Emergent Nanomaterials (Critical Mass Proposal)
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
In recent work we have identified a very powerful and extensive phenomenon, the constrained production of nanoparticles that opens up a new field impinging on chemistry, materials science and physics. The dispersion, stability, versatility and coherence with the substrate impart quite significant properties to the emergent nanoparticles opening up a major new topic. The process is driven by the lattice decomposition of a metal oxide under reduction by various means. Conventional thinking considers this as a simple phase separation; however, by careful control of the defect chemistry and reduction conditions, a very different process can be achieved. These nanoparticles emerge from the substrate in a constrained manner reminiscent of fungi emerging from the earth. The emergent nanoparticles are generally dispersed evenly with a very tight distribution often separated by less than one particle diameter.
Here we will explore the composition and reaction space conditions necessary to optimise functionality, structure and applocability. We will also seek to better understand this phenomenology relating to correlated diffusion, driving energetics and mechanism of emergence. Further work is necessary to understand the critical dependence of composition in a very extensive domain of composition space depending upon charge and size of the A-site cations, oxygen stoichiometry and transition metal redox chemistry. Of particular importance is to understand the nature of the interaction between the nanoparticle and the substrate addressing the evolution of the nanoparticles from the surface and how the particles become anchored to the substrate. Exolved metals can react to form compounds whilst maintaining the integrity of the nanostructural array and this offers much potential for further elaboration of the concept.
We will investigate the important catalytic, electrocatalytic and magnetic physics properties arising at constrained emergent particles, driven by dimensional restriction. Emergent nanomaterials provide very significant surface-particle interactions and promise new dimensions in catalysis. The electrochemical reactions in devices such as batteries and fuel cells are restricted to the domain very close to the electrolyte electrode interface. Emergent materials can be applied in exactly this zone.
Here we will explore the composition and reaction space conditions necessary to optimise functionality, structure and applocability. We will also seek to better understand this phenomenology relating to correlated diffusion, driving energetics and mechanism of emergence. Further work is necessary to understand the critical dependence of composition in a very extensive domain of composition space depending upon charge and size of the A-site cations, oxygen stoichiometry and transition metal redox chemistry. Of particular importance is to understand the nature of the interaction between the nanoparticle and the substrate addressing the evolution of the nanoparticles from the surface and how the particles become anchored to the substrate. Exolved metals can react to form compounds whilst maintaining the integrity of the nanostructural array and this offers much potential for further elaboration of the concept.
We will investigate the important catalytic, electrocatalytic and magnetic physics properties arising at constrained emergent particles, driven by dimensional restriction. Emergent nanomaterials provide very significant surface-particle interactions and promise new dimensions in catalysis. The electrochemical reactions in devices such as batteries and fuel cells are restricted to the domain very close to the electrolyte electrode interface. Emergent materials can be applied in exactly this zone.
Planned Impact
We are proposing to develop our understanding and ability to control Emergent Nanomaterials, a new class of materials that due to their constrained nature and specific dimensionality offer remarkable new functionalities and capabilities. This could offer step-change new technologies and applications.
The work will be of considerable interests to chemists, physicists and materials scientists interested in structure property relations and the fundamental science determining functional properties. The area will also be of great interest to engineers looking to develop new devices, for energy storage and conversion, information storage, catalytic conversion and optoelectronics. There are also interesting synergies with biological structures and geochemical transformations.
The possible technological implications are very significant and there is already considerable excitement in the catalytic and energy conversion arenas. Companies such as Johnson Matthey, AFC Energy, Ceres Power and Rolls Royce are already interested and engaged. These new structures offer considerably improved stability and functionality and there is already a clear home for emergent nanomaterials in these arenas. Likely examples are exhaust catalysts, bioenergy reforming, low and high temperature fuel cell/electrolyser electrodes, plasmonic solar cell, lithium batteries and sensors. As we learn more we see opportunities to greatly reduce cost over existing systems and there are clear possibilities to greatly reduce precious metal requirements or even remove the need altogether. This addresses the strategic availability of the so-called critical elements.
We also expect to find important new physical phenomena as we know how much strain and constrained dimensions impacts upon such properties. This in turn may yield important new technologies that we can see commercialised in the UK.
There are important prospects to benefit society, not only do we see exciting technological advances, but also we see great prospects to improve energy security, energy efficiency and energy storage in environmentally friendly processes. In other words, appropriate introduction of new materials concepts such as these will greatly reduce CO2 production and can even assist in CO2 removal through utilisation. Undoubtedly these new technology advances, in energy and beyond, offer secured employment and new jobs. In turn this provides taxes and reduces cost for government to mediate climate change and hence benefits society and government.
Last but not least, this project will help shape the training and vision of the next generation of researchers by placing them in a truly multidisciplinary programme which will encourage fertile scientific thinking across techniques and disciplines, while providing clear scope of high-level scientific and national strategic targets.
The work will be of considerable interests to chemists, physicists and materials scientists interested in structure property relations and the fundamental science determining functional properties. The area will also be of great interest to engineers looking to develop new devices, for energy storage and conversion, information storage, catalytic conversion and optoelectronics. There are also interesting synergies with biological structures and geochemical transformations.
The possible technological implications are very significant and there is already considerable excitement in the catalytic and energy conversion arenas. Companies such as Johnson Matthey, AFC Energy, Ceres Power and Rolls Royce are already interested and engaged. These new structures offer considerably improved stability and functionality and there is already a clear home for emergent nanomaterials in these arenas. Likely examples are exhaust catalysts, bioenergy reforming, low and high temperature fuel cell/electrolyser electrodes, plasmonic solar cell, lithium batteries and sensors. As we learn more we see opportunities to greatly reduce cost over existing systems and there are clear possibilities to greatly reduce precious metal requirements or even remove the need altogether. This addresses the strategic availability of the so-called critical elements.
We also expect to find important new physical phenomena as we know how much strain and constrained dimensions impacts upon such properties. This in turn may yield important new technologies that we can see commercialised in the UK.
There are important prospects to benefit society, not only do we see exciting technological advances, but also we see great prospects to improve energy security, energy efficiency and energy storage in environmentally friendly processes. In other words, appropriate introduction of new materials concepts such as these will greatly reduce CO2 production and can even assist in CO2 removal through utilisation. Undoubtedly these new technology advances, in energy and beyond, offer secured employment and new jobs. In turn this provides taxes and reduces cost for government to mediate climate change and hence benefits society and government.
Last but not least, this project will help shape the training and vision of the next generation of researchers by placing them in a truly multidisciplinary programme which will encourage fertile scientific thinking across techniques and disciplines, while providing clear scope of high-level scientific and national strategic targets.
Organisations
- University of St Andrews (Lead Research Organisation)
- Haldor Topsoe (Denmark) (Project Partner)
- Rolls-Royce (United Kingdom) (Project Partner)
- Hexis (Switzerland) (Project Partner)
- AFC Energy (United Kingdom) (Project Partner)
- Ceres Power (United Kingdom) (Project Partner)
- Johnson Matthey (United Kingdom) (Project Partner)
Publications
Calì E
(2023)
Real-time insight into the multistage mechanism of nanoparticle exsolution from a perovskite host surface
in Nature Communications
Calì E
(2020)
Exsolution of Catalytically Active Iridium Nanoparticles from Strontium Titanate.
in ACS applied materials & interfaces
Chattopadhyay S
(2023)
Room Temperature Exsolution of Cds Nanodots on A-site Deficient Cotton-Ball Like Titanate Perovskite Nanoparticles for H 2 Production Under Visible Light
in Advanced Energy Materials
Flokstra M
(2021)
Meissner screening as a probe for inverse superconductor-ferromagnet proximity effects
in Physical Review B
Flokstra M
(2019)
Manifestation of the electromagnetic proximity effect in superconductor-ferromagnet thin film structures
in Applied Physics Letters
Flokstra M
(2023)
Spin-orbit driven superconducting proximity effects in Pt/Nb thin films.
in Nature communications
Han H
(2019)
Lattice strain-enhanced exsolution of nanoparticles in thin films.
in Nature communications
Han H
(2019)
Author Correction: Lattice strain-enhanced exsolution of nanoparticles in thin films.
in Nature communications
Han H
(2022)
Anti-phase boundary accelerated exsolution of nanoparticles in non-stoichiometric perovskite thin films.
in Nature communications
Khalid H
(2022)
Rapid Plasma Exsolution from an A-site Deficient Perovskite Oxide at Room Temperature
in Advanced Energy Materials
Kothari M
(2021)
Platinum incorporation into titanate perovskites to deliver emergent active and stable platinum nanoparticles
in Nature Chemistry
Lee J
(2021)
Use of Interplay between A-Site Non-Stoichiometry and Hydroxide Doping to Deliver Novel Proton-Conducting Perovskite Oxides
in Advanced Energy Materials
Lee J
(2021)
Use of Interplay between A-Site Non-Stoichiometry and Hydroxide Doping to Deliver Novel Proton-Conducting Perovskite Oxides
in Advanced Energy Materials
Lee J
(2020)
Replacement of Ca by Ni in a Perovskite Titanate to Yield a Novel Perovskite Exsolution Architecture for Oxygen-Evolution Reactions
in Advanced Energy Materials
McDonald C
(2019)
Nanostructured Perovskite Solar Cells.
in Nanomaterials (Basel, Switzerland)
Neagu D
(2023)
Roadmap on exsolution for energy applications
in Journal of Physics: Energy
Ni C
(2021)
Iron-based electrode materials for solid oxide fuel cells and electrolysers
in Energy & Environmental Science
Sha Z
(2023)
Understanding surface chemical processes in perovskite oxide electrodes
in Journal of Materials Chemistry A
Stewart R
(2019)
Controlling the electromagnetic proximity effect by tuning the mixing between superconducting and ferromagnetic order
in Physical Review B
Wang M
(2023)
The Exsolution of Cu Particles from Doped Barium Cerate Zirconate via Barium Cuprate Intermediate Phases
in Advanced Functional Materials
Wang X
(2023)
Phase Selectivity and Stability in Compositionally Complex Nano ( n A 1/ n )Co 2 O 4
in Chemistry of Materials
Xu M
(2023)
Electrochemical Activation Applied to Perovskite Titanate Fibers to Yield Supported Alloy Nanoparticles for Electrocatalytic Application.
in Small (Weinheim an der Bergstrasse, Germany)
Xu M
(2023)
Nanoparticle exsolution via electrochemical switching in perovskite fibers for solid oxide fuel cell electrodes
in Journal of Materials Chemistry A
Zuo S
(2024)
Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.
in Small (Weinheim an der Bergstrasse, Germany)
Description | New approaches have been developed to exolve nanoparticles at low temperature and important advances made in exolving platinum group metals at low loadings and high activities. This work has enabled important catalytic function in pollution control and energy conversion to be achieved with lower loadings of platinum group metals whilst retaining good stability. |
Exploitation Route | Under discussion with relevant companies in both catalysis and fuel cell application |
Sectors | Chemicals,Energy,Environment |
Description | (EPISTORE) - Thin Film Reversible Solid Oxide Cells for Ultracompact Electrical Energy Storage |
Amount | € 4,599,129 (EUR) |
Funding ID | 101017709 |
Organisation | European Commission |
Sector | Public |
Country | European Union (EU) |
Start | 01/2021 |
End | 12/2024 |
Title | Electron microscopy characterisation |
Description | Raman spectroscopy coupled with optical (light) microscopy. Tungsten filament SEM: user-friendly, low cost & high throughput, an ideal workhorse instrument. Field emission gun (FEG) SEM: high resolution & stability and soft X-ray emission spectrometer (SXES) for light element detection. Electron probe micro-analyser (EPMA): high precision compositional measurement, including light elements. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2021 |
Provided To Others? | Yes |
Impact | Increased industrial and external engagement. Promotion of interdisciplinary collaboration. |
URL | https://e-microscopy.wp.st-andrews.ac.uk/ |
Title | Data underpinning: Manifestation of the electromagnetic proximity effect in superconductor-ferromagnet thin film structures |
Description | M(H) squid data; LEM stopping profiles and raw data sets (in .root and .nemu format) |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/data-underpinning-manifestation-of-the-electromag... |
Title | Lattice strain-enhanced exsolution of nanoparticles in thin films (dataset) |
Description | .opj files can be opened and viewed using freely available software: https://www.originlab.com/viewer/ |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk:443/portal/en/datasets/lattice-strainenhanced-exsolution-of-nanopart... |
Title | Platinum incorporation into titanate perovskites to deliver emergent active and stable platinum nanoparticles (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/platinum-incorporation-into-titanate-perovskites-... |
Title | Use of interplay between A-site non-stoichiometry and hydroxide doping to deliver novel proton-conducting perovskite oxides (dataset) |
Description | A draft for submission to a journal |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/use-of-interplay-between-asite-nonstoichiometry-a... |
Title | METHOD FOR PRODUCING AN ELECTRODE CATALYST FROM A PEROVSKITE METAL OXIDE |
Description | The invention relates to a method of producing electrode materials for solid oxide cells which comprises applying an electric potential to a metal oxide which has a perovskite crystal structure. The resultant electrode catalyst exhibits excellent electrochemical performance. The invention extends to the electrode catalyst itself, and to electrodes and solid oxide cells comprising the electrode catalyst. |
IP Reference | CA3030088 |
Protection | Patent application published |
Year Protection Granted | 2018 |
Licensed | Commercial In Confidence |
Impact | - |
Description | EMRS, Virtual Conference |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | The VIRTUAL 2021 Spring Meeting will consist of parallel symposia with invited speakers, oral and poster presentations, assorted by plenary sessions and a number of workshops and training courses. As a new item for posters, short oral presentation will give each attendee the opportunity to highlight the major results. The high quality scientific program will address different topics organized into 19 symposia arranged in 4 clusters covering the fields of energy materials, nanomaterials and advanced characterization, biomaterials and soft materials, as well as materials for electronics, magnetics and photonics. In parallel with the technical sessions, international exhibitors will have the opportunity to promote their equipment, systems, products, software, publications and services during the meeting. |
Year(s) Of Engagement Activity | 2021 |
URL | https://www.european-mrs.com/meetings/2021-spring-meeting-0 |
Description | EnergyCeram |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | European School on Ceramics for Energy Conversion and Storage (EnergyCeram) The online school aims at presenting a current overview of ceramic materials and technologies for selected energy applications. A topical focus is put on high-temperature power generation (gas turbines, concentrated solar power) and electrochemical applications based on ionic transport (solid oxide fuel cells, gas separation membranes, electrochemical storage). After a brief introduction of each application field including targets for properties, the relevant ceramic materials will be reviewed and evaluated. In order to be integrated in real devices, they need to fulfil numerous, often contradictory conditions, such as highest ionic and/ or electronic conductivity, stability during operation, processability, etc. The used online platform will allow for personal interactions (including video chat and screen sharing). Enough breaks are foreseen to stimulate exchanges, offering the opportunity to chat with other participants and meet new people face-to-face or in small groups! |
Year(s) Of Engagement Activity | 2020 |
URL | https://congress.dkg.de/event/eu_spring_school_001/ |
Description | ICTN-KLC, India |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | International Conference on Thin Films & Nanotechnology: Knowledge, Leadership, & Commercialization The ICTN-KLC: 2021, the first one of its kind, aims to bring together students, academicians, scientists, technologists, and entrepreneurs working on development and applications of thin films and nanomaterials from lab to commercial (industrial) scale. The inaugural 3-days conference will be organized virtually from the foundation day of the Thin Film Lab (TFL). In addition to scientific talks, there will be sessions dedicated to research ethics, leadership, and entrepreneurship targeted mainly for early career researchers. The conference will consist of plenary/invited talks and contributed papers on various focus areas in Thin Films & Nanotechnology. |
Year(s) Of Engagement Activity | 2021 |
URL | http://www.ictn-klc.org/ |
Description | IVWFC 2021, Italy |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Virtual Workshop on Fuel cells - Oral contributions in the different fields of fuel cells/ electrolysers science and technology. Delivered by national and international specialists. |
Year(s) Of Engagement Activity | 2021 |
URL | https://ivwfc.mater.unimib.it/ |
Description | Invited Talk |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | The greatest challenge facing Solid oxide cells (SOC), in both fuel and electrolysis cell modes (i.e SOFCs and SOECs) is to deliver high, long-lasting electrocatalytic activity while ensuring cost and time-efficient electrode manufacture. Ultimately, this can best be achieved by growing appropriate nanoarchitectures under operationally relevant conditions, rather than through intricate ex situ procedures. In our approach, metal particles are grown directly from the oxide support though in situ redox exsolution. We demonstrated that by understanding and manipulating the surface chemistry of an oxide support with adequately designed bulk (non)stoichiometry, one can control the size, distribution and surface coverage of produced particles. We also revealed that the emergent particles are generally epitaxially socketed in the parent perovskite which appears to be the underlying origin of their remarkable stability, including unique resistance of metal particles to agglomeration and to hydrocarbon coking, whilst retaining catalytic activit. Operando redox treatments yield emergent nanomaterials at potentials in excess of 2V. Here we apply this technique to drive steam, CO2 and coelectrolysis processes at emergent metals and alloy particles. |
Year(s) Of Engagement Activity | 2020 |
URL | https://ecs.confex.com/ecs/prime2020/meetingapp.cgi/Paper/143913 |
Description | MEMP 2021 |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Centre for Materials for Electronics Technology (C-MET), Pune is organizing an International Conference on Multifunctional Electronic Materials & Processing (MEMP 2021) at Pune, India during 8-10 March 2021. MEMP-2021 provide an opportunity to scientists, researchers, academicians and young students to interact with eminent scientists/technologists working in the field of multifunctional electronic materials for various applications & their processing for making devices. Materials required for energy storage, energy generation, Nanostructured materials, Quantum dots, Sensors, Neutrino Energy Conversion /storage. Flexible devices, Photonic devices and processing techniques like Additive Manufacturing (3D printing) will be discussed here. MEMP 2021 will serve as a common platform for discussing the new ideas developments/ breakthroughs and future prospects pertaining to multifunctional electronic materials with some of the leading scientists/ technologists as well as to be acquainted with their experience and knowledge. |
Year(s) Of Engagement Activity | 2021 |
URL | https://journalsofindia.com/multifunctional-electronic-materials-processing-memp-2021/ |
Description | STACEES Network Launch |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Supporters |
Results and Impact | The launch of The St Andrews Network for Climate, Energy, Environment and Sustainability (STACEES) is an interdisciplinary research-focused initiative launched in April 2021 at The University of St Andrews. STACEES' objective is to drive cohesion and capacity in environmental sustainability research at St Andrews, boosting its impact and visibility. The network's vision is to build ambitious, lasting research capabilities that position the University at the centre of international conversations on climate change, energy research and environmental sustainability. |
Year(s) Of Engagement Activity | 2021 |
URL | https://events.st-andrews.ac.uk/events/sta-cees-network-launch-with-guest-speaker-prof-john-irvine/ |
Description | UKRI at COP26 |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Policymakers/politicians |
Results and Impact | Our role in supporting a Year of Climate Action. The UN Climate Change Conference (COP26) is underway. We are supporting activities and events that inspire and engage people and promote positive climate action. Whether you are at COP26 or not, register to access our events, exhibitor booths and engage with researchers and innovators. On these pages you will find out more about: the role research and innovation play in tackling climate change events that UK Research and Innovation is hosting and promoting for COP26, and how to sign up and attend how to join the climate conversation and share your work and ideas. |
Year(s) Of Engagement Activity | 2021 |
URL | https://www.ukri.org/our-work/responding-to-climate-change/ukri-towards-cop26/ |