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Scanning tunneling microscopy (STM) Atomic force microscopy (AFM) Scanning electrochemical microscopy (SECM) UV & visible spectroscopy Transmission experiments.

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Presentation on theme: "Scanning tunneling microscopy (STM) Atomic force microscopy (AFM) Scanning electrochemical microscopy (SECM) UV & visible spectroscopy Transmission experiments."— Presentation transcript:

1 Scanning tunneling microscopy (STM) Atomic force microscopy (AFM) Scanning electrochemical microscopy (SECM) UV & visible spectroscopy Transmission experiments Specular reflectance & ellipsometry Internal reflection spectroelectrochemistry Second harmonic spectroscopy Vibrational spectroscopy: IR spectroscopy, Raman spectroscopy Electron & ion spectroscopy XPS, AES, LEED, HREELS, mass spectroscopy Magnetic resonance methods: ESR, NMR Quartz crystal microbalance X-ray methods: XAS, XRD B Spectroelectrochemistry (ch. 17)

2 Vibration spectroscopy Infrared spectroscopy Infrared spectroelectrochemistry (IR-SEC)

3 Cell for IR-SEC

4 EMIRS (electrochemically modulated infrared reflectance spectrosocpy) Potential is modulated between one where the species of interest is absent & one where it is electrochemically generated

5 SNIFTIRS (subtractively normalized interfacial Fourier transform IRS) or PDIRS (potential difference IRS) or SPAIRS (single potential alteration) Spectra obtained separately at two potentials → subtraction

6 IRRAS (IR reflection absorption spectroscopy) IR absorption at fixed potential

7 SEIRA (surface enhanced IR absorption) IR to study adsorbed species (reactants, intermediates, products) → orientation & potential dependence of the adsorbed species SNIFTIRS

8  Attenuated Total Reflectance Spectroscopy (ATR)  Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT) IR incidence sample ZnSe or KRS-5 crystal *Transmission measurement *Reflection-Aborption infrared Spectroscopy (RAS) *Photoacoustic Spectroscopy (PAS) *Surface Electromagnetic Wave spectroscopy (SEW) In-situ FT-IR spectroscopy

9 In-situ FT-IR In situ FT- IR cell

10 In situ FT-IR CO/Pt

11 Raman spectroscopy

12 Raman spectroscopy: molecular vibrational information complementing IR spec. Raman in electrochemical system: signal enhancement - Resonance Raman spectroscopy (RRS) - Surface enhanced Raman spec. (SERS): molecules adsorbed on certain surfaces (Ag or Au)

13 RRS of TCNQ & electrochemically generated TCNQ -

14 Transients in Raman intensity

15 SERS for Os compound on Ag electrode as ftn of potential

16 SER spectra for benzene on Pd

17 In-situ Raman Spectroscopy

18 In-situ Raman microscopy ( 탄소재 음극과 LiCoO 2 양극재 분석 ) LiCoO 2 graphite acetylene black Fresh anode Brodd (2003) 25 o C 60 o C

19 Electron and ion spectrometry Ultra high vacuum (UHV) Excitation Detection X-ray photoelectron spectroscopy (XPS) Photons(X-ray) Electrons UV photoelectron spectroscopy (UPS) Photons (UV) Electrons Auger electron spectroscopy (AES) Electrons Electrons Low-energy electron diffraction (LEED) Electrons Electrons High resolution e - E loss spec. (HREELS) Electrons Electrons Rutherford backscattering (RBS) H+ or He+ H+ or He+ Secondary ion mass spec. (SIMS) Ions Ions Laser desorption mass spec. (LDMS) Photons Ions

20 Detection limits, sampling depth, spot size (spatial resolution)

21 UHV-electrochemistry

22 X-ray photoelectron spectroscopy (XPS, or ESCA)

23 Schematic diagram of XPS

24 XPS for Pt 4f levels:

25 XPS for gassy carbon electrodes

26 XPS for copper electrodeposition (a) Bulk Cu (b) Cu UPD

27 Electrochemical X-ray Photoelectron Spectroscopy Univ. of Illinois

28 Ex-situ Analysis without Contamination Glove BoxUHV-XPS Electrochemical XPS

29 Auger electron spectroscopy

30 Ni oxide on Au

31 AES Depth profiles for GaAs

32 AES depth profiles for MgPc

33 Electrochemical Auger Electron Spectroscopy

34 Low-energy electron diffraction

35 High resolution electron energy loss spectroscopy SCN - on Ag(111) (a)-0.3 V (b)+0.14 V

36 Mass spectrometry Differential electrochemical mass spectrometry (DEMS)

37 DEMS: fuel cell catalysts for methanol(solid) & formic acid(dotted) oxidation

38 Magnetic resonance methods Electron spin resonance & NMR

39 Electrochemical ESR

40 Quartz crystal microbalance

41 QCM: PVF on Au

42 X-ray methods Synchrotron X-ray absorption spectroscopy Absorption edge (energy that is just needed to eject a particular core electron, e.g., 1s e - (K edge), 2p 3/2 e - (L 3 edge) Fe & Fe oxides K-edge: 7.112 keV Within 10-40 eV: X-ray absorption near-edge structure (XANES) (or near-edge absorption fine structure (NEXAFS)) → oxidation state & ligand envirionment About 50 keV: extended X-ray absorption Fine structure (EXAFS) → distance & arrangement of atoms

43 X-ray diffraction techniques

44 In-situ XRD In-situ XRD patterns of Li x FeSnO 4 during initial lithium intercalation and deintercalation.


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