The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a ...The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a novel dual-functional marigold-like Zn_(x)Cd_(1-x)S homojunction has been the production of lactic acid with high-yield and H_(2)with high-efficiency by selective glucose photoreforming.The optimized Zn_(0.3)Cd_(0.7)S exhibits outstanding H_(2)generation(13.64 mmol h^(-1)g^(-1)),glucose conversion(96.40%),and lactic acid yield(76.80%),over 272.80 and 19.21 times higher than that of bare ZnS(0.05 mmol h^(-1)g^(-1))and CdS(0.71 mmol h^(-1)g^(-1))in H_(2)generation,respectively.The marigold-like morphology provides abundant active sites and sufficient substrates accessibility for the photocatalyst,while the specific role of the homojunction formed by hexagonal wurtzite(WZ)and cubic zinc blende(ZB)in photoreforming biomass has been demonstrated by density functional theory(DFT)calculations.Glucose is converted to lactic acid on the WZ surface of Zn_(0.3)Cd_(0.7)S via the photoactive species·O_(2)^(-),while the H_(2)is evolved from protons(H^(+))in H_(2)O on the ZB surface of Zn_(0.3)Cd_(0.7)S.This work paves a promising road for the production of sustainable energy and products by integrating photocatalysis and biorefine.展开更多
Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunc...Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunction constructing strategy,Ni4Mo alloys were in-situ grown on the unsaturated coordinated sulfur atoms of sulfur vacancies-rich ZCS(Sv-ZCS)via interfacial Ni-S covalent bonds.The experimental and theoretical results reveal that these unsaturated sulfur atoms induced by sulfur vacancies vastly facilitate to anchor more Ni-Mo nanoparticles and form abundant Ni-S covalent bonds,meanwhile,these sulfur vacancies could form dual internal electric field(IEF)and work with Ni-S covalent bonds as“Electron Bridge”to further accelerate photoelectrons transfer,as well as promote the activation of water molecules and the desorption of hydrogen proton.Accordingly,the optimized Ni_(4)Mo/Sv-ZCS composite achieves an improved photocatalytic hydrogen evolution(PHE)rate of 94.69 mmol h^(-1)g^(-1)without an evident decrease after 6 cycles of photocatalytic tests,which is 21.2 and 1.94 times higher than those of Pt/ZCS and Ni_(4)Mo/ZCS,respectively.This tactic opens a new way for optimizing Zn_(x)Cd_(1-x)S-based heterojunctions by constructing sulfur vacancies and covalent bonds as“Electron Bridge”to enhance the activity of PHE.展开更多
While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,...While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.展开更多
Cu_(2)ZnSnS_(4)薄膜因其元素地壳含量丰富、无毒且具有优异的光电性能,受到研究者的广泛关注。本文基于纳米墨水法用Cd部分取代Zn制成了Cu_(2)(Cd x Zn_(1-x))SnS_(4)(CCZTS)薄膜,研究退火时间和后退火温度对薄膜及其太阳电池性能的影...Cu_(2)ZnSnS_(4)薄膜因其元素地壳含量丰富、无毒且具有优异的光电性能,受到研究者的广泛关注。本文基于纳米墨水法用Cd部分取代Zn制成了Cu_(2)(Cd x Zn_(1-x))SnS_(4)(CCZTS)薄膜,研究退火时间和后退火温度对薄膜及其太阳电池性能的影响。研究结果表明,所制备的薄膜为CCZTS相,无其他杂相,薄膜表面平整且致密,结晶性较好。随着退火时间增加,薄膜的晶粒尺寸有所增大,薄膜太阳电池的pn结质量得到提升,其性能也随之提高。通过对薄膜太阳电池进行后退火处理,分析了吸收层的元素扩散对电池性能的影响,在Cd元素形成梯度分布时,电池性能有所提高。随着后退火温度的增加,其电池性能和pn结质量呈现先提高后下降的趋势。经后退火300℃处理后,电池转换效率最佳,为3.13%。展开更多
Cd_(1-x)Zn_(x)S thin films were deposited by chemical bath deposition(CBD)on the glass substrate to study the influence of cadmium sulfate concentration on the structural characteristics of the thin film.The SEM resul...Cd_(1-x)Zn_(x)S thin films were deposited by chemical bath deposition(CBD)on the glass substrate to study the influence of cadmium sulfate concentration on the structural characteristics of the thin film.The SEM results show that the thin film surfaces under the cadmium sulfate concentration of 0.005 M exhibit better compactness and uniformity.The distribution diagrams of thin film elements illustrate the film growth rate changes on the trend of the increase,decrease,and increase with the increase of cadmium sulfate concentration.XRD studies exhibit the crystal structure of the film is the hexagonal phase,and there are obvious diffraction peaks and better crystallinity when the concentration is 0.005 M.Spectrophotometer test results demonstrate that the relationship between zinc content x and optical band gap value E_(g) can be expressed by the equation E_(g)(x)=0.59x^(2)+0.69x+2.43.Increasing the zinc content can increase the optical band gap,and the absorbance of the thin film can be improved by decreasing the cadmium sulfate concentration,however,all of them have good transmittance.At a concentration of 0.005 M,the thin film has good absorbance in the 300-800 nm range,80%transmittance,and band gap value of 3.24 eV,which is suitable for use as a buffer layer for solar cells.展开更多
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
目的探究Zn_(x)Ni_(1-x)S@DOX纳米结构在肿瘤光热-化学疗法联合治疗中的应用,为肿瘤治疗方法的研究提供新思路。方法通过透射电子显微镜等方法对Zn_(x)Ni_(1-x)S纳米结构进行表征测试;通过红外热成像仪探究光热性能;通过荧光光谱仪研究...目的探究Zn_(x)Ni_(1-x)S@DOX纳米结构在肿瘤光热-化学疗法联合治疗中的应用,为肿瘤治疗方法的研究提供新思路。方法通过透射电子显微镜等方法对Zn_(x)Ni_(1-x)S纳米结构进行表征测试;通过红外热成像仪探究光热性能;通过荧光光谱仪研究了不同温度和不同pH条件下Zn_(x)Ni_(1-x)S@DOX纳米结构的药物释放情况;通过MTT实验探究Zn_(x)Ni_(1-x)S纳米结构的生物安全性及Zn_(x)Ni_(1-x)S@DOX纳米结构的体外抗肿瘤性能。结果所制备的Zn_(x)Ni_(1-x)S纳米结构分散性良好且尺寸均一;光热性能测试结果显示Zn x Ni 1-x S纳米结构具有良好的光热升温效果;Zn_(x)Ni_(1-x)S@DOX纳米结构的药物释放行为具有温度和pH响应性;细胞实验表明,Zn_(x)Ni_(1-x)S纳米结构对正常细胞无明显毒性,在近红外光照射下,Zn_(x)Ni_(1-x)S@DOX纳米结构能够显著地抑制肿瘤细胞的生长。结论Zn_(x)Ni_(1-x)S纳米结构是一种生物相容性良好的纳米材料,在此基础上构建的Zn_(x)Ni_(1-x)S@DOX纳米结构具有良好的抗肿瘤性能,能够用于肿瘤的光热-化学疗法联合治疗研究。展开更多
Zn_(1-x)Mg_(x)O alloy films are important deep ultraviolet photoelectric materials.In this work,we used plasma-assisted molecular beam epitaxy to prepare Zn_(1-x)Mg_(x)O films with different magnesium contents on pola...Zn_(1-x)Mg_(x)O alloy films are important deep ultraviolet photoelectric materials.In this work,we used plasma-assisted molecular beam epitaxy to prepare Zn_(1-x)Mg_(x)O films with different magnesium contents on polar(0001)and nonpolar(1010)ZnO substrates.The nanoscale structural features of the grown alloy films as well as the interfaces were investigated.It was observed that the cubic phases of the alloy films emerged when the Mg content reached 20%and 37%for the alloy films grown on the(0001)and(1010)ZnO substrates,respectively.High-resolution transmission electron microscopy images revealed cubic phases without visible hexagonal phases for the alloy films with more than 70%magnesium,and the cubic phases exhibited three-fold and two-fold rotations for the alloy films on the polar(0001)and nonpolar(1010)ZnO substrates,respectively.This work aims to provide references for monitoring the Zn_(1-x)Mg_(x)O film structure with respect to different substrate orientations.展开更多
Roman scattering measurement of （ 1 - x ） GeS2-x Ga2S3 system glasses was conducted in order to understand the microstructural change caused by the addition of Ga2S3 . According to the change of Raman spectra with t...Roman scattering measurement of （ 1 - x ） GeS2-x Ga2S3 system glasses was conducted in order to understand the microstructural change caused by the addition of Ga2S3 . According to the change of Raman spectra with the addition of Ga2S3, two main structural transformations were deduced ： the gradual enhancement of ethane- like structural units S3 Ge- GeS3 （ 250 cm ^- 1） and S3 Ga- GaS3 （270 cm ^- 1 ） and the appearance of charge imbalanced units [ Ga2 S2 （ S1/2 ）4 ]^2- and [Ga（ S1/2 ）4 ]^- . And this change of structural aspect seems to give as a clue to understanding the cause of the increased rare-earth solubility.展开更多
基金supported by the National Natural Science Foundation of China(No.32071713)the Outstanding Youth Foundation Project of Heilongjiang Province of China(JQ2019C001)。
文摘The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a novel dual-functional marigold-like Zn_(x)Cd_(1-x)S homojunction has been the production of lactic acid with high-yield and H_(2)with high-efficiency by selective glucose photoreforming.The optimized Zn_(0.3)Cd_(0.7)S exhibits outstanding H_(2)generation(13.64 mmol h^(-1)g^(-1)),glucose conversion(96.40%),and lactic acid yield(76.80%),over 272.80 and 19.21 times higher than that of bare ZnS(0.05 mmol h^(-1)g^(-1))and CdS(0.71 mmol h^(-1)g^(-1))in H_(2)generation,respectively.The marigold-like morphology provides abundant active sites and sufficient substrates accessibility for the photocatalyst,while the specific role of the homojunction formed by hexagonal wurtzite(WZ)and cubic zinc blende(ZB)in photoreforming biomass has been demonstrated by density functional theory(DFT)calculations.Glucose is converted to lactic acid on the WZ surface of Zn_(0.3)Cd_(0.7)S via the photoactive species·O_(2)^(-),while the H_(2)is evolved from protons(H^(+))in H_(2)O on the ZB surface of Zn_(0.3)Cd_(0.7)S.This work paves a promising road for the production of sustainable energy and products by integrating photocatalysis and biorefine.
基金supported by the National Natural Science Foundation of China under Grant(51871078 and 52071119)the Fundamental Research Funds for the Central Universities(HIT.OCEF.2021025)Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(ES202211)。
文摘Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunction constructing strategy,Ni4Mo alloys were in-situ grown on the unsaturated coordinated sulfur atoms of sulfur vacancies-rich ZCS(Sv-ZCS)via interfacial Ni-S covalent bonds.The experimental and theoretical results reveal that these unsaturated sulfur atoms induced by sulfur vacancies vastly facilitate to anchor more Ni-Mo nanoparticles and form abundant Ni-S covalent bonds,meanwhile,these sulfur vacancies could form dual internal electric field(IEF)and work with Ni-S covalent bonds as“Electron Bridge”to further accelerate photoelectrons transfer,as well as promote the activation of water molecules and the desorption of hydrogen proton.Accordingly,the optimized Ni_(4)Mo/Sv-ZCS composite achieves an improved photocatalytic hydrogen evolution(PHE)rate of 94.69 mmol h^(-1)g^(-1)without an evident decrease after 6 cycles of photocatalytic tests,which is 21.2 and 1.94 times higher than those of Pt/ZCS and Ni_(4)Mo/ZCS,respectively.This tactic opens a new way for optimizing Zn_(x)Cd_(1-x)S-based heterojunctions by constructing sulfur vacancies and covalent bonds as“Electron Bridge”to enhance the activity of PHE.
基金financially supported by the Natural Science Foundation of Jiangsu Province of China(BK20211172)the Jiangsu Provincial Department of Science and Technology Innovation Support Program(BK20222004,BZ2022036)+1 种基金the National Natural Science Foundation of China(52002366,22075263)the Fundamental Research Funds for the Central Universities(WK2060000039)。
文摘While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.
文摘Cu_(2)ZnSnS_(4)薄膜因其元素地壳含量丰富、无毒且具有优异的光电性能,受到研究者的广泛关注。本文基于纳米墨水法用Cd部分取代Zn制成了Cu_(2)(Cd x Zn_(1-x))SnS_(4)(CCZTS)薄膜,研究退火时间和后退火温度对薄膜及其太阳电池性能的影响。研究结果表明,所制备的薄膜为CCZTS相,无其他杂相,薄膜表面平整且致密,结晶性较好。随着退火时间增加,薄膜的晶粒尺寸有所增大,薄膜太阳电池的pn结质量得到提升,其性能也随之提高。通过对薄膜太阳电池进行后退火处理,分析了吸收层的元素扩散对电池性能的影响,在Cd元素形成梯度分布时,电池性能有所提高。随着后退火温度的增加,其电池性能和pn结质量呈现先提高后下降的趋势。经后退火300℃处理后,电池转换效率最佳,为3.13%。
基金This work was supported by the Tianjin Municipal Education Commission,Horizontal subject(grant number 70304901).
文摘Cd_(1-x)Zn_(x)S thin films were deposited by chemical bath deposition(CBD)on the glass substrate to study the influence of cadmium sulfate concentration on the structural characteristics of the thin film.The SEM results show that the thin film surfaces under the cadmium sulfate concentration of 0.005 M exhibit better compactness and uniformity.The distribution diagrams of thin film elements illustrate the film growth rate changes on the trend of the increase,decrease,and increase with the increase of cadmium sulfate concentration.XRD studies exhibit the crystal structure of the film is the hexagonal phase,and there are obvious diffraction peaks and better crystallinity when the concentration is 0.005 M.Spectrophotometer test results demonstrate that the relationship between zinc content x and optical band gap value E_(g) can be expressed by the equation E_(g)(x)=0.59x^(2)+0.69x+2.43.Increasing the zinc content can increase the optical band gap,and the absorbance of the thin film can be improved by decreasing the cadmium sulfate concentration,however,all of them have good transmittance.At a concentration of 0.005 M,the thin film has good absorbance in the 300-800 nm range,80%transmittance,and band gap value of 3.24 eV,which is suitable for use as a buffer layer for solar cells.
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.
文摘目的探究Zn_(x)Ni_(1-x)S@DOX纳米结构在肿瘤光热-化学疗法联合治疗中的应用,为肿瘤治疗方法的研究提供新思路。方法通过透射电子显微镜等方法对Zn_(x)Ni_(1-x)S纳米结构进行表征测试;通过红外热成像仪探究光热性能;通过荧光光谱仪研究了不同温度和不同pH条件下Zn_(x)Ni_(1-x)S@DOX纳米结构的药物释放情况;通过MTT实验探究Zn_(x)Ni_(1-x)S纳米结构的生物安全性及Zn_(x)Ni_(1-x)S@DOX纳米结构的体外抗肿瘤性能。结果所制备的Zn_(x)Ni_(1-x)S纳米结构分散性良好且尺寸均一;光热性能测试结果显示Zn x Ni 1-x S纳米结构具有良好的光热升温效果;Zn_(x)Ni_(1-x)S@DOX纳米结构的药物释放行为具有温度和pH响应性;细胞实验表明,Zn_(x)Ni_(1-x)S纳米结构对正常细胞无明显毒性,在近红外光照射下,Zn_(x)Ni_(1-x)S@DOX纳米结构能够显著地抑制肿瘤细胞的生长。结论Zn_(x)Ni_(1-x)S纳米结构是一种生物相容性良好的纳米材料,在此基础上构建的Zn_(x)Ni_(1-x)S@DOX纳米结构具有良好的抗肿瘤性能,能够用于肿瘤的光热-化学疗法联合治疗研究。
基金Project supported by the National Natural Science Foundation of China(Grant No.11804050).
文摘Zn_(1-x)Mg_(x)O alloy films are important deep ultraviolet photoelectric materials.In this work,we used plasma-assisted molecular beam epitaxy to prepare Zn_(1-x)Mg_(x)O films with different magnesium contents on polar(0001)and nonpolar(1010)ZnO substrates.The nanoscale structural features of the grown alloy films as well as the interfaces were investigated.It was observed that the cubic phases of the alloy films emerged when the Mg content reached 20%and 37%for the alloy films grown on the(0001)and(1010)ZnO substrates,respectively.High-resolution transmission electron microscopy images revealed cubic phases without visible hexagonal phases for the alloy films with more than 70%magnesium,and the cubic phases exhibited three-fold and two-fold rotations for the alloy films on the polar(0001)and nonpolar(1010)ZnO substrates,respectively.This work aims to provide references for monitoring the Zn_(1-x)Mg_(x)O film structure with respect to different substrate orientations.
文摘Roman scattering measurement of （ 1 - x ） GeS2-x Ga2S3 system glasses was conducted in order to understand the microstructural change caused by the addition of Ga2S3 . According to the change of Raman spectra with the addition of Ga2S3, two main structural transformations were deduced ： the gradual enhancement of ethane- like structural units S3 Ge- GeS3 （ 250 cm ^- 1） and S3 Ga- GaS3 （270 cm ^- 1 ） and the appearance of charge imbalanced units [ Ga2 S2 （ S1/2 ）4 ]^2- and [Ga（ S1/2 ）4 ]^- . And this change of structural aspect seems to give as a clue to understanding the cause of the increased rare-earth solubility.
