Lecture #17 of 18 - UCI Department of Chemistryardo/echem/UCI-CHEM248-2017W_lectur… · There is...
Transcript of Lecture #17 of 18 - UCI Department of Chemistryardo/echem/UCI-CHEM248-2017W_lectur… · There is...
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1237
Lecture #17 of 18
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1238
Q: What’s in this set of lectures?
A: B&F Chapter 3 main concepts:
● Sections 3.1 & 3.6: Homogeneous Electron-Transfer
(ET) (Arrhenius, Eyring, TST (ACT),
Marcus Theory)
● Sections 3.2, 3.3, 3.4 & 3.6: Heterogeneous ET (Butler–Volmer
Eq, Tafel Eq, Volcano Plot,
Gerischer Theory, Quantum
Mechanical Tunneling)
● Section 3.5: Multistep ET Mechanisms
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But wait! You told us that Marcus Theory led to an inverted region
… where is evidence for the inverted region by electrochemistry?
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-lecture.pdf
–ΔG0 < λ –ΔG0 > λ
–ΔG0 = λ
• Three regions of electron transfer• (I) Normal, (II) Barrierless, (III) Inverted
1239
… and you told us that this had a Gaussian shape…
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There is no inverted region! Thank you, Fermi, Marcus & Gerischer! 1240
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states
from Wiki andhttp://www.fhi-berlin.mpg.de/
pc/PChistory.html
Enrico Fermi(1901–1954)
Physicist
Heinz Gerischer(1919–1994)
Electrochemist
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There is no inverted region! Thank you, Fermi, Marcus & Gerischer! 1241
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states
ρ has units of
cm-2 eV-1
Enrico Fermi(1901–1954)
Physicist
Heinz Gerischer(1919–1994)
Electrochemist
from Wiki andhttp://www.fhi-berlin.mpg.de/
pc/PChistory.html
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There is no inverted region! Thank you, Fermi, Marcus & Gerischer! 1242
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states & molecule states
ρ has units of cm-2 eV-1
… and has units of cm-3 eV-1
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There is no inverted region! Thank you, Fermi, Marcus & Gerischer! 1243
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states & molecule states
ρ has units of cm-2 eV-1
… and has units of cm-3 eV-1
… it’s that Gaussian
term!
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… the rate of electron transfer is dictated by the law of mass action 1244
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states & molecule states
constant(cm3 eV)
area(cm2)
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… the rate of electron transfer is dictated by the law of mass action 1245
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states & molecule states
constant(cm3 eV)
area(cm2)
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… the rate of electron transfer is dictated by the law of mass action 1246
Ebias varies the probability function (0, 1)
… resulting in (D)istributions of occupied metal states & molecule states
≈ 0
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… experimental validation of the theory and lack of inverted region 1247
Sikes, Smalley, Dudek, Cook, Newton, Chidsey & Feldberg, Science, 2001, 291, 1519Chidsey, Science, 1991, 251, 919
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… experimental validation of the theory and lack of inverted region 1248
λ = 0.85 eV
λλ
Chidsey, Science, 1991, 251, 919
RC double layer charging 1st order electron-transfer kinetics
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… experimental validation of the theory and lack of inverted region 1249
λ = 0.85 eV
λλ
Chidsey, Science, 1991, 251, 919
… and there was no inverted region because at large driving forces there was
always a state in the metal that overlapped the most probable DO
Ebias
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… experimental validation of the theory and lack of inverted region 1250
λ = 0.85 eV
λλ
Ebias
Chidsey, Science, 1991, 251, 919
… and there was no inverted region because at large driving forces there was
always a state in the metal that overlapped the most probable DO
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… experimental validation of the theory and lack of inverted region 1251
λ = 0.85 eV
λλ
Ebias
Chidsey, Science, 1991, 251, 919
… and there was no inverted region because at large driving forces there was
always a state in the metal that overlapped the most probable DO
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1252Well, that was disappointing… when is there an inverted region?
… at semiconductors!
… but how?
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
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1253Well, that was disappointing… when is there an inverted region?
… at semiconductors!
… but how?
Ebias
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
inverted
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1254
Ebias
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
Well, that was disappointing… when is there an inverted region?
… at semiconductors!
… but how?
… Vary the molecule, not the bias!
… but λ must be “the same” for each!
barrierless
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1255Well, that was disappointing… when is there an inverted region?
… at semiconductors!
Ebias
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
normal
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1256Well, that was disappointing… when is there an inverted region?
… at semiconductors!
Ebias
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
λ = 0.67 eV
… cm4 s-1… a second order rate
constant (… x concentration2)
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1257Well, that was disappointing… when is there an inverted region?
… at semiconductors!
Ebias
bandgapHamann, Gstrein, Brunschwig & Lewis,
JACS, 2005, 127, 7815 and JACS, 2005, 127, 13949
λ = 0.67 eV
… cm4 s-1… a second order rate
constant (… x concentration2)
… but more work is still needed
in order to nail this!
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1258
Q: What was in this set of lectures?
A: B&F Chapter 3 main concepts:
● Sections 3.1 & 3.6: Homogeneous Electron-Transfer
(ET) (Arrhenius, Eyring, TST (ACT),
Marcus Theory)
● Sections 3.2, 3.3, 3.4 & 3.6: Heterogeneous ET (Butler–Volmer
Eq, Tafel Eq, Volcano Plot,
Gerischer Theory, Quantum
Mechanical Tunneling)
● Section 3.5: Multistep ET Mechanisms
Electrode kinetics, … DONE!
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1259Let’s summarize the steady-state behavior from the entire course…
… by looking at data on stirred (non-hysteretic) I–E (J–E) curves
… and at each location, let’s think about what resistance is limiting the
observed behavior…
Circuit representation of electrochemical cell
RuRET RMTRDL
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1260RECALL: Let’s compare total capacitance (C) and differential
capacitance (Cd) as follows:
Ez = pzc
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1261Let’s summarize the steady-state behavior from the entire course…
… by looking at data on stirred (non-hysteretic) I–E (J–E) curves
… and at each location, let’s think about what resistance is limiting the
observed behavior
… so, we want to know what dictates at each E
Fe3+/2+ and H+
electrocatalysis
H+/H2electrocatalysis
𝑅 =𝜕𝐼
𝜕𝐸
−1
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1262Let’s summarize the steady-state behavior from the entire course…
… by looking at data on stirred (non-hysteretic) I–E (J–E) curves
… and at each location, let’s think about what resistance is limiting the
observed behavior
… so, we want to know what dictates at each E
… but this will be hard because we have several convoluting factors
… what are the limiting behaviors of each major resistance and can we
even begin to piece out which component is responsible, while recalling
that the total Eapp(I) = EET(I) + EDL(I) + EMT(I) + Eu(I) + …? …
𝑅 =𝜕𝐼
𝜕𝐸
−1
Circuit representation of electrochemical cell
RuRET RMTRDL
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1263… what are the limiting behaviors of each major resistance and can
we even begin to piece out which component is responsible? …
electrocatalysis
masstransport
resistance(iR drop)
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1264Let’s try some examples… EXAMPLE #1
electrocatalysis
masstransport
resistance(iR drop)
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1265Let’s try some examples… EXAMPLE #1
electrocatalysis
masstransport
resistance(iR drop)
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1266Let’s try some examples… EXAMPLE #2
electrocatalysis
masstransport
resistance(iR drop)
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1267Let’s try some examples… EXAMPLE #2
electrocatalysis
masstransport
resistance(iR drop)
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1268Let’s try some examples… EXAMPLE #3
electrocatalysis
masstransport
resistance(iR drop)
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1269Let’s try some examples… EXAMPLE #3
electrocatalysis
masstransport
resistance(iR drop)
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1270Let’s try some examples… EXAMPLE #4
electrocatalysis
masstransport
resistance(iR drop)
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1271Let’s try some examples… EXAMPLE #4
electrocatalysis
masstransport
resistance(iR drop)
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1272Let’s try some examples… EXAMPLE #5
electrocatalysis
masstransport
resistance(iR drop)
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1273Let’s try some examples… EXAMPLE #5… You get the idea! …
… and what does ELJ or EDonnan do to these plots? Shifts them left/right
electrocatalysis
masstransport
resistance(iR drop)
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1274
Q: What’s in this set of lectures?
A: B&F Chapters 9, 10, and 6 main concepts:
● Sections 9.1 – 9.4: Rotating (Ring-)Disk
Electrochemistry
● Sections 10.1 – 10.4: Electrochemical Impedance
Spectroscopy
● Sections 6.1 – 6.6, 11.7, 14.3: Linear Sweep Voltammetry
(LSV), Cyclic Voltammetry
(CV), Thin-Layer
Electrochemistry
To really learn about your laboratory systems
… move beyond steady-state conditions!
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1275RDE is also a steady-state technique (slide 1 of 3)…
At high rotation rates, C(0,t) = C*
… and then series current limited by electron-transfer at electrode (iK)
B&F 9.3.1 B&F 9.3.4
Levich Equation (term)
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1276RDE is also a steady-state technique (slide 2 of 3)…
By doing this as a function of
potential, one can determine k0
and α… kinetic parameters
without dealing with trying to
stir “perfectly” as required for
B–V kinetics
At high rotation rates, C(0,t) = C*
… and then series current limited by electron-transfer at electrode (iK)
Levich Equation (term)
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1277… and RRDE is very useful, too! (slide 3 of 3)…
* Chemistry at disk can be confirmed at ring if ω is fast enough
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1278How do we learn anything from complex systems?
Steady-state reactions and processes can be amazingly complex (e.g. see
everything we have covered thus far)… ideally, we need to piece out each
mechanistic component from interrelated processes… we do this by
performing studies over various time regimes… thus, we need to change
the temporal response of our measurements!
• R(R)DE: stirring removes mass-transport limits, which is nice… rotating
the electrode does the same thing… so precisely change the rotation
rate… we can also surround the disk/button by a second ring electrode
to observe products of electron transfer
• EIS: sweep/scan potentials over very small range… but then change the
region (DC)… and also change the scan rate (AC)?
• CV: change the scan rate… mechanisms by Saveant’s “Foot of the
Wave” (e.g. ECE, etc.)… modeling using BASi DigiSim, EC Lab, etc.
• UME: sweep/scan VERY fast forward and backward
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1279
capacitor only:
capacitor &
resistor in series:
a few words about electrochemical impedance spectroscopy (EIS)
What is the “resistance”?
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1280
capacitor only:
capacitor &
resistor in series:
a few words about electrochemical impedance spectroscopy (EIS)
What is the “resistance”?( )
( )
E tR
I t
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1281we need a compact way to represent this impedance…
http://en.wikipedia.org/wiki/Electrical_impedance
Z = R + iX
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1282a complex plane representation of the total electrical impedance…
… It’s called a Nyquist plot.
http://en.wikipedia.org/wiki/Electrical_impedance
the total impedance
the resistivecomponent of the impedance
the capacitivecomponent of the impedance(reactance)
Z = R + iX
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Zim
(x 1
06)
1283let’s look at Nyquist plots for a few simple circuits:
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Zim
(x 1
06)
1284first, a series RC circuit… like with double-layer charging
𝑋 = 𝑍im =1
ω𝐶=
1
0.01 10−5 F= 107 Ω = 10 MΩ
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Zim
(x 1
06)
1285first, a series RC circuit… like with double-layer charging
for a capacitor, as
frequency increases
(max ~1 MHz), ZIm
decreases…
… until you hit the x-
axis, which is the
uncompensated
resistance in the cell
𝑋 = 𝑍im =1
ω𝐶=
1
0.01 10−5 F= 107 Ω = 10 MΩ
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1286… what about a parallel RC circuit?
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1287
at low frequency, Zim << ZRe
(= R), and the circuit
behaves like there is no
capacitor, and just a resistor
… a semi-circle… does this make sense?
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1288
at high frequency, Zim = 0,
and the circuit behaves like
there is no capacitor and no
resistor… so here, Ru = 0
… a semi-circle… does this make sense?
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1289
in between these limits, the
circuit has both capacitive
and resistive behavior
… a semi-circle… does this make sense?
maximum
phase angle
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1290
… to an electrical engineer, an electrochemical cell looks like this:
Zf is the Faradaic impedance
… called the Randles equivalent circuit
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1291
Here is the Nyquist plot for the “full” Randles equivalent circuit:
Angle is theoretically 45°
for a Warburg impedance, ZW
Finally, a simple way to measure Ru… assuming our potentiostat can do it
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1292… that was a brief primer on EIS, where S is for spectroscopy?
For example, from Wiki,
one type of IS is dielectric
spectroscopy which
monitors the screening
(permittivity) of systems as
a function of the frequency
of light (which is an EM
wave and is related to
wavelength by the speed
(of light))… Our data was
based on EM AC signals as
a function of frequency
too… Also, “impedance is
the opposition to the flow of
alternating current (AC) in a
complex system” and so
EI"S" is appropriate (but
confusing).
FOR YOUR REFERENCE
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1293
Q: What’s in this set of lectures?
A: B&F Chapters 9, 10, and 6 main concepts:
● Sections 9.1 – 9.4: Rotating (Ring-)Disk
Electrochemistry
● Sections 10.1 – 10.4: Electrochemical Impedance
Spectroscopy
● Sections 6.1 – 6.6, 11.7, 14.3: Linear Sweep Voltammetry
(LSV), Cyclic Voltammetry
(CV), Thin-Layer
Electrochemistry
To really learn about your laboratory systems
… move beyond steady-state conditions!