Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocata...Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis.Herein,we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces.The Ag/AgCl and Ag/Ag_(2)O electrodes are used as the reference electrode in the acidic and the alkaline systems,respectively.The working electrode is made of a transparent carbon thin film which loads the electrocatalysts.The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes.The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.展开更多
Proteins and peptides perform a vital role in living systems, however it remains a challenge for accurate description of proteins at the molecular level. Despite that surface-enhanced Raman spectroscopy (SERS) can pro...Proteins and peptides perform a vital role in living systems, however it remains a challenge for accurate description of proteins at the molecular level. Despite that surface-enhanced Raman spectroscopy (SERS) can provide the intrinsic fingerprint information of samples with ultrahigh sensitivity, it suffers from the poor reproducibility and reliability. Herein, we demonstrate that the silver nanorod array fabricated by an oblique angle deposition method is a powerful substrate for SERS to probe the protein secondary structures without exogenous labels. With this method, the SERS signals of two typical proteins (lysozyme and cytochrome c) are successfully obtained. Additionally, by analyzing the spectral signals of the amide Ⅲ of protein backbone, the influence of concentration on the folding status of proteins has been elucidated. With the concentration increasing, the components of α-helix and β-sheet structures of lysozyme increase while the secondary structures of cytochrome c almost keep constant. The SERS method in this work offers an effective optical marker to characterize the structures of proteins.展开更多
Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescen...Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ＂breathing＂ of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.展开更多
Nitrogen-containing heterocyclic compounds are fundamental biochemical components of all life on Earth and,presumably,life elsewhere in our solar system.Detection and characterization of these compounds by traditional...Nitrogen-containing heterocyclic compounds are fundamental biochemical components of all life on Earth and,presumably,life elsewhere in our solar system.Detection and characterization of these compounds by traditional solvent extraction,chromatographic separation,and GC-MS analysis require more sample mass than will be available from samples returned to Earth from Mars.With its small sample mass requirement,Surface Enhanced Raman Spectroscopy could be an appropriate technique for analysis of returned samples.We have developed a SERS method for the detection of maleimide(2,5-pyrroledione),an N-containing heterocycle with a structure that is widespread in biochemicals.This semi-quantitative methodology accurately determines maleimide concentration in the range from 60 mg/mL to 120 mg/mL.We present a maleimide SERS standard spectrum which will be useful as a reference for future works.The present work demonstrates an easy,accurate,and effective method for the non-destructive qualitative and semi-quantitative study of maleimide as a first step toward developing a method for analysis of related compounds.展开更多
Objective To establish Surface-enhanced Raman Spectroscopy（SERS） can be used as a rapid and reliable method to distinguish virulent strain and mild strain of L. pneumophila. Methods We isolated and characterized of ...Objective To establish Surface-enhanced Raman Spectroscopy（SERS） can be used as a rapid and reliable method to distinguish virulent strain and mild strain of L. pneumophila. Methods We isolated and characterized of bacterial strains from ATCC and water samples strains, while we analyzed data from SERS technology using gold nanoparticles as a base and cell infections were employed to rapidly detect L. pneumophila strains. Origin 8.0 was used to collect Raman spectra, smooth and homogenize data, and to contrast spectra. Principal component analysis（PCA） was conducted to discriminate differences between groups using the multivariate analysis package Py Chem 3.0.5. Results Our results indicated that the peaks of high virulence strains reached ≥4000. This criterion was verified by subsequent cell experiments. In addition, we also conducted SERS rapid identification on the virulence of several collected clinical strains and obtained accurate results. Conclusion The present study indicates that the established SERS protocol can be used as a rapid and reliable method to distinguish virulent and mildly virulent strains of L. pneumophila, which can be further used in clinical samples.展开更多
As an ultrasensitive sensing technology,the application of surface enhanced Raman spectroscopy(SERS)is one interesting topic of nano-optics,which has huge application prospectives in plenty of research fields.In recen...As an ultrasensitive sensing technology,the application of surface enhanced Raman spectroscopy(SERS)is one interesting topic of nano-optics,which has huge application prospectives in plenty of research fields.In recent years,the bottleneck in SERS application could be the fabrication of SERS substrate with excellent enhancement.In this work,a two-dimensional(2D)Ag nanorice film is fabricated by self-assembly method as a SERS substrate.The collected SERS spectra of various molecules on this 2D plasmonic film demonstrate quantitative detection could be performed on this SERS substrate.The experiment data also demonstrate this 2D plasmonic film consisted of anisotropic nanostructures has no obvious SERS polarization dependence.The simulated electric field distribution points out the SERS enhancement comes from the surface plasmon coupling between nanorices.And the SERS signals is dominated by molecules adsorbed at different regions of nanorice surface at various wavelengths,which could be a good near IR SERS substrate for bioanalysis.Our work not only enlarges the surface plasmon properties of metal nanostructure,but also exhibits the good application prospect in SERS related fields.展开更多
As an effective and universal acaricide, amitraz is widely used on beehives against varroasis caused by the mite Varroa jacobsoni. Its residues in honey pose a great danger to human health. In this study, a sensitive,...As an effective and universal acaricide, amitraz is widely used on beehives against varroasis caused by the mite Varroa jacobsoni. Its residues in honey pose a great danger to human health. In this study, a sensitive, rapid, and environmentally friendly surface-enhanced Raman spectroscopy method (SERS) was developed for the determination of trace amount of amitraz in honey with the use of silver nanorod (AgNR) array substrate. The AgNR array substrate fabricated by an oblique angle deposition technique exhibited an excellent SERS activity with an enhancement factor of -10^7. Density function theory was employed to assign the characteristic peak of amitraz. The detection of amitraz was further explored and amitraz in honey at concentrations as low as 0.08 mg/kg can be identified. Specifically, partial least square regression analysis was employed to correlate the SERS spectra in full-wavelength with Camitraz to afford a multiple-quantitative amitraz predicting model. Preliminary results show that the predicted concentrations of amitraz in honey samples are in good agreement with their real concentrations. Compared with the conventional univariate quantitative model based on single peak’s intensity, the proposed multiple-quantitative predicting model integrates all the characteristic peaks of amitraz, thus offering an improved detecting accuracy and anti-interference ability.展开更多
Noble metal-reducible oxide interfaces have been regarded as one of the most active sites for water-gas shift reaction.However,the molecular reaction mechanism of water-gas shift reaction at these interfaces still rem...Noble metal-reducible oxide interfaces have been regarded as one of the most active sites for water-gas shift reaction.However,the molecular reaction mechanism of water-gas shift reaction at these interfaces still remains unclear.Herein,water-gas shift reaction at Pt-NiO interfaces has been in-situ explored using surface-enhanced Raman spectroscopy by construction of Au@Pt@NiO nanostructures.Direct Raman spectroscopic evidence demonstrates that water-gas shift reaction at Pt-NiO interfaces proceeds via an associative mechanism with the carbonate species as a key intermediate.The carbonate species is generated through the reaction of adsorbed CO with gaseous water,and its decomposition is a slow step in water-gas shift reaction.Moreover,the Pt-NiO interfaces would promote the formation of this carbonate intermediate,thus leading to a higher activity compared with pure Pt.This spectral information deepens the fundamental understanding of the reaction mechanism of water-gas shift reaction,which would promote the design of more efficient catalysts.展开更多
Surface-enhanced Raman spectroscopy(SERS) based on two-dimensional(2 D) materials has attracted great attention over the past decade. Compared with metallic materials, which enhance Raman signals via the surface plasm...Surface-enhanced Raman spectroscopy(SERS) based on two-dimensional(2 D) materials has attracted great attention over the past decade. Compared with metallic materials, which enhance Raman signals via the surface plasmon effect, 2 D materials integrated on silicon substrates are ideal for use in the fabrication of plasmon-free SERS chips, with the advantages of outstanding fluorescence quenching capability, excellent biomolecular compatibility, tunable Fermi levels, and potentially lowcost material preparation. Moreover, recent studies have shown that the limits of detection of 2 D-material-based SERS may be comparable with those of metallic substrates, which has aroused significant research interest. In this review, we comprehensively summarize the advances in SERS chips based on 2 D materials. As several excellent reviews of graphene-enhanced Raman spectroscopy have been published in the past decade, here, we focus only on 2 D materials beyond graphene, i.e., transition metal dichalcogenides, black phosphorus, hexagonal boron nitride, 2 D titanium carbide or nitride, and their heterostructures. We hope that this paper can serve as a useful reference for researchers specializing in 2 D materials, spectroscopy, and diverse applications related to chemical and biological sensing.展开更多
Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and opera...Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.展开更多
Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-s...Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.展开更多
To determine the solubility of CO_(2)in n-dodecane at T=303.15-353.15 K,P≤11.00 MPa,an integrated fused silica capillary and in-situ Raman spectroscopy system was built.The Raman peak intensity ratio(I_(CO_(2))/IC-H)...To determine the solubility of CO_(2)in n-dodecane at T=303.15-353.15 K,P≤11.00 MPa,an integrated fused silica capillary and in-situ Raman spectroscopy system was built.The Raman peak intensity ratio(I_(CO_(2))/IC-H)between the upper band of CO_(2)Fermi diad(I_(CO_(2)))and the C-H stretching band of n-dodecane(IC-H)was employed to determine the solubility of CO_(2)in n-dodecane based on the calibrated correlation equation between the known CO_(2)molality in n-dodecane and the I_(CO_(2))/IC-Hratio with R^(2)=0.9998.The results indicated that the solubility of CO_(2)decreased with increasing temperature and increased with increasing pressure.The maximum CO_(2)molality(30.7314 mol/kg)was obtained at 303.15 K and7.00 MPa.Finally,a solubility prediction model(lnS=(P-A)/B)based on the relationship with temperature(T in K)and pressure(P in MPa)was developed,where S is CO_(2)molality,A=-8×10^(-6)T^(2)+0.0354T-8.1605,and B=0.0405T-10.756.The results indicated that the solubilities of CO_(2)derived from this model were in good agreement with the experimental data.展开更多
Electrocatalysis offers a promising approach towards chemical synthesis driven by renewable energy.Molecular level understanding of the electrochemical interface remains challenging due to its compositional and struct...Electrocatalysis offers a promising approach towards chemical synthesis driven by renewable energy.Molecular level understanding of the electrochemical interface remains challenging due to its compositional and structural complexity.In situ interfacial specific characterization techniques could help uncover structure-function relationships and reaction mechanism.To this end,electrochemical surface-enhanced Raman spectroscopy(SERS)and surface-enhanced infrared absorption spectroscopy(SEIRAS)thrive as powerful techniques to provide fingerprint information of interfacial species at reaction conditions.In this review,we first introduce the fundamentals of SERS and SEIRAS,followed by discussion regarding the technical challenges and potential solutions.Finally,we highlight future directions for further development of surface-enhanced spectroscopic techniques for electrocatalytic studies.展开更多
Vickers indentation was introduced into the originally in-plane and out-of-plane poled PLZT ceramics.The Raman spectra were in-situ recorded at selected crack tips before and after the indentations,as well as after th...Vickers indentation was introduced into the originally in-plane and out-of-plane poled PLZT ceramics.The Raman spectra were in-situ recorded at selected crack tips before and after the indentations,as well as after the applications of external electric field.The results show that the changes in Raman intensities of optical modes could be sensitively related to 90° domain switching around the crack tips which are strongly dependent on the directions of original polarization and geometric locations.When the direction of electric field was perpendicular to the direction of original polarization,the 90° domain switching at crack tips of the Vickers indentation on the originally in-plane poled PLZT ceramics caused most significant change in the Raman intensity,which inhibited the crack growth.However,when the direction of electric field was parallel to the direction of original polarization,the growth of crack tips became predominantly without the 90° domain switching,which led to the crack growth.展开更多
Noble metallic nanostructures with strong electric near-field enhancement can significantly improve nanoscale light-matter interactions and are critical for high-sensitivity surface-enhanced Raman spectroscopy[SERS].H...Noble metallic nanostructures with strong electric near-field enhancement can significantly improve nanoscale light-matter interactions and are critical for high-sensitivity surface-enhanced Raman spectroscopy[SERS].Here,we use an azimuthal vector beam[AVB]to illuminate the plasmonic tips circular cluster[PTCC]array to enhance the electric near-field intensity of the PTCC array,and then use it to improve SERS sensitivity.The PTCC array was prepared based on the self-assembled and inductive coupled plasmon[ICP]etching methods.The calculation results show that,compared with the linearly polarized beam[LPB]and radial vector beam excitations,the AVB excitation can obtain stronger electric near-field enhancement due to the strong resonant responses formed in the nanogap between adjacent plasmonic tips.Subsequently,our experimental results proved that AVB excitation increased SERS sensitivity to 10-13mol/L,which is two orders of magnitude higher than that of LPB excitation.Meanwhile,the PTCC array had excellent uniformity with the Raman enhancement factor calculated to be~2.4×10^[8].This kind of vector light field enhancing Raman spectroscopy may be applied in the field of sensing technologies,such as the trace amount detection.展开更多
文摘Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis.Herein,we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces.The Ag/AgCl and Ag/Ag_(2)O electrodes are used as the reference electrode in the acidic and the alkaline systems,respectively.The working electrode is made of a transparent carbon thin film which loads the electrocatalysts.The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes.The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.
基金the National Natural Science Foundation of China (No.61805109 and No.61575087)the Natural Science Foundation of Jiangsu Province (No.BK20170229)+1 种基金the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (No.18KJB180004 and No.16KJB510009)the Natural Science Foundation of Jiangsu Normal University (No.16XLR021).
文摘Proteins and peptides perform a vital role in living systems, however it remains a challenge for accurate description of proteins at the molecular level. Despite that surface-enhanced Raman spectroscopy (SERS) can provide the intrinsic fingerprint information of samples with ultrahigh sensitivity, it suffers from the poor reproducibility and reliability. Herein, we demonstrate that the silver nanorod array fabricated by an oblique angle deposition method is a powerful substrate for SERS to probe the protein secondary structures without exogenous labels. With this method, the SERS signals of two typical proteins (lysozyme and cytochrome c) are successfully obtained. Additionally, by analyzing the spectral signals of the amide Ⅲ of protein backbone, the influence of concentration on the folding status of proteins has been elucidated. With the concentration increasing, the components of α-helix and β-sheet structures of lysozyme increase while the secondary structures of cytochrome c almost keep constant. The SERS method in this work offers an effective optical marker to characterize the structures of proteins.
文摘Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ＂breathing＂ of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.
基金supported through the“Terrestrial and Planetary Alteration Processes”strategic project(ref.PES 18/57)funded by the University of the Basque Country(UPV/EHU).
文摘Nitrogen-containing heterocyclic compounds are fundamental biochemical components of all life on Earth and,presumably,life elsewhere in our solar system.Detection and characterization of these compounds by traditional solvent extraction,chromatographic separation,and GC-MS analysis require more sample mass than will be available from samples returned to Earth from Mars.With its small sample mass requirement,Surface Enhanced Raman Spectroscopy could be an appropriate technique for analysis of returned samples.We have developed a SERS method for the detection of maleimide(2,5-pyrroledione),an N-containing heterocycle with a structure that is widespread in biochemicals.This semi-quantitative methodology accurately determines maleimide concentration in the range from 60 mg/mL to 120 mg/mL.We present a maleimide SERS standard spectrum which will be useful as a reference for future works.The present work demonstrates an easy,accurate,and effective method for the non-destructive qualitative and semi-quantitative study of maleimide as a first step toward developing a method for analysis of related compounds.
基金supported by National Key Technologies Research and Development Program of China(2013ZX10004-610)China Ministry of Science and Technology(MOST)Project 973(2012CB955501)WL is a principal investigator of the NSFC Innovative Research Group(Grant No.81321063)
文摘Objective To establish Surface-enhanced Raman Spectroscopy（SERS） can be used as a rapid and reliable method to distinguish virulent strain and mild strain of L. pneumophila. Methods We isolated and characterized of bacterial strains from ATCC and water samples strains, while we analyzed data from SERS technology using gold nanoparticles as a base and cell infections were employed to rapidly detect L. pneumophila strains. Origin 8.0 was used to collect Raman spectra, smooth and homogenize data, and to contrast spectra. Principal component analysis（PCA） was conducted to discriminate differences between groups using the multivariate analysis package Py Chem 3.0.5. Results Our results indicated that the peaks of high virulence strains reached ≥4000. This criterion was verified by subsequent cell experiments. In addition, we also conducted SERS rapid identification on the virulence of several collected clinical strains and obtained accurate results. Conclusion The present study indicates that the established SERS protocol can be used as a rapid and reliable method to distinguish virulent and mildly virulent strains of L. pneumophila, which can be further used in clinical samples.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11974067)Natural Scienceof CQ CSTC (Grant Nos. cstc2019jcyj-msxmX0145, cstc2019jcyj-bshX0042, and cstc2019jcyj-msxmX0828)Sharing Fund of Chongqing University&Large-scale Equipment
文摘As an ultrasensitive sensing technology,the application of surface enhanced Raman spectroscopy(SERS)is one interesting topic of nano-optics,which has huge application prospectives in plenty of research fields.In recent years,the bottleneck in SERS application could be the fabrication of SERS substrate with excellent enhancement.In this work,a two-dimensional(2D)Ag nanorice film is fabricated by self-assembly method as a SERS substrate.The collected SERS spectra of various molecules on this 2D plasmonic film demonstrate quantitative detection could be performed on this SERS substrate.The experiment data also demonstrate this 2D plasmonic film consisted of anisotropic nanostructures has no obvious SERS polarization dependence.The simulated electric field distribution points out the SERS enhancement comes from the surface plasmon coupling between nanorices.And the SERS signals is dominated by molecules adsorbed at different regions of nanorice surface at various wavelengths,which could be a good near IR SERS substrate for bioanalysis.Our work not only enlarges the surface plasmon properties of metal nanostructure,but also exhibits the good application prospect in SERS related fields.
基金supported by the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (No.16KJB510009 and No.17KJB510017)Jiangsu Province Natural Science Foundation of China (BK20150228)
文摘As an effective and universal acaricide, amitraz is widely used on beehives against varroasis caused by the mite Varroa jacobsoni. Its residues in honey pose a great danger to human health. In this study, a sensitive, rapid, and environmentally friendly surface-enhanced Raman spectroscopy method (SERS) was developed for the determination of trace amount of amitraz in honey with the use of silver nanorod (AgNR) array substrate. The AgNR array substrate fabricated by an oblique angle deposition technique exhibited an excellent SERS activity with an enhancement factor of -10^7. Density function theory was employed to assign the characteristic peak of amitraz. The detection of amitraz was further explored and amitraz in honey at concentrations as low as 0.08 mg/kg can be identified. Specifically, partial least square regression analysis was employed to correlate the SERS spectra in full-wavelength with Camitraz to afford a multiple-quantitative amitraz predicting model. Preliminary results show that the predicted concentrations of amitraz in honey samples are in good agreement with their real concentrations. Compared with the conventional univariate quantitative model based on single peak’s intensity, the proposed multiple-quantitative predicting model integrates all the characteristic peaks of amitraz, thus offering an improved detecting accuracy and anti-interference ability.
文摘Noble metal-reducible oxide interfaces have been regarded as one of the most active sites for water-gas shift reaction.However,the molecular reaction mechanism of water-gas shift reaction at these interfaces still remains unclear.Herein,water-gas shift reaction at Pt-NiO interfaces has been in-situ explored using surface-enhanced Raman spectroscopy by construction of Au@Pt@NiO nanostructures.Direct Raman spectroscopic evidence demonstrates that water-gas shift reaction at Pt-NiO interfaces proceeds via an associative mechanism with the carbonate species as a key intermediate.The carbonate species is generated through the reaction of adsorbed CO with gaseous water,and its decomposition is a slow step in water-gas shift reaction.Moreover,the Pt-NiO interfaces would promote the formation of this carbonate intermediate,thus leading to a higher activity compared with pure Pt.This spectral information deepens the fundamental understanding of the reaction mechanism of water-gas shift reaction,which would promote the design of more efficient catalysts.
基金supported by the National Natural Science Foundation of China (61805175)the Promotion of Science (JP18K13798)China Postdoctoral Sci-ence Foundation (2020M670641)。
文摘Surface-enhanced Raman spectroscopy(SERS) based on two-dimensional(2 D) materials has attracted great attention over the past decade. Compared with metallic materials, which enhance Raman signals via the surface plasmon effect, 2 D materials integrated on silicon substrates are ideal for use in the fabrication of plasmon-free SERS chips, with the advantages of outstanding fluorescence quenching capability, excellent biomolecular compatibility, tunable Fermi levels, and potentially lowcost material preparation. Moreover, recent studies have shown that the limits of detection of 2 D-material-based SERS may be comparable with those of metallic substrates, which has aroused significant research interest. In this review, we comprehensively summarize the advances in SERS chips based on 2 D materials. As several excellent reviews of graphene-enhanced Raman spectroscopy have been published in the past decade, here, we focus only on 2 D materials beyond graphene, i.e., transition metal dichalcogenides, black phosphorus, hexagonal boron nitride, 2 D titanium carbide or nitride, and their heterostructures. We hope that this paper can serve as a useful reference for researchers specializing in 2 D materials, spectroscopy, and diverse applications related to chemical and biological sensing.
基金supported by the Singapore National Research Foundation Central Gap Fund(grant no.NRF2020NRF-CG001-010)Competitive Research Programme,Singapore(grant no.NRF-CRP26-2021-0002)+6 种基金National Research Foundation Investigatorship,Singapore(grant no.NRF-NRFI08-2022-0011)the Agency for Science,Technology,and Research in Advanced Manufacturing and Engineering(A*STAR AME)Individual Research Grant,Singapore(grant no.A20E5c0082)Institute for Digital Institute for Digital Molecular Analytics and Science,Singapore(IDMxS)J.R.T.C.acknowledges scholarship support from Nanyang Technological University,Singaporethe funding support from the Jiangsu Specially-Appointed Professor project(grant no.1046010241230830)the National Natural Science Foundation of China(NSFC,grant no.22108030)the Natural Science Foundation of Shanghai,China(grant no.22ZR1401500).
文摘Surface-enhanced Raman scattering spectroscopy(SERS)has emerged as a powerful analytical technique to enable nanoscale investigations of energy systems.This mini-review focuses on the applications of in-situ and operando SERS in energy-related research,highlighting its unique capabilities and significant contributions to understanding energy storage and conversion processes.We first introduce the fundamental principles of SERS,key SERS-derived techniques,and commonly employed platforms.Subsequently,we delve into the diverse applications of in-situ and operando SERS across various energy systems,encompassing photocatalytic and electrocatalytic systems,fuel cells,solar cells,and batteries.Finally,we conclude with our perspective on the current challenges and prospects in this area.We hope thismini-review serves as an essential overview to guide the design and implementation of in-situ and operando SERS studies of energy systems.
基金financially supported by the National Natural Science Foundation of China(31972149)funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnologythe Dodd-Walls Centre for Photonic and Quantum Technologies。
文摘Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.
基金supported by the National Key Research and Development Program of China(2019YFE0117200)the Natural Science Foundation of China(41977304)
文摘To determine the solubility of CO_(2)in n-dodecane at T=303.15-353.15 K,P≤11.00 MPa,an integrated fused silica capillary and in-situ Raman spectroscopy system was built.The Raman peak intensity ratio(I_(CO_(2))/IC-H)between the upper band of CO_(2)Fermi diad(I_(CO_(2)))and the C-H stretching band of n-dodecane(IC-H)was employed to determine the solubility of CO_(2)in n-dodecane based on the calibrated correlation equation between the known CO_(2)molality in n-dodecane and the I_(CO_(2))/IC-Hratio with R^(2)=0.9998.The results indicated that the solubility of CO_(2)decreased with increasing temperature and increased with increasing pressure.The maximum CO_(2)molality(30.7314 mol/kg)was obtained at 303.15 K and7.00 MPa.Finally,a solubility prediction model(lnS=(P-A)/B)based on the relationship with temperature(T in K)and pressure(P in MPa)was developed,where S is CO_(2)molality,A=-8×10^(-6)T^(2)+0.0354T-8.1605,and B=0.0405T-10.756.The results indicated that the solubilities of CO_(2)derived from this model were in good agreement with the experimental data.
文摘Electrocatalysis offers a promising approach towards chemical synthesis driven by renewable energy.Molecular level understanding of the electrochemical interface remains challenging due to its compositional and structural complexity.In situ interfacial specific characterization techniques could help uncover structure-function relationships and reaction mechanism.To this end,electrochemical surface-enhanced Raman spectroscopy(SERS)and surface-enhanced infrared absorption spectroscopy(SEIRAS)thrive as powerful techniques to provide fingerprint information of interfacial species at reaction conditions.In this review,we first introduce the fundamentals of SERS and SEIRAS,followed by discussion regarding the technical challenges and potential solutions.Finally,we highlight future directions for further development of surface-enhanced spectroscopic techniques for electrocatalytic studies.
基金Project(2006L2003)supported by the Fujian Key Laboratory of Advanced Materials,ChinaProject(10802070)supported by the National Natural Science Foundation of China
文摘Vickers indentation was introduced into the originally in-plane and out-of-plane poled PLZT ceramics.The Raman spectra were in-situ recorded at selected crack tips before and after the indentations,as well as after the applications of external electric field.The results show that the changes in Raman intensities of optical modes could be sensitively related to 90° domain switching around the crack tips which are strongly dependent on the directions of original polarization and geometric locations.When the direction of electric field was perpendicular to the direction of original polarization,the 90° domain switching at crack tips of the Vickers indentation on the originally in-plane poled PLZT ceramics caused most significant change in the Raman intensity,which inhibited the crack growth.However,when the direction of electric field was parallel to the direction of original polarization,the growth of crack tips became predominantly without the 90° domain switching,which led to the crack growth.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.11974282 and 91950207)the Doctoral Dissertation Innovation Fund of Northwestern Polytechnical University(No.CX2021039)。
文摘Noble metallic nanostructures with strong electric near-field enhancement can significantly improve nanoscale light-matter interactions and are critical for high-sensitivity surface-enhanced Raman spectroscopy[SERS].Here,we use an azimuthal vector beam[AVB]to illuminate the plasmonic tips circular cluster[PTCC]array to enhance the electric near-field intensity of the PTCC array,and then use it to improve SERS sensitivity.The PTCC array was prepared based on the self-assembled and inductive coupled plasmon[ICP]etching methods.The calculation results show that,compared with the linearly polarized beam[LPB]and radial vector beam excitations,the AVB excitation can obtain stronger electric near-field enhancement due to the strong resonant responses formed in the nanogap between adjacent plasmonic tips.Subsequently,our experimental results proved that AVB excitation increased SERS sensitivity to 10-13mol/L,which is two orders of magnitude higher than that of LPB excitation.Meanwhile,the PTCC array had excellent uniformity with the Raman enhancement factor calculated to be~2.4×10^[8].This kind of vector light field enhancing Raman spectroscopy may be applied in the field of sensing technologies,such as the trace amount detection.
