EC2/BIG-NSE INTERVIEW

Lic. Emiliano Sebastian Dal Molin

April 2020
 ELECTIVE SUBJECTS
STUDIES AT THE UBA - Organometallic Chemistry
(University of Buenos Aires) - Supramolecular Chemistry
- Liquid Crystals

DEGREE OBTAINED
GRADUATE COURSES
Licenciatura en Ciencias Químicas - 6 years - - Estimation of uncertainty in chemical analysis
methodologies
GRADE AVERAGE
8.13/10 (Historical average for 2017: 7.22) - Statistical design and analysis of experiments

LANGUAGES
Spanish OTHER COURSES

English - Matlab simulation

Portuguese - Basic Fluid mechanics
German (Ongoing - Level B1-B2) - Data analysis & Automatization with
Python

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 EXPERIENCE IN THE FIELD

CNEA INQUIMAE-CONICET AMPACET KIT-LTI

Research activities Research activities R&D supervisor role Research activities

2,5 years 1 year 5 months

2 years
- undergraduate researcher under Dr. - Research assistant under Dr. San - Research assistant under Prof. Dr.
- Research and Managerial activities -
Roncaroli- Roman & Dr. Rodriguez - Lemmer -

Electrochemical catalysis Photocatalyzed Generation of Plastic and plastic additives, Nanoparticle and organic
singlet oxygen. product development semiconductor synthesis.
Ink development for
screen printing

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HIGHLIGHTED ACHIEVEMENTS

Leading over 30 projects as a Product developer in Ampacet

10 of which ended up being new specialty products, with one profiting over 200k USD
in its first quarter.

Building and fine tuning a custom measurement set up to measure singlet

oxygen production.

Publication of an Electrocatalysis article in Electrochimica Acta.

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 Article presentation –
Cobalt and Iron Complexes with N-heterocyclic Ligands as
Pyrolysis Precursors for Oxygen Reduction Catalysts.
- Electr. Acta 174 (2015) 66-77

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INTRODUCTION & AIM
• The ORR has a high energy barrier

• It requires a high load of catalyst to produce

useful currents

• Industry standard is Pt supported on Vulcan

Figure 1:
Basic functioning of a PEMFC , along with the net
carbon reactions.

Garraín, Daniel et al. “Polymer Electrolyte Membrane Fuel Cells

(PEMFC) in Automotive Applications: Environmental Relevance of the
Manufacturing Stage.” (2011).

• Alternative: pyrolyzed Fe/Co N-heterocyclic

complexes.

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INTRODUCTION & AIM

• Aim of the study: Screen several catalysts to

develop insight and tools for the rational design of
ORR catalysts in acidic media
• Exact nature of the active center for this catalysts is
still unknown.
• Possible alternatives include:
• Metal particles
• Metal-N4 fragments
Figure 2:
• Metal-free active center, where the N atoms Co(phen)3 nCl2 ,the best performing precursor in this
study.

catalyze the reaction

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INTRODUCTION & AIM
Pyrrolic- type ligands (5 membered rings) Pyridinic-type Ligands (6 membered rings)

Figure 2: Several of the ligands used in the study

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INTRODUCTION & AIM
Pyrrolic- type ligands (5 membered rings) Pyridinic-type Ligands (6 membered rings)

Figure 2: Several of the ligands used in the study

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EXPERIMENTAL DESIGN
- Catalyst Preparation -

ADDITION OF CARBON,
DISSOLUTION AND
SONICATION AND PYROLYSIS INK
COMPLEXATION
DRYING

PHYSICAL ELECTROCHEMICAL
CHARACTERIZATION CHARACTERIZATION

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EXPERIMENTAL DESIGN
- Physical Characterization -

● TGA – Thermo Gravimetric Analysis

● XPS – X-Ray Photoelectric Spectroscopy

● EDX-Energy Dispersive X-Ray Spectroscopy

● XRD- X-Ray Diffraction

● Raman Spectroscopy

● SEM-Scanning Electron Microscopy

● TEM-Transmission Electron Microscopy

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EXPERIMENTAL DESIGN
- Electrochemical Characterization -

MEASUREMENTS

● Cyclic Voltammetry
● Rotating Ring and Disk Electrode Voltammetry

Figure 3
Flow on the surface of an RRDE.
Image property of AZO Materials.
https://www.azom.com/article.aspx?ArticleID=14363
Figure 4
1-step and 2-step ORR in the surface of an RRDE.
Image property of AZO Materials. Taken from
https://www.azom.com/article.aspx?ArticleID=14363
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EXPERIMENTAL DESIGN
- Electrochemical Characterization -

KEY PERFORMANCE INDICATORS

TAFEL SLOPE AVG. NUMBER OF

ELECTRONS TRANSFERRED
PER MOLECULE

EQUILIBRIUM POTENTIAL

HYDROGEN
PEROXIDE YIELD
EXCHANGE CURRENT
DENSITY

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RESULTS
- Physical Characterization -
TGA

Figure 6
Thermogravimetric analysis of selected catalyst precursors:
1. Vulcan REF
2. Phenanthroline on Vulcan REF
3. Co(ATZC) on Vulcan 5
4. Co(bis-Me-Im) on Vulcan 5
5. Co (CO2Pz) on Vulcan 6
6. FeCo(TPTZ) on Vulcan 6
7. Co(phen) on Vulcan 6
All catalysts were obtained under a N2 flow of 20 ml min^-1 and a
heating rate of 10 C min^-1.

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RESULTS
- Physical Characterization -
XPS

Figure 7
High resolution XPS spectra in the N 1s region for some selected
catalysts and reference compounds:
1. Phenanthroline REF
2. Co(phen)3Cl2 REF
3. Co(ATZC) Vulcan 700 C 5
4. Co(bis-Me-Im) Vulcan 700 C 5
5. Co(CO2Pz) Vulcan 700 C 6
6. FeCo(TPTZ) Vulcan 700 C 6
7. Co(phen) Vulcan 700 C 6
8. Co(phen) meso 700 C. 6
Simulations were done using Gaussian line shapes and are shown in
color. Solid black lines correspond to experimental spectra.

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RESULTS
- Physical Characterization -
XPS & EDX
Table 1 and Figure 8
Element composition for selected catalyst
(% weight) obtained from EDX and XPS spectra.

• No nitrogen content in the bulk. Only in the

surface!

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RESULTS
- Physical Characterization -
XPS & EDX

Figure 9
Element composition for selected catalyst
(% weight) obtained from EDX and XPS spectra.

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RESULTS
- Electrochemical Characterization -
CYCLIC VOLTAMMETRY

Figure 10
Cyclic voltammetry of the Co(CO2Pz) Vulcan 700 C catalysts supported
on a gold disk, in N2 or O2-saturated 0.5 M H2SO4 solution, 25 C, scan
rate 5 mV s-1 .

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RESULTS
- Electrochemical Characterization - TAFEL SLOPES

< + Overpotential 1. Carbon support

2. Carbon support + metal salt
3 + 4. 5 membered ring Ligands
5 + 6 + 7. 6 membered ring Ligands
8. 6 membered ring Ligand on Mesoporous carbon (Higher
specific surface + double catalyst load)

Figure 11 Figure 12
Example of a Tafel plot, for the linear region. By Jakobswiki - Own work, CC BY 3.0,
Current–potential curves for ORR on selected catalysts obtained in an O 2- saturead 0.5 M H2SO4 solution on Au disk at 2500 rpm
https://commons.wikimedia.org/w/index.php?curid=11393375
and 25 C. The catalysts were obtained at 700 C and supported on Vulcan carbon, otherwise stated. 1. Vulcan, 2. CoCl 2 Vulcan, 3.
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Co(ATZC), 4. Co(bis-Me-Im), 5. Co(CO2Pz), 6. FeCo(TPTZ), 7. Co (phen), 8. Co(phen) x2 on Mesoporous carbon (higher complex
load), 9. Pt 10% on Vulcan (not pyrolyzed).
RESULTS
- Electrochemical Characterization -
• Optimal pyrolysis temperature
• Higher specific surface area
• 6 membered ring ligand
• High retention in TGA

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 RESULTS
- Electrochemical Characterization -
6 members:
• High correlation between Surface N 5,6,7,8,9,10,11,12,13,14
% and current intensity. 5 members: 3,4
• Low to no correlation with %Co Control: 1,2

Figure 13
Plot of the Logarithm of the disk intensity (at 0.7 V vs Ag/AgCl, O 2 saturated 0.5 M H2SO4) vs nitrogen content (% w/w, from XPS). 1. Vulcan, 2. CoCl 2 Vulcan 700 C, 3. Co(ATZC) Vulcan 700 C, 4. Co (bis-Me-Im)
Vulcan 700 C, 5. Co (CO2Pz) Vulcan 700 C, 6. FeCo(TPTZ) Vulcan 700 C, 7. Co(phen) Vulcan 700 C, 8. Co (phen) x2 meso 700 C (higher complex load), 9. Co(phen) meso 700 C, 10. Co (phen) x2 Vulcan 700 C
(higher complex load), 11. Co(phen) meso 900 C, 12. Co (phen) Vulcan 900 C, 13. Co(phen) Vulcan 500 C, 14. Co(phen) x2 Vulcan 700 C 0.5 M H 2SO4 leached (8 h, 100 C), 15. Phenanthroline Vulcan 700 C.
Inset: analogous plot for the Co content (% w/w, from XPS).

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CONCLUSION
● The influence of the nature of the nitrogenated ligand in the precursor complex on the catalytic activity for the
oxygen reduction reaction was investigated.

● After pyrolysis, all of the catalysts had a similar Nitrogen speciation profile. Consequently, it is not possible to
identify whether the Pyrrolic-N or the Pyridinic-N are responsible for the catalytic activity.
● The catalysts with 6 membered ring ligand precursors had better electrochemical properties, as well as higher
TGA retention and higher superficial N content.
● The results discourage the metal particle active center hypothesis. (No current correlation with metal content)

● Further studies with Co-(CO2-Pz) MOFs took place, reaching levels comparable to those of Pt 20% in test fuel
cells.

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Research Plans
in
BIG/NSE

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Proposal 13- Carbonylation and Carboxylation of Alkanes in Fluorinated Solvents
or scCO2
● Main objective: Design of a scCO2-soluble binuclear Ir-Rh complex for the coupling of Alkane
activation and carbonylation/carboxylation reactions.
● Using already proven behavior for Ir (activation of alkanes) and Rh (carbonylation of Alkyl
Ligands) .
● Adding fluorinated moieties (RF) to impart solubility in supercritical CO2 and Fluorinated
solvents
● Controlling the distance between the metal centers by adding tension to the bonds using
different (progressively bulkier) side chains (R).
● Studies to understand the nature of interaction between the RF fragments and fluorinated solvents
will be carried out via 19F-NMR and DFT calculations.
● Mechanistic studies in fluorinated solvents will be carried out via NMR , FTIR, and Raman
Spectroscopy as well as in silico.

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Proposal 13- Carbonylation and Carboxylation of Alkanes in Fluorinated
Solvents or scCO2

Synthesis of different Synthesis of Binuclear Evaluation of

bidentate Ligands Complexes catalytic activity. Mechanistic Studies

Computational studies

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Proposal 9- Additive manufacturing (3D printing) of chemo- and biocatalysts with
control over spatial composition and dynamic functionalities

● Main objective: Development of Additive manufacturing techniques for an array of catalysts

including metal NPs, Metal-organic Complexes, and Enzymes, with a focus on maximizing
catalysis performance through optimization of 3D geometry.

● Two work proposals are put forward:

● WP1: Printing heterogeneous catalyst-loaded slurries by DIW.

● This work proposal will center around obtaining optimal ink rheological behavior for the
proposed catalysts , by systematic variation of parameters such as pH, ionic strength, binder,
plasticizer, etc.

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Proposal 9- Additive manufacturing (3D printing) of chemo- and biocatalysts with
control over spatial composition and dynamic functionalities – WP1

Slurry preparation and rheological Reactor Evaluation of Working

characterization printing KPIs. prototype

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Proposal 9- Additive manufacturing (3D printing) of chemo- and biocatalysts with
control over spatial composition and dynamic functionalities

● WP2: Obtaining porous Si-containing thermoset hydrogels printed by SLA which can then be
loaded with Hydrogenases or other enzymes.

● The second proposal will explore different printing techniques, enzyme immobilization methods
and geometrical arrangements (including pore size and geometry) to produce and evaluate
reactor designs.
These prototypes will then be characterized by a variety of methods. The Biocatalyst mechanism
will also be investigated by computational methods.

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Proposal 9- Additive manufacturing (3D printing) of chemo- and biocatalysts with
control over spatial composition and dynamic functionalities – WP2

Hydrogel electrode design

and printing
Reactor Evaluation of
characterization KPIs.
Enzyme Loading
Studies

Working prototype

Enzyme Mechanism
Computational studies Studies

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Thank you!

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Questions?

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