In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)an...In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.展开更多
Cation exchange(CE)has been emerged as a promising post-synthesis strategy of colloidal nanocrystals.However,it is unclear how the cation precursor affects the CE process and the final colloidal nanocrystals.Herein,we...Cation exchange(CE)has been emerged as a promising post-synthesis strategy of colloidal nanocrystals.However,it is unclear how the cation precursor affects the CE process and the final colloidal nanocrystals.Herein,we utilized two Zn-B Lewis acidbase adduct complexes(B=oleylamine(OAM)and methanol(MeOH))as Zn precursors for CE with Ag_(2)S quantum dots(QDs).Our study revealed that the steric hindrance and complexing capabilities of Zn precursor significantly affect the CE kinetics.As a result,the Zn-doped Ag_(2)S(Zn:Ag_(2)S)and Ag_(2)S@ZnS core–shell QDs were successfully obtained with enormous enhancement of their photoluminescence(PL)intensities.Theoretical simulation showed that the Zn-OAM with higher desolvation energy and spatial hindrance tended to form doped Zn:Ag_(2)S QDs due to the inefficient cation exchange.Whereas the Zn-MeOH with lower exchange barrier promoted the conversion of Ag-S to Zn-S,thus forming Ag_(2)S@ZnS core–shell QDs.We anticipate that this finding will enrich the regulatory approaches of post-synthesis of colloidal nanocrystals with desirable properties.展开更多
Although many plasmonic nanosenosrs have been established for the detection of mercury(Ⅱ)(Hg^(2+)),few of them is feasible for analyzing natural samples with very complex matrices because of insufficient method selec...Although many plasmonic nanosenosrs have been established for the detection of mercury(Ⅱ)(Hg^(2+)),few of them is feasible for analyzing natural samples with very complex matrices because of insufficient method selectivity.To address this challenge,we propose an epitaxial and lattice-mismatch approach to the synthesis of a unique Au/Ag_(2)S dimeric nanostructure,which consists of an Au segment with excellent plasmonic characteristics,and a highly stable Ag_(2)S portion with minimum solubility product (K_(sp)(Ag_(2)S)=6.3×10^(-50)).The detection relies on the chemical conversion of Ag_(2)S to HgS when reacting with Hg^(2+),resulting in a red shift in the absorption band of the connecting Au NPs.The concurrent color changes of the solution from gray purple to dark green and finally to navy correlate well with Hg^(2+)concentration,thus enables UV-vis quantitation and a naked-eye readout of the Hg^(2+)concentration.This method exhibits superior selectivity towards Hg^(2+) over other interfering ions tested because Hg^(2+) is the only ion that can react with Ag_(2)S to form HgS with even smaller solubility product (K_(sp)(HgS)=4×10^(-53)).The detection limit of this method is 1.21μmol/L,calculated by the signal-to-noise of 3.The practicability of the method was verified by analyzing the Hg^(2+)in sewage water samples without sample pretreatment with satisfactory recoveries (93.1%-102.8%) and relative standard deviations (1.38%-2.89%).We believe this method holds great potential for on-the-spot detection of Hg^(2+) in environmental water samples with complex matrices.展开更多
The production of renewable fossil fuels such as CH_(4) and CO by photocatalytic CO_(2)reduction has attracted more and more attention.However,single photocatalyst is less efficient for photocatalytic reduction of CO_...The production of renewable fossil fuels such as CH_(4) and CO by photocatalytic CO_(2)reduction has attracted more and more attention.However,single photocatalyst is less efficient for photocatalytic reduction of CO_(2)due to the fast recombination of photogenerated electron pairs.Herein,we successfully prepare CdS-Ag_(2)S composite by assembling the Ag_(2)S QDs cocatalyst on the surface of CdS nanosheet-assembled flower through oil-bath solvothermal method.This composite is prepared through a simple self-assembly strategy using cadmium chloride,ammonia and thiourea as precursors of the CdS nanosheet-assembled flower and silver nitrate and 3-mercaptopropionic acid as the precursors of Ag_(2)S QDs.The average diameter of Ag_(2)S QDs is apparently 6.0 nm.The light absorption edge of the composite is at around 560 nm,with the corresponding band gap at 2.14 eV.The CdS-Ag_(2)S QDs composite with 5 wt%Ag_(2)S QDs loaded achieves CO evolution rate of 16.6μmol·g^(-1)·h^(-1)without noble-metal cocatalysts.This strengthened photocatalytic performance and photocatalytic stability were attributed to the energy band broadening of Ag_(2)S QDs caused by quantum size effect and the large specific surface area due to the assembled flower.The mechanism underlying the enhanced photocatalytic CO_(2)reduction activity is further proposed.This study demonstrates that semiconductor-based quantum dots are strong candidates for excellent cocatalysts in photocatalysis.展开更多
The development of nanotechnology has accelerated the use of silver nanoparticles(AgNPs)in household chemicals and the accumulation of Ag in sewage treatment systems.The application of sewage sludge products to soils ...The development of nanotechnology has accelerated the use of silver nanoparticles(AgNPs)in household chemicals and the accumulation of Ag in sewage treatment systems.The application of sewage sludge products to soils raises concerns over the safety of Ag in the function and biogeochemical cycles of the soil belowground ecosystem.Here,we assess the potential risk of the accumulation and transfer of Ag under AgNPs exposure and its effects on the trophic transfer of nitrogen(N)through a soil animal food chain(Folsomia candida–Hypoaspis aculeifer).The formation of stable silver sulfide(Ag_(2)S)was also studied via a single species test using F.candida.Concentrations of Ag in F.candida increased with increasing AgNPs concentration,as did those in the predator H.aculeifer,but the Ag bioaccumulation factors of both animals were<1.Folsomia candida body tissue 15 N abundance declined markedly compared with that of H.aculeifer.Silver sulfide did have adverse effects on the survival and reproduction of F.candida.The Ag concentrations of F.candida increased with increasing Ag_(2)S concentration in sludge-treated soils.Silver sulfide showed ecotoxicity to the collembolan,therefore ecotoxicity resulting from the transformation and fate of AgNPs in soils needs to be considered before biosolid products are applied to agricultural soils.展开更多
基金financially supported by National Natural Science Foundation of China (Grant No. 22172144)Nature Science Foundation of Zhejiang Province (Grant No. LY20B030004)。
文摘In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.
基金the National Key Research and Development Program of China(No.2021YFF0701804)the financial support from the National Natural Science Foundation of China(Nos.21934007,22001262,22177128,and 22271308)+1 种基金the Science and Technology Project of Suzhou(No.SZS201904)the Natural Science Foundation of Jiangsu Province(Nos.BK20222016,BK20200254,and BK20221262).
文摘Cation exchange(CE)has been emerged as a promising post-synthesis strategy of colloidal nanocrystals.However,it is unclear how the cation precursor affects the CE process and the final colloidal nanocrystals.Herein,we utilized two Zn-B Lewis acidbase adduct complexes(B=oleylamine(OAM)and methanol(MeOH))as Zn precursors for CE with Ag_(2)S quantum dots(QDs).Our study revealed that the steric hindrance and complexing capabilities of Zn precursor significantly affect the CE kinetics.As a result,the Zn-doped Ag_(2)S(Zn:Ag_(2)S)and Ag_(2)S@ZnS core–shell QDs were successfully obtained with enormous enhancement of their photoluminescence(PL)intensities.Theoretical simulation showed that the Zn-OAM with higher desolvation energy and spatial hindrance tended to form doped Zn:Ag_(2)S QDs due to the inefficient cation exchange.Whereas the Zn-MeOH with lower exchange barrier promoted the conversion of Ag-S to Zn-S,thus forming Ag_(2)S@ZnS core–shell QDs.We anticipate that this finding will enrich the regulatory approaches of post-synthesis of colloidal nanocrystals with desirable properties.
基金supported by the National Natural Science Foundation of China(No.21876206)the Key Fundamental Project of Shandong Natural Science Foundation(No.ZR2020ZD13)+1 种基金the Science and Technology Projects of Qingdao(No.21–1–4-sf-7-nsh)the Youth Innovation and Technology project of Universities in Shandong Province(No.2020KJC007)。
文摘Although many plasmonic nanosenosrs have been established for the detection of mercury(Ⅱ)(Hg^(2+)),few of them is feasible for analyzing natural samples with very complex matrices because of insufficient method selectivity.To address this challenge,we propose an epitaxial and lattice-mismatch approach to the synthesis of a unique Au/Ag_(2)S dimeric nanostructure,which consists of an Au segment with excellent plasmonic characteristics,and a highly stable Ag_(2)S portion with minimum solubility product (K_(sp)(Ag_(2)S)=6.3×10^(-50)).The detection relies on the chemical conversion of Ag_(2)S to HgS when reacting with Hg^(2+),resulting in a red shift in the absorption band of the connecting Au NPs.The concurrent color changes of the solution from gray purple to dark green and finally to navy correlate well with Hg^(2+)concentration,thus enables UV-vis quantitation and a naked-eye readout of the Hg^(2+)concentration.This method exhibits superior selectivity towards Hg^(2+) over other interfering ions tested because Hg^(2+) is the only ion that can react with Ag_(2)S to form HgS with even smaller solubility product (K_(sp)(HgS)=4×10^(-53)).The detection limit of this method is 1.21μmol/L,calculated by the signal-to-noise of 3.The practicability of the method was verified by analyzing the Hg^(2+)in sewage water samples without sample pretreatment with satisfactory recoveries (93.1%-102.8%) and relative standard deviations (1.38%-2.89%).We believe this method holds great potential for on-the-spot detection of Hg^(2+) in environmental water samples with complex matrices.
基金supported by the National Key Research and Development Program of China(2017YFC1309100 and 2017YFA0205200)the National Natural Science Foundation of China(21804104 and 91959124)+2 种基金the Research Fund of the State Key Laboratory of Solidification Processing(NPU,2020-QZ-01)the Fundamental Research Fund for the Central University(3102019jcc005)the Youth Innovation Team of Shaanxi Universities,Natural Science Foundation of Shaanxi Province(2020PT-020)。
基金partially supported by the National Natural Science Foundation of China(No.51672099 and 52073263)the Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices(No.KFJJ202105)Fundamental Research Funds for the Central Universities(No.2017-QR-25)。
文摘The production of renewable fossil fuels such as CH_(4) and CO by photocatalytic CO_(2)reduction has attracted more and more attention.However,single photocatalyst is less efficient for photocatalytic reduction of CO_(2)due to the fast recombination of photogenerated electron pairs.Herein,we successfully prepare CdS-Ag_(2)S composite by assembling the Ag_(2)S QDs cocatalyst on the surface of CdS nanosheet-assembled flower through oil-bath solvothermal method.This composite is prepared through a simple self-assembly strategy using cadmium chloride,ammonia and thiourea as precursors of the CdS nanosheet-assembled flower and silver nitrate and 3-mercaptopropionic acid as the precursors of Ag_(2)S QDs.The average diameter of Ag_(2)S QDs is apparently 6.0 nm.The light absorption edge of the composite is at around 560 nm,with the corresponding band gap at 2.14 eV.The CdS-Ag_(2)S QDs composite with 5 wt%Ag_(2)S QDs loaded achieves CO evolution rate of 16.6μmol·g^(-1)·h^(-1)without noble-metal cocatalysts.This strengthened photocatalytic performance and photocatalytic stability were attributed to the energy band broadening of Ag_(2)S QDs caused by quantum size effect and the large specific surface area due to the assembled flower.The mechanism underlying the enhanced photocatalytic CO_(2)reduction activity is further proposed.This study demonstrates that semiconductor-based quantum dots are strong candidates for excellent cocatalysts in photocatalysis.
基金This research was funded by the National Natural Science Foundation of China(41977136).
文摘The development of nanotechnology has accelerated the use of silver nanoparticles(AgNPs)in household chemicals and the accumulation of Ag in sewage treatment systems.The application of sewage sludge products to soils raises concerns over the safety of Ag in the function and biogeochemical cycles of the soil belowground ecosystem.Here,we assess the potential risk of the accumulation and transfer of Ag under AgNPs exposure and its effects on the trophic transfer of nitrogen(N)through a soil animal food chain(Folsomia candida–Hypoaspis aculeifer).The formation of stable silver sulfide(Ag_(2)S)was also studied via a single species test using F.candida.Concentrations of Ag in F.candida increased with increasing AgNPs concentration,as did those in the predator H.aculeifer,but the Ag bioaccumulation factors of both animals were<1.Folsomia candida body tissue 15 N abundance declined markedly compared with that of H.aculeifer.Silver sulfide did have adverse effects on the survival and reproduction of F.candida.The Ag concentrations of F.candida increased with increasing Ag_(2)S concentration in sludge-treated soils.Silver sulfide showed ecotoxicity to the collembolan,therefore ecotoxicity resulting from the transformation and fate of AgNPs in soils needs to be considered before biosolid products are applied to agricultural soils.
