This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of...This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.展开更多
Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-...Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.展开更多
文摘This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.
基金Project(21406273)supported by the National Natural Science Foundation of China
文摘Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.
