Cocatalyst plays key roles in photogenerated charge separation and surface catalytic reactions in photocatalysis.However,it is not clear if the chemical states of cocatalysts changed or remains unchanged under photoca...Cocatalyst plays key roles in photogenerated charge separation and surface catalytic reactions in photocatalysis.However,it is not clear if the chemical states of cocatalysts changed or remains unchanged under photocatalytic reaction conditions.Herein,taking NaTaO3 as an example,we systemically investigated the chemical states of nickel‐based cocatalysts during photocatalytic water splitting reaction.It was found that photo‐induced self‐formation of Ni and NiO cocatalyst species take place on the surface of NaTaO3 nanocrystals.The self‐formation of dual‐cocatalysts not only occurs on 26‐facet NaTaO3,but also takes place on a more general 6‐facet NaTaO3.Our work clarified that the chemical states of cocatalysts are changing and the redox dual‐cocatalysts are redistributed on the semiconductor surface owing to the reaction induced by photogenerated charges under the condition of photocatalytic reactions.展开更多
With the implementation of the GEOTRACES program, the biogeochemical cycle and distribution of tellurium （Te） in marine environments are becoming increasing environmental concerns. In this study, the concentration o...With the implementation of the GEOTRACES program, the biogeochemical cycle and distribution of tellurium （Te） in marine environments are becoming increasing environmental concerns. In this study, the concentration of dissolved Te in the Changjiang （Yangtze） River estuary and nearby waters was determined in May 2009 by hydride-generation atomic fluorescence spectrometry to elucidate the abundance, dominant species, distribution, and relationship with environmental factors. Results show that： （1） dissolved Te was low owing to its low abundance in the Earth＇s crust, high insolubility in water, and strong affinity to particulate matter; （2） Te（IV） and Te（VI） predominated in surface water. Te（VI） was the dominant species in bottom water, and Te（IV） was the minor species; （3） Horizontally, resulting from low phytoplankton metabolism and the weak reduction from Te（VI） to Te（IV） in the shore, Te（IV） was concentrated in the central zone instead of the coastal region. However, Te（VI） was abundant near the mouth of the Changjiang River where the Changjiang water is diluted and in the area to the south where the Taiwan Warm Current invaded. In the adsorption-desorption process, Te（IV） was negatively related to suspended paniculate matter （SPM）, indicating that it was adsorbed by particulate matter. While for Te（VI）, the positive correlation with SPM suggested that it was desorbed from the solid phase. In the estuary, dissolved Te had a negative correlation to salinity. However, it deviated from the dilution line in high-salinity regions due to the invasion of the Taiwan Warm Current and the mineralization of organic matter. The relationship between Te（IV） and SPM nutrients indicated that it was more bioavailable and more related to phosphorus than to nitrogen. Progress in the field is slow and more research is needed to quantify the input of Te to the estuary and evaluate the biochemical role of organisms.展开更多
In this paper, two different diameter particles （TSP, PM10） were collected by TH-16A four-channels classification air sampler. The samples were treated by HNO3. Analysis of cadmium was carried out by hydride generat...In this paper, two different diameter particles （TSP, PM10） were collected by TH-16A four-channels classification air sampler. The samples were treated by HNO3. Analysis of cadmium was carried out by hydride generation atomic fluorescence spectrometry （HG-AFS） method, and distribution proportions of elements in four phases were calculated. This method was based on the reaction of cadmium with 1.5% （m/v） KBH4 solution and 0.5% KOH（m/v） solution to form the hydride gas in medium of 2% （v/v） HCl. The detection limit for cadmium as low as 0.008μg/L was obtained. The lineally correlation coefficient was 0.99992. The relative standard deviation （n=5, C=1.00μg/L） was 3.26%. The proposed method was applied for the determination of cadmium in atmosphere aerosol samples and the recoveries in the range of 95-102.2% were obtained. This method was simple, rapid, less matrix interference and high sensitivity.展开更多
Hens＇ eggs and corresponding feeds were sampled at commercial farms. The eggs were separated into egg yolk and egg white and freeze dried. After pressure digestion, total element contents of Ca, P, Mg, S, Na, Fe, Mn,...Hens＇ eggs and corresponding feeds were sampled at commercial farms. The eggs were separated into egg yolk and egg white and freeze dried. After pressure digestion, total element contents of Ca, P, Mg, S, Na, Fe, Mn, Zn, Sr, Cu and Ba were detected by ICP-OES in the eggs, whereas, Pb, Ni, Sb, Sn, AI, Cd, Cr, Mo and V were all or largely below the detection limits. In addition, iodine was done by ICP-MS and Se after ashing with Mg-nitrate by hydride-generation-AAS. There were significant accumulations of P, S, Se and I in the egg yolk versus feed levels, as well as S and Na in the egg white. Just a few correlations between concentrations in feed and egg white resp. egg yolk were detected, indicating regulation mechanisms by homeostasis. Strontium showed the strongest trends between feeds and egg white and egg yolk, whereas, there was none for calcium. Among the main elements in the feeds, sulfur had the strongest effects on the egg compositions, e.g., on iodine and iron in the yolk and on sodium in the white, some of them might be non-linear.展开更多
One solid-state electrochemiluminescence （ECL） protein biosensor based on the competing reaction and substitute reaction between protein-to-DNA aptamer and DNA-to-DNA aptamer was proposed. Additionally, the biosenso...One solid-state electrochemiluminescence （ECL） protein biosensor based on the competing reaction and substitute reaction between protein-to-DNA aptamer and DNA-to-DNA aptamer was proposed. Additionally, the biosensor was based on ECL photo-quenching effect of ferrocene （Fc） to tris（2,2-bipyridyl）ruthenium（II） （Ru（bpy）2＋）. It was built up by modification of Au nanoparticles （AuNPs） and Ru（bpy）32＋ on one Au electrode firstly, and then self-assembly of one special double-stranded DNA （dsDNA） onto the electrode. This dsDNA was prepared by hybridization of one Fc labeled molecular beacon single-stranded DNA（ssDNA） and one anti-thrombin aptamer ssDNA. Without the target protein, this Fc-dsDNA/Ru（bpy）2＋- AuNPs/Au elec- trode trigged strong ECL signal, so we called it ECL ＂signal on＂ state. When thrombin was present in the sensing solution, the protein reacted with its aptamer from the Fc-dsDNA/Ru（bpy）3^2＋-AuNPs/Au electrode. Then the left molecular beacon ssDNA on the electrode recovered to its normal stem-loop structure and consequently its Fc labeler was close enough to the electrode surface to quench the ECL signal from Ru（bpy）3^2＋. It was in ECL ＂signal off＂ state. We measured the decrease in ECL intensity to sense the target protein. This was one endeavour to sense protein by using un-labeling target or probe strategy, which gave higher sensitivity and selectivity due to the better combination efficiency of protein and the un-labeled aptamer. 6.25 fmo/L thrombin was detected out,展开更多
High-throughput pyrosequencing,carried out in millions of picoliter-sized reactors on a fiber-optic slide,is known for its longer read length.However,both optical crosstalk(which reduces the signal-to-noise ratio of C...High-throughput pyrosequencing,carried out in millions of picoliter-sized reactors on a fiber-optic slide,is known for its longer read length.However,both optical crosstalk(which reduces the signal-to-noise ratio of CCD images)and chemical retention adversely affect the accuracy of chemiluminescence determination,and ultimately decrease the read length and the accuracy of pyrosequencing results.In this study,both titanium and oxidized aluminum films were deposited on the side walls and upper faces of micro-reactor slides to enhance optical isolation;the films reduced the inter-well crosstalk by one order of magnitude.Subsequently,chemical retention was shown to be caused by the lower diffusion coefficient of the side walls of the picolitersized reactors because of surface roughness and random pores.Optically isolated fiber-optic slides over-coated with silicon oxide showed smoother surface morphology,resulting in little chemical retention;this was further confirmed with theoretical calculations.Picoliter-sized micro-reactors coated with titanium-silicon oxide films showed the least inter-well optical crosstalk and chemical retention;these properties are expected to greatly improve the high-throughput pyrosequencing performance.展开更多
We present temperature and power dependent photoluminescence measurements on CdSe nanowires synthesized via vapor-phase with and without the use of a metal catalyst. Nanowires produced without a catalyst can be optimi...We present temperature and power dependent photoluminescence measurements on CdSe nanowires synthesized via vapor-phase with and without the use of a metal catalyst. Nanowires produced without a catalyst can be optimized to yield higher quantum efficiency, and narrower and spatially uniform emission, when compared to the catalyst-assisted ones. Emission at energies lower than the band-edge is also found in both cases. By combining spatially-resolved photoluminescence and electron microscopy on the same nanowires, we show that catalyst-free nanowires exhibit a low-energy peak with sharp phonon replica, whereas for catalyst-assisted nanowires low-energy emission is linked to the presence of nanostructures with extended morphological defects.展开更多
Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing u...Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing under illumination or in the dark with a charge-carrier injection in both hybrid and inorganic perovskites results in bandgap instability and current-density-voltage(J-V)hysteresis,which can significantly hamper their application.Here,we demonstrate that halide segregation and J-V hysteresis in mixed halide inorganic CsPbIBr_(2)solar cells can be effectively mitigated by introducing an intermediate phase-enhanced Ostwald ripening through the control of the chemical composition in the CsPbIBr_(2)precursor solution.Excess amounts of either PbBr_(2)or CsI are incorporated into originally even molar amounts of PbBr_(2)and CsI precursor solutions.With the PbBr_(2)-excess,we observed an enlarged perovskite grain size,no detectable halide phase segregation at the grain boundaries nor the perovskite/TiO2 interface,an increased minority carrier lifetime,a reduced J-V hysteresis,and an improved solar-cell performance.However,different CsI:PbBr_(2)stoichiometric ratios were found to have different effects on the performance of the perovskite solar cell.The excessive lead phase is reactive with the dimethyl sulfoxide(DMSO)in the precursor solution to form the Pb(I,Br)2·DMSO complex and the quasi-twodimensional(2D)CsPb_(2)(I,Br)5,which are conducive to Ostwald maturation and defect extinction.Finally,the CsPbIBr_(2)solar cell with a PbBr_(2)-excess precursor composition reaches a power conversion efficiency(PCE)of 9.37%(stabilized PCE of 8.48%)and a maximum external quantum efficiency of over 90%.展开更多
文摘Cocatalyst plays key roles in photogenerated charge separation and surface catalytic reactions in photocatalysis.However,it is not clear if the chemical states of cocatalysts changed or remains unchanged under photocatalytic reaction conditions.Herein,taking NaTaO3 as an example,we systemically investigated the chemical states of nickel‐based cocatalysts during photocatalytic water splitting reaction.It was found that photo‐induced self‐formation of Ni and NiO cocatalyst species take place on the surface of NaTaO3 nanocrystals.The self‐formation of dual‐cocatalysts not only occurs on 26‐facet NaTaO3,but also takes place on a more general 6‐facet NaTaO3.Our work clarified that the chemical states of cocatalysts are changing and the redox dual‐cocatalysts are redistributed on the semiconductor surface owing to the reaction induced by photogenerated charges under the condition of photocatalytic reactions.
基金Supported by the National Basic Research Program of China(973 Program)(No.2011CB403602)the National Natural Science Foundation of China(No.41121064)
文摘With the implementation of the GEOTRACES program, the biogeochemical cycle and distribution of tellurium （Te） in marine environments are becoming increasing environmental concerns. In this study, the concentration of dissolved Te in the Changjiang （Yangtze） River estuary and nearby waters was determined in May 2009 by hydride-generation atomic fluorescence spectrometry to elucidate the abundance, dominant species, distribution, and relationship with environmental factors. Results show that： （1） dissolved Te was low owing to its low abundance in the Earth＇s crust, high insolubility in water, and strong affinity to particulate matter; （2） Te（IV） and Te（VI） predominated in surface water. Te（VI） was the dominant species in bottom water, and Te（IV） was the minor species; （3） Horizontally, resulting from low phytoplankton metabolism and the weak reduction from Te（VI） to Te（IV） in the shore, Te（IV） was concentrated in the central zone instead of the coastal region. However, Te（VI） was abundant near the mouth of the Changjiang River where the Changjiang water is diluted and in the area to the south where the Taiwan Warm Current invaded. In the adsorption-desorption process, Te（IV） was negatively related to suspended paniculate matter （SPM）, indicating that it was adsorbed by particulate matter. While for Te（VI）, the positive correlation with SPM suggested that it was desorbed from the solid phase. In the estuary, dissolved Te had a negative correlation to salinity. However, it deviated from the dilution line in high-salinity regions due to the invasion of the Taiwan Warm Current and the mineralization of organic matter. The relationship between Te（IV） and SPM nutrients indicated that it was more bioavailable and more related to phosphorus than to nitrogen. Progress in the field is slow and more research is needed to quantify the input of Te to the estuary and evaluate the biochemical role of organisms.
文摘In this paper, two different diameter particles （TSP, PM10） were collected by TH-16A four-channels classification air sampler. The samples were treated by HNO3. Analysis of cadmium was carried out by hydride generation atomic fluorescence spectrometry （HG-AFS） method, and distribution proportions of elements in four phases were calculated. This method was based on the reaction of cadmium with 1.5% （m/v） KBH4 solution and 0.5% KOH（m/v） solution to form the hydride gas in medium of 2% （v/v） HCl. The detection limit for cadmium as low as 0.008μg/L was obtained. The lineally correlation coefficient was 0.99992. The relative standard deviation （n=5, C=1.00μg/L） was 3.26%. The proposed method was applied for the determination of cadmium in atmosphere aerosol samples and the recoveries in the range of 95-102.2% were obtained. This method was simple, rapid, less matrix interference and high sensitivity.
文摘Hens＇ eggs and corresponding feeds were sampled at commercial farms. The eggs were separated into egg yolk and egg white and freeze dried. After pressure digestion, total element contents of Ca, P, Mg, S, Na, Fe, Mn, Zn, Sr, Cu and Ba were detected by ICP-OES in the eggs, whereas, Pb, Ni, Sb, Sn, AI, Cd, Cr, Mo and V were all or largely below the detection limits. In addition, iodine was done by ICP-MS and Se after ashing with Mg-nitrate by hydride-generation-AAS. There were significant accumulations of P, S, Se and I in the egg yolk versus feed levels, as well as S and Na in the egg white. Just a few correlations between concentrations in feed and egg white resp. egg yolk were detected, indicating regulation mechanisms by homeostasis. Strontium showed the strongest trends between feeds and egg white and egg yolk, whereas, there was none for calcium. Among the main elements in the feeds, sulfur had the strongest effects on the egg compositions, e.g., on iodine and iron in the yolk and on sodium in the white, some of them might be non-linear.
文摘One solid-state electrochemiluminescence （ECL） protein biosensor based on the competing reaction and substitute reaction between protein-to-DNA aptamer and DNA-to-DNA aptamer was proposed. Additionally, the biosensor was based on ECL photo-quenching effect of ferrocene （Fc） to tris（2,2-bipyridyl）ruthenium（II） （Ru（bpy）2＋）. It was built up by modification of Au nanoparticles （AuNPs） and Ru（bpy）32＋ on one Au electrode firstly, and then self-assembly of one special double-stranded DNA （dsDNA） onto the electrode. This dsDNA was prepared by hybridization of one Fc labeled molecular beacon single-stranded DNA（ssDNA） and one anti-thrombin aptamer ssDNA. Without the target protein, this Fc-dsDNA/Ru（bpy）2＋- AuNPs/Au elec- trode trigged strong ECL signal, so we called it ECL ＂signal on＂ state. When thrombin was present in the sensing solution, the protein reacted with its aptamer from the Fc-dsDNA/Ru（bpy）3^2＋-AuNPs/Au electrode. Then the left molecular beacon ssDNA on the electrode recovered to its normal stem-loop structure and consequently its Fc labeler was close enough to the electrode surface to quench the ECL signal from Ru（bpy）3^2＋. It was in ECL ＂signal off＂ state. We measured the decrease in ECL intensity to sense the target protein. This was one endeavour to sense protein by using un-labeling target or probe strategy, which gave higher sensitivity and selectivity due to the better combination efficiency of protein and the un-labeled aptamer. 6.25 fmo/L thrombin was detected out,
基金supported by the Scientific Equipment Research Project of Chinese Academy of Sciences(YZ200823)
文摘High-throughput pyrosequencing,carried out in millions of picoliter-sized reactors on a fiber-optic slide,is known for its longer read length.However,both optical crosstalk(which reduces the signal-to-noise ratio of CCD images)and chemical retention adversely affect the accuracy of chemiluminescence determination,and ultimately decrease the read length and the accuracy of pyrosequencing results.In this study,both titanium and oxidized aluminum films were deposited on the side walls and upper faces of micro-reactor slides to enhance optical isolation;the films reduced the inter-well crosstalk by one order of magnitude.Subsequently,chemical retention was shown to be caused by the lower diffusion coefficient of the side walls of the picolitersized reactors because of surface roughness and random pores.Optically isolated fiber-optic slides over-coated with silicon oxide showed smoother surface morphology,resulting in little chemical retention;this was further confirmed with theoretical calculations.Picoliter-sized micro-reactors coated with titanium-silicon oxide films showed the least inter-well optical crosstalk and chemical retention;these properties are expected to greatly improve the high-throughput pyrosequencing performance.
文摘We present temperature and power dependent photoluminescence measurements on CdSe nanowires synthesized via vapor-phase with and without the use of a metal catalyst. Nanowires produced without a catalyst can be optimized to yield higher quantum efficiency, and narrower and spatially uniform emission, when compared to the catalyst-assisted ones. Emission at energies lower than the band-edge is also found in both cases. By combining spatially-resolved photoluminescence and electron microscopy on the same nanowires, we show that catalyst-free nanowires exhibit a low-energy peak with sharp phonon replica, whereas for catalyst-assisted nanowires low-energy emission is linked to the presence of nanostructures with extended morphological defects.
基金the National Natural Science Foundation of China(51802241 and 91963209)the Fundamental Research Funds for the Central Universities(WUT:2019IVB055 and 2019IVA066)+1 种基金ARC Discovery Grant DP150104483,ARC Centre of Excellence in Exciton Science(CE170100026)the Australian Government through the Australian Renewable Energy Agency(ARENA).
文摘Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing under illumination or in the dark with a charge-carrier injection in both hybrid and inorganic perovskites results in bandgap instability and current-density-voltage(J-V)hysteresis,which can significantly hamper their application.Here,we demonstrate that halide segregation and J-V hysteresis in mixed halide inorganic CsPbIBr_(2)solar cells can be effectively mitigated by introducing an intermediate phase-enhanced Ostwald ripening through the control of the chemical composition in the CsPbIBr_(2)precursor solution.Excess amounts of either PbBr_(2)or CsI are incorporated into originally even molar amounts of PbBr_(2)and CsI precursor solutions.With the PbBr_(2)-excess,we observed an enlarged perovskite grain size,no detectable halide phase segregation at the grain boundaries nor the perovskite/TiO2 interface,an increased minority carrier lifetime,a reduced J-V hysteresis,and an improved solar-cell performance.However,different CsI:PbBr_(2)stoichiometric ratios were found to have different effects on the performance of the perovskite solar cell.The excessive lead phase is reactive with the dimethyl sulfoxide(DMSO)in the precursor solution to form the Pb(I,Br)2·DMSO complex and the quasi-twodimensional(2D)CsPb_(2)(I,Br)5,which are conducive to Ostwald maturation and defect extinction.Finally,the CsPbIBr_(2)solar cell with a PbBr_(2)-excess precursor composition reaches a power conversion efficiency(PCE)of 9.37%(stabilized PCE of 8.48%)and a maximum external quantum efficiency of over 90%.
