WEBINAR

Photocatalytic synthesis
for a carbon neutral
production of fuels
and chemicals

28th April 20210

Presenter: name, name of organization, department

#SunCoChem This project has received funding from the European
Email: @SunCoChem_EU Union’s Horizon 2020 research and innovation
www.suncochem.eu programme under grant agreement No. 862192
AGENDA
15.00 – Welcome and introduction
16.05 - FlowPhotoChem: heterogenous
Maria Navarro, SunCoChem project coordinator, Eurecat
photo(electro)catalysis in flow using concentrated
Ricard Garcia-Valls, Director of the Chemical Technology Unit, Eurecat light
Pau Farràs, Director of the ChemLight group, Lecturer in Inorganic Chemistry
at the School of Chemistry, National University of Ireland – Galway
15.10 - Understanding the mechanism of (NUIG)
(photo)electrochemical transformations in functional
architectures for artificial photosynthesis
Francesca Toma, CSD staff scientist, Joint Center for Artificial Photosynthesis (JCAP), 16.20 - DECADE: photoelectrocatalysis for the
Lawrence Berkeley National Laboratory
conversion of CO2 avoiding water oxidation
Gabriele Centi, Full Professor in Industrial Chemistry, University of Messina,
15.40 – Questions & answers President, European Research Institute of Catalysis (ERIC)

15.50 - SunCoChem: photoelectrocatalysis for CO2 16.35 – Q&A and discussion

conversion for in-situ carbonylation through renewable
energies
Míriam Díaz de los Bernardos, SunCoChem Scientific Coordinator, Head of the Synthesis and 16.55 – Closure, end of the session
Catalysis Line at Chemical Technologies Unit, Eurecat
Simelys Hernandez, SunCoChem Technical Coordinator, Associate Professor, Politecnico di
Torino

PHOTOCATALYTIC SYNTHESIS FOR A

CARBON NEUTRAL PRODUCTION OF
FUELS AND CHEMICALS
2
SPEAKERS INTRODUCTION

Ricard Garcia-Valls María Navarro Francesca Toma

Director of Chemical SunCoChem project coordinator, CSD staff scientist,
Technologies Unit Project Manager Joint Center for Artificial Photosynthesis (JCAP)
Eurecat Eurecat Lawrence Berkeley National Laboratory

Miriam Diaz de los Bernardos Pau Farràs Gabriele Centi

SunCoChem scientific coordinator, Head of the Synthesis Director of the ChemLight group, Lecturer in Full Professor in Industrial Chemistry,
and Catalysis Line at Chemical Technologies Unit Inorganic Chemistry at the School of Chemistry University of Messina – Italy
Eurecat National University of Ireland – Galway (NUIG) President of European Research Institute of Catalysis (ERIC)

PHOTOCATALYTIC SYNTHESIS FOR A #SunCoChem

CARBON NEUTRAL PRODUCTION OF @SunCoChem_EU 3
FUELS AND CHEMICALS www.suncochem.eu
Eurecat Chemical Technology Unit

Strategic lines
The team

Development of new synthetic and catalytic methods

Membrane Technology and Encapsulation

Polymer chemistry and technology

Process development: lab to pre-comercial scale

PHOTOCATALYTIC SYNTHESIS FOR A #SunCoChem

CARBON NEUTRAL PRODUCTION OF @SunCoChem_EU 4
FUELS AND CHEMICALS www.suncochem.eu
CE-NMBP-25-2019: Photocatalytic synthesis (RIA)

Scope:
• Development of cheap materials and integrated processes/devices for the direct photocatalytic conversion of CO2 (from
anthropogenic CO2 sources and/or from air) and H2O to fuels and/or chemicals, with an overall solar-to-hydrogen
efficiency of >20%

TRL:
• Activities should start at TRL 3 and achieve TRL 5 at the end of the project.

Challenge:
• The efficient storage and utilisation of solar energy in the form of chemicals or chemical energy will play a key role to
transform the European industry into a low carbon economy. In the long term, there will be a need for highly integrated
solutions enabling the carbon-neutral production of high-value chemicals or energy, which is crucial to reduce CO2
emissions. The development of integrated processes will require a systems-catalysis approach that includes engineering
aspects as small scale and intermittent operation.

PHOTOCATALYTIC SYNTHESIS FOR A #SunCoChem

CARBON NEUTRAL PRODUCTION OF @SunCoChem_EU 5
FUELS AND CHEMICALS www.suncochem.eu
 Thank you!

#SunCoChem This project has received funding from the European

@SunCoChem_EU Union’s Horizon 2020 research and innovation
www.suncochem.eu programme under grant agreement No. 862192
 WEBINAR

Photocatalytic synthesis
for a carbon neutral
production of fuels
and chemicals
Understanding the mechanism of (photo)electrochemical
transformations in functional architectures for artificial
photosynthesis
Francesca Maria Toma,
Chemical Sciences Division
Lawrence Berkeley National Laboratory
https://www.tomaresearchgroup.org/
fmtoma@lbl.gov

Presenter: name, name of organization, department

#SunCoChem This project has received funding from the European
Email: @SunCoChem_EU Union’s Horizon 2020 research and innovation programme
www.suncochem.eu under grant agreement No. 862192
Sunny California or not? 9 September 2020
 Energy Problem and Climate Change

climate.nasa.gov

United Nations sustainable development goal 7: Affordable and clean energy

By 2030:
• increase share of renewable energy in the global energy mix
• enhance international cooperation to facilitate access to
clean energy research and technology
 Global Temperature Increase: A Closer Look

• The global temperature record represents an average over the entire surface of the planet

• Consequences may involve very cold winters and warm summers that can cause natural disasters (fires,
flooding, draughts…)

What is the solution?

https://earthobservatory.nasa.gov/world-of-change/DecadalTemp
Renewable Energy Options: Path to Zero Emissions

Adapted from: Nat. Mater. 2016, 16-22

Renewable Energy Options: Path to Zero Emissions
• The price of solar power
modules <0.5 US$ W-1
• On track to meet the target
for residential solar power
by 2030.

• High energy is crucial for electric vehicles batteries

• Stability (>20 years) is essential for grid storage

• Solar and chemical fuels are a convenient

way to store electricity as their volumetric
and gravimetric energy density outperform
batteries

Adapted from: Nat. Mater. 2016, 16-22

In focus: Fuels vs. Batteries in numbers

Less
volume

(Gravimetric) Weighs less Credit: Prof. Joel Ager

 The Solar Fuel Hub
5 Reserch Institution Collaboration with >130 Scientists and Engineers

2010-2016: Integrated H2 Generator 2016-2020/2021-2026: CO2 Reduction

Towards a New Concept of Functional Interfaces

Walczak, Sharp et al. Adv. Energy Mater. 2017, Toma, Deutsch, Weber, Danilovic et al. Adv. Energy Mater. 2020
 Integrated Solar Fuel Generator
Catalysts, light absorbers and interfaces – stable, efficient, and scalable

• Catalysts: Oxygen Evolving Catalyst (OER) and Hydrogen Evolving Catalyst (HER)

• Light absorbers: Photoanode (oxidation) and Photocathode (reduction)

• Interfaces and contacts: catalyst/light absorber interface and fluorine doped

SnOx (FTO)
 Research Focus
Interface engineering for solar to Advanced characterization of
chemical transformations chemical transformations
Nat. Comm. 2016
ChemSusChem 2015, Nat. Comm. 2016
Energy Environ. Sci. J. Mater. Chem, A 2017
2016, Nat. Comm. 2018
J. Phys. Chem. Lett 2015, ACS Appl. Mater. Interface 2018,
Suistainable Energy and Eichhorn et al in prep. 2019
Fuels 2019,

Synthesis of novel electrocatalysts Addressing challenges in CO2

for CO2 reduction photoelectroreduction

JACS 2019, ACS AEM 2020 J. Mater. Chem, A 2017, Liu et al submitted 2020
Artificial Photosynthesis
Transparent
Recombination
Layer

H2 2e-
~0.6 V
2H+ 2H2O
4h+
~1.1 V
E O2 + 4H+

p-type n-type
x photocathode photoanode

O2 + 4H+ + 4e- 2H2O

4H+ + 4e- 2H2 Thermodynamic requirements E = 1.23 V
2H2O 2H2 + O2 with kinetics E = 1.7 V
 Outline

• Understanding heterogeneity in
integrated photoelectrodes
100 nm

• Mechanistic understanding of dynamic

transformations in Si/GaN photocathode

• Harnessing nanointerfaces and local

environments for chemical reactions
 Outline

• Understanding heterogeneity in
integrated photoelectrodes
100 nm

• Mechanistic understanding of dynamic

transformations in Si/GaN photocathode

• Harnessing nanointerfaces and local

environments for chemical reactions
 Synthesis of Homogeneous and Reproducible BiVO4
Substrates
Reactive Sputtering pH 6.8, 1M KPi, 0.1 M Na2SO3

Mo-BiVO4
2 um 1 sun

Undoped-
BiVO4
1 sun
200 nm
dark

• Scalable and reproducible synthesis

• Improved performance

Demonstrate stability over a prolonged (100 h) amount of time

L. Chen, F. M. Toma, J. K. Cooper, A. Lyon, Y. Lin, I. D. Sharp, J. W. Ager, ChemSusChem 2015, 8, 1066-1071
 Stability Analysis of PEC Activity

Ideal behavior pristine BiVO4

SEM: As Deposited After 60’ at pH 6.8 After 20’ at pH 12.3

1M KPi
pH 6.8

1M KPi
pH 12.3
500 nm 500 nm 500 nm

Understanding chemical instability in situ characterization

F. M. Toma* et al, Nat. Commun. 2016, 7, 12012
Real-Time Transformations with EC-AFM
• Real-time observation of dissolution process of BiVO4

• Degradation starts at solid/liquid interfaces

• Development of a multimodal approach under operating conditions

SEM: As Deposited After 60’ at pH 6.8 After 20’ at pH 12.3

500 nm 500 nm 500 nm

Measurements performed at pH 12.3 (1 M KPi) under dark at 1.23 V vs RHE

nm F. M. Toma* et al, Nat. Commun. 2016, 7, 12012

 Mapping Local Heterogeneity at the Nanoscale

Absence of high current at grain boundaries indicate defect tolerance of BiVO4

There is a high heterogeneity at the nanoscale which influence macroscale

performance
 Elucidating chemical heterogeneity via STXM
Energy stacks Spectra

• STXM is a powerful technique to locally resolve variations in the

electronic and chemical structure of materials with a lateral
resolution of ~20 nm

• STXM provides spatially resolved spectra, images at specific X-ray

energies, or image-sequences across absorption edges
 Correlation between nanoscale morphology and
chemical heterogeneity
• Principal component analysis can help infer
the main spectral components

• We can exactly assign spectral changes to

specific variation in the chemical
composition across the sample

• Grain centers and grain boundaries/voids

correspond to different spectral
components
These changes are compatible with the presence of V2O5 at grain boundaries
J. Eichhorn, […], F. M. Toma* et al, Small 2020
 Outline

• Understanding heterogeneity in
integrated photoelectrodes
100 nm

• Mechanistic understanding of dynamic

transformations in Si/GaN photocathode

• Harnessing nanointerfaces and local

environments for chemical reactions
Increased Photocurrent and Onset Potential as a
Function of Time

Anodic shift of the

onset potential
Increase in the
photocurrent density

G. Zeng, […], F. M. Toma* et al, Nat. Mater. 2021,

Chemical Mapping as a Function of Time

Cease
Galliumofoxynitride
growth emerged
growing

Keeps increasing with

Saturated lower
Photocurrent rate
increased

G. Zeng, […], F. M. Toma* et al, Nat. Mater. 2021,

Chemical Mapping as a Function of Time After test
Pristine sample

Increased oxygen
concentration in the after
testing GaN
Top surface
Top surface
sidewall

sidewall

G. Zeng, […], F. M. Toma* et al, Nat. Mater. 2021,

DFT Calculations – Formation Energy
GaN m-plane (1010) • The stable surface of the non-polar plane is
Ga partially O-substituted

N
• Free energy of hydrogen adsorption is
O optimal on the non-polar plane
Top surface
Top surface 3.5 suns
sidewall

sidewall

G. Zeng, […], F. M. Toma* et al, Nat. Mater. 2021,

 Outline

• Understanding heterogeneity in
integrated photoelectrodes
100 nm

• Mechanistic understanding of dynamic

transformations in Si/GaN photocathode

• Harnessing nanointerfaces and local

environments for chemical reactions
Challenges of CO2RR
O C O

O H

Grand challenge:
Controlled catalysis that can
HCOOH reduce CO2 with high selectivity
and efficiency.
Catalyst Design – Drawing Inspiration from Nature
Photosynthesis

O C O

Glucose

Catalytic pocket that can capture

and transform CO2

Enzyme for CO2 fixation in plant

 Identification of Structure-Reactivity Relationships for
CO2R at Modified Cu Surfaces

From the property to

the structure, from the
structure to the
property

• Identify structures that result in divergent selectivity

• Characterize various structures with common selectivity and identify structurally
common features
• Develop understanding of how structures can be optimized for desired selectivity
Hydrophobic/philic Modifiers – Different Selectivity
more hydrophilic more hydrophobic
more formic acid more CO

Balance is H2

Buckley, et. al. J. Am. Chem. Soc. 2019 141, 7355

Mechanism for Tuning Selectivity

• Hydrophilic surfaces promote weaker M-H, more formic acid

• Cationic hydrophobic surfaces suppress formic acid, allow CO to predominate
Buckley, et. al. J. Am. Chem. Soc. 2019 141, 7355
 Summary

• Disentangling local functional

heterogeneity in complex material
100 nm

systems

• Mechanistic understanding of self-

improving mechanism of GaN

• Tuning local environments to address

reaction selectivity
 LDRD Program
Acknowledgments BiVO4 Johanna Eichhorn
Ian Sharp Guosong Zeng
Jason Cooper Aya Buckley
Sebastian Reyes Lillo
Joel Ager

GaN
DOE-EERE
CO2 Reduction
Zetian Mi Dean Toste
Tadashi Ogitsu Bill Goddard
Anh Tuan Pham Tao Cheng
Jason Cooper
Srinivas Vanka
DOE-BES
 Thank you!

Francesca Maria Toma,

Chemical Sciences Division
Lawrence Berkeley National Laboratory
https://www.tomaresearchgroup.org/
fmtoma@lbl.gov

#SunCoChem This project has received funding from the European

@SunCoChem_EU Union’s Horizon 2020 research and innovation programme
www.suncochem.eu under grant agreement No. 862192
PhotoElectroCatalytic Device for
Sun-Driven CO2 conversion into Green
Chemicals

Miriam Díaz de los Bernardos, Eurecat

miriam.diaz@eurecat.org
28/04/2021
Consortium
14 partners from 8 European countries

6 3 1 3 1
Research R&D SMEs Standardisation Chemical EU International
institutions body industries Cooperation partner

2
 Transition towards a low-emission
European Chemical Industry

30 95%
gigatons of CO2 Chemicals based
emitted yearly on fossil fuels

The Chemical Industry is the third Photoelectrocatalytic

larger greenhouse gas emitter in Device
Europe, with over 30 GtCO2 yearly.

3
 SunCoChem solution
Three sustainable oxo-products produced from CO2
• Oxo-products produced from the use of CO2 as a renewable carbon
source, in comparison to actual routes based on fossil fuels.

GLYCOLIC ACID VALERALDHEYDE

LIMOXAL TM
Hydroformylation of Hydroformylation of Butene
Hydroformylation of limonene
formaldehyde (DOW waste by-product)

Building block applied in dying Building block applied as food Building block applied as a
and tanning, flavoring flavouring, in resin and rubber perfuming agent, in personal care
preservative and emulsion products and house cleaning products
additive.

4
 Scientific challenges for practical SUN-driven organic
chemical production from captured CO 2

Overall solar-to-chemical
CO conversion efficiency
> 10%
Photo-electrodes development
Multi-heterojunction photoelectrodes for Z-scheme mimicking:
i) Cheap and earth-abundant metal oxide nanoparticles
ii) Molecular organometallic chromophores
iii) Molecular catalysts for water oxidation, CO2 reduction and hydroformylation

FE ≥ 90%
j ≥ 20 mA/cm2
QE ≥ 90%
Overpotential ≤ 0.6 V
OXO-product yield ≥ 90%
5.2 Tn/year Limonene
2.7 Tn/year Valeraldehyde
2.4 Tn/year Glycolic Acid

5
 Scientific challenges for practical SUN-driven organic
chemical production from captured CO 2

Ionic Liquid’s development

Overall solar-to-chemical i) Better physical sorption
CO conversion efficiency ii) Lower viscosity
> 10% iii) Higher CO2 and organic reagent solubility
iv) Higher electrochemical stability window

FE ≥ 90%
j ≥ 20 mA/cm2
QE ≥ 90%
Overpotential ≤ 0.6 V
OXO-product yield ≥ 90%
5.2 Tn/year Limonene
2.7 Tn/year Valeraldehyde
2.4 Tn/year Glycolic Acid

6
 Scientific challenges for practical SUN-driven organic
chemical production from captured CO 2

Overall solar-to-chemical Transparent bipolar membrane development

CO conversion efficiency Bipolar Membrane-electrode assembly to maximize catalyst performance:
> 10% i) Maintain constant pH and ionic gradients at both anode and cathode compartment
ii) Use of different electrolytes

FE ≥ 90%
j ≥ 20 mA/cm2
QE ≥ 90%
Overpotential ≤ 0.6 V
OXO-product yield ≥ 90%
5.2 Tn/year Limonene
2.7 Tn/year Valeraldehyde
2.4 Tn/year Glycolic Acid

7
 Scientific challenges for practical SUN-driven organic
chemical production from captured CO 2
Loss of performance < 5% in 1000h
Cost reduction > 30%
CO2 emission reduction > 50%
Device engineering and scale-up
Three-chamber configuration:
ANODIC CHAMBER
Water oxidation to O2
CATHODIC CHAMBER
Photo- and non-photoassisted coupled reactions
1. Selective PEC CO2 reduction to CO
2. CO-hydroformylation of OXO-products
Ionic Liquids electrolytes
MEA via a transparent bipolar membrane
FLUE GAS & CO2 CAPTURE CHAMBER
1. CO2 capture from flue gas stream with an
asymmetric polysulfone membrane
2. CO2 concentration in Ionic Liquids
Low-cost PV solar cells to boost internal photo-voltage
8
 Project phases

• SunCoChem is planned with 4 major phases and 7 work packages in a 48 month perdiod:

Development of Integration and Socio-economic

Upscaling, testing
materials and optimisation of and environmental
and validation of
components of the materials and impact
TPER cell the TPER device
components assessment

Synthesis and Manufacturing of the full
1 characterisation of new
2 3
size TPER reactor and the
photocatalytic materials for test bench plant. Testing for
the development of optimal the 3 oxo-products of study
photo-electrodes and new with simulated and real
membranes. feedstocks for process
optimisation and validation.
Integration of
photoelectrodes and 4
TBM in a MEA, and
CO2 capture with ILs in
the CO2 capture and
concentration system.
Design and construction
of the first TPER module.
Risk assessment of the new
process and materials
compared with current
industrial processes, including
risks for human health and for
the environment. Socio-
economic impact based on
cost analysis and social
perception.

9
 SunCoChem solution
• The TPER (1m2) will be validated in an industrial plant environment at the production facility of IFF for the
conversion of anthropogenic CO2 emissions from Dow plant, to produce three added-value chemicals.

10
 Thank you!

PhotoElectroCatalytic Device for www.suncochem.eu

Sun-Driven CO2 conversion into Green @SunCoChem_EU

Chemicals
info@suncochem.eu

A project coordinated by:

This project has received funding from the EU’s Horizon
2020 research and innovation programme under grant
agreement No 862192.
 FlowPhotoChem:
Heterogenous Photo(electro)catalysis in Flow
using Concentrated Light
Webinar: Photocatalytic synthesis for a carbon-neutral production of
fuels and chemicals
28th April 2021

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 862453. The
material presented and views expressed here are the responsibilities of the author(s) only. The EU Commission takes no responsibility for any use made of
the information set out.
 Project background

Greenhouse gas emissions in the EU-28 1990-2018, by sector

Published by Ian Tiseo, Apr 22, 2021

2
 Project background

Greening the chemical industry

Galán-Martín et al., 2021, One Earth 4, 565–583

3
 Project Aim

Design, develop and translate to market new materials (photoabsorbers, catalysts,

membranes) and flow reactors which can use solar energy, H2O and CO2 to produce a
variety of fuels and chemicals, such as hydrogen, ethylene, syngas, acrylic acid, propionic
acid and alcohols.

4
 Project Vision

>7% sunlight to
Helping
chemical
chemical
conversion
manufacturing
efficiency and
performance contribute to
Europe’s vision
loss <5% in
of a climate
1,000 hours
neutral society
by 2050

Lower costs to
alternative non-
fossil fuel-based
methods but
with improved
efficiency and
negative CO2
emissions

5
M. Jouny et al. Ind. Eng. Chem. Res., 2018, 57, 2165.
 Project Delivery

6
 Project Implementation - Timings

7
 Photoelectrochemical reactor – WP1

821 mg/h H2 8300 mg/h H2

➢ Reactor scale-up

➢ Reduce PGM in
OER and HER

➢ Reduce cost
photoabsorber

➢ Improve
membrane

Tembhurne, S., Nandjou, F., Haussener, S. Nat Energy 4, 399–407 (2019)

8
 Photocatalytic reactor – WP2

w reactors, a) PEC at EPFL; b) PC1 at UPV; c) PC2 at TUE; d) EC at HZB

G. Chen et al., Adv. Mater. 2018, 30, 1704663

➢ Selectivity
towards CO

➢ Reduce operating 63 g/h CO

temperature and
pressure

➢ Reactor scale-up

9 J. Albero et al., ACS Catal. 2020, 10, 5734−5749

 Electrocatalytic reactor – WP3

J. Sisler et al. ACS Energy Lett. 2021, 6, 997−1002

B. Endrődi et al., Energy Environ. Sci., 2020, 13, 4098-4105

➢ Reactor scale-
up

62.5 g/h C2H4 ➢ Improve

selectivity

➢ Improve
membrane

B. Endrődi et al. ACS Energy Lett., 2019, 4, 1770.

10
 System integration – WP4

➢ DLR’s Xenon-High-Flux Solar Simulator

➢ 100 h continuous testing (24/7) at design conditions
➢ 50 h extended operation conditions and stress tests
(8 h/day) including 375 on-off-cycles
➢ Proof for stability at 1000 h period

11
 Route to market

12
 14 Partners, 8 countries

Catalyst design, manufacture & Modelling

characterisation

Exploitation & Commercialisation

Prototype reactors & integrated Lifecycle analysis & sustainability

demonstrator

Communication, Dissemination
www.flowphotochem.eu

@flowphotochem

13
 The team(s)

pau.farras@nuigalway.ie
www.nuigalway.ie/chemlight

Thank you for listening

14
 FlowPhotoChem:
Heterogenous Photo(electro)catalysis in Flow
using Concentrated Light
Webinar: Photocatalytic synthesis for a carbon-neutral production of
fuels and chemicals
28th April 2021

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 862453. The
material presented and views expressed here are the responsibilities of the author(s) only. The EU Commission takes no responsibility for any use made of
the information set out.
 SUNCOCHEM WEBINAR
April 28th, 2021 (on-line)

ID#862030

The large initiative

on solar fuels
1/5/2020 – 30/04/2024

Gabriele CENTI
Coordinator of DECADE EU project European
Research Institute of Catalysis,
INSTM and University Messina centi@unime.it

Humboldt Fellows ERC Synergy Grant 1

 WORKING TOGETHER TO CREATE A
COMMUNITY TO ADDRESS THIS CHALLENGE

SOLAR FUEL CHALLENGE

Positioning DECADE role

2
 From linear to circular economy

The Catalyst Review 4 (2021) 8-13 (part 1) 3

 The on-going transformation

Initial transition from FF to a mixed FF & bio-based economy

 adapting thermal catalysts
Next step  solar-based economy (in symbiosis with bio-based
economy) conceptually new catalysts, indicated as reactive
catalysts.

The Catalyst Review 10 (2020) 6-15 4

 from small and biobased molecules to a framework of
e-Refinery chemical production (e-chemistry) alternative to that
based on fossil fuels (petrochemistry)

The Catalyst Review 4 (2021) 8-13 (part 1) 5

DECADE CONCEPT
and novel (breakthrough)
approach

6
 Challenges addressed
• A novel PEC concept engineered to form the SAME
product on both sides of the cell, and avoid the formation of
O2 (common in H2O splitting & most CO2RR approaches)
▪ because in most of artificial leaf applications oxygen is a waste
product (which reduces the effective overall efficiency)
• Integrate solar use in biorefineries ( e-refinery)
• Develop flexible solutions with multiple market (chemicals
and fuels)
• Novel solution to improve circular economy and lower
carbon footprint in chemical & energy processes
• Develop compact design PEC cells, with easier scalability
to be used as artificial leaf
• Realize process intensification
7
 PEC approach Motivations

• Enhanced efficiencies (higher

current densities)
• Hìgher stability

EES (2021) submitted 8

 DECADE project concept
• Input
▪ (bio)ethanol and CO2 (biorefinery)
• PV/EC system
• ANODE
▪ Ethanol oxidative dimerization  ethylacetate
• CATHODE
▪ CO2 reduction (to acetate) with its catalytic reaction with ethanol to
form ethylacetate (EA)
• Formate also formation and reaction of
ethylformate (EF)
• Products and Uses
▪ EA+EF mixture in ethanol used as
green solvents and fuel additives

9
PV-EC DECADE device

10
 DECADE project concept & consortium

R&D Institutions Industry or industry-

TRL 3 oriented centers
Electrocatalyst
development

PEC reactor &

components
developers

System
integration &
prototyping

System validation
& assessment

TRL 5

Prof. Domen for

A similar chemistry benchmarking results
also from methanol

11
DECADE: an integrated approach
with prototype at the core

12
 DECADE approach
Integrated development of materials and PEC reactor/prototype with
technologic, economic, LCA, market & social assessments to guide the
increase of Technology Readiness Level (TRL) from 3 to 5.

Technology assessment to guide

development (from TRL 3 to 5)

Markets prospects and

business cases are part of
the project

13
 Concept design for the GDL-type
cathode for CO2 reduction
GDL membrane integrating element that biomimetic multi-functional core-shell
improved the three-phase boundary at Pd@TiO2/ox- SWCNHs (Single-walled carbon
the electrocatalyst between CO2, catalyst nanohorns) heterostructures
and protons

confined-space distribution of nanoparticles

within a metal-oxide phase that envelops a
CNS (carbon nanostructures) scaffold
14
 Conclusions
• DECADE will develop a novel PV/EC device engineered
to use waste CO2 and bio-alcohols as feeding inputs to
synthetize value-added products.
▪ enhanced energy efficiency and better addressing market
requirements and needs for moving to a solar economy
• Focus on ethanol, but also methanol case to lower the carbon
footprint in methanol plants producing added-value chemicals.
• Explore potential use of this novel PEC device for a multi-
purpose solution to improve circular economy and lower
carbon footprint in chemical & energy processes.

15