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
Attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)has recently been proven to be a powerful tool for bioanalysis.It enables in situ and in real-time observation of dynamic proces...Attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)has recently been proven to be a powerful tool for bioanalysis.It enables in situ and in real-time observation of dynamic processes occurring on specific interface,revealing rich structural and functional information of biomolecules at sub monolayer level.The aim of this general review was to give an overview of the cutting edge applications of ATRSEIRAS.We start with description of the basic configuration of the standard ATR-SEIRAS platform.The enhanced mechanisms and methods to fabricate enhanced substrates are then presented.We discuss the recent developments,challenges and applications of ATR-SEIRAS in bioanalysis,mainly focusing on DNA analysis,protein behavior and cell properties.Finally,further development of the ATRSEIRAS technique with enhanced sensitivity,improved time and spatial resolutions will be prospected.展开更多
Plasmonic nanoantennas offer new applications in mid-infrared(mid-IR)absorption spectroscopy with ultrasensitive detection of structural signatures of biomolecules,such as proteins,due to their strong resonant near-fi...Plasmonic nanoantennas offer new applications in mid-infrared(mid-IR)absorption spectroscopy with ultrasensitive detection of structural signatures of biomolecules,such as proteins,due to their strong resonant near-fields.The amide I fingerprint of a protein contains conformational information that is greatly important for understanding its function in health and disease.Here,we introduce a non-invasive,label-free mid-IR nanoantenna-array sensor for secondary structure identification of nanometer-thin protein layers in aqueous solution by resolving the content of plasmonically enhanced amide I signatures.We successfully detect random coil to crossβ-sheet conformational changes associated withα-synuclein protein aggregation,a detrimental process in many neurodegenerative disorders.Notably,our experimental results demonstrate high conformational sensitivity by differentiating subtle secondary-structural variations in a nativeβ-sheet protein monolayer from those of crossβ-sheets,which are characteristic of pathological aggregates.Our nanoplasmonic biosensor is a highly promising and versatile tool for in vitro structural analysis of thin protein layers.展开更多
Supported metal clusters with the integrated advantages of single-atom catalysts and conventional nanoparticles held great promise in the electrocatalytic carbon dioxide reduction(ECO_(2)R)operated at low overpotentia...Supported metal clusters with the integrated advantages of single-atom catalysts and conventional nanoparticles held great promise in the electrocatalytic carbon dioxide reduction(ECO_(2)R)operated at low overpotential and high current density.However,its precise synthesis and the understanding of synergisti-cally catalytic effects remain challenging.Herein,we report a facile method to synthesize the bimetallic Cu and Ni clusters anchored on porous carbon(Cu/Ni-NC)and achieve an enhanced ECO_(2)R.The aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy were employed to verify the metal dispersion and the coordination of Cu/Ni clusters on NC.As a result of this route,the target Cu/Ni-NC exhibits excellent electrocatalytic performance including a stable 30 h electrolysis at 200 mA cm^(-2) with carbon monoxide Faradaic efficiency of∼95.1%using a membrane electrode assembly electrolysis cell.Combined with the in situ analysis of the surface-enhanced Fourier transform infrared spectroelectrochemistry,we propose that the synergistic effects between Ni and Cu can effectively promote the H_(2)O dissociation,thereby accelerate the hydrogenation of CO_(2)to*COOH and the overall reaction process.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
Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption(SEIRA)spectroscopy,and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes.Ph...Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption(SEIRA)spectroscopy,and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes.Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative,since they exhibit large quality factors,which go far beyond those of their plasmonic counterparts.The recent emergence of van der Waals crystals enables the fabrication of highquality nanophotonic resonators based on phonon polaritons,as reported for the prototypical infrared-phononic material hexagonal boron nitride(h-BN).In this work we use,for the first time,phonon-polariton-resonant h-BN ribbons for SEIRA spectroscopy of small amounts of organic molecules in Fourier transform infrared spectroscopy.Strikingly,the interaction between phonon polaritons and molecular vibrations reaches experimentally the onset of the strong coupling regime,while numerical simulations predict that vibrational strong coupling can be fully achieved.Phonon polariton nanoresonators thus could become a viable platform for sensing,local control of chemical reactivity and infrared quantum cavity optics experiments.展开更多
Plasmonics based on localized surface plasmon resonance （LSPR） has found many exciting appli- cations recently. Those applications usually require a good morphological and structural control of metallic nanostructur...Plasmonics based on localized surface plasmon resonance （LSPR） has found many exciting appli- cations recently. Those applications usually require a good morphological and structural control of metallic nanostructures. Oblique angle deposition （OAD） has been demonstrated as a powerful technique for various plasmonic applications due to its advantages in controlling the size, shape, and composition of metallic nanostructures. In this review, we focus on the fabrication of metallic nanostructures by OAD and their applications in plasmonics. After a brief introduction to OAD technique, recent progress of applying OAD in fabricating noble metallic nanostructures for LSPR sensing, surface-enhanced Raman scattering, surface-enhanced infrared absorption, metal-enhanced fluorescence, and metamaterials, and their corresponding properties are reviewed. The future requirements for OAD plasmonics applications are also discussed.展开更多
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This work was supported by grants from the National Natural Science Foundation of China(21327902,21635004,21675079,21627806).
文摘Attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)has recently been proven to be a powerful tool for bioanalysis.It enables in situ and in real-time observation of dynamic processes occurring on specific interface,revealing rich structural and functional information of biomolecules at sub monolayer level.The aim of this general review was to give an overview of the cutting edge applications of ATRSEIRAS.We start with description of the basic configuration of the standard ATR-SEIRAS platform.The enhanced mechanisms and methods to fabricate enhanced substrates are then presented.We discuss the recent developments,challenges and applications of ATR-SEIRAS in bioanalysis,mainly focusing on DNA analysis,protein behavior and cell properties.Finally,further development of the ATRSEIRAS technique with enhanced sensitivity,improved time and spatial resolutions will be prospected.
基金supported by the European Research Council(ERC)under the European Union’s Horizon 2020 research and innovation programme(Grant No.682167)European Commission Horizon 2020(grant no.FETOPEN-737071)Swiss National Foundation for Science(Grant No.152958,SNF31003A_146680,P2ELP2_162116 and P300P2_171219).
文摘Plasmonic nanoantennas offer new applications in mid-infrared(mid-IR)absorption spectroscopy with ultrasensitive detection of structural signatures of biomolecules,such as proteins,due to their strong resonant near-fields.The amide I fingerprint of a protein contains conformational information that is greatly important for understanding its function in health and disease.Here,we introduce a non-invasive,label-free mid-IR nanoantenna-array sensor for secondary structure identification of nanometer-thin protein layers in aqueous solution by resolving the content of plasmonically enhanced amide I signatures.We successfully detect random coil to crossβ-sheet conformational changes associated withα-synuclein protein aggregation,a detrimental process in many neurodegenerative disorders.Notably,our experimental results demonstrate high conformational sensitivity by differentiating subtle secondary-structural variations in a nativeβ-sheet protein monolayer from those of crossβ-sheets,which are characteristic of pathological aggregates.Our nanoplasmonic biosensor is a highly promising and versatile tool for in vitro structural analysis of thin protein layers.
基金This work was supported by National Key R&D Program of China(2020YFE0204500)the National Natural Science Foundation of China(52273277,52072362,52071311)+1 种基金Jilin Province Science and Technology Development Plan Funding Project(20220201112GX)Youth Innovation Promotion Association CAS(2020230 and 2021223).H.X.Z.thanks funding from National Natural Science Foundation of China Outstanding Youth Science Foundation of China(Overseas).These authors thank the staff of beamline BL13SSW at Shanghai Synchrotron Radiation Facility for experiments supports.The authors also gratefully appreciate the support of the morphology characterization and analysis from Prof.Jiuhui Han(Tianjin University of Technology).
文摘Supported metal clusters with the integrated advantages of single-atom catalysts and conventional nanoparticles held great promise in the electrocatalytic carbon dioxide reduction(ECO_(2)R)operated at low overpotential and high current density.However,its precise synthesis and the understanding of synergisti-cally catalytic effects remain challenging.Herein,we report a facile method to synthesize the bimetallic Cu and Ni clusters anchored on porous carbon(Cu/Ni-NC)and achieve an enhanced ECO_(2)R.The aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy were employed to verify the metal dispersion and the coordination of Cu/Ni clusters on NC.As a result of this route,the target Cu/Ni-NC exhibits excellent electrocatalytic performance including a stable 30 h electrolysis at 200 mA cm^(-2) with carbon monoxide Faradaic efficiency of∼95.1%using a membrane electrode assembly electrolysis cell.Combined with the in situ analysis of the surface-enhanced Fourier transform infrared spectroelectrochemistry,we propose that the synergistic effects between Ni and Cu can effectively promote the H_(2)O dissociation,thereby accelerate the hydrogenation of CO_(2)to*COOH and the overall reaction process.
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support from the European Commission under the Graphene Flagship(GrapheneCore1,Grant no.696656)the Marie Sklodowska-Curie individual fellowship(SGPCM-705960)+4 种基金the Spanish Ministry of Economy and Competitiveness(Maria de Maetzu Units of Excellence Programme MDM-2016-0618 and national projects FIS2014-60195-JIN,MAT2014-53432-C5-4-R,MAT2015-65525-R,MAT2015-65159-R,FIS2016-80174-P,MAT2017-88358-C3-3-R)the Basque government(PhD fellowship PRE-2016-1-0150,PRE-2016-2-0025)the Department of Industry of the Basque Government(ELKARTEK project MICRO4FA)the Regional Council of Gipuzkoa(project no.100/16)the ERC starting grant 715496,2DNANOPTICA.
文摘Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption(SEIRA)spectroscopy,and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes.Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative,since they exhibit large quality factors,which go far beyond those of their plasmonic counterparts.The recent emergence of van der Waals crystals enables the fabrication of highquality nanophotonic resonators based on phonon polaritons,as reported for the prototypical infrared-phononic material hexagonal boron nitride(h-BN).In this work we use,for the first time,phonon-polariton-resonant h-BN ribbons for SEIRA spectroscopy of small amounts of organic molecules in Fourier transform infrared spectroscopy.Strikingly,the interaction between phonon polaritons and molecular vibrations reaches experimentally the onset of the strong coupling regime,while numerical simulations predict that vibrational strong coupling can be fully achieved.Phonon polariton nanoresonators thus could become a viable platform for sensing,local control of chemical reactivity and infrared quantum cavity optics experiments.
文摘Plasmonics based on localized surface plasmon resonance （LSPR） has found many exciting appli- cations recently. Those applications usually require a good morphological and structural control of metallic nanostructures. Oblique angle deposition （OAD） has been demonstrated as a powerful technique for various plasmonic applications due to its advantages in controlling the size, shape, and composition of metallic nanostructures. In this review, we focus on the fabrication of metallic nanostructures by OAD and their applications in plasmonics. After a brief introduction to OAD technique, recent progress of applying OAD in fabricating noble metallic nanostructures for LSPR sensing, surface-enhanced Raman scattering, surface-enhanced infrared absorption, metal-enhanced fluorescence, and metamaterials, and their corresponding properties are reviewed. The future requirements for OAD plasmonics applications are also discussed.
