Electrochemical Camp 2012 Chapter 6 Potential Sweep Method Speaker : Yu-Yan Li Advisor : Kuo-Chuan Ho Aug, 6 th, 2012 1 Electro-Optical Materials Lab.,

Slides:



Advertisements
Similar presentations
Thin Film Cyclic Voltammetry
Advertisements

Impedance Spectroscopy (Or, how a sinusoidally varying voltage is used to probe multiple electrical properties of materials) Yun-Ju (Alex) Lee June 13,
Lecture 6a Cyclic Voltammetry.
Evans Diagrams.
Chapter 4 Electrochemical kinetics at electrode / solution interface and electrochemical overpotential.
Cyclic voltammetry: a fingerprint of electrochemically active species
ELECTROCHEMISTRY CHEM 4700 CHAPTER 2
Voltammetry Nov 16, 2004 Lecture Date: April 28th, 2008.
Introduction to Electroanalytical Chemistry
VOLTAMMETRY A.) Comparison of Voltammetry to Other Electrochemical Methods 1.) Voltammetry: electrochemical method in which information about an analyte.
Yat Li Department of Chemistry & Biochemistry University of California, Santa Cruz CHEM 146C_Experiment #8 Surface Electrochemistry: Adsorption of Polyoxometalate.
Electrochemistry Why are we doing this experiment?
Introduction to electrochemistry - Basics of all techniques -
ELECTROCHEMISTRY INTRO1 !? THINGS THAT WE ARE FAMILIAR WITH : !? Ohm’s law ( and Kirchoff’s…) (ABC... electrical circuits) U = I  R, R =   L / S Faraday’s.
Five slide on cyclic voltammetry Chip Nataro Lafayette College.
LINEAR SWEEP VOLTAMMETRY AND CYCLIC VOLTAMMETRY
VOLTAMMETRY A.) Comparison of Voltammetry to Other Electrochemical Methods 1.) Voltammetry: electrochemical method in which information about an analyte.
Controlled potential microelectrode techniques—potential sweep methods
Voltammetry Nov 16, 2004 Lecture Date: March 27th, 2006.
Electrochemistry for Engineers LECTURE 4 Lecturer: Dr. Brian Rosen Office: 128 Wolfson Office Hours: Sun 16:00.
INTRODUCTION TO ELECTROCHEMICAL CELLS AND BASIC ELECTROANALYTICAL MEASUREMENTS ANDREA MARDEGAN JAN 17th 2013.
Electrochemistry for Engineers
Cyclic Voltammetry for the Detection of Dopamine in vivo
2 Structure of electrified interface
Electro-Kinetics.
Analytical Electrochemistry : The Basic Concepts
November 14, 2008 Application of Galvanic Exchange Reaction for Preparation of Pt coated Fe Nanoparticles supported by Single-Walled Carbon Nanotubes:
16-1 Voltammetry Electrochemistry techniques based on current (i) measurement as function of voltage (E appl ) Working electrode §(microelectrode) place.
Development of Affordable Bioelectronic Devices Based on Soluble and Membrane Proteins 80 th ACS Colloids and Surface Science Symposium University of Colorado.
Electrochemistry Introduction
Constructing a Kinetics Database Types of kinetic data: Electrochemistry Dennis H. Evans Department of Chemistry University of Arizona Tucson, AZ
America’s Smartest City by Movoto Blog Rated Most Livable City by Places Rated Almanac and The Economist Named among Best in the World Places to Visit.
M. Meyyappan Director, Center for Nanotechnology NASA Ames Research Center Moffett Field, CA 94035
Five Slides about Cyclic Voltammetry
Chapter 5 Mechanism of complex electrode reaction.
Characterization Technique: Voltammetry Reading: Bard & Faulkner 1 st week: ch. 1 & ch. 2 (pp ) 2 nd week: ch. 1, ch. 3 (pp ), & ch. 6 (pp.
Influence of product adsorption on catalytic reaction determined by Michaelis-Menten kinetics Šebojka Komorsky-Lovrić and Milivoj Lovrić Department of.
VOLTAMMETRY A.) Comparison of Voltammetry to Other Electrochemical Methods 1.) Voltammetry: electrochemical method in which information about an analyte.
Section 13 Analytical Voltammetry.
Electrochemistry for Engineers
Electrochemistry for Engineers
Mass-transfer-controlled electrochemical process (传质控制的电化学过程)
Linear Potential Sweep Voltammetry
Best seen broken into four categories Part 1: Ion Selective Electrodes Part 3: Step Voltammetry Part 2: Amperometric Sensors Part 4: Cyclic Voltammetry.
INTRODUCTION TO ELECTROCHEMICAL CELLS AND BASIC ELECTROANALYTICAL MEASUREMENTS Sunny Holmberg January 19 th
Graphene Hysteresis Response
Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd.
Instrumental Analysis Polarography and Voltammetry
America’s Smartest City by Movoto Blog Rated Most Livable City by Places Rated Almanac and The Economist Named among Best in the World Places to Visit.
Introduction to Electroanalytical Chemistry
CH5715 Energy Conversion and Storage
ANALYTICAL CHEMISTRY PRACTICE II
Protein Film Voltammetry: Cyt P450s
Voltammetry and Polarography
Lecture 7a Cyclic Voltammetry.
Electrochemistry: Introduction Electrochemistry at your finger tips
Electrochemistry: Introduction Electrochemistry at your finger tips
Voltammetry and Polarography
Speciation and Lability of Zn(II) in River Waters
Probing electron transfer mechanisms
Complex Anode Kinetics Chronocoulometry Evidence
Chapter Fifteen VOLTAMMETRY AND ELECTROCHEMICAL SENSORS
The separation between reverse peak and forward peak is so large The reduction potential is more cathodic than formal electrode potential The separation.
2.4. Chronoamperometry measurement of currents as a function of time a kind of ‘controlled-potential voltammetry’ or ‘controlled-potential micro electrolysis.
towards more negative values towards more positive values Second-order irreversible chemical reaction following a reversible electron transfer:
Voltametric techniques Chapter 2 Prof. Rezvani.
2. Electrochemical techniques complementary to cyclic voltammetry.
Linear Diffusion at a Planar Electrode The diffusive event involves two aspects: The variation of the concentration of the active species along.
Cyclic Voltammetry Dr. A. N. Paul Angelo Associate Professor,
4 Slides About: Electrocatalysis
Presentation transcript:

Electrochemical Camp 2012 Chapter 6 Potential Sweep Method Speaker : Yu-Yan Li Advisor : Kuo-Chuan Ho Aug, 6 th, Electro-Optical Materials Lab., Dept. Chem. Eng., NTU

Outline Introduction to Linear Sweep Method (LSV) and Cyclic Voltammetry (CV) Three cases (rev, quasi-rev, irrev) Detection limit of LSV Multi-component system Electrode reaction coupled with chemical reaction (Chapter 12) Application 2 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU

6.1 Introduction What is Linear Sweep voltammetry (LSV)? 3 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Cottrell eq. (i-t) Voltage ramp Limiting Current Plateau (i-E) Linear sweep voltammetry (LSV) Linear sweep voltammetry (LSV)

Linear Sweep Method (LSV) Why there is a peak? 4 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Surface concentration E→ E p + C o (0,t) → 0 E→ E p - Depletion effect results in small i E→ E p + C o (0,t) → 0 E→ E p - Depletion effect results in small i

Linear Sweep Method (LSV) 5 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Reduction begins and current starts to flow A +e - →A ‧ Mass transfer of A reaches maximum rate Nonfaradaic current flow Co approaches to zero and diffuse layer grows

Cyclic Voltammetry (CV) 6 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Reverse the potential scan Reduction Oxidation

6.2 Nernstian (Reversible) Systems Scanning potential Planar electrode 7 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (5.4.2) (5.4.3) (5.4.4) (5.4.5) (5.4.6)

Reversible Systems Time-dependent form Laplace transform → Convolution theorem 8 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.2.2) (6.2.3)

Reversible Systems The current 9 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Find the maximum (6.2.17) (6.2.16)

Reversible Systems Peak current (at 25 ℃ ) Peak potential Half-peak potential 10 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.2.19) (6.2.20) (6.2.21)

Reversible Systems 11 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.2.22) i p ∝ ν 1/2 i ∝ ν 1/2 E p ≠E p (ν) i p ∝ ν 1/2 i ∝ ν 1/2 E p ≠E p (ν) For reversible rxn

Detection limit of LSV [Definition] The ratio of charging to Faradaic current Absence of adsorption/desorption influence either double layer or Faradaic process 12 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Faradaic current Charging current Charging current

Detection limit of LSV Capacitance of double layer 13 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU For DME noise signal

Detection limit of LSV Effect of double layer charging at different sweep rate 14 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU ν ↑ → i c /i p ↑ C o * ↓ → i c /i p ↑ The noise grows! ν ↑ → i c /i p ↑ C o * ↓ → i c /i p ↑ The noise grows!

6.3 Totally Irreversible Systems Irreversible reaction Boundary condition The current 15 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.3.1) (6.3.6)

Totally Irreversible Systems Peak current Peak potential 16 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU i p ∝ ν 1/2 i ∝ ν 1/2 E p =E p (ν) i p ∝ ν 1/2 i ∝ ν 1/2 E p =E p (ν) For totally irrev. (6.3.8) (6.3.10) (6.3.11)

6.4 Quasi-reversible Systems Boundary condition Parameter Λ 17 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU D o =D R =D Λ ↑, easy to reach equilibrium ( k 0 ↑) (6.4.4&5) (6.4.2)

Quasi-reversible Systems Peak current Peak potential 18 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU For quasi-rev i p ∝ ν 1/2 (6.4.7) (6.4.8)

Summary Zone boundary for LSV 19 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Λ = Λ(ν)

6.5 Cyclic Voltammetry Scanning potential Two parameters 1. E p,a – E p,c 2. i p,a / i p,c ΔEp=| E p,c – E p,a | Formal potential approaching to E 0’ = (E p,c + E p,a )/2 20 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.4.1) (6.4.2)

Reversible System Find i p,a & i p,c If no i p,a / i p,c 21 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.5.4)

Quasi-reversible System Wave shape & ΔE p ∝ f(ν, α,k 0,E λ ) Equivalent parameter For 0.3 <α< 0.7 the ΔE p is nearly independent of α Ψ↑ as k 0 ↑ or ν ↓ then ΔE p ↓ 22 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.5.5)

6.6 Multicomponent Systems and Multistep Charge Transfers For independent reactions 23 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU O +ne - →R O’ +n’e - →R’ O +n 1 e - →R 1 R 1 +n 2 e - →R 2 For stepwise reduction

Peak Search 24 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Method for obtaining baseline for measurement of i p ’ of second wave Method of allowing current of first wave to decay before scanning second wave

Electrode reaction coupled with chemical reaction (Chapter 12) 1. O +ne - ⇌ R O +ne - →R O +ne - ⇌ R R ⇌ Z O +ne - ⇌ R R → Z O +ne - ⇌ R R +Z →O O +ne - → R R +Z →O Z ⇌ O O +ne - ⇌ R Z ⇌ O O +ne - → R ErEr EiEi CrErCrEr CrEiCrEi ErCrErCr ErCiErCi ErCi’ErCi’ EiCi’EiCi’ Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Catalytic

CV Application –Diffusion control or Kinetic control Diffusion control Surface reaction control 26 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU (6.2.19) ( ) For diffusion control i p ∝ ν 1/2 For surface reaction control i p ∝ ν For diffusion control i p ∝ ν 1/2 For surface reaction control i p ∝ ν

CV Application – Surface reaction control PEDOT/FAD Electrode ( 達人 ‘s work) 27 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Modified electrode – surface reaction control Modified electrode – surface reaction control

CV Application – Diffusion control 28 Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Diffusion control

Homework 1. Bard Ch6 Problem Search a paper including the CV method (1) Introduce the materials briefly (2) Explain the graph ( ex: redox reaction, formal potential, reversible/irreversible……) 29 TPTA and BP system Electro-Optical Materials Lab., Dept. Chem. Eng., NTU

Reference 1. J. Bard and L. R. Faulkner, Electrochemical methods: fundamentals and applications, 2 nd ed., John Wiley & Sons, Inc., New York (2001). 2. Applied Electrochemistry Notes ( 嘉筠、仲偉 ) 3. Handout of Ch 6 ( 瑋翰 ) 4. Joseph Wang, Analytical Electrochemistry, 3 rd ed., John Wiley & Sons, Inc., (2006) 5. 達人學長 ’s work 6. M. Y. Yen et al., RSC Adv., 2012, 2, Electro-Optical Materials Lab., Dept. Chem. Eng., NTU Thanks for your attention!