) patterns refined by Rietveld confirm that these compounds exhibit single phase structure with orthorhombic symmetry (Pnma). The lattice parameters, Mn—O bond length and Mn—O—Mn bond angle vary with La-vacancy concentration, as an indication of the occurrence of the local Jahn-Teller effect. The measurement result of V-LCMO compounds shows that the maximum magnetoresistance(MR) is about 220% at TIM=268 K and La-vacancy content x=0.04. For V-LYCMO compounds, there exists metal-insulator transition at about 50 K, and a very large MR (over 106%) is observed at the temperature ranging from 40 K to 50 K.
文摘Samples of manganese oxides La（1-x）2/3Ca1/3MnO3（x 〈 0.10） with Lavacancy were prepared by standard solid-state reaction method. All the samples are single phase, with orthorhombic symmetry （Pnma ）, analyzed by XRD and with Rietveld Refinement. The effect of different La-site vacancies concentration on electronic transport of La（1-x）2/3Ca1/3MnO3 was investigated. The insulator-metal transition temperature （about 267 K） nearly remains unchanged with the increase of vacancy concentration, which indicates that small La-vacancy does not destroy the double exchange interaction. But the electronic resistance increases and MR value decreases with La-vacancy content x 〉 0.04. The maximum of the MR value （8 T） is about 220% at transition temperature （TMI）.
基金supported by the National Natural Science Foundation of China (21506156, 21676193)the Tianjin Municipal Natural Science Foundation (15JCZDJC37300, 16JCQNJC05200)~~
文摘Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2（WO3-xQDS/TiO2） were fabricated by solvothermal and hydrogen-reduction methods.Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO3-x QDs could be tuned by modulating the addition of the W precursor.Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy（W^5＋/Vo） defects in WO3.These defects led to ohmic contact between WO3-x and TiO2,which altered the charge-transfer pathway from type Ⅱ heterojunction to Z-scheme,and maintained the highly reductive and oxidative ability of TiO2 and WO3-x,respectively.Therefore,the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO2 in hydrogen generation.These results suggest that the formation of W^5＋/Vo defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts.
