The dispersion relations of normal modes in the layered constructions are studied. In the frequency region with negative permittivity, we investigate the normal modes near the air-metal and the air-matematerial interf...The dispersion relations of normal modes in the layered constructions are studied. In the frequency region with negative permittivity, we investigate the normal modes near the air-metal and the air-matematerial interfaces and compare them. An extra bulk mode appearing in a pass band of two media is found near the air-matematerial interface, which is different from the air-metal case. Moreover, the bulk mode will be further proved by the attenuated total reflection (ATR) technique, in which the coupling between the incident electromagnetic waves and the normal modes is studied. For p-polarized incident waves, the ATR spectra based on the Otto and the Kretschmann configurations are obtained numerically, where the dips present the excitations of the surface and bulk modes. Furthermore, we also discuss the influences of the middle layer thickness, the incident angle and the damping term on the reflection in detail. It is found that the coupling frequencies and the maximum strength are strongly dependent on the above media parameters.展开更多
For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the proc...For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality.The present study aims at characterizing a well-known industrial process,the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters(FAME)for usage as biodiesel in a continuous micro reactor set-up.To this end,a design of experiment approach is applied,where the effects of two process factors,the molar ratio and the total flow rate of the reactants,are investigated.The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield.The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression.The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis.A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination(R^(2))of 0.9608.Thus,we applied a PAT approach to generate further insight into this established industrial process.展开更多
The study of the mineral and organic content of the Allende meteorite is important for our understanding of the molecular evolution of the universe as well as the ancient Earth. Previous studies have characterized the...The study of the mineral and organic content of the Allende meteorite is important for our understanding of the molecular evolution of the universe as well as the ancient Earth. Previous studies have characterized the magnetic minerals present in ordinary and carbonaceous chondrites, providing information on the evolution of magnetic fields. The interaction of organic compounds with magnetic minerals is a possible source of chemical diversity, which is crucial for molecular evolution. Carbon compounds in meteorites are of great scientific interest for a variety of reasons, such as their relevance to the origins of chirality in living organisms. This study presents the characterization of organic and mineral compounds in the Allende meteorite. The structural and physicochemical characterization of the Allende meteorite was accomplished through light microscopy, powder X-ray diffraction with complementary Rietveld refinement, Raman and infrared spectroscopy, mass spectrometry, scanning electron microscopy, and atomic force microscopy using magnetic signal methods to determine the complex structure and the interaction of organic compounds with magnetic Ni-Fe minerals. The presence of Liesegang-like patterns of chondrules in fragments of the Allende structure may also be relevant to understanding how the meteorite was formed. Other observations include the presence of magnetic materials and nanorod-like solids with relatively similar sizes as well as the heterogeneous distribution of carbon in chondrules. Signals observed in the Raman and infrared spectra resemble organic compounds such as carbon nanotubes and peptide-like molecules that have been previously reported in other meteorites, making the Mexican Allende meteorite a feasible sample for the study of the early Earth and exoplanetary bodies.展开更多
Since numerous characteristic absorption lines caused by molecular vibration exist in the midinfrared(MIR)wavelength region,selective excitation or selective dissociation of molecules is possible by tuning the laser w...Since numerous characteristic absorption lines caused by molecular vibration exist in the midinfrared(MIR)wavelength region,selective excitation or selective dissociation of molecules is possible by tuning the laser wavelength to the characteristic absorption lines of target molecules.By applying this feature to the medical fields,less-invasive treatment and non-destructive diagnosis with absorption spectroscopy are possible using tunable MIR lasers.A high-energy nanosecond pulsed MIR tunable laser was obtained with difference-frequency generation(DFG)between a Nd:YAG and a tunable Cr:forsterite lasers.The MIR-DFG laser was tunable in a wavelength range of 5.5–10μm and generated laser pulses with energy of up to 1.4mJ,a pulse width of 5 ns,and a pulse repetition rate of 10 Hz.Selective removal of atherosclerotic lesion was successfully demonstrated with the MIR-DFG laser tuned at a wavelength of 5.75μm,which corresponds to the characteristic absorption of the ester bond in cholesterol esters in the atherosclerotic lesions.We have developed a non-destructive diagnostic probe with an attenuated total reflection(ATR)prism and two hollow optical fibers.An absorption spectrum of cholesterol was measured with the ATR probe by scanning the wavelength of the MIR-DFG laser,and the spectrum was in good agreement with that measured with a commercial Fourier transform infrared spectrometer.展开更多
Hydrophobic mismatch between the hydrophobic length of membrane proteins and hydrophobic thickness of membranes is a crucial factor in controlling protein function and assembly.We combined fluorescence with circular d...Hydrophobic mismatch between the hydrophobic length of membrane proteins and hydrophobic thickness of membranes is a crucial factor in controlling protein function and assembly.We combined fluorescence with circular dichroism(CD) and attenuated total reflection infrared(ATR-IR) spectroscopic methods to investigate the behaviors of the peptide and lipids under hydrophobic mismatch using a model peptide from the fourth transmembrane domain of natural resistance-associated macrophage protein 1(Nramp1),the phosphatidylcholines(PCs) and phosphatidylglycerols(PGs) with different lengths of acyl chains(14:0,16:0 and 18:0).In all PG lipid membranes,the peptide forms stable α-helix structure,and the helix axis is parallel to lipid chains.The helical span and orientation hardly change in varying thickness of PG membranes,while the lipid chains can deform to accommodate to the hydrophobic surface of embedded peptide.By comparison,the helical structures of the model peptide in PC lipid membranes are less stable.Upon incorporation with PC lipid membranes,the peptide can deform itself to accommodate to the hydrophobic thickness of lipid membranes in response to hydrophobic mismatch.In addition,hydrophobic mismatch can increase the aggregation propensity of the peptide in both PC and PG lipid membranes and the peptide in PC membranes has more aggregation tendency than that in PG membranes.展开更多
The p and s-polarized surface plasmon polaritons (SPPs) of symmetric and asymmetric slabs formed arbitrarily by four types of conventional materials: dielectrics, negative dielectric permittivity materials, negativ...The p and s-polarized surface plasmon polaritons (SPPs) of symmetric and asymmetric slabs formed arbitrarily by four types of conventional materials: dielectrics, negative dielectric permittivity materials, negative magnetic permeability materials, and left-handed materials are comprehensively analysed. The existence regions, dispersion relations, and excitation of SPPs in different frequency regions are investigated in detail. For symmetric slabs, the numbers and the frequency positions of surface polariton branches are quite different. At the same time, the pairs of the p or s-polarized SPP branches occur in the same frequency range. For asymmetric slabs, the SPP branches in mid- and high-frequency ranges are greatly different. In addition, the slab thickness has a great effect on SPPs of asymmetric and symmetric slabs. The attenuated total reflection spectra for the cases of p and s polarizations in these slabs are also calculated.展开更多
This work describes synthesis of graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant using one-pot solvothermal reaction method. Effect of sodium lauryl sulfate surfactant amount on surface...This work describes synthesis of graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant using one-pot solvothermal reaction method. Effect of sodium lauryl sulfate surfactant amount on surface modification level of graphene sheets was investigated. Ether (-S-OR- at 762 cm<sup>-1</sup> - 863 cm<sup>-1</sup>), thiocarbonyl (=C=S at 1050 cm<sup>-1</sup> - 1176 cm<sup>-1</sup>) and sulfoxide (S-O, V<sub>s</sub> and V<sub>as</sub> at 1030 cm<sup>-1</sup> - 1450 cm<sup>-1</sup>) functional groups released from sodium lauryl sulfate (SLS) surfactant during solvothermal reaction and attached on the surface of graphene sheets were detected by (attenuated total reflectance-fast Fourier infrared) ATR-FTIR spectroscopy. (Atomic force microscope) AFM observations revealed apparent surface of graphene sheets modified by surfactant molecules with an average multiple profile of graphene nanosheets ≈ 4.8 nm high. This synthesis way of surface modified graphene sheets can be considered as easy, one-step and cheap method for manufacturing of novel biosurface with graphene, as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWPE), metallic biomaterials (Ti and Ti alloys) and bioceramics as hydroxyapatite (HA).展开更多
The development of efficient non-precious metal catalysts is important for the large-scale application of alkaline hydrogen evolution reaction(HER).Here,we synthesized a composite catalyst of Cu and Mo_(2)C(Cu/Mo_(2)C...The development of efficient non-precious metal catalysts is important for the large-scale application of alkaline hydrogen evolution reaction(HER).Here,we synthesized a composite catalyst of Cu and Mo_(2)C(Cu/Mo_(2)C)using Anderson-type polyoxometalates(POMs)synthesized by the facile soaking method as precursors.The electronic interaction between Cu and Mo_(2)C drives the positive charge of Cu,alleviating the strong adsorption of hydrogen at the Mo site by modulating the d-band center of Mo_(2)C.By studying the interfacial water structure using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS),we determined that the positively charged Cu crystals have the function of activating water molecules and optimizing the interfacial water structure.The interfacial water of Cu/Mo_(2)C contains a large amount of free water,which could facilitate the transport of reaction intermediates.Due to activated water molecules and optimized interfacial water structure and hydrogen adsorption energy,the overpotential of Cu/Mo_(2)C is 24 mV at a current density of 10 mA·cm^(-2) and 178 mV at a current density of 1000 mA·cm^(-2).This work improves catalyst performance in terms of interfacial water structure optimization and deepens the understanding of water-mediated catalysis.展开更多
Electrocatalytic CO_(2)reduction to CH_(4)remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbo...Electrocatalytic CO_(2)reduction to CH_(4)remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbon nanotubes(NixCuy-NCNT)for electrocatalytic CO_(2)reduction reaction(CO_(2)RR)via hydrothermal method followed by pyrolysis.The optimized Ni_(1)Cu_(1)-NCNT demonstrated a superior CO_(2)RR performance,achieving 99.7%FECH_(4)(FE=Faradaic efficiency)and 11.54 mA·cm^(−2)current density at−1.2 V vs.reversible hydrogen electrode(RHE),which outperformed single metal counterparts.Its outstanding performance was due to the electrons transferred from Cu to Ni and Ni-Cu alloy shifted the d-band center toward the Fermi level,which was more conducive to the intermediate formation.In situ electrochemical attenuated total reflection(EC-ATR)and density functional theory(DFT)calculations revealed the appearance of*CHO intermediate and the pathway during the CO_(2)RR process.The design of the bimetallic electrocatalyst in this study provides a new perspective for the highly selective reduction of CO_(2).展开更多
Through interface engineering and content control strategy,a PdBi bimetallic interface structure was constructed for the first time to selectively convert CO_(2)to formate with a remarkably high Faraday efficiency(FEf...Through interface engineering and content control strategy,a PdBi bimetallic interface structure was constructed for the first time to selectively convert CO_(2)to formate with a remarkably high Faraday efficiency(FEformate)of 94%and a partial current density(jformate)of 34 mA·cm^(−2)at−0.8 V vs.reversible hydrogen electrode(RHE)in an H-cell.Moreover,the PdBi interface electrocatalyst even exhibited a high current density of 180 mA·cm^(−2)with formate selectivity up to 92%in a flow cell and could steadily operate for at least 20 h.Electrochemical in-situ attenuated total reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)confirmed that the PdBi interface could greatly weaken the adsorption of*CO intermediates due to electronic and geometric effects.Density functional theory(DFT)calculations also established that the PdBi interface regulated the CO_(2)-to-formate pathway by reducing the energy barrier toward HCOOH and largely weakening the adsorption of*CO intermediates on the catalyst surface.This study reveals that the unique PdBi bimetallic interface can provide a novel platform to study the reaction mechanism through combining in-situ ATR-SEIRAS and DFT calculations.展开更多
We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/Ti02-spindle composite as a promising photocatalyst under mild conditions with over 97%conversion and 83%s...We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/Ti02-spindle composite as a promising photocatalyst under mild conditions with over 97%conversion and 83%selectivity.The catalysts are obtained via precise depositing of CuO nanoclusters(size:~3.5 nm)at the{101}facet of the TiO2 to optimally tune exciton recombination through oxygen vacancies generation,evidenced by photoluminescence and Raman spectroscopy measurements.The turnover frequency(TOF)and the apparent quantum efficiency(AQE)of the 7%CuO/TiO2-spindle composites reach up to 23.8 molmethanol·gcat^-1·h^-1 and 55.2%at 25℃,respectively,which are substantially higher than these previously reported photocatalysts.Further,the in-situ attenuated total reflection infrared spectroscopy analysis reveals that the methanol oxidation most likely takes place through the conversion of adsorbed methoxy(CH30^*)to formaldehyde(CHO^*)intermediate,a subject of major debate for a long time.The adsorbed formaldehyde(CHO^*)thus produced reacts with another CH30^*species in its close proximity to form the final product of methyl formate.Results of this study provide insights into the reaction mechanism,and offer guidelines to systematically develop and apply photocatalysts for methanol conversion and related reactions via surface engineering.展开更多
Herein,we report on surface plasmon(SP)-sensitive semitransparent inverted polymer photovoltaic(PV)devices that are based on multilayered material systems consisting of poly(3-hexylthiophene):fullerene-derivative bulk...Herein,we report on surface plasmon(SP)-sensitive semitransparent inverted polymer photovoltaic(PV)devices that are based on multilayered material systems consisting of poly(3-hexylthiophene):fullerene-derivative bulk-heterojunction PV layers and thin gold or silver anodes.We demonstrate that these PV devices allow the simultaneous generation of both electrical power and SPs on their anodes for photoexcitation just above the optical absorption edge of the PV layers,resulting not only in attenuated total reflection,but also in attenuated photocurrent generation(APG)under the SP resonance(SPR)condition.Moreover,we also confirm that the biomolecular interaction of biotin–streptavidin on the PV devices can be precisely detected via apparent SPR angle shifts in the APG spectra,even without the need for complex attenuated total reflection configurations.We highlight our view that APG measurements made using these PV devices show great potential for the development of future generations of compact and highly sensitive SPR-based optical sensors.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.10775055)
文摘The dispersion relations of normal modes in the layered constructions are studied. In the frequency region with negative permittivity, we investigate the normal modes near the air-metal and the air-matematerial interfaces and compare them. An extra bulk mode appearing in a pass band of two media is found near the air-matematerial interface, which is different from the air-metal case. Moreover, the bulk mode will be further proved by the attenuated total reflection (ATR) technique, in which the coupling between the incident electromagnetic waves and the normal modes is studied. For p-polarized incident waves, the ATR spectra based on the Otto and the Kretschmann configurations are obtained numerically, where the dips present the excitations of the surface and bulk modes. Furthermore, we also discuss the influences of the middle layer thickness, the incident angle and the damping term on the reflection in detail. It is found that the coupling frequencies and the maximum strength are strongly dependent on the above media parameters.
文摘For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality.The present study aims at characterizing a well-known industrial process,the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters(FAME)for usage as biodiesel in a continuous micro reactor set-up.To this end,a design of experiment approach is applied,where the effects of two process factors,the molar ratio and the total flow rate of the reactants,are investigated.The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield.The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression.The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis.A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination(R^(2))of 0.9608.Thus,we applied a PAT approach to generate further insight into this established industrial process.
文摘The study of the mineral and organic content of the Allende meteorite is important for our understanding of the molecular evolution of the universe as well as the ancient Earth. Previous studies have characterized the magnetic minerals present in ordinary and carbonaceous chondrites, providing information on the evolution of magnetic fields. The interaction of organic compounds with magnetic minerals is a possible source of chemical diversity, which is crucial for molecular evolution. Carbon compounds in meteorites are of great scientific interest for a variety of reasons, such as their relevance to the origins of chirality in living organisms. This study presents the characterization of organic and mineral compounds in the Allende meteorite. The structural and physicochemical characterization of the Allende meteorite was accomplished through light microscopy, powder X-ray diffraction with complementary Rietveld refinement, Raman and infrared spectroscopy, mass spectrometry, scanning electron microscopy, and atomic force microscopy using magnetic signal methods to determine the complex structure and the interaction of organic compounds with magnetic Ni-Fe minerals. The presence of Liesegang-like patterns of chondrules in fragments of the Allende structure may also be relevant to understanding how the meteorite was formed. Other observations include the presence of magnetic materials and nanorod-like solids with relatively similar sizes as well as the heterogeneous distribution of carbon in chondrules. Signals observed in the Raman and infrared spectra resemble organic compounds such as carbon nanotubes and peptide-like molecules that have been previously reported in other meteorites, making the Mexican Allende meteorite a feasible sample for the study of the early Earth and exoplanetary bodies.
基金supported by Takeda Science Foundation,Japanese Foundation for Research and Promotion of Endoscopy,and Grants-in-Aid for Scientific Research(KAKENHI).
文摘Since numerous characteristic absorption lines caused by molecular vibration exist in the midinfrared(MIR)wavelength region,selective excitation or selective dissociation of molecules is possible by tuning the laser wavelength to the characteristic absorption lines of target molecules.By applying this feature to the medical fields,less-invasive treatment and non-destructive diagnosis with absorption spectroscopy are possible using tunable MIR lasers.A high-energy nanosecond pulsed MIR tunable laser was obtained with difference-frequency generation(DFG)between a Nd:YAG and a tunable Cr:forsterite lasers.The MIR-DFG laser was tunable in a wavelength range of 5.5–10μm and generated laser pulses with energy of up to 1.4mJ,a pulse width of 5 ns,and a pulse repetition rate of 10 Hz.Selective removal of atherosclerotic lesion was successfully demonstrated with the MIR-DFG laser tuned at a wavelength of 5.75μm,which corresponds to the characteristic absorption of the ester bond in cholesterol esters in the atherosclerotic lesions.We have developed a non-destructive diagnostic probe with an attenuated total reflection(ATR)prism and two hollow optical fibers.An absorption spectrum of cholesterol was measured with the ATR probe by scanning the wavelength of the MIR-DFG laser,and the spectrum was in good agreement with that measured with a commercial Fourier transform infrared spectrometer.
基金Supported by the National Natural Science Foundation of China(Nos.20973083,20934002)
文摘Hydrophobic mismatch between the hydrophobic length of membrane proteins and hydrophobic thickness of membranes is a crucial factor in controlling protein function and assembly.We combined fluorescence with circular dichroism(CD) and attenuated total reflection infrared(ATR-IR) spectroscopic methods to investigate the behaviors of the peptide and lipids under hydrophobic mismatch using a model peptide from the fourth transmembrane domain of natural resistance-associated macrophage protein 1(Nramp1),the phosphatidylcholines(PCs) and phosphatidylglycerols(PGs) with different lengths of acyl chains(14:0,16:0 and 18:0).In all PG lipid membranes,the peptide forms stable α-helix structure,and the helix axis is parallel to lipid chains.The helical span and orientation hardly change in varying thickness of PG membranes,while the lipid chains can deform to accommodate to the hydrophobic surface of embedded peptide.By comparison,the helical structures of the model peptide in PC lipid membranes are less stable.Upon incorporation with PC lipid membranes,the peptide can deform itself to accommodate to the hydrophobic thickness of lipid membranes in response to hydrophobic mismatch.In addition,hydrophobic mismatch can increase the aggregation propensity of the peptide in both PC and PG lipid membranes and the peptide in PC membranes has more aggregation tendency than that in PG membranes.
基金supported by the Science Foundation of Shanghai Education Committee, China (Grant No. 06AZ092)
文摘The p and s-polarized surface plasmon polaritons (SPPs) of symmetric and asymmetric slabs formed arbitrarily by four types of conventional materials: dielectrics, negative dielectric permittivity materials, negative magnetic permeability materials, and left-handed materials are comprehensively analysed. The existence regions, dispersion relations, and excitation of SPPs in different frequency regions are investigated in detail. For symmetric slabs, the numbers and the frequency positions of surface polariton branches are quite different. At the same time, the pairs of the p or s-polarized SPP branches occur in the same frequency range. For asymmetric slabs, the SPP branches in mid- and high-frequency ranges are greatly different. In addition, the slab thickness has a great effect on SPPs of asymmetric and symmetric slabs. The attenuated total reflection spectra for the cases of p and s polarizations in these slabs are also calculated.
文摘This work describes synthesis of graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant using one-pot solvothermal reaction method. Effect of sodium lauryl sulfate surfactant amount on surface modification level of graphene sheets was investigated. Ether (-S-OR- at 762 cm<sup>-1</sup> - 863 cm<sup>-1</sup>), thiocarbonyl (=C=S at 1050 cm<sup>-1</sup> - 1176 cm<sup>-1</sup>) and sulfoxide (S-O, V<sub>s</sub> and V<sub>as</sub> at 1030 cm<sup>-1</sup> - 1450 cm<sup>-1</sup>) functional groups released from sodium lauryl sulfate (SLS) surfactant during solvothermal reaction and attached on the surface of graphene sheets were detected by (attenuated total reflectance-fast Fourier infrared) ATR-FTIR spectroscopy. (Atomic force microscope) AFM observations revealed apparent surface of graphene sheets modified by surfactant molecules with an average multiple profile of graphene nanosheets ≈ 4.8 nm high. This synthesis way of surface modified graphene sheets can be considered as easy, one-step and cheap method for manufacturing of novel biosurface with graphene, as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWPE), metallic biomaterials (Ti and Ti alloys) and bioceramics as hydroxyapatite (HA).
基金supported by National Natural Science Foundation of China(Nos.52376060 and 51976081).
文摘The development of efficient non-precious metal catalysts is important for the large-scale application of alkaline hydrogen evolution reaction(HER).Here,we synthesized a composite catalyst of Cu and Mo_(2)C(Cu/Mo_(2)C)using Anderson-type polyoxometalates(POMs)synthesized by the facile soaking method as precursors.The electronic interaction between Cu and Mo_(2)C drives the positive charge of Cu,alleviating the strong adsorption of hydrogen at the Mo site by modulating the d-band center of Mo_(2)C.By studying the interfacial water structure using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS),we determined that the positively charged Cu crystals have the function of activating water molecules and optimizing the interfacial water structure.The interfacial water of Cu/Mo_(2)C contains a large amount of free water,which could facilitate the transport of reaction intermediates.Due to activated water molecules and optimized interfacial water structure and hydrogen adsorption energy,the overpotential of Cu/Mo_(2)C is 24 mV at a current density of 10 mA·cm^(-2) and 178 mV at a current density of 1000 mA·cm^(-2).This work improves catalyst performance in terms of interfacial water structure optimization and deepens the understanding of water-mediated catalysis.
基金supported by the National Natural Science Foundation of China(No.52170065).
文摘Electrocatalytic CO_(2)reduction to CH_(4)remains challenging due to multi-electron transfer and intermediates adsorption.Herein,we synthesized electrocatalysts by growing Ni-Cu alloy structure on nitrogen-doped carbon nanotubes(NixCuy-NCNT)for electrocatalytic CO_(2)reduction reaction(CO_(2)RR)via hydrothermal method followed by pyrolysis.The optimized Ni_(1)Cu_(1)-NCNT demonstrated a superior CO_(2)RR performance,achieving 99.7%FECH_(4)(FE=Faradaic efficiency)and 11.54 mA·cm^(−2)current density at−1.2 V vs.reversible hydrogen electrode(RHE),which outperformed single metal counterparts.Its outstanding performance was due to the electrons transferred from Cu to Ni and Ni-Cu alloy shifted the d-band center toward the Fermi level,which was more conducive to the intermediate formation.In situ electrochemical attenuated total reflection(EC-ATR)and density functional theory(DFT)calculations revealed the appearance of*CHO intermediate and the pathway during the CO_(2)RR process.The design of the bimetallic electrocatalyst in this study provides a new perspective for the highly selective reduction of CO_(2).
基金supported by the National Natural Science Foundation of China(Nos.22003074 and 22002087)Youth Innovation Promotion Association CAS,Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials(No.2021MCIMKF03)Baoshan Iron&Steel Co.,Ltd.(Baosteel),located in Shanghai,China.
文摘Through interface engineering and content control strategy,a PdBi bimetallic interface structure was constructed for the first time to selectively convert CO_(2)to formate with a remarkably high Faraday efficiency(FEformate)of 94%and a partial current density(jformate)of 34 mA·cm^(−2)at−0.8 V vs.reversible hydrogen electrode(RHE)in an H-cell.Moreover,the PdBi interface electrocatalyst even exhibited a high current density of 180 mA·cm^(−2)with formate selectivity up to 92%in a flow cell and could steadily operate for at least 20 h.Electrochemical in-situ attenuated total reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)confirmed that the PdBi interface could greatly weaken the adsorption of*CO intermediates due to electronic and geometric effects.Density functional theory(DFT)calculations also established that the PdBi interface regulated the CO_(2)-to-formate pathway by reducing the energy barrier toward HCOOH and largely weakening the adsorption of*CO intermediates on the catalyst surface.This study reveals that the unique PdBi bimetallic interface can provide a novel platform to study the reaction mechanism through combining in-situ ATR-SEIRAS and DFT calculations.
基金Q.Q.S.thanks the Postdoctoral Science Foundation of China(No.223232),the Natural Science Foundation of Inner Mongolia Autonomous Region(No.2018BS02004)the major special topics of Inner Mongolia science and technology department(No.20181351)+3 种基金Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(No.NJYT-20-B20)the Program of Higher-level Talents of Inner Mongolia Agricultural University(No.NDYB2016-03)LiaoNing Revitalization Talents Program(No.XLYC1807121)Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme(2019)for financial support.
文摘We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/Ti02-spindle composite as a promising photocatalyst under mild conditions with over 97%conversion and 83%selectivity.The catalysts are obtained via precise depositing of CuO nanoclusters(size:~3.5 nm)at the{101}facet of the TiO2 to optimally tune exciton recombination through oxygen vacancies generation,evidenced by photoluminescence and Raman spectroscopy measurements.The turnover frequency(TOF)and the apparent quantum efficiency(AQE)of the 7%CuO/TiO2-spindle composites reach up to 23.8 molmethanol·gcat^-1·h^-1 and 55.2%at 25℃,respectively,which are substantially higher than these previously reported photocatalysts.Further,the in-situ attenuated total reflection infrared spectroscopy analysis reveals that the methanol oxidation most likely takes place through the conversion of adsorbed methoxy(CH30^*)to formaldehyde(CHO^*)intermediate,a subject of major debate for a long time.The adsorbed formaldehyde(CHO^*)thus produced reacts with another CH30^*species in its close proximity to form the final product of methyl formate.Results of this study provide insights into the reaction mechanism,and offer guidelines to systematically develop and apply photocatalysts for methanol conversion and related reactions via surface engineering.
基金The authors thank H Takezoe for his careful reading and helpful comments on this paper.This work was supported by the Basic Science Research Program through National Research Foundations of Korea(NRF)Grant funded by the Korea Government(MSIP)(NRF-2010-0027963,2012R1A2A2A01015654 and 2014R1A2A1A10054643)by Kwangwoon University(2014)The authors also thank GC Kwon,JH Shin and J Choi for their helpful comments.
文摘Herein,we report on surface plasmon(SP)-sensitive semitransparent inverted polymer photovoltaic(PV)devices that are based on multilayered material systems consisting of poly(3-hexylthiophene):fullerene-derivative bulk-heterojunction PV layers and thin gold or silver anodes.We demonstrate that these PV devices allow the simultaneous generation of both electrical power and SPs on their anodes for photoexcitation just above the optical absorption edge of the PV layers,resulting not only in attenuated total reflection,but also in attenuated photocurrent generation(APG)under the SP resonance(SPR)condition.Moreover,we also confirm that the biomolecular interaction of biotin–streptavidin on the PV devices can be precisely detected via apparent SPR angle shifts in the APG spectra,even without the need for complex attenuated total reflection configurations.We highlight our view that APG measurements made using these PV devices show great potential for the development of future generations of compact and highly sensitive SPR-based optical sensors.