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Selective Electrochemical Reduction of CO2 to High Value Chemicals

Deliverables

Report on in-situ observations of catalyst structure and localized activity using electrochemical AFM system

This deliverable will report on in-situ observations of catalyst structure and localized activity using electrochemical AFM system as described in Task 4.2 The report will show how activity varies as a function of the localized structure of the catalyst, and determine how and if the catalyst surface restructures under different conditions.

Report on optimized AEM's and AEI's

This deliverable will report on benchmarking of optimized AEMs and AEIs as described in Task 63 The AEMs will be tested for CO2 crossover and the AEIs will be tested for improvements in selectivity

Final report on WP achievements in terms of activity of new catalysts

This deliverable will report on WP achievements in terms of activity of new catalysts as described The results will show the optimal catalysts for high current denisty low overpotential and high selectivity

Report on recycle and temperature effects on ECO2R

This deliverable will report on the findings in Task 33 related to using a recycle loop and elevated temperatures The report will show the effectiveness of operating at high temperatures and then condensing a product as well as how a reactor operates with a nonpure CO2 inlet flow

Technical Consistency Plan

This task involves the creation and management of a TCP, which is essential for integrating the various WPs to allow for synergistic results. The TCP will create: • Standardizing of different types of catalysis testing relating to testing in H-cell, gas diffusion electrode, and membrane electrode assembly. • Standardized testing sequences of catalysis (chronamperometry, chromoptentiometry, etc.) • Standardization protocols relating to ionomer, ionomer concentration and membranes. • Standardization protocols relating to purity in electrolytes, gases, equipment, etc. • Standardization protocols relating to current density and conversion in relation to matching modeling and experimental • Standardizing of anode electrodes • Other standardizing procedures that WP leaders feel necessary

Report on benchmark of GDE from CO2 to Carbon monoxide, ethanol and ethylene

This deliverable will be a report on the benchmark activity of the gas diffusion layers for CO, ethanol, and ethylene as described in Task 5.1. This will show how variation in gas diffusion layer effects performance.

SELECTCO2 benchmarking analysis with other CO2 valorization techniques

This deleverable will provide a report benchmarking the CO2 vaolrization approach from SELECTCO2 against other CO2 valorisation techniques Tehcniques such as the Reverse Water Gas shift reaction combined with Fischer Tropsch synthesis and biomass conversion are two likely candidates to compare this approach to

Pathways towards CO, ethylene, ethanol on Cu facets

This deliverable will report on mechanistic pathways towards CO, ethylene, ethanol on Cu facets using computational modeling. This approach is described in detail in Task 7.4

Combining atom-, meso-, and device-scale models

This deliverable will be a report combining the atom meso and devicescale models to provide a unified model scaling from atomic to the device scale This will allow for a detailed modeling of reactors allowing the effects of catalytic improvements to be modeled at the device scale

Project Management Plan

The PMP wil be a document that includes a formalized procedure for report preparation and delivery linked to the SC. The ISO project management system will be applied to this project to ensure quality standards are met. This is done by establishing and following a set of procedures that ensure implementation according to the schedule, processes and standards defined in the PMP. The PMP will also define the necessary resources and their use, as well as the standards the procedures for the implementation of quality assurance.

Report on the impact of reaction intermediates on ECO2R selectivity towards ethylene

This deliverable will report on the impact of reaction intermediates on ECO2R selectivity towards ethylene via the approach described in Task 4.1. Various intermediates will be inserted into an ECO2R reactor and the catalytic activity and product distribution will be measured.

Market analysis Market analysis and opportunities for SELECTCO2 technology

This deliverable will report on a market analysis and opportunities for SELECTCO2 technology as described in Task 82 This analysis will focus on CO ethanol and ethylene

Report on promising M-N-C catalyst activity showing progress toward WP targets

This deliverable will report on promising M-N-C catalyst activity showing progress toward WP targets as described in Task 2.3 and Task 2.4. This report will show how improved functionality increases activity.

Report on Sniffer Chip discoveries relating to ethanol/ethylene branching mechanism

This deliverable will report on Sniffer Chip discoveries relating to ethanol/ethylene branching mechanism as described in Task 3.2. Results from low current density tests with the goal of giving insight into which conditions favor either ethanol or ethylene production.

Developed device model

This deliverable will report on a developed device model for CO2 electrolysis as described in Task 72 This should encompass macro scale mass transport effects

Library of digitalized porous electrodes

This deliverable will provide a report on the creation of a library of digitalized porous electrodes as described in Task 7.1. This will allow for modeling of mass transfer flow throughout the electrode.

First update of Project Management Plan

All partners will review the project management plan. The plan will be updated where necessary.

Second update of Project Management Plan

All partners will review the project management plan The plan will be updated where necessary

Report on Co-catalyst approach towards ethanol production

This deliverable will report on Co-catalyst approach towards ethanol production. Co-catalysts such as Ag and/or Au will be intermixed with Cu with the goal of achieving higher ethanol production

Survey of dissemination activities

This deliverable will present a final survey of all dissemination activities This will also be the final plan for the dissemination and exploitation of project results

Developed pore-level transport model

This deliverable will report on a developed porelevel transport model This should allow a better understanding of mass transport throughout this regime

Final report on WP achievements in terms of ECO2R selectivity to ethylene at high current density

This deliverable will be the final report on WP achievements in terms of ECO2R selectivity to ethylene at high current densities This will completely optimize the device towards ethylene production using knowledge gained from the other WPs

Report on benchmarking of initial AEM’s

This deliverable will report on benchmarking of initial AEM’s as described in Task 6.3. The AEM's will be tested for CO2 crossover and ohmic resistance losses.

Determination of the impact of reaction conditions on ECR activity and selectivity towards high value products

This deliverable will report on using computational modeling to determining the impact of reaction conditions on ECR activity and selectivity towards high value products as described in Task 74

Report on site density and turn over frequency of selected benchmark catalysts

This report will describe the site density and turn over frequency of selected benchmark catalysts from Task 2.1 The active sites of the M-N-C type catalysts will be identified using XAS and XPS, while the SD and TOF values will be evaluated using literature-established methods such as low temperature CO chemisorption, and the combined BET and XPS quantifications (developed at TUB). We will assess how the characteristic methodologies correlate with each other. These, in combination with the H-cell delivered electrochemical performance, will be used as a baseline to guide the needs to either increase the SD or TOF for reaching the activity targets of the call, to better assess the activity improvements of the new M-N-C catalysts prepared in Task 2.3, and to establish a common base level activity to compare the newly developed catalysts to the catalytic activity and selectivity.

Report on synchrotron measurements discoveries relating to ethanol/ethylene branching mechanism

This deliverable will report on synchrotron based findings in regards to ethanol to ethylene branching ratio This report will primarily be related to the collaboration with Mission Innovation member SLAC and their synchrotron facilities Task 32 describes the work that will be done in relation to this report

Report on performances obtained from single cell testing of CO2 reduction with optimized GDE

This deliverable is a final report on the gas diffusion electrodes developed in this WP specifically via Task 53 It will show how durable and effective these GDEs are for various reactions

Report on DFT prediction of selected benchmark catalysts

This deliverable will report on DFT prediction of selected benchmark catalysts as described in Task 2.1. Specifically reaction energetics determined using GGA functionals will be benchmarked against hybrid functionals and truncated cluster calculations using coupled cluster methods for a range of representative systems Solvation energies as well as adsorbate-field interactions determined with implicit solvent calculations will be benchmarked and fitted against fully explicit ab initio molecular dynamics simulations

Report on applying mass transport findings and new gas-diffusion electrodes for reducing H2 and C1 production

This deliverable will report on applying mass transport findings and new gasdiffusion electrodes for reducing H2 and C1 production thus promoting ethylene current selectivity The report will show how reducing the activity for side products influences ethylene production

Final report on WP achievements in terms of ECO2R selectivity to ethanol at high current density

This deliverable will report on the achievements in terms of ECO2R selectivity to ethanol at high current density as described in Task 33 The report will show how combining high temperature and a recycle loop can lead to low overpotential high selectivity formation of either acetaldehyde or ethanol

Device model validation report

This report will demonstrate validation of the device model as described in Task 73 TU Delft will show how well their experimental data matches the device models

Report on modifying catalyst layer thickness, morphology, surface structure for high efficiency ethylene production and suppression of competing reactions

This deliverable will report on modifying catalyst layer thickness morphology surface structure for high efficiency ethylene production It will also report on the suppression of competing reactions as described in Task 43 as a result of these system and catalyst variations

Implementation of a project website

This deliverable will create and implement a project website as described in Task 9.3. This will be the main dissemination channel towards the scientific community and the public. It will provide news and information on project publications with a link to open-access documents and other project output.

Stakeholders Engagement Meeting

The Stakeholder Engagement Meeting SEM will be part of the 2nd annual meeting This will include talks and discussion geared towards specific stakeholders to give them the optimal information to allow them to promote take advantage or help develop this technology to benefit society This will also include the industrial advisory board to have inperson meeting and discussions

Organization of a SELECTCO2 dedicated symposium

Relevant conferences will be contacted ECS EMRS MRS ACS ISE NanoGe and SELECTCO2 will convene a symposium at part of the conference relating to the topics of this project ECO2R specific catalysis and reaction environment effects on catalysis The symposium will consist of speakers that relate to all the major directions of this project catalyst membranes modeling gas diffusion layers impact etc

Design of a project visual identity set

This deliverable will provide a design of the project visual identity set and project templates (presentations, logo). This will be done working with all partners to ensure the optimal identity is created to promote this project.

Benchmarking gas diffusion layers delivered to TUB, DTU, TUD

This deliverable will be the physical delivery of gas diffusion layers produced at IDN and delivered to TUB, DTU, and TUD. All 3 partners will acknoweldge they received the gas diffusion layers and they are in a condition in which they can be tested.

Publications

In operando investigations of oscillatory water and carbonate effects in MEA-based CO2 electrolysis devices

Author(s): Moss, AB Garg, S. Mirolo, M. Giron Rodriguez, C.A. Ilvonen, R. Chorkendorff, I. Drnec, J. Seger, B.
Published in: Joule, Issue 7, 2, 2023, Page(s) 350-365, ISSN 2542-4351
Publisher: Elsevier
DOI: 10.1016/j.joule.2023.01.013

The mechanism for acetate formation in electrochemical CO<sub>(2)</sub> reduction on Cu:selectivity with potential, pH, and nanostructuring

Author(s): Hendrik H. Heenen; Haeun Shin; Georg Kastlunger; Sean Overa; Joseph A. Gauthier; Feng Jiao; Karen Chan
Published in: Energy & Environmental Science, Issue 2, 2022, Page(s) 3978-3990, ISSN 1754-5692
Publisher: Royal Society of Chemistry
DOI: 10.1039/d2ee01485h

Force-based method to determine the potential dependence in electrochemical barriers

Author(s): Sudarshan Vijay, Georg Kastlunger, Joseph A. Gauthier, Anjli Patel, and Karen Chan
Published in: Journal of Physical Chemistry Letters, Issue 13, 25, 2022, Page(s) 5719–5725, ISSN 1948-7185
Publisher: American Chemical Society
DOI: 10.1021/acs.jpclett.2c01367

Covalent Organic Framework (COF) derived Ni-N-C Catalysts for Electrochemical CO2 Reduction: unraveling fundamental kinetic and structural parameters of the active sites

Author(s): . Li, W. Ju, S. Vijay, J. Timoshenko, K. Mou, D. A. Cullen, J. Yang, X. Wang, P. Pachfule, S. Brückner, H. Sang Jeon, F. T. Haase, S.-C. Tsang, C. Rettenmaier, K. Chan, B. Roldan Cuenya, A. Thomas, P. Strasser
Published in: Angew. Chem. Int. Ed, 2022, ISSN 1097-0037
Publisher: Wiley Online Library
DOI: 10.1002/anie.202114707

Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium

Author(s): Jun Gu, Shuo Liu, Weiyan Ni, Wenhao Ren, Sophia Haussener & Xile Hu
Published in: Nature Catalysis, 2022, ISSN 2520-1158
Publisher: Nature Publishing Group
DOI: 10.1038/s41929-022-00761-y

How to extract adsorption energies, adsorbate-adsorbate interaction parameters, and saturation coverages from temperature programmed desorption experiments

Author(s): S. Vijay, H. H. Kristoffersen, Y. Katayama, Y. Shao Horn, I. Chorkendorff, B. Seger, K. Chan
Published in: Phys. Chem. Chem. Phys, Issue 23, 2021, Page(s) 24396-24402, ISSN 1463-9084
Publisher: Royal Society of Chemistry
DOI: 10.1039/d1cp01992a

2022 roadmap on low temperature electrochemical CO2 reduction

Author(s): Ifan E L Stephens, Karen Chan, Alexander Bagger, Shannon W Boettcher, Julien Bonin, Etienne Boutin, Aya K Buckley, Raffaella Buonsanti, Etosha R Cave, Xiaoxia Chang, See Wee Chee, Alisson H M da Silva, Phil de Luna, Oliver Einsle, Balázs Endrődi, Maria Escudero-Escribano, Jorge V Ferreira de Araujo, Marta C Figueiredo, Christopher Hahn, Kentaro U Hansen, Sophia Haussener, Sara Hunegnaw, Ziyang H
Published in: Journal of Physics: Energy, 2022, Page(s) 4-77, ISSN 1029-8479
Publisher: Institute of Physics Publishing
DOI: 10.1088/2515-7655/ac7823

Computational Screening of Single and Di-Atom Catalysts for Electrochemical CO<sub>2</sub> Reduction

Author(s): Naiwrit Karmodak; Sudarshan Vijay; Georg Kastlunger; Karen Chan
Published in: ACS Catalysis, Issue 2, 2022, Page(s) 4818−4824, ISSN 2155-5435
Publisher: American Chemical Society
DOI: 10.1021/acscatal.1c05750

How membrane characteristics influence the performance of CO2 and CO electrolysis

Author(s): Garg, S.; Giron Rodriguez, C.A.; Rufford, T.E.; Varcoe, J.R.; Seger, B.
Published in: Energy and Environmental Science, Issue 15, 2022, Page(s) 4440-4469, ISSN 1754-5692
Publisher: Royal Society of Chemistry
DOI: 10.1039/d2ee01818g

Influence of Headgroups in Ethylene-Tetrafluoroethylene-Based Radiation-Grafted Anion Exchange Membranes for CO2 Electrolysis

Author(s): Carlos A. Giron Rodriguez, Bjørt Óladottir Joensen, Asger Barkholt Moss, Gastón O. Larrazábal, Daniel K. Whelligan, Brian Seger*, John R. Varcoe*, and Terry R. Willson
Published in: ACS Sustainable Chemical Engineering, Issue 11, 4, 2023, Page(s) 1508–1517, ISSN 2168-0485
Publisher: American Chemical Society
DOI: 10.1021/acssuschemeng.2c06205

Combining First-Principles Kinetics and Experimental Data to Establish Guidelines for Product Selectivity in Electrochemical CO2 Reduction

Author(s): Georg Kastlunger, Hendrik H. Heenen, and Nitish Govindarajan
Published in: ACS Catalysis, 2023, Page(s) 5062-5072, ISSN 2155-5435
Publisher: American Chemical Society
DOI: 10.1021/acscatal.3c00228

The product selectivity zones in gas diffusion electrodes during the electrocatalytic reduction of CO2

Author(s): Tim Möller, Trung Ngo Thanh , Xingli Wang, Wen Ju, Zarko Jovanov and Peter Strasser
Published in: Energy and Environmental Science, Issue 14, 2021, Page(s) 5995-6006, ISSN 1754-5692
Publisher: Royal Society of Chemistry
DOI: 10.1039/d1ee01696b

Cation-driven increases of CO2 utilization in a bipolar membrane electrode assembly for CO2 electrolysi

Author(s): K. Yang, M. Li, S. Subramanian, M. A. Blommaert, W. A. Smitha, T. Burdyny
Published in: ACS Energy Letter, Issue 6, 12, 2021, Page(s) 4291–4298, ISSN 2380-8195
Publisher: ACS
DOI: 10.1021/acsenergylett.1c02058

Design of NiNC single atom catalyst layers and AEM electrolyzers for stable and efficient CO2-to-CO electrolysis: Correlating ionomer and cell performance

Author(s): J. Wang, T. R. Willson, S. Brückner, D. K. Whelligan, C. Sun, Li. Liang, X. Wang, P. Strasser, J. Varcoe, and W. Ju
Published in: Electrochimica Acta, 2023, ISSN 0013-4686
Publisher: Pergamon Press Ltd.
DOI: 10.1016/j.electacta.2023.142613

A Comprehensive Approach to Investigate CO 2 Reduction Electrocatalysts at High Current Densities

Author(s): Gastón O. Larrazábal, Ming Ma, Brian Seger
Published in: Accounts of Materials Research, Issue 2/4, 2021, Page(s) 220-229, ISSN 2643-6728
Publisher: American Chemical Society
DOI: 10.1021/accountsmr.1c00004

CO2 Electrolysis via Surface-Engineering Electrografted Pyridines on Silver Catalysts

Author(s): Maryam Abdinejad, Erdem Irtem, Amirhossein Farzi, Mark Sassenburg, Siddhartha Subramanian, Hugo-Pieter Iglesias van Montfort, Davide Ripepi, Mengran Li, Joost Middelkoop, Ali Seifitokaldani*, and Thomas Burdyny
Published in: ACS Catalysis, Issue 12, 13, 2022, Page(s) 7862–7876, ISSN 2155-5435
Publisher: American Chemical Society
DOI: 10.1021/acscatal.2c01654

n Situ Analysis of the Facets of Cu-Based Electrocatalysts in Alkaline Media Using Pb Underpotential Deposition

Author(s): Degenhart Hochfilzer, Aarti Tiwari, Ezra L. Clark, Anton Simon Bjørnlund, Thomas Maagaard, Sebastian Horch, Brian Seger, Ib Chorkendorff, and Jakob Kibsgaard
Published in: Langmuir, 2022, Page(s) 1514-1521, ISSN 0743-7463
Publisher: American Chemical Society
DOI: 10.1021/acs.langmuir.1c02830

Unified mechanistic understanding of CO2 reduction to CO on transition metal and single atom catalysts

Author(s): Sudarshan Vijay, Wen Ju, Sven Brückner, Sze-Chun Tsang, Peter Strasser & Karen Chan
Published in: Nature Catalysis, Issue 4, 2021, Page(s) 1024–1031, ISSN 2520-1158
Publisher: Nature
DOI: 10.1038/s41929-021-00705-y

Best practices for electrochemical reduction of carbon dioxide

Author(s): Brian Seger, Marc Robert & Feng Jiao
Published in: Nature Sustainability, 2023, Page(s) 236-238, ISSN 2398-9629
Publisher: Springer Nature
DOI: 10.1038/s41893-022-01034-z

Role of ion-selective membranes in the carbon balance for CO 2 electroreduction via gas diffusion electrode reactor designs

Author(s): Ming Ma, Sangkuk Kim, Ib Chorkendorff, Brian Seger
Published in: Chemical Science, Issue 11/33, 2020, Page(s) 8854-8861, ISSN 2041-6520
Publisher: Royal Society of Chemistry
DOI: 10.1039/d0sc03047c

Using pH Dependence to Understand Mechanisms in Electrochemical CO Reduction

Author(s): Georg Kastlunger, Lei Wang, Nitish Govindarajan, Hendrik H. Heenen, Stefan Ringe, Thomas Jaramillo, Christopher Hahn, and Karen Chan
Published in: ACS Catalysis, Issue 12, 8, 2022, Page(s) 4344–4357, ISSN 2155-5435
Publisher: American Chemical Society
DOI: 10.1021/acscatal.1c05520

Highly selective and scalable CO2 to CO - Electrolysis using coral-nanostructured Ag catalysts in zero-gap configuration

Author(s): Woong Hee Lee, Young-Jin Ko, Yongjun Choi, Si Young Lee, Chang Hyuck Choi, Yun Jeong Hwang, Byoung Koun Min, Peter Strasser, Hyung-Suk Oh
Published in: Nano Energy, Issue 76, 2020, Page(s) 105030, ISSN 2211-2855
Publisher: Elsevier BV
DOI: 10.1016/j.nanoen.2020.105030

Enriching Surface Accessible CO2 in the Zero Gap Anion Exchange Membrane Based CO2 Electrolyzer

Author(s): Xu, Q.; Xu, A.; Garg, S.; Moss, A.; Chorkendorff, I.; Bligaard, T.; Seger. B.
Published in: Angewandte International, Issue 135, 3, 2022, Page(s) e202214383, ISSN 1433-7851
Publisher: John Wiley & Sons Ltd.
DOI: 10.1002/ange.202214383

Limits to scaling relations between adsorption energies?

Author(s): Sudarshan Vijay, Georg Kastlunger, Karen Chan, and Jens K. Nørskov
Published in: The Journal of Chemical Physics, Issue 156, 23, 2022, Page(s) 231102, ISSN 0021-9606
Publisher: American Institute of Physics
DOI: 10.1063/5.0096625

Interaction of CO with Gold in an Electrochemical Environment

Author(s): S. Vijay, T. V. Hogg, J. Ehlers, H. H. Kristoffersen, Y. Katayama, Y. Shao Horn, I. Chorkendorff, K. Chan, B. Seger
Published in: J. Phys. Chem. C, Issue 125, 32, 2021, Page(s) 17684-17689, ISSN 1932-7447
Publisher: American Chemical Society
DOI: 10.1021/acs.jpcc.1c04013

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