Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded forma...Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate （HCOOD） is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH- containing solution at constant potential （E=0.4 V vs. RHE）, we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.展开更多
We applied near-infrared(NIR)spectroscopy with chemometrics for the rapid and reagent-fee analysis of serum urea nitrogen(SUN).The modeling is based on the average effect of multiple sample partitions to achieve param...We applied near-infrared(NIR)spectroscopy with chemometrics for the rapid and reagent-fee analysis of serum urea nitrogen(SUN).The modeling is based on the average effect of multiple sample partitions to achieve parameter selection with stability.A multiparameter optimization platform with Norris derivative filter-partial least squares(Norris-PLS)was developed to select the most suitable mode(d=2,s=33,g=15).Using equidistant combination PLS(EC-PLS)with four parameters(initial wavelength I,number of wavelengths N,number of wavelength gaps G and latent variables LV),we performed wavelength screening after eliminating high-absorption wavebands.The optimal EC-PLS parameters were I=1228 nm,N=26,G=16 and LV=12.The root-mean square error(SEP),correlation coefficient(R_(p))for prediction and ratio of performance-to-deviation(RPD)for validation were 1.03 mmol L^(-1),0.992 and 7.6,respectively.We proposed the wavelength step-by-step phase-out PLS(WSP-PLS)to remove redun-dant wavelengths in the top 100 EC-PLS models with improved prediction performance.The combination of 19 wavelengths was identifed as the optimal model for SUN.The SEP,Rp and RPD in validation were 1.01 mmol L^(-1),0.992 and 7.7,respectively.The prediction effect and wavelength complexity were better than those of EC-PIS.Our results showed that NIR spectroscopy combined with the EC-PLS and WSP-PLS methods enabled the high-precision analysis ofSUN.WSP-PLS is a secondary optimization method that can further optimize any wavelength moc odel obtained through other continuous or discrete strategies to establish a simple and better model.展开更多
Fourier transform infrared (FTIR) spectroscopy has beenextensively employed in flotation research. The work done by theauthor and co-workers has been reported. A comparison has been madeamong the different FTIR spectr...Fourier transform infrared (FTIR) spectroscopy has beenextensively employed in flotation research. The work done by theauthor and co-workers has been reported. A comparison has been madeamong the different FTIR spectroscopic techniques, e.g., transmissionFTIR spectroscopy, diffuse reflectance infrared Fourier transform(DRIFT) spectroscopy, and attenuated total reflectance (ATR) FTIRspectroscopy.展开更多
The Raman and IR spectra of LnTPPTS·10H 2O[Ln=La,Sm,TPPTS=P(m C 6H 4SO 3)3-3]complexes are reported.Based on the observed Raman and IR characteristic frequencies,a vibrational assignments has been made for these ...The Raman and IR spectra of LnTPPTS·10H 2O[Ln=La,Sm,TPPTS=P(m C 6H 4SO 3)3-3]complexes are reported.Based on the observed Raman and IR characteristic frequencies,a vibrational assignments has been made for these complexes.Coordination induces a lengthening of the S—O bonds and a shortening of the C—S bond.The C—S stretching frequencies should therefore increase while the position of the v(SO 3)should move to a lower wavenumber.Vibrational modes of metal oxygen polyhedronν(Ln—Ο)at 146,168,253 cm-1 are the structural charactrization for coordinate bond of LnTPPTS complexes.展开更多
Infrared spectra of (n-C_9H_(19)NH_3)_2CuCl_4 in three solid phases were investigated. It was found that the phase transition at T_(cl)(25℃) arises from the change of the interaction and packing structure of the chai...Infrared spectra of (n-C_9H_(19)NH_3)_2CuCl_4 in three solid phases were investigated. It was found that the phase transition at T_(cl)(25℃) arises from the change of the interaction and packing structure of the chain. The phase transition at T_(c2)(34℃)is related to the change of a partial conformational order-disorder. The GTC or GTG' and small concentration of TG structure near CH_3 group exist in phase Ⅲ (above 38℃).展开更多
The molecular interactions between Nd^(3+), Gd^(3+)and Yb^(3+) and DPPC in multibilayer have been studied by Fourier transform infrared spectroscopy. The results show that incorporations of the lanthanide ions conside...The molecular interactions between Nd^(3+), Gd^(3+)and Yb^(3+) and DPPC in multibilayer have been studied by Fourier transform infrared spectroscopy. The results show that incorporations of the lanthanide ions considerably shift the gel to liquid-crystal phase transition to higher temperatures. The incorporations of Gd^(3+) and Yb^(3+) obviously reduce the cooperations of the transition. The phosphate region of the spectra indicates that the Ln^(3+) binding to DPPC forms DPPC-Ln^(3+)complex and the Lna^(3+)binding is not dependent on the phase state of DPPC. The C-H stretching region of the spectra suggests that the incorporation of Ln^(3+)increases the conformational order of DPPC both in gel and in liquid-crystal phase as a result of the reduction of gauche rotamers.展开更多
The moving window bis corelation coefficients(MW BiCC)was proposed and employed for the discriminant analysis of transgenic sugarcane leaves and B-thalassemia with visible and near-infrared(Vis NIR)spectroscopy.The we...The moving window bis corelation coefficients(MW BiCC)was proposed and employed for the discriminant analysis of transgenic sugarcane leaves and B-thalassemia with visible and near-infrared(Vis NIR)spectroscopy.The well-performed moving window principal component analysis linear discriminant analysis(MWPCA-LDA)was also conducted for comparison.A total of 306 transgenic(positive)and 150 nont ransgenic(negative)leave samples of sugarcane were collected and divided to calibration,prediction,and validation.The diffuse reflection spectra were corected using Savitzky-Golay(SG)smoothing with first-order derivative(d=1),third-degree polynomial(p=3)and 25 smpothing points(m=25).The selected waveband was 736-1054nm with MW-BiCC,and the positive and negative validation recognition rates(V_REC^(+),VREC^(-))were 100%,98.0%,which achieved the same effect as MWPCA-LDA.Another example,the 93 B-thalassemia(positive)and 148 nonthalassemia(negative)of human hemolytic samples were colloctod.The transmission spectra were corrected using SG smoothing withd=1,p=3 and m=53.Using M W-BiCC,many best wavebands were selected(e.g.,1116-1146,17941848 and 22842342nm).The V_REC^(+)and V_REC^(-)were both 100%,which achieved the same effect as MW-PCA-LDA.Importantly,the BICC only required ca lculating correlation cofficients between the spectrum of prediction sample and the average spectra of two types of calibration samples.Thus,BiCC was very simple in algorithm,and expected to obtain more applications.The results first confirmed the feasibility of distinguishing B-thalassemia and normal control samples by NIR spectroscopy,and provided a promising simple tool for large population thalassemia screening.展开更多
The carbonization process of a sucrose‐RuCl3/SBA‐15composite towards a Ru‐containing ordered mesoporous carbon(Ru‐OMC)catalyst was studied by in situ temperature‐programmed infrared spectroscopy to identify the s...The carbonization process of a sucrose‐RuCl3/SBA‐15composite towards a Ru‐containing ordered mesoporous carbon(Ru‐OMC)catalyst was studied by in situ temperature‐programmed infrared spectroscopy to identify the stabilization role of organic carbon precursors during the formation of highly dispersed Ru nanoparticles.The results show that the formation of metal carbonyl species results in the formation of homogeneously distributed Ru nanoparticles,and the rigid silica support and carbon matrix around the Ru(CO)x complex can significantly avoid the sintering and agglomeration of Ru metal particles during elevated temperature thermal treatment.These results ultimately demonstrate that sucrose plays important roles in the formation of homogeneously distributed Ru nanoparticles in a porous carbon matrix.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Potassium carbonate-based sorbents are prospective materials for direct air capture(DAC).In the present study,we examined and revealed the influence of the temperature swing adsorption(TSA)cycle conditions on the CO_(...Potassium carbonate-based sorbents are prospective materials for direct air capture(DAC).In the present study,we examined and revealed the influence of the temperature swing adsorption(TSA)cycle conditions on the CO_(2) sorption properties of a novel aerogel-based K_(2)CO_(3)/ZrO_(2) sorbent in a DAC process.It was shown that the humidity and temperature drastically affect the sorption dynamic and sorption capacity of the sorbent.When a temperature at the sorption stage was 29℃ and a water vapor pressure P_(H2O) in the feed air was 5.2 mbar(1 bar=105 Pa),the composite material demonstrated a stable CO_(2) sorption capacity of 3.4%(mass).An increase in sorption temperature leads to a continuous decrease in the CO_(2) absorption capacity reaching a value of 0.7%(mass)at T=80℃.The material showed the retention of a stable CO_(2) sorption capacity for many cycles at each temperature in the range.Increasing PH2O in the inlet air from 5.2 to 6.8 mbar leads to instability of CO_(2) sorption capacity which decreases in the course of 3 consecutive TSA cycles from 1.7%to 0.8%(mass)at T=29℃.A further increase in air humidity only facilitates the deterioration of the CO_(2) sorption capacity of the material.A possible explanation for this phenomenon could be the filling of the porous system of the sorbent with solid reaction products and an aqueous solution of potassium salts,which leads to a significant slowdown in the CO_(2) diffusion in the composite sorbent grain.To investigate the regeneration step of the TSA cycle in situ,the macro ATRFTIR(attenuated total reflection Fourier-transform infrared)spectroscopic imaging was applied for the first time.It was shown that the migration of carbonate-containing species over the surface of sorbent occurs during the thermal regeneration stage of the TSA cycle.The movement of the active component in the porous matrix of the sorbent can affect the sorption characteristics of the composite material.The revealed features make it possible to formulate the requirements and limitations that need to be taken into account for the practical implementation of the DAC process using the K_(2)CO_(3)/ZrO_(2) composite sorbent.展开更多
The effects of Al2O3 addition on both the sintering behavior and microwave dielectric properties of PbO-B203-SiO2 glass ceramics were investigated by Fourier transform infrared spectroscope （FTIR）, differential ther...The effects of Al2O3 addition on both the sintering behavior and microwave dielectric properties of PbO-B203-SiO2 glass ceramics were investigated by Fourier transform infrared spectroscope （FTIR）, differential thermal analysis （DTA）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that with the increase of Al2O3 content the bands assigned to [SiO4] nearly disappear. Aluminum replaces silicon in the glass network, which is helpful for the formation of boron-oxygen rings. The increase of the transition temperature Tg and softening temperature Tf of PbO-B2O3-SiO2 glass ceramics leads to the increase of liquid phase precipitation temperature and promotes the structure stability in the glasses, and consequently contributes to the decreasing trend of crystallization. Densification and dielectric constants increase with the increase of Al2O3 content, but the dielectric loss is worsened. By contrast, the 3% （mass fraction） Al2O3-doped glass ceramics sintered at 725℃ have better properties of density p=2.72 g/cm3, dielectric constant Er=6.78, dielectric loss tan8=2.6×10^-3 （measured at 9.8 GHz）, which suggest that the glass ceramics can be applied in multilayer microwave devices requiring low sintering temperatures.展开更多
A quantum cascade laser（QCL） based system for simultaneous detection of CO and CO_2 is developed.The QCL can scan over two neighboring CO（2055.40 cm^（-1）） and CO_2（2055.16 cm^（-1）） lines with a single curren...A quantum cascade laser（QCL） based system for simultaneous detection of CO and CO_2 is developed.The QCL can scan over two neighboring CO（2055.40 cm^（-1）） and CO_2（2055.16 cm^（-1）） lines with a single current scan.The wavelength modulation spectroscopy（ f = 20 k Hz） is utilized to enhance the signal-to-noise ratio.A white cell with an effective optical path length of 74 m is used.The calibration of the sensor is performed and minimum detection limits of 1.3 ppb（1 × 10^（-9））for CO and 0.44 ppm（1 × 10^（-6）） for CO_2 are achieved.展开更多
文摘Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate （HCOOD） is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH- containing solution at constant potential （E=0.4 V vs. RHE）, we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.
基金supported by the Science and Technology Project of Guangdong Province of China(Nos.2014A020213016,2014A020212445)the University-enterprise Joint Research Project"Intelligent detection network technology joint research centre"(No.40115031).
文摘We applied near-infrared(NIR)spectroscopy with chemometrics for the rapid and reagent-fee analysis of serum urea nitrogen(SUN).The modeling is based on the average effect of multiple sample partitions to achieve parameter selection with stability.A multiparameter optimization platform with Norris derivative filter-partial least squares(Norris-PLS)was developed to select the most suitable mode(d=2,s=33,g=15).Using equidistant combination PLS(EC-PLS)with four parameters(initial wavelength I,number of wavelengths N,number of wavelength gaps G and latent variables LV),we performed wavelength screening after eliminating high-absorption wavebands.The optimal EC-PLS parameters were I=1228 nm,N=26,G=16 and LV=12.The root-mean square error(SEP),correlation coefficient(R_(p))for prediction and ratio of performance-to-deviation(RPD)for validation were 1.03 mmol L^(-1),0.992 and 7.6,respectively.We proposed the wavelength step-by-step phase-out PLS(WSP-PLS)to remove redun-dant wavelengths in the top 100 EC-PLS models with improved prediction performance.The combination of 19 wavelengths was identifed as the optimal model for SUN.The SEP,Rp and RPD in validation were 1.01 mmol L^(-1),0.992 and 7.7,respectively.The prediction effect and wavelength complexity were better than those of EC-PIS.Our results showed that NIR spectroscopy combined with the EC-PLS and WSP-PLS methods enabled the high-precision analysis ofSUN.WSP-PLS is a secondary optimization method that can further optimize any wavelength moc odel obtained through other continuous or discrete strategies to establish a simple and better model.
文摘Fourier transform infrared (FTIR) spectroscopy has beenextensively employed in flotation research. The work done by theauthor and co-workers has been reported. A comparison has been madeamong the different FTIR spectroscopic techniques, e.g., transmissionFTIR spectroscopy, diffuse reflectance infrared Fourier transform(DRIFT) spectroscopy, and attenuated total reflectance (ATR) FTIRspectroscopy.
文摘The Raman and IR spectra of LnTPPTS·10H 2O[Ln=La,Sm,TPPTS=P(m C 6H 4SO 3)3-3]complexes are reported.Based on the observed Raman and IR characteristic frequencies,a vibrational assignments has been made for these complexes.Coordination induces a lengthening of the S—O bonds and a shortening of the C—S bond.The C—S stretching frequencies should therefore increase while the position of the v(SO 3)should move to a lower wavenumber.Vibrational modes of metal oxygen polyhedronν(Ln—Ο)at 146,168,253 cm-1 are the structural charactrization for coordinate bond of LnTPPTS complexes.
文摘Infrared spectra of (n-C_9H_(19)NH_3)_2CuCl_4 in three solid phases were investigated. It was found that the phase transition at T_(cl)(25℃) arises from the change of the interaction and packing structure of the chain. The phase transition at T_(c2)(34℃)is related to the change of a partial conformational order-disorder. The GTC or GTG' and small concentration of TG structure near CH_3 group exist in phase Ⅲ (above 38℃).
文摘The molecular interactions between Nd^(3+), Gd^(3+)and Yb^(3+) and DPPC in multibilayer have been studied by Fourier transform infrared spectroscopy. The results show that incorporations of the lanthanide ions considerably shift the gel to liquid-crystal phase transition to higher temperatures. The incorporations of Gd^(3+) and Yb^(3+) obviously reduce the cooperations of the transition. The phosphate region of the spectra indicates that the Ln^(3+) binding to DPPC forms DPPC-Ln^(3+)complex and the Lna^(3+)binding is not dependent on the phase state of DPPC. The C-H stretching region of the spectra suggests that the incorporation of Ln^(3+)increases the conformational order of DPPC both in gel and in liquid-crystal phase as a result of the reduction of gauche rotamers.
基金supported by the Science and Technology Project of Guangdong Province of China(Nos.2014A020213016 and 2014A020212445).
文摘The moving window bis corelation coefficients(MW BiCC)was proposed and employed for the discriminant analysis of transgenic sugarcane leaves and B-thalassemia with visible and near-infrared(Vis NIR)spectroscopy.The well-performed moving window principal component analysis linear discriminant analysis(MWPCA-LDA)was also conducted for comparison.A total of 306 transgenic(positive)and 150 nont ransgenic(negative)leave samples of sugarcane were collected and divided to calibration,prediction,and validation.The diffuse reflection spectra were corected using Savitzky-Golay(SG)smoothing with first-order derivative(d=1),third-degree polynomial(p=3)and 25 smpothing points(m=25).The selected waveband was 736-1054nm with MW-BiCC,and the positive and negative validation recognition rates(V_REC^(+),VREC^(-))were 100%,98.0%,which achieved the same effect as MWPCA-LDA.Another example,the 93 B-thalassemia(positive)and 148 nonthalassemia(negative)of human hemolytic samples were colloctod.The transmission spectra were corrected using SG smoothing withd=1,p=3 and m=53.Using M W-BiCC,many best wavebands were selected(e.g.,1116-1146,17941848 and 22842342nm).The V_REC^(+)and V_REC^(-)were both 100%,which achieved the same effect as MW-PCA-LDA.Importantly,the BICC only required ca lculating correlation cofficients between the spectrum of prediction sample and the average spectra of two types of calibration samples.Thus,BiCC was very simple in algorithm,and expected to obtain more applications.The results first confirmed the feasibility of distinguishing B-thalassemia and normal control samples by NIR spectroscopy,and provided a promising simple tool for large population thalassemia screening.
基金supported by the Natural Science Foundation of Zhejiang Province(LY17B030010)~~
文摘The carbonization process of a sucrose‐RuCl3/SBA‐15composite towards a Ru‐containing ordered mesoporous carbon(Ru‐OMC)catalyst was studied by in situ temperature‐programmed infrared spectroscopy to identify the stabilization role of organic carbon precursors during the formation of highly dispersed Ru nanoparticles.The results show that the formation of metal carbonyl species results in the formation of homogeneously distributed Ru nanoparticles,and the rigid silica support and carbon matrix around the Ru(CO)x complex can significantly avoid the sintering and agglomeration of Ru metal particles during elevated temperature thermal treatment.These results ultimately demonstrate that sucrose plays important roles in the formation of homogeneously distributed Ru nanoparticles in a porous carbon matrix.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金This work was supported by Russian Science Foundation(19-73-00079).The authors also thank Leonova A.A.for performing N2 adsorption measurements.
文摘Potassium carbonate-based sorbents are prospective materials for direct air capture(DAC).In the present study,we examined and revealed the influence of the temperature swing adsorption(TSA)cycle conditions on the CO_(2) sorption properties of a novel aerogel-based K_(2)CO_(3)/ZrO_(2) sorbent in a DAC process.It was shown that the humidity and temperature drastically affect the sorption dynamic and sorption capacity of the sorbent.When a temperature at the sorption stage was 29℃ and a water vapor pressure P_(H2O) in the feed air was 5.2 mbar(1 bar=105 Pa),the composite material demonstrated a stable CO_(2) sorption capacity of 3.4%(mass).An increase in sorption temperature leads to a continuous decrease in the CO_(2) absorption capacity reaching a value of 0.7%(mass)at T=80℃.The material showed the retention of a stable CO_(2) sorption capacity for many cycles at each temperature in the range.Increasing PH2O in the inlet air from 5.2 to 6.8 mbar leads to instability of CO_(2) sorption capacity which decreases in the course of 3 consecutive TSA cycles from 1.7%to 0.8%(mass)at T=29℃.A further increase in air humidity only facilitates the deterioration of the CO_(2) sorption capacity of the material.A possible explanation for this phenomenon could be the filling of the porous system of the sorbent with solid reaction products and an aqueous solution of potassium salts,which leads to a significant slowdown in the CO_(2) diffusion in the composite sorbent grain.To investigate the regeneration step of the TSA cycle in situ,the macro ATRFTIR(attenuated total reflection Fourier-transform infrared)spectroscopic imaging was applied for the first time.It was shown that the migration of carbonate-containing species over the surface of sorbent occurs during the thermal regeneration stage of the TSA cycle.The movement of the active component in the porous matrix of the sorbent can affect the sorption characteristics of the composite material.The revealed features make it possible to formulate the requirements and limitations that need to be taken into account for the practical implementation of the DAC process using the K_(2)CO_(3)/ZrO_(2) composite sorbent.
基金Project(2007AA03Z0455) supported by the National High Technology Research and Development Program of ChinaProject supported by the Priority Academic Program Development of Jiangsu Higher Education Institution, China
文摘The effects of Al2O3 addition on both the sintering behavior and microwave dielectric properties of PbO-B203-SiO2 glass ceramics were investigated by Fourier transform infrared spectroscope （FTIR）, differential thermal analysis （DTA）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that with the increase of Al2O3 content the bands assigned to [SiO4] nearly disappear. Aluminum replaces silicon in the glass network, which is helpful for the formation of boron-oxygen rings. The increase of the transition temperature Tg and softening temperature Tf of PbO-B2O3-SiO2 glass ceramics leads to the increase of liquid phase precipitation temperature and promotes the structure stability in the glasses, and consequently contributes to the decreasing trend of crystallization. Densification and dielectric constants increase with the increase of Al2O3 content, but the dielectric loss is worsened. By contrast, the 3% （mass fraction） Al2O3-doped glass ceramics sintered at 725℃ have better properties of density p=2.72 g/cm3, dielectric constant Er=6.78, dielectric loss tan8=2.6×10^-3 （measured at 9.8 GHz）, which suggest that the glass ceramics can be applied in multilayer microwave devices requiring low sintering temperatures.
基金Project supported by the National Key Scientific Instrument and Equipment Development Project of China(Grnat No.2014YQ060537)the National Basic Research Program of China(Grant No.2013CB632803)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA05040102)the National Natural Science Foundation of China(Grant No.41405134)
文摘A quantum cascade laser（QCL） based system for simultaneous detection of CO and CO_2 is developed.The QCL can scan over two neighboring CO（2055.40 cm^（-1）） and CO_2（2055.16 cm^（-1）） lines with a single current scan.The wavelength modulation spectroscopy（ f = 20 k Hz） is utilized to enhance the signal-to-noise ratio.A white cell with an effective optical path length of 74 m is used.The calibration of the sensor is performed and minimum detection limits of 1.3 ppb（1 × 10^（-9））for CO and 0.44 ppm（1 × 10^（-6）） for CO_2 are achieved.
