This deliverable defines the operating procedures of the SELECTCO2 project. It contains a wide variety of information relating to meeting dates and structures, internal communications, financial management and procedures for deliverables, milestones, and project reviews. This is a living document and will be reviewed at least annually to see if any necessary modifications are needed.
This report sets the standard operating parameters for testing electrochemical CO2 reduction catalysts, gas diffusion electrodes, and membranes used in the SELECTCO2 project. The purpose of this report is to allow for a set of conditions all partners can use as a guide to ensure consistency among different partners. While these guidelines are primarily meant to be used for consistency among SELECTCO2 partners, the consortium welcomes other entities to use these parameters as well to achieve consistency throughout the entire electrochemical CO2 reduction field. It should be noted that this is a living document and may be modified if deemed necessary by the consortium.
D2.1 - Report on site density and turn over frequency of selected benchmark catalysts
TOF and SD are two key descriptors in evaluating the single-site M-N-C catalysts for their ECO2R performance. In this WP, we improved the TOF and SD in our studied M-N-C candidates and deconvoluted their catalytic impacts.
D2.2 - Report on DFT prediction of selected benchmark catalysts
This deliverable reports on density functional theory (DFT) predictions of the activity and stability of single atom metal catalysts supported on nitrogen-doped graphene for CO2 reduction to CO. We find several candidates beyond Fe- and Ni- single site catalysts with promising activity. These efforts are part of the objective for SELECTCO2 to design electrolyzers with with 90% selectivity for CO2R to CO at high current densities. Promising candidates will be tested by the Strasser group at TU Berlin (WP2 leader).
D2.3 - Report on promising M-N-C catalyst activity showing progress toward WP targets
D2.4 - Final report on WP achievements in terms of activity of new catalysts
D3.1 Report on Co-catalyst approach towards ethanol production
Sluggish kinetics related to C-C coupling products limit the effectiveness of electrochemical CO2 reduction to ethanol over Cu catalysts. The preparation of tandem catalysts by the deposition of two independent and adjacent layers on gas diffusion electrodes can enhance the reaction kinetics by increasing the local CO concentration. A series of Cu/Ag and Cu/Au electrodes were prepared, varying the composition through the deposition of a CO-selective layer on top of the Cu using both thin films and nanoparticles. This approach allows the Ag or Au to efficiently produce CO that can further diffuse, couple, and reduce to form ethanol and other C2 or C3 products. The ethanol faradaic efficiency increased from 11% to 17% at 150 mA/cm2, when switching from a pure copper catalyst to a layered catalyst consisting of 60% Cu and 40% Ag. More broadly the faradaic efficiency of all C2+ products reached a maximum value of 67% with this catalyst.
D3.2 - Report on Sniffer Chip discoveries relating to ethanol/ethylene branching mechanism
D3.3 - Report on recycle and temperature effects on ECO2R
D3.4 - Report on synchrotron measurements discoveries relating to ethanol/ethylene branching mechanism
D3.5 - Final report on WP achievements in terms of ECO2R selectivity to ethanol/acetaldehyde at high current density
D4.1 - Report on the impact of reaction intermediates on ECO2R selectivity towards ethylene
Electrochemical CO2 reduction (ECO2R) on a copper catalyst leads to a wide product composition of various value-added chemicals such as CO, ethanol, and ethylene. A number of additional minor products have been reported, namely acetate, acetaldehyde, formate and glyoxal. These compounds are typically measured in only minor amounts of ~1% each. However, these compounds play an important role as reaction intermediates to some of the major product pathways that we would like to manipulate to steer product selectivity. This deliverable investigates the effects of these reaction intermediates on the experimental selectivity of ethylene, the targeted product for WP4.
Specifically, the controlled addition of reaction intermediates into an operational ECO2R system is performed for a number of crucial intermediates, and the resulting change in product selectivity measured. We find that the direct reduction of acetaldehyde and glyoxal in even minor concentrations at elevated current densities will shift electrons away from the target product ethylene. Measured ethanol and acetaldehyde concentrations indicate that this is also occurring during ECO2R without additives.
The conclusions from these results provide strategies to increase the selectivity of ethylene formation via glyoxal and acetaldehyde scavengers, which remove the intermediates prior to their subsequent reduction to alcohols. If successful, such a strategy may shift ~10% of electrons from the alcohol to hydrocarbon pathways.
D4.2 - Report on in-situ observations of catalyst structure and localized activity using electrochemical AFM system
D4.3 - Report on modifying catalyst layer thickness, morphology, surface structure for high efficiency ethylene production and suppression of competing reactions
D4.4 - Report on applying mass transport findings and new gas-diffusion electrodes for reducing H2 and C1 production
D5.1 - Benchmarking gas diffusion layers delivered to TUB, DTU, TUD
The use of Gas Diffusion Electrodes (GDEs) has been identified as a key tool to obtain an efficient CO2 electrochemical conversion to valuable chemicals. Work Package 5 will focus on obtaining an optimized GDE, which pass through the development of an optimized Gas Diffusion Layer (GDL, i.e. GDE without the catalytic layer) in order to achieve the performance targets.
Such development phase begins with the evaluation of the currently commercially available GDLs, in order to setting the basis and have a reference benchmark to start from. For this reason, commercial DeNora GDL for Fuel Cells (code DN908) was shipped to DTU, TUB, TUD and EPFL. The first three universities will deposit a reactive layer with benchmarking catalysts and test the commercial GDL performances, while EPFL will perform structural studies (3D Tomography) to evaluate the GDL features and support the mass transport model development.
D5.2 - Report on benchmark results of GDE from CO2 to carbon monoxide, ethanol and ethylene - CONFIDENTIAL
The deliverable describes the digitalization approach of the gas diffusion layer (GDL) and gas diffusion electrode (GDE). The adopted strategy consists of using computed tomography techniques of different resolutions and subsequent segmentation techniques, followed by the characterization and quantification of structural properties (porosity, surface area, homogeneity, anisotropy, pore and fibre size distributions). These structural details can then be used to guide optimization of the GDL and GDE for enhanced transport and, ultimately, enhanced device performance. Furthermore, this digitalization and characterization activity feeds into the pore-level simulations performed in WP7, and this interface is also described.
D5.3 - Report on approaches for optimization of GDL porous structure from digitalized GDE - CONFIDENTIAL
The deliverable describes the digitalization approach of the gas diffusion layer (GDL) and gas diffusion electrode (GDE). The adopted strategy consists of using computed tomography techniques of different resolutions and subsequent segmentation techniques, followed by the characterization and quantification of structural properties (porosity, surface area, homogeneity, anisotropy, pore and fibre size distributions). These structural details can then be used to guide optimization of the GDL and GDE for enhanced transport and, ultimately, enhanced device performance. Furthermore, this digitalization and characterization activity feeds into the pore-level simulations performed in WP7, and this interface is also described..
D5.4 - Supply 3 types of GDE with electrocatalysts selective for CO, ethylene and ethanol
D5.5 - Report on performances obtained from single cell testing of CO2 reduction with optimized GDE
D6.1 - Supply initial AEMs to DTU team for CO2 crossover screening. (2 sheets: 25 cm x 25 cm of each type) - CONFIDENTIAL
The aim of this deliverable was to supply initial batches of anion-exchange membranes (AEM) to the DTU-EX team to allow them to evaluate in small sized carbon dioxide electro-reduction (CO2ER) cells. The purpose of this is to allow a down-selection of thickness and head-group chemistry to reduce the number of variables that need to be considered when SURREY is developing the next generation of RG-AEMs (tailored specifically for CO2ER). Six different batches of RG-AEM were sent to DTU-EX. The deliverable report contains key characterisation data and initial life cycle analyses-relevant data for the RG-AEMs supplied.
D6.2 - Supply (2 g of each type) AEIs to TUB, DTU, and TUD for investigations into how different head-group chemistries affect the catalysis of the different CO2 reduction pathways. - CONFIDENTIAL
The aim of this deliverable (WP6, D6.2) was to supply initial batches of (current generation) radiation-grafted anion-exchange ionomer (RG-AEI) to the DTU-EX, TUD, and TUB teams to allow them to evaluate how useful these ionomer powders will be in carbon dioxide electro-reduction (CO2ER) cells. This report contains key characterisation data and initial life cycle analyses-relevant data for the RG-AEIs supplied.
D6.3 - Supply initial amounts (5 sheets: 25 cm x 25 cm) of the next-generation AEMs (with co-monomer components) to DTU and small amounts of next-generation AEIs (500 mg) to catalyst WPs (for catalyst evaluation).
D6.4 - Supply of large batches of finalized (fully characterized) AEM (Minimum of 10 sheets: 25 cm x 25 cm) and AEIs (Minimum of 10 g batch) to project partners who require them.
D6.5 - Report on benchmarking of initial AEM’s
This deliverable demonstrates the effectiveness of US current-generation anion exchange membranes (AEM) with the following head groups (supplied in D6.1): trimethylamine (TMA), N-methylpyrrolidine (MPY), and (3) N-methylpiperidine (MPIP) in relation to a benchmark commercial Sustainion membrane. We tested for CO2 electrolysis to CO using a standard Ag catalyst to allow the focus to be on the membranes. We tested for CO selectivity versus hydrogen, operating potential, ohmic resistance and CO2 crossover in the membrane across a range of current densities 50-300 mA/cm2. We tested AEMS made from 25 µm and 50 µm thickness ETFE with only the 25 µm variants being effective. We also did long term studies of 24 hours and 200 hours. The end conclusion is that the US synthesized membranes are very competitive with the commercial Sustainion membranes with the MPIP membrane showing the most promise.
D6.6 - Report on optimized AEM’s and AEI’s
D7.1 - Library of digitalized porous electrodes - CONFIDENTIAL
The deliverable presents the methodology used for the digitalization of gas diffusion electrodes (and specifically the catalyst layers) and their quantitative structural characterization. It represents an (extendable) digital electrode library and specifically presents the three characteristic electrodes from the three partners involved in the catalyst design (TUD, TUB and DTU).
D7.2 - Developed pore-level transport model
D7.3 - Developed device model
D7.4 - Device model validation report
D7.5 - Parametrization of implicit solvent models against AIMD - PDF
This deliverable reports on density functional theory (DFT) based analysis on the mechanism of CO(2) reduction towards ethylene and ethanol. Both a thermodynamic assessment and a kinetic analysis have been performed. We identified the rate limiting step shared by the products as the dimerization of two *CO molecules and its reaction to the applied potential. We propose the selectivity determining steps between ethylene and ethanol as the competition between two protonation reactions of HCCO*. This result is consistent with the dependence of ethylene vs. oxygenated products on potential observed in existing experimental studies. For further validation of the computed mechanism, experimental studies on the basis of kinetic isotope effects are planned in collaboration with WP3.
D7.6 - Pathways towards CO, ethylene, ethanol on Cu facets
D7.7 - Determination of the impact of reaction conditions on ECR activity and selectivity towards high value products
D7.8 - Combining atom-, meso-, and device-scale models
D8.1 - Integrated analysis of the new technologies based on sustainability pillars and circularity analysis – baseline LCA/LCC/S-LCA
The present report summarizes the results of Deliverable 8.1 aimed at assessing: i) the environmental, ii) economic, iii) social and iv) sustainability performance of the CO2 reactor manufactured and used for producing CO, ethanol and ethylene.
D8.2 - Conclusions on circularity potential of SELECTCO2 solution
D8.3 - Market analysis and opportunities for SELECTCO2 technology
D8.4 - SELECTCO2 benchmarking analysis with other CO2 valorization techniques
D8.5 - Business models for the promotion of SELECT CO2 technology
The communication of the project will be unified along a common visual entity. A coherent visual chart (colours, fonts, designs) will be derived from the project logo and provided in several shapes and formats (document templates etc.). This visual identity will be used extensively throughout the project, creating a distinguishable brand that will be recognized by the various communities.
The SELECTCO2 project website is designed to fulfil project communication and dissemination needs for the benefit of the whole scientific community and the public through relevant information including: project overall objectives, partner & work packages information ; project activities: news, meetings ; project progress: technical publications, conference presentations, public domain reports ; project resources: links, related events … ; project contact information All the partners will collectively participate in the dissemination objective of the website by providing up-to-date information
D9.3 - Dissemination and knowledge management protocol - CONFIDENTIAL
This report presents the dissemination protocol for the SELECTCO2 project, the procedure for “Open Access” to peer reviewed research articles, internal rules, information on support from the EU members and the strategy for Knowledge Management within the project.
D9.4 - Organization of a SELECTCO2 dedicated symposium
D9.5 - Stakeholders Engagement Meeting
D9.6 - Survey of dissemination activities and final plan for dissemination and exploitation of project results