PIKE Technologies FTIR Spectroelectrochemistry
PIKE Technologies FTIR Spectroelectrochemistry
Introduction to ATR-SEIRAS 3
How It Works 4
J1 model 12
Surface-Sensitive Spectroelectrochemistry 14
J2 model 16
J3 “EEL” model 20
Additional reading 23
J4 H-Cell model 24
About PIKE 28
Our Technology 28
Contact Us 29
The PIKE
Technologies
Jackfish J1 cell.
ATR-SEIRAS:
A Powerful IR
Spectroelectro-
Chemistry
Measurement
Technique
2
Introduction to ATR-SEIRAS
Attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a
surface-sensitive FTIR spectroelectrochemical technique which exploits the enhanced electromagnetic
field produced by surface plasmon polaritons (SPPs) at the interface of a textured metal film.
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How It Works
4
Reconditioning Ag/AgCl
wires for the user-serviceable
reference electrodes.
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Jackfish Electrochemical Cells
The ease-of-use of the cells lets you hit the ground running and also
provides a flexible platform to grow as the requirements for your
spectroelectrochemical experiments change. Configurations are modular,
meaning you can upgrade and add on at any time.
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About Jackfish
Jackfish SEC was founded in
2018 in Saskatoon, Canada by
electrochemists at the University of
Saskatchewan. The team has spent
15 years designing, innovating and
testing spectroelectrochemical
cells for attenuated total reflectance
surface-enhanced infrared
spectroscopy (ATR-SEIRAS). Over
a decade of experiment-based
design improvements has led to
an innovative and commercially
available ATR-SEIRAS cell
design. Jackfish SEC is dedicated
to making advanced infrared
spectroelectrochemical technology
easily accessible to new users with
off-the-shelf solutions that allow you
to easily equip your laboratory with
ATR-SEIRAS capabilities.
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Choose Your VeeMAX Model
The VeeMAX III is a continuous variable-angle FTIR sampling accessory, and may
be configured for ATR and specular measurements. The angle of incidence may be
changed by simply turning an angular selection knob located at the bottom of the
VeeMax III. For more precise angular settings, an automated model is available.
Two optical configurations are available. The standard VeeMAX III fits into the
sample compartment of most commercial FTIR instruments and is designed
for use with a focused beam. For those using a collimated beam like found
with a laser-based instrument or optical tables, the VeeMAX III – Laser model
is recommended.
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Pick Your ATR Elements
Jackfish cells may be configured for use with VeeMAX face angled crystal (FAC) or micromachined
Si wafers. With the mix-and-match modular design, you can configure the cell to let you conduct
measurements with either ATR element format or the wafers. Each internal reflection element (IRE)
type has its advantages, and having access to either could be beneficial.
The FAC has high energy throughput to maximized sensitivity, and is available in several materials
including ZnSe, Si and Ge and face angles (45° and 60°). These are also easily polished. The Si FAC is
especially suitable for electroless gold deposition using an optional electroless deposition fixture.
The main advantage of the wafer is the reduced optical pathlength, which minimizes the attenuation
due to Si phonon modes. The wafers are low cost and can be reused; however, they are also more
fragile. The small dimensions of the wafer (9 x 11 mm) make it easy to deposit films on multiple wafers
at a time in a PVD chamber.
Two wafer models differing in the effective angle of incidence of the beam are available. The
ATR-SEIRAS optimized wafer model has a 55° micromachined prisms to couple the beam into
the wafer, and is ideal for direct coating with a metal film. The universal wafer model has a 35°
micromachined prisms, and is ideal for coating with a hybrid metal-metal oxide film. The hybrid film
offers a robust film that can hold over multiple uses.
If you still cannot decide on your IRE element, Jackfish combination cells are available, which includes
a single set of glassware, and both bases to allow you to use either crystal option, FAC or wafers.
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Jackfish Cell Models
Four cell models are available, J1, J2, J3 and J4. All are
fully compatible with the VeeMAX III variable-angle
ATR sampling accessory.
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J1 Model
The J1 uses ground glass joints designed for use with aqueous electrolytes and
offers a reference arm separated with a stopcock, which acts as a salt bridge
preventing migration of the reference electrode filling solution into the cell
body. There are three ports at the top of the cell and side ports for a reference
electrode arm and a short bubbler. Typical uses of the ports are to support the
counter electrode, and to accommodate glass bubblers and an exhaust gas trap.
The long glass bubbler allows sparging of the solution volume with inert gas to
remove atmospheric oxygen, enabling high-quality electrochemistry and ensuring
stability of the thin film electrode. The short gas bubbler is used to create an inert
atmosphere above the electrolyte.
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Long bubbler.
Counter electrode.
Exhaust gas trap.
Reference electrode.
Short
bubbler.
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APP NOTE
Surface-Sensitive
Spectroelectrochemistry
Experimental Conditions
The VeeMAX III fitted with the J1 cell was used as the FT-IR sampling accessory.
We sputtered a ca. 30 nm Au film electrode on a 60° angled Si ATR crystal. We
then cycled the potential of the film in 50 mM KClO4 supporting electrolyte
between -100 and +1100 mV vs Ag/AgCl. This cleans the film and textures the
surface to improve SEIRAS intensity. The VeeMAX III was set to 60° to match the
crystal face angle. FTIR spectra were collected at 4 cm-1 resolution, 128 scans, and
40 kHz scanning velocity using an MCT detector.
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Results
We used the potential-dependent adsorption of 4-methoxypyridine (MOP), a
nanoparticle shape-directing ligand, as a test system. We collected a reference
spectrum of supporting electrolyte, then a sample spectrum with 0.1 mM MOP,
both at the open circuit potential. The result is shown below. We observe two
strong ring vibrations (1) and the methoxy C-O-C asymmetric stretch (2). A third
ring vibration (3) has its transition dipole moment (TDM) mostly parallel to the
electrode-solution interface when adsorbed, so (3) is very weak. Only vibrations
with their TDM normal to the interface are IR active. This confirms the surface
sensitivity of the measurement.
ATR-SEIRAS spectra of
4-methoxypyridine (MOP).
(b) MOP
potential difference
spectrum. Sample: +200
mV (MOP adsorbed).
Reference: -700 mV.
Conclusion
With PIKE’s variable-angle VeeMAX III ATR accessory and J1 cell, we have
demonstrated a surface-sensitive technique which can resolve minute changes in
interfacial composition.
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J2 Model
The J2 offers a simple sealed design compatible with volatile solvents, where
the electrodes are inserted directly into the cell in close proximity to the
working electrode, reducing the impedance to the reference electrode. With a
compression-style fitting, the J2 accepts reference and counter electrodes having
diameters between 5 and 7 mm.
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Liquid example
Below are spectral data for the analysis of carbohydrate content in a soft drink
sample. The red (high) spectrum was collected using a 10-reflection HATR
accessory, while the blue (low) spectrum was collected using a single-reflection
ATR. Both use an identical scaling factor.
In this case, the minor carbohydrate bands are more readily apparent in the
multi-reflection ATR
Top cap with accessory.
septum
for Schlenk technique.
Ag/AgCl reference
electrode.
Counter electrode.
Soft drink sample using 10-reflection (red, high) and 1-reflection (blue, low) ATR.
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Which Do You Need?
J1 Model J2 Model
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J3 “EEL” Model
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Gas trap.
Reference electrode.
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APP NOTE
The EEL In Application
The most apparent use of a flow cell is for dynamic studies, in particular,
irreversible reactions where reagents must be continually introduced. ATR-SEIRAS
can provide information to help determine electrocatalytic reaction mechanisms
by providing structural information of surface species. Noteworthy applications
include CO2 electroreduction as well as electro-oxidation of small molecules such
as methanol and formic acid. Any catalyst material that can be deposited as a thin
film on the ATR internal reflection element can be studied with the EEL cell.
The small volume of the cell enables high flow rates without excessive electrolyte
use. Note: the pulsed flow from the use of a peristaltic pump induces current
fluctuations which increase in frequency as the flow rate is increased.
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Additional Reading
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J4 H-Cell Model
Multiple ports are provided to facilitate the introduction of gases to the cell and
accommodate a wide variety of experimental setups.
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Gas sparger.
Reference
electrode.
Counter electrode.
H-union for
semipermeable membrane.
Quartz window.
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DID YOU
KNOW?
Electrolessly
deposited films require
scrupulously clean
surfaces, while the
cleanliness conditions
are relaxed somewhat
if a conductive metal
oxide underlayer
is used for electro-
depositing a metal film.
Electrochemical Cleaning
After deposition of gold on a Si internal reflection element (IRE), electrochemical
cleaning is required to obtain a SEIRAS active gold layer. The guidelines below
give a brief description on how to perform electrochemical cleaning and
determine the SEIRAS activity of a gold thin film using acetate adsorption.
Complete three cycles at this potential window, increase the positive limit by 100
mV and perform an additional three cycles. When the positive limit has reached
+600 mV (vs Ag/AgCl) start monitoring the IR activity of adsorbed acetate
following the steps outlined here.
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IR Monitoring of Acetate Adsorption during Cleaning
The symmetric COO- stretching of acetate adsorbed on gold is observed at 1400 cm-1. The
potential dependence of acetate adsorption/desorption on the gold surface is an indication
of the SEIRAS activity of the gold layer. Use the following method during the electrochemical
cleaning procedure.1
Start monitoring acetate adsorption/desorption as the positive potential limit extends beyond
+600 mV (vs Ag/AgCl). After three cycles at each potential window hold the potential at -100
mV (vs Ag/AgCl) for reference potential and +600 mV (vs Ag/AgCl) for sample potential.
Measure an IR spectrum at each of the sample and reference potentials. Monitor COO-
stretching vibration at 1400 cm-1 and continue the electrochemical cleaning.
Figure 1. (a) Typical CV of gold electrochemical cleaning using acetate buffer,100 mM acetate at pH 3.6
and 20 mV/sec scan rate and Ag/AgCl reference electrode. (b) Potential dependence of symmetric COO-
stretching of adsorbed acetate on clean gold surface after electrochemical cleaning procedure. Absorbance
spectrum for 630 mV, 430 mV, 230 mV, and 30 mV (vs Ag/AgCl) all referenced to -100 mV (vs Ag/AgCl).
When gold oxidation and reduction is reached in the CV, increase the potential limits by 50
mV increments. Gold oxidation typically starts at about +1.0 V (vs Ag/AgCl). Refer to Figure 1
for a typical CV of electrochemical cleaning of gold on Si IRE and the potential dependence of
COO- stretching at 1400 cm-1 on a clean gold surface.
1
Delgado, J. M.; Orts, J. M.; Pérez, J. M.; Rodes, A. Journal of Electroanalytical Chemistry 2008, 617, 130.
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Contact Us
As you review our catalog, know that our team is always available to help
you choose the best accessory for your application and answer any technical
questions you may have.
To place an order
Please include the following information when placing an order: your name, phone
number, product part number, quantity, ship to address, bill to address, purchase
order number and spectrometer model on which the accessory will be used.
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About PIKE
In 1989, Phil and Irene Brierley had a dream. They envisioned an enterprise that
would specialize in imaginative design and manufacture of custom spectroscopic
accessories. They wanted to integrate new technology that would make the life of
a spectroscopist easier and more efficient—all at an outstanding value. Together,
Phil and Irene founded PIKE Technologies.
Throughout the years, Phil and his team created a comprehensive line of sampling
accessories. Phil passed away in 1999, but his legacy lives on.
Our Technology
AT PIKE Technologies, we manufacture a wide range of spectroscopic accessories
and sampling solutions:
- Team PIKE
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Notes
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Notes
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© PIKE Technologies, Inc.
6125 Cottonwood Drive,
Madison WI 53719
608.274.2721
[email protected]
www.piketech.com