Understanding and Improving Electrochemical Carbon Dioxide Capture

Lead Research Organisation: University of Cambridge
Department Name: Chemistry

Abstract

This transformative research fellowship will advance electrochemical carbon dioxide capture as a greenhouse gas mitigation technology.

To limit global warming to 1.5C and avoid catastrophic climate change we must greatly reduce our emissions of greenhouse gases. To this end the UK has recently committed to net zero greenhouse gas emissions by the year 2050. Carbon dioxide capture and storage (CCS) is a critical technology that must be deployed at scale if the UK is to meet this goal. CCS is a process where carbon dioxide is first captured at point sources (industrial processes, fossil fuel power) or directly from the atmosphere, before subsequently being stored underground.

State of the art CCS technology uses amine molecules to absorb carbon dioxide. Subsequently a large amount of energy must be supplied in the form of heat (or a vacuum) to regenerate the amines and release pure carbon dioxide for storage, thereby increasing the cost of CCS. The amine process also suffers from (i) limited carbon dioxide capacities, (ii) amine evaporation into the atmosphere and (iii) amine degradation in the presence of oxygen and other contaminant gases.

This programme will explore the use of electricity to capture and release carbon dioxide as a more energy-efficient method of CCS that can overcome the limitations of amines. In electrochemical carbon dioxide capture, the charging of an energy storage device such as a battery or a supercapacitor causes the selective absorption of carbon dioxide. When the device is discharged, pure carbon dioxide is released (for subsequent storage), and much of the energy supplied during charging is recovered. Initial work suggests that this technology may be more energy-efficient than existing approaches, and there is still vast room for improvement, especially if the molecular mechanisms of capture can be understood and manipulated.

We will (i) advance the understanding of electrochemical carbon dioxide capture and (ii) discover new materials and devices that capture carbon dioxide more efficiently. Specifically we will focus on electrochemical carbon dioxide capture by (i) supercapacitors and (ii) batteries. We will measure the amount of carbon dioxide that can be captured by these devices and we will vary the structures of the materials used to guide their improvement.

A proper understanding of the molecular mechanism of electrochemical carbon dioxide capture may lead to breakthroughs for this technology. A key thrust of the programme is therefore mechanistic studies of the molecular-level capture mechanism. We will use a suite of experimental techniques to study the chemical structures of the electrode materials, and we will correlate these structures with their carbon capture properties. We will develop nuclear magnetic resonance studies that allow the molecular form of the bound carbon dioxide to be determined at different stages of the capture process.

Our mechanistic studies will inform the design and synthesis of improved materials for electrochemical carbon dioxide capture. We will synthesise the next generation of materials with (i) larger carbon dioxide uptake capacities, (ii) lower energy requirements for regeneration and (iii) faster uptake rates. New technology generated by this work will be prototyped and developed into new products. The developed technology will generate clean economic growth and will help the UK meet its 2050 net-zero emissions target. The research background of ACF combined with the assembled team of partners and excellent institutional support will lead to new knowledge and technology that will make the UK world-leading in electrochemical carbon dioxide capture.

Planned Impact

The possible impacts of this fellowship include:
1. The discovery of transformative new carbon capture technologies that are more energy-efficient than existing approaches.

2. The deployment of these new technologies in the UK and abroad for carbon dioxide emissions mitigation, which will contribute to tackling global climate change.

3. The development of the first detailed molecular-level understanding of the chemistry of electrochemical carbon dioxide capture.

4. An improved public understanding and acceptance of carbon capture technologies.

This fellowship is expected to lead to new materials and devices for energy-efficient electrochemical carbon dioxide capture. The industrial application of this technology, and the development of new knowledge on electrochemical carbon dioxide capture, will benefit a large number of groups including:

(i) The wider public. Climate change has direct implications for the general public that include increased extreme weather events and flooding, sea level rise, scarcity of water and food, and economic recession. The Committee on Climate Change stress that carbon capture and storage is a necessity and not an option as the UK aims for net-zero greenhouse gas emissions by 2050. Our technology can therefore help the UK to meet its net-zero goal and can further influence the ambition of other countries. Together these efforts will help to limit global climate change and will greatly improve the lives of the general public. The public will further benefit via the creation of new jobs through the businesses mentioned below. Finally, they will further benefit from obtaining an increased understanding of carbon capture technologies through outreach activities.

(ii) Businesses. Existing businesses and new businesses that would be involved in the prototyping, scaling, manufacture, distribution and operation of this technology will benefit from this fellowship. Improved carbon capture technology offers clean economic growth and would provide these companies with new sources of sustainable revenue. In the UK alone carbon capture and storage may amount to a £5B market by 2050, highlighting the massive opportunities for clean growth in this area. Our new carbon capture technologies can help the UK to become an international leader in this emerging area of low carbon technology.

(iii) Academia in the UK. Through the development of new techniques, new knowledge on electrochemical carbon dioxide capture, and new research collaborations, the UK can become leaders in this emerging field. This improved reputation will benefit universities and academics in the UK and will help us to attract large scale funding from international sources, including from climate-focussed philanthropists, overseas research councils and multinational companies. At a more local level, this fellowship will lead to the training of multiple post-doctoral research fellows, and will establish Dr Forse as an international leader on carbon capture technologies. Undergraduate students will further benefit as Dr Forse will incorporate new material on carbon dioxide capture into his upcoming lectures on materials chemistry.

Publications

10 25 50
 
Description This project seeks to understand and improve new carbon dioxide capture technology. Specifically the project investigates the use of electrochemical energy storage devices (batteries and supercapacitors) to capture carbon dioxide. Some key findings so far:
- Experiments on electrochemical carbon dioxide capture by supercapacitor energy storage devices found that new charging protocols could be used to more than double the quantity of carbon dioxide that these devices can capture.
- Experiments and theoretical calculations on quinone batteries found a "trade-off" between carbon dioxide binding energy and the predicted stability to oxygen gas. Quinones that bind carbon dioxide more strongly, are less likely to be able to function in the presence of oxygen. This work will guide the design of quinones for electrochemical carbon dioxide capture, where both strong carbon dioxide binding and oxygen-stable carbon capture are needed.
- We have developed new nuclear magnetic resonance (NMR) spectroscopy methodologies that reveal carbon dioxide binding modes. Specifically, for the first time we pioneered the use of 17O NMR spectroscopy to reveal binding modes in a series of porous adsorbent materials.
- We have developed new supercapacitor electrode materials known as metal-organic frameworks, and we have uncovered how the electrode micro-structure impacts energy storage. Electrodes with plate-like particles charge more rapidly than electrodes with rod-like particles.
Exploitation Route In academia, the developed NMR spectroscopy methods for understanding carbon dioxide capture may be used by other researchers to explore carbon dioxide uptake mechanisms in a range of different materials.
In industry, our developments on improving electrochemical carbon dioxide capture by supercapacitors and batteries may lead to improved carbon dioxide capture technology being developed and deployed.
Sectors Chemicals,Electronics,Energy,Environment,Manufacturing, including Industrial Biotechology

 
Title 17O NMR spectroscopy methods for revealing carbon capture mechanisms 
Description We have developed 17O NMR spectroscopy as a powerful new method for revealing carbon dioxide capture mechanisms, in carbon capture materials. 
Type Of Material Technology assay or reagent 
Year Produced 2021 
Provided To Others? Yes  
Impact pending 
URL https://chemrxiv.org/engage/chemrxiv/article-details/617a6c746c5aa08509276d68
 
Title Method for calculating electrochemical carbon dioxide capture behaviour 
Description We have developed computational chemistry methods for exploring electrochemical carbon dioxide capture performance. 
Type Of Material Technology assay or reagent 
Year Produced 2022 
Provided To Others? Yes  
Impact to be added 
URL https://pubs.acs.org/doi/full/10.1021/acs.jpcc.2c03752
 
Title Methods for measuring electrochemical CO2 capture 
Description Electrochemical gas cell equipment and methodology for quantifying electrochemical gas adsorption. 
Type Of Material Technology assay or reagent 
Year Produced 2022 
Provided To Others? Yes  
Impact Publication on 10.26434/chemrxiv-2022-1c73h which reveals new insight into electrochemical CO2 capture by supercapacitors. 
URL https://chemrxiv.org/engage/chemrxiv/article-details/61fa7fb4c0a868753f3ac9bd
 
Title Dataset for Revealing Carbon Capture Chemistry with 17-Oxygen NMR Spectroscopy 
Description This .zip file contains: - source data for Figure 2 (.xlxs format). This is a table of the calculated 17-oxygen NMR parameters for a range of different MOF structures. The data is the same as that presented in Table 2. - NMR spectroscopy data (.dx format). Raw solid state NMR spectroscopy data is provided. The raw data is for all of the solid-state NMR work presented in this study. Solution-state NMR spectra of acid-digested MOFs are also provided. - X-ray diffraction data (.csv format). Raw powder X-ray diffraction data for the studied MOFs is provided. - Computationally-derived structure files (.cif and .xyz). Geometry-optimised computational structures are provided for amine-functionalised MOFs (.cif format) and amine-functionalised silicas (.xyz format). See the main manuscript for more details. 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
Impact none known 
URL https://www.repository.cam.ac.uk/handle/1810/344237
 
Title Research Data Supporting "Enhancing the Performance of Layered Metal-Organic Framework Supercapacitors by Coordination Modulation 
Description Experimental data supporting "Enhancing the Performance of Layered Metal-Organic Framework Supercapacitors by Coordination Modulation". This data set contains six primary files: - Conductivity Measurement Data (.xlsx, .txt - contains results from the measurements used to calculate conductivity values). - Electrochemistry Data (.txt - contains CV, GCD and EIS data from electrocehmcial cells assembled with a variety of different samples and either 1 M NEt4BF4 in ACN or EMIM-BF4 IL electrolytes, along with the metafiles for the cells). - Elemental Analysis Data (.pdf, .xlsx, .txt - contains elemental analysis data). - Gas Sorption Data (.txt - contains results from gas sorption measurements). - SEM Data (.tif - contains SEM images from a range of samples). - TEM Data (.tif, .txt - contains TEM images from samples of A-CuHHTP and B-CuHHTP, intesnity plot data for an image of B-CuHHTP, and results from simulations). - XRD Data (.txt - contains synchrotron XRD data). 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
Impact n/a 
URL https://www.repository.cam.ac.uk/handle/1810/341868
 
Title Research data supporting "Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks" 
Description This data is primarily related to the synthesis and characterisation of Cu3(HHTP)2, and its electrochemical characterisation in symmetric electric double-layer capacitors with 1 M NEt4BF4 in acetonitrile electrolyte. The data provided here consists of: - CIF Files (contains information of the CIF files used during modelling and simulations. These can also be found at: https://doi.org/10.5281/zenodo.4694845). - Conductivity Measurement Data (contains results from the measurements used to calculate conductivity values). - Electrochemistry Data (contains CV data from 3-electrode cells; CV, GCD, EIS, and long-term cycling stability data from composite Cu3(HHTP)2 EDLCs with 1 M NEt4BF4 in acetonitrile electrolyte; CV, GCD, and EIS data from a Cu3(HHTP)2 EDLCs with 1 M NEt4BF4 in acetonitrile electrolyte; characterisation data for a YP50F EDLC with 1 M NEt4BF4 in acetonitrile; and characterisation data for an acetylene black EDLC with 1 M NEt4BF4 in acetonitrile). - Elemental Analysis Data (contains elemental analysis data). - Gas Sorption Data (.xlsx, .txt - contains results from gas sorption measurements). - XANES Data (contains XANES data from powder samples of Cu3(HHTP)2, pristine Cu3(HHTP)2 electrodes, cycled Cu3(HHTP)2 electrodes from EDLCs, and standard samples). - XRD Data (contains PXRD data). 
Type Of Material Database/Collection of data 
Year Produced 2021 
Provided To Others? Yes  
Impact n/a 
URL https://www.repository.cam.ac.uk/handle/1810/325118
 
Title Research data supporting "Trade-off between redox potential and the strength of electrochemical CO2 capture in quinones" 
Description See README.txt file for a detailed description of this dataset. It contains all QChem input files and output files, optimised geometries for the DFT calculations. There are four sub-directories: 1) AQ-F-series: multiple substitutions of F on anthraquinone 2) AQ-monosub: mono-substitutions of different functional groups on anthranquinone 3) BQ-F-series: multiple substitutions of F on benzoquinone 4) C: unreacted CO2. 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
Impact n/a 
 
Description Academic Collaboration with Prof Aron Walsh 
Organisation Imperial College London
Country United Kingdom 
Sector Academic/University 
PI Contribution We are working on conductive metal-organic frameworks for energy storage, where we are leading the effort on energy storage.
Collaborator Contribution We are working on conductive metal-organic frameworks for energy storage, where the Imperial team is leading the computational effort.
Impact One publication so far, with other publications in preparation.
Start Year 2021
 
Description Academic Collaboration with Prof Céline Merlet 
Organisation Paul Sabatier University (University of Toulouse III)
Country France 
Sector Academic/University 
PI Contribution Academic collaboration on electrochemical carbon dioxide capture, where we have contributed experimental work.
Collaborator Contribution Academic collaboration on electrochemical carbon dioxide capture, where the partner has contributed theory calculations.
Impact N/A
Start Year 2021
 
Description Academic collaboration with Dr Alex Thom 
Organisation University of Cambridge
Department Department of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution We have launched a new academic collaboration with the group of Dr Alex Thom on electrochemical carbon dioxide capture. We have contributed with project ideas and with experimental data on electrochemical carbon dioxide capture.
Collaborator Contribution The Thom group has contributed ideas to the project, and have carried out quantum chemical calculations of carbon dioxide capture.
Impact One pre-print has been published: 10.26434/chemrxiv-2022-8zt6r-v2
Start Year 2021
 
Description Collaboration with BP 
Organisation BP (British Petroleum)
Country United Kingdom 
Sector Private 
PI Contribution We have initiated an icase PhD studentship funded between EPSRC and BP.
Collaborator Contribution We have initiated an icase PhD studentship funded between EPSRC and BP.
Impact N/A
Start Year 2022
 
Description Collaboration with Cambridge Display Technology 
Organisation Cambridge Display Technology
Country United Kingdom 
Sector Private 
PI Contribution We are working on electrochemical carbon dioxide capture with supercapacitors.
Collaborator Contribution They have contributed funds for consumables for a CDT-funded PhD student. They are also contributing their time to advise on the project, and provide industrial supervision of the PhD student.
Impact NA
Start Year 2021
 
Description Chemistry World Article 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact A chemistry world article highlighted our study on electrochemical carbon dioxide capture by supercapacitors.
Year(s) Of Engagement Activity 2022
URL https://www.chemistryworld.com/news/switching-protocol-doubles-carbon-capture-capacity-of-supercapac...
 
Description Chemistry at Cambridge Magazine Article 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact The "Chem at Cam" magazine at Cambridge published an article on our work on electrochemical carbon dioxide capture by supercapacitors.
Year(s) Of Engagement Activity 2022
 
Description Interview on publication on capture of carbon dioxide by supercapacitors 
Form Of Engagement Activity A press release, press conference or response to a media enquiry/interview
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact Press release for our publication on electrochemical carbon dioxide capture by supercapacitors reached a large range of online news outlets, including, The Independent and Yahoo News.
see: https://rsc.altmetric.com/details/128582855/news
Year(s) Of Engagement Activity 2022
URL https://rsc.altmetric.com/details/128582855/news
 
Description Poster at Gordon Conference on Carbon Dioxide Capture 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a poster presentation on the group's research on electrochemical carbon dioxide capture. A new collaboration with the Aziz group at Harvard was formed.
Year(s) Of Engagement Activity 2022
URL https://www.grc.org/carbon-capture-utilization-and-storage-conference/2022/
 
Description Presentation at Carbon Conference, London 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a presentation at the 2022 Carbon Conference. New contacts were made in the area.
Year(s) Of Engagement Activity 2022
 
Description Presentation at ISEECAP meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a presentation at the 2022 edition of ISEECAP, attended by over 200 people.
Year(s) Of Engagement Activity 2022
 
Description Presentation to Peterhouse Science Society 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Undergraduate students
Results and Impact A research presentation was given on electrochemical carbon dioxide capture and direct air capture. New connections were forged between Dr Forse and undergraduate students, and a number of students applied for research internships in the Forse Group.
Year(s) Of Engagement Activity 2023
 
Description Seminar at Oxford Chemistry Department 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a seminar on electrochemical carbon dioxide capture.
Year(s) Of Engagement Activity 2022
 
Description Seminar at University of Leoben 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Postgraduate students
Results and Impact An research presentation was given on energy storage and electrochemical carbon dioxide capture. This led to a new research collaboration between the University of Cambridge and the Mountain University of Leoben.
Year(s) Of Engagement Activity 2023
 
Description Talk at Cambridge Zero Climate Festival 2021 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact Dr Forse gave a keynote talk on: "New Chemistry for Carbon Dioxide Capture"
There was very good questions and discussion afterwards which stimulated some ideas.
Year(s) Of Engagement Activity 2021
URL https://www.energy.cam.ac.uk/news/energy-irc-energy-transformations-cambridge-zero-climate-change-fe...
 
Description Talk at Cambridge Zero Event: Carbon Capture & Climate Repair Symposium 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a presentation on carbon dioxide capture, and joined a panel discussion.
Year(s) Of Engagement Activity 2022
URL https://www.zero.cam.ac.uk/what-we-do/events/carbon-capture-climate-repair-symposium
 
Description Talk by PDRA at American Chemical Society Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact One of the post-doctoral research associates funded on the award gave a presentation of NMR spectroscopy studies of carbon dioxide capture.
Year(s) Of Engagement Activity 2022
 
Description Talk by PDRA at BRSG NMR Christmas Meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact A PDRA from our team gave a presentation on NMR spectroscopy studies of carbon dioxide capture.
Year(s) Of Engagement Activity 2021
 
Description Webinar on electrochemical carbon dioxide capture with the electrochemical society (ECS) 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr Forse gave an online webinar on electrochemically driven carbon dioxide capture.
Year(s) Of Engagement Activity 2022
URL https://www.electrochem.org/ecsnews/ecs-webinar-batteries-supercapacitors/
 
Description Zoominar on using NMR to study CO2 capture 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Dr Forse gave a live streamed lecture on using NMR spectroscopy to study carbon dioxide capture mechanisms.
Year(s) Of Engagement Activity 2022
URL https://www.youtube.com/watch?v=2tDbUl6t_i0