To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide par...To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures （pCO2） at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake,Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4（mean±standard deviation）μatm （latm=1.013 25×10^5pa）, 416.3±217.0μatm, 576.5±758.8μatm, 304.2±9.43.5μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic （4 053.7μatm） and the eutrophic （3.2 μatm） areas. The riverine mouth areas have the maximum fluxes （82.0±62.8 mmol/m^2a）. But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum （--0.58±12.9mmol/m^2a）. In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×10^4 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.展开更多
Proteins adsorption at solid surfaces are of paramount important for many natural processes. However, the role of specific water in influencing the adsorption process has not been well understood. We used molecular dy...Proteins adsorption at solid surfaces are of paramount important for many natural processes. However, the role of specific water in influencing the adsorption process has not been well understood. We used molecular dynamics simulation to study the adsorption of BPTI on Au surface in three water environments （dielectric constant model, partial and full solvation models）. The result shows that a fast and strong adsorption can occur in the dielectric environment, which leads to significant structure changes, as confirmed by great deviation from the crystal structure, largely spreading along the Au surface, rapid lose in all secondary structures and the great number of atoms in contact with the surface. Compared to the dielectric model, slower adsorption and fewer changes in the calculated properties above are observed in the partial solvation system since the specific water layer weakens the adsorption effects. However, in the partial solvation system, the adsorption of polar Au surface causes a significant decrease in the specific hydration around the protein, which still results in large structure changes similar to the dielectric system, but with much less adsorption extent. Enough water molecules in the full solvation system could allow the protein to rotate, and to large extent preserve the protein native structure, thus leading to the slowest and weakest adsorption. On the whole, the effects of non-specific and specific solvation on the protein structure and adsorption dynamics are significantly different, highlighting the importance of the specific water molecule in the protein adsorption.展开更多
The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the o...The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the orientational structure of the low concentrated aqueous solution of [bmim] [BF4] at the air/liquid interface was investigated by sum frequency gener ation vibrational spectroscopy. It has been found that at very low concentrations, the butyl chain exhibited a significant gauche defect, indicating a disordered conformation; and the cation ring oriented with a fairly small tilting angle at the surface. When the concentration increased, the cation ring tended to lie flat at the surface, and the gauche defects of the butyl chain decreased due to the intermolecular chainchain interactions and the consequent more ordered interfacial molecular arrangement. Additionally, the antisymmetric stretching mode in the PPP and SPS spectra exhibited a peak shift, showing that there exists more than one kind of orientation or chemical environment for the butyl CH3 group. These results may shed new light on understanding the surface behavior of watermiscible ionic liquids as well as the imidazolium based surfactants.展开更多
General application of ＂greener methods＂ to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrysta...General application of ＂greener methods＂ to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrystalline side products. These impurities seriously diminish the solution processability and potential applications of colloidal nanocrystals. A protocol was established for evaluating purification schemes. The results revealed that commonly applied purification schemes and their variants do not exhibit a high level of performance and may degrade the ligand surface coverage. A new scheme involving chloroformacetonitrile precipitation quantitatively removed all impurities from colloidal solutions of CdSe and CdS nanocrystals coated with a variety of carboxylate ligands. The new scheme was benign to the surface structure of nanocrystaMigands complexes and resulted in each nanocrystal bearing a close-packed monolayer of carboxylate ligands.展开更多
Traditional post-treatment of colloidal nanoparticles （NPs） usually involves repeated centrifugation-wash-sonication processes to separate NPs from the original synthetic environment; however, such separation proces...Traditional post-treatment of colloidal nanoparticles （NPs） usually involves repeated centrifugation-wash-sonication processes to separate NPs from the original synthetic environment; however, such separation processes have either high energy cost or low efficiency and tend to cause aggregation. Here we show a general and scalable colloid post-processing technique based on density gradient centrifugation through water/oil interfaces. Such a one-step technique can switch the solvent in a colloid at almost any concentration without aggregation, and meanwhile purify colloidal nanoparticles by separating them from by-products and environmental impurities. Droplet sedimentation was shown to be the mechanism of this one-step concentration/purification process, and mathematical modeling was established to quantify the accumulation and sedimentation velocities of different NPs.展开更多
Halide perovskite single crystals(HPSCs)provide a unique platform to study the optoelectronic properties of such emerging semiconductor materials,while the temperature induced crystal growth method often has an increa...Halide perovskite single crystals(HPSCs)provide a unique platform to study the optoelectronic properties of such emerging semiconductor materials,while the temperature induced crystal growth method often has an increased solute integration speed and/or unavoidable solute consumption,resulting in a soaring or slumping crystal growth rate of HPSCs.Here,we developed a universal and facile solvent-vola tilization-limited-growth(SVG)strategy to finely control the crystal growth rate by the fine-control-valve for high quality crystal grown through solution processes.The grown HPSCs by SVG method exhibited a record low trap density of 2.8×10^(8)cm^(-3)and a high charge carrier mobility-lifetime product(μτproduct)of 0.021 cm2/V,indicating the excellent crystal quality.The crystal surface defects were further passivated by oxygen suppliers as Lewis base,which led to a reduction of surface leakage current by two times when using for low dose rate X-ray detection.Such HPSC X-ray detector displayed a high sensitivity of 1274μC/(Gyair cm^(2))with a lowest detectable dose rate of 0.56μGyair/s under 120 keV hard X-ray.Further applications including alloy composition analysis and metal flaw detection by HPSC detectors were also demonstrated,which not only shows the bright future for product quality inspection and non-destructive materials analysis,but also paves the way for growing high quality single crystals and fabricating polycrystalline films.展开更多
A pot experiment was conducted to investigate the action mechanisms phorus （P） uptake of Capsicum annuum L. in a sterilized fossil Oxisol of arbuscular mycorrhizal （AM） fungi in phos- Three P levels of 0, 10 and 2...A pot experiment was conducted to investigate the action mechanisms phorus （P） uptake of Capsicum annuum L. in a sterilized fossil Oxisol of arbuscular mycorrhizal （AM） fungi in phos- Three P levels of 0, 10 and 200 mg kg-1 soil （P0, P10 and P200, respectively） without and with AM fungal inoculation were applied as Ca（H2PO4）2-H20. Shoot dry matter yields and shoot P uptake increased significantly （P 〉 0.05） by the inoculation of AM fungi at P0 and P10. Root length and P concentration in soil solution increased with the inoculation of AM fungi but the root：shoot ratio decreased or remained constant. Around 50% roots of inoculated plants were infected by AM and the external hyphae amounted to 20 m g^-1 soil at P10 and P200. The hyphae surface area of the infected root cylinder amounted to 11 and 2 cm^2 cm^-2 root at P0 and P10, respectively. The increased P uptake of inoculated plants was mainly because of an up to 5 times higher P influx of the infected root. Model calculations showed that the root alone could not have achieved the measured P influx in both infected and non-infected roots. But the P influx for hyphae calculated by the model was even much higher than the measured one. The P uptake capacity of hyphae introduced in the model was too high. Model calculations further showed that the depletion zone around roots or hyphae was very narrow. In the case of the root only 7% of the soil volume would contribute P to the plant, while in the case of hyphae it would be 100%. The results together with the model calculations showed that the increased P uptake of AM inoculated plants could be explained partly by the increased P concentration in the soil solution and by the increased P absorbing surface area coming from the external hyphae.展开更多
Surface and grain boundary defects in halide perovskite solar cells are highly detrimental,reducing efficiencies and stabilities.Widespread halide anion and organic cation defects usually aggravate ion diffusion and m...Surface and grain boundary defects in halide perovskite solar cells are highly detrimental,reducing efficiencies and stabilities.Widespread halide anion and organic cation defects usually aggravate ion diffusion and material degradation on the surfaces and at the grain boundaries of perovskite films.In this study,we employ an in-situ green method utilizing nontoxic cetyltrimethylammonium chloride(CTAC)and isopropanol(IPA)as anti-solvents to effectively passivate both surface and grain boundary defects in hybrid perovskites.Anion vacancies can be readily passivated by the chloride group due to its high electronegativity,and cation defects can be synchronously passivated by the more stable cetyltrimethylammonium group.The results show that the charge trap density was significantly reduced,while the carrier recombination lifetime was markedly extended.As a result,the power conversion efficiency of the cell can reach 23.4%with this in-situ green method.In addition,the device retains 85%of its original power conversion efficiency after 600 h of operation under illumination,showing that the stability of perovskite solar cells is improved with this in-situ passivation strategy.This work may provide a green and effective route to improve both the stability and efficiency of perovskite solar cells.展开更多
基金This research was supported by the Knowledge Innovation Project of Chinese Academy of Sciences (KZCX1-SW-01-15) and (KZCX1- SW-12)
文摘To obtain carbon dioxide （CO2） flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures （pCO2） at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake,Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4（mean±standard deviation）μatm （latm=1.013 25×10^5pa）, 416.3±217.0μatm, 576.5±758.8μatm, 304.2±9.43.5μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic （4 053.7μatm） and the eutrophic （3.2 μatm） areas. The riverine mouth areas have the maximum fluxes （82.0±62.8 mmol/m^2a）. But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum （--0.58±12.9mmol/m^2a）. In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×10^4 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.
文摘Proteins adsorption at solid surfaces are of paramount important for many natural processes. However, the role of specific water in influencing the adsorption process has not been well understood. We used molecular dynamics simulation to study the adsorption of BPTI on Au surface in three water environments （dielectric constant model, partial and full solvation models）. The result shows that a fast and strong adsorption can occur in the dielectric environment, which leads to significant structure changes, as confirmed by great deviation from the crystal structure, largely spreading along the Au surface, rapid lose in all secondary structures and the great number of atoms in contact with the surface. Compared to the dielectric model, slower adsorption and fewer changes in the calculated properties above are observed in the partial solvation system since the specific water layer weakens the adsorption effects. However, in the partial solvation system, the adsorption of polar Au surface causes a significant decrease in the specific hydration around the protein, which still results in large structure changes similar to the dielectric system, but with much less adsorption extent. Enough water molecules in the full solvation system could allow the protein to rotate, and to large extent preserve the protein native structure, thus leading to the slowest and weakest adsorption. On the whole, the effects of non-specific and specific solvation on the protein structure and adsorption dynamics are significantly different, highlighting the importance of the specific water molecule in the protein adsorption.
文摘The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the orientational structure of the low concentrated aqueous solution of [bmim] [BF4] at the air/liquid interface was investigated by sum frequency gener ation vibrational spectroscopy. It has been found that at very low concentrations, the butyl chain exhibited a significant gauche defect, indicating a disordered conformation; and the cation ring oriented with a fairly small tilting angle at the surface. When the concentration increased, the cation ring tended to lie flat at the surface, and the gauche defects of the butyl chain decreased due to the intermolecular chainchain interactions and the consequent more ordered interfacial molecular arrangement. Additionally, the antisymmetric stretching mode in the PPP and SPS spectra exhibited a peak shift, showing that there exists more than one kind of orientation or chemical environment for the butyl CH3 group. These results may shed new light on understanding the surface behavior of watermiscible ionic liquids as well as the imidazolium based surfactants.
基金This work was supported by the National Natural Science Foundation of China （Nos. 21233005 and 91433204） and Fundamental Research Funds for the Central Universities （No. 2014FZA3006）.
文摘General application of ＂greener methods＂ to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrystalline side products. These impurities seriously diminish the solution processability and potential applications of colloidal nanocrystals. A protocol was established for evaluating purification schemes. The results revealed that commonly applied purification schemes and their variants do not exhibit a high level of performance and may degrade the ligand surface coverage. A new scheme involving chloroformacetonitrile precipitation quantitatively removed all impurities from colloidal solutions of CdSe and CdS nanocrystals coated with a variety of carboxylate ligands. The new scheme was benign to the surface structure of nanocrystaMigands complexes and resulted in each nanocrystal bearing a close-packed monolayer of carboxylate ligands.
文摘Traditional post-treatment of colloidal nanoparticles （NPs） usually involves repeated centrifugation-wash-sonication processes to separate NPs from the original synthetic environment; however, such separation processes have either high energy cost or low efficiency and tend to cause aggregation. Here we show a general and scalable colloid post-processing technique based on density gradient centrifugation through water/oil interfaces. Such a one-step technique can switch the solvent in a colloid at almost any concentration without aggregation, and meanwhile purify colloidal nanoparticles by separating them from by-products and environmental impurities. Droplet sedimentation was shown to be the mechanism of this one-step concentration/purification process, and mathematical modeling was established to quantify the accumulation and sedimentation velocities of different NPs.
基金the Fundamental Research Funds for the Central Universities,Jilin UniversityJilin University Scinece and Technology Innovation Research Team(2017TD-06)。
文摘Halide perovskite single crystals(HPSCs)provide a unique platform to study the optoelectronic properties of such emerging semiconductor materials,while the temperature induced crystal growth method often has an increased solute integration speed and/or unavoidable solute consumption,resulting in a soaring or slumping crystal growth rate of HPSCs.Here,we developed a universal and facile solvent-vola tilization-limited-growth(SVG)strategy to finely control the crystal growth rate by the fine-control-valve for high quality crystal grown through solution processes.The grown HPSCs by SVG method exhibited a record low trap density of 2.8×10^(8)cm^(-3)and a high charge carrier mobility-lifetime product(μτproduct)of 0.021 cm2/V,indicating the excellent crystal quality.The crystal surface defects were further passivated by oxygen suppliers as Lewis base,which led to a reduction of surface leakage current by two times when using for low dose rate X-ray detection.Such HPSC X-ray detector displayed a high sensitivity of 1274μC/(Gyair cm^(2))with a lowest detectable dose rate of 0.56μGyair/s under 120 keV hard X-ray.Further applications including alloy composition analysis and metal flaw detection by HPSC detectors were also demonstrated,which not only shows the bright future for product quality inspection and non-destructive materials analysis,but also paves the way for growing high quality single crystals and fabricating polycrystalline films.
基金Supported by the Higher Education Commission of Pakistan
文摘A pot experiment was conducted to investigate the action mechanisms phorus （P） uptake of Capsicum annuum L. in a sterilized fossil Oxisol of arbuscular mycorrhizal （AM） fungi in phos- Three P levels of 0, 10 and 200 mg kg-1 soil （P0, P10 and P200, respectively） without and with AM fungal inoculation were applied as Ca（H2PO4）2-H20. Shoot dry matter yields and shoot P uptake increased significantly （P 〉 0.05） by the inoculation of AM fungi at P0 and P10. Root length and P concentration in soil solution increased with the inoculation of AM fungi but the root：shoot ratio decreased or remained constant. Around 50% roots of inoculated plants were infected by AM and the external hyphae amounted to 20 m g^-1 soil at P10 and P200. The hyphae surface area of the infected root cylinder amounted to 11 and 2 cm^2 cm^-2 root at P0 and P10, respectively. The increased P uptake of inoculated plants was mainly because of an up to 5 times higher P influx of the infected root. Model calculations showed that the root alone could not have achieved the measured P influx in both infected and non-infected roots. But the P influx for hyphae calculated by the model was even much higher than the measured one. The P uptake capacity of hyphae introduced in the model was too high. Model calculations further showed that the depletion zone around roots or hyphae was very narrow. In the case of the root only 7% of the soil volume would contribute P to the plant, while in the case of hyphae it would be 100%. The results together with the model calculations showed that the increased P uptake of AM inoculated plants could be explained partly by the increased P concentration in the soil solution and by the increased P absorbing surface area coming from the external hyphae.
基金the National Key Research and Development Program of China(2016YFA0202400 and 2016YFA0202404)the National Natural Science Foundation of China(61904076 and U19A2089)+3 种基金the Natural Science Foundation of Guangdong Province(2020A1515010980 and 2019B1515120083)the Peacock Team Project funding from the Shenzhen Science and Technology Innovation Committee(KQTD2015033110182370)the Shenzhen Engineering R&D Center for Flexible Solar Cells Project funding from Shenzhen Development and Reform Committee(2019-126)the GuangdongHong Kong-Macao Joint Laboratory(2019B121205001)。
文摘Surface and grain boundary defects in halide perovskite solar cells are highly detrimental,reducing efficiencies and stabilities.Widespread halide anion and organic cation defects usually aggravate ion diffusion and material degradation on the surfaces and at the grain boundaries of perovskite films.In this study,we employ an in-situ green method utilizing nontoxic cetyltrimethylammonium chloride(CTAC)and isopropanol(IPA)as anti-solvents to effectively passivate both surface and grain boundary defects in hybrid perovskites.Anion vacancies can be readily passivated by the chloride group due to its high electronegativity,and cation defects can be synchronously passivated by the more stable cetyltrimethylammonium group.The results show that the charge trap density was significantly reduced,while the carrier recombination lifetime was markedly extended.As a result,the power conversion efficiency of the cell can reach 23.4%with this in-situ green method.In addition,the device retains 85%of its original power conversion efficiency after 600 h of operation under illumination,showing that the stability of perovskite solar cells is improved with this in-situ passivation strategy.This work may provide a green and effective route to improve both the stability and efficiency of perovskite solar cells.
