Emergent Nanomaterials (Critical Mass Proposal)

Lead Research Organisation: Newcastle University
Department Name: Sch of Engineering

Abstract

Abstracts are not currently available in GtR for all funded research. This is normally because the abstract was not required at the time of proposal submission, but may be because it included sensitive information such as personal details.

Publications

10 25 50
 
Description Initially, efficient use of noble metals in automotive exhaust has been achieved through exsolving from dilute compositions. Secondly, a mechanistic insight into the formation of emergent nanomaterials was achieved. That led to the design of new interesting nanostructures that, through strain engineering, have enhanced oxygen storage and exchange capacity as well as catalytic activity and selectivity towards methane conversion. Lastly, durable (as far as coking resistance and agglomeration) and efficient (electricity demands) materials have been designed for methane conversion to syngas via electrolysis cells or chemical redox processes.
Exploitation Route The outcomes of this project can help efficiently reduce the use of resources needed for energy conversion through targeted design of controlled and durable materials. These principles can be adopted by other areas of research since the design of such materials underpins most processes.
Sectors Chemicals

Energy

 
Description We have been in discussion with a number of companies who wish to exploit the materials/techniques developed in this grant. There are a number of possible applications in the areas of chemicals and energy.
First Year Of Impact 2021
Sector Chemicals,Energy
Impact Types Economic

 
Title Combining exsolution and infiltration for redox low temperature CH4 conversion to syngas 
Description Exsolution of surface and bulk nanoparticles in perovskites has been recently employed in chemical looping methane partial oxidation because of the emergent materials' properties like oxygen capacity, redox stability, durability, coke resistance, and enhanced activity. Here we attempt to further lower the temperature of methane conversion by complementing exsolution with infiltration. We prepare an endo/exo particle system by exsolution and infiltrate it with minimal amount of Rh (0.1 wt%) in order to functionalize the surface and induce low temperature activity. We achieve a temperature decrease by almost 220 °C and increase of the activity up to 40%. We also show that the initial microstructure of the perovskite plays a key role in controlling nanoparticle anchorage and carbon deposition. Our results demonstrate that microstructure tuning and surface functionalization are important aspects to consider when designing materials for redox cycling applications. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact Publications 
URL https://data.ncl.ac.uk/articles/Combining_exsolution_and_infiltration_for_redox_low_temperature_CH4_...
 
Title Data for Enhanced Stability of Iridium Nanocatalysts via Exsolution for the CO2 Reforming of Methane 
Description The raw data is the experimental data of the paper 'Enhanced Stability of Iridium Nanocatalysts via Exsolution for the CO2 Reforming of Methane' which is accepted in the Journal ACS Applied Nano Materials. All the listed files include the catalytic data and material characterisation including SEM, TEM and XPS. The figures are denoted as Fig Xy-w, where X is the number of the figure, y is the part of the figure and w is explanation of each figure. The format includes txt, pdf, tiff and png file. The file format is open access format. The reforming reactions of greenhouse gases require catalysts with high reactivity, coking resistance, and structural stability for efficient and durable use. Among the possible strategies, exsolution has been shown to demonstrate the requirements needed to produce appropriate catalysts for the dry reforming of methane, the conversion of which strongly depends on the choice of active species, its interaction with the support, and the catalyst size and dispersion properties. Here, we exploit the exsolution approach, known to produce stable and highly active nanoparticle-supported catalysts, to develop iridium nanoparticle-decorated perovskites and apply them as catalysts for the dry reforming of methane. By studying the effect of several parameters, we tune the degree of exsolution, and consequently the catalytic activity, thereby identifying the most efficient sample - 0.5 at% Ir-BaTiO3, which showed 82% and 86% conversion of CO2 and CH4, respectively. By comparison with standard impregnated catalysts (e.g., Ir/Al2O3), we benchmark the activity and stability of our exsolved systems. We find almost identical conversion and syngas rates of formation, but observe no carbon deposition for the exsolved samples after catalytic testing; such deposition was significant for the traditionally prepared impregnated Ir/Al2O3, with almost 30 mgC/gsample measured, compared to 0 mgC/gsample detected for the exsolved system. These findings highlight the possibility of achieving in a single step the mutual interaction of the parameters enhancing catalytic efficiency, leading to a promising pathway for the design of catalysts for reforming reactions. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL https://openresearch.surrey.ac.uk/esploro/outputs/dataset/99793864902346
 
Title Endogenous Nanoparticles Strain Perovskite Host Lattice Providing Oxygen Capacity and Driving Oxygen Exchange and CH4 Conversion to Syngas 
Description Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electro- photo- and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self-strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox-active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
Impact Publications 
URL https://data.ncl.ac.uk/articles/Endogenous_Nanoparticles_Strain_Perovskite_Host_Lattice_Providing_Ox...
 
Title Exsolution of Catalytically Active Ir Nanoparticles from Strontium Titanate_Raw Data 
Description Raw data files. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact Publications 
URL https://zenodo.org/record/4110654
 
Title Low temperature methane conversion via exsolved Co particles 
Description Lowering the temperature at which CH4 is converted to useful products has been long-sought in energy conversion applications. Selective conversion to syngas is additionally desirable. Generally, most of the current CH4 activation processes operate at temperatures between 600 and 900 °C when non-noble metal systems are used. These temperatures can be even higher for redox processes where a gas phase-solid reaction must occur. Here we employ the endogenous-exsolution concept to create a perovskite oxide with surface and embedded metal nanoparticles able to activate methane at temperatures as low as 450 °C in a cyclic redox process. We achieve this by using a non-noble, Co-Ni-based system with tailored nano- and micro-structure. The materials designed and prepared in this study demonstrate long-term stability and resistance to deactivation mechanisms while still being selective when applied for chemical looping partial oxidation of methane. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact Publications 
URL https://data.ncl.ac.uk/articles/Low_temperature_methane_conversion_via_exsolved_Co_particles/9892238
 
Title Symmetrical Exsolution of Rh Nanoparticles in Solid Oxide Cells 
Description Data supporting publication. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact Publication 
 
Title Tracking the evolution of a single composite particle during redox cycling for application in H2 production 
Description Composite materials consisting of metal and metal oxide phases are being researched intensively for application in various energy conversion and storage technologies. In these applications, composites are often expected to operate under redox conditions at elevated temperature. The understanding of the dynamics of composite phase and morphology evolution during redox cycling is still very limited, yet critical to maximising performance and increasing durability. Here we track the microstructural evolution of a single composite particle over 200 redox cycles for hydrogen production by chemical looping, using multi-length scale X-ray computed tomography. We show that redox cycling triggers a centrifugal redispersion of the metal phase and a centripetal clustering of porosity, both seemingly driven by the asymmetric nature of oxygen exchange in composites. We show that initially the particle develops a large amount of internal porosity which boosts activity, but on the long term this facilitates structural and compositional reorganisation and eventually degradation. We also correlate the microstructural data with phase and activity analysis to identify structure-property correlations which not only provide valuable insight into the evolution of composite materials under redox conditions but also for the design of new composite materials with enhanced durability. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact Publication 
URL https://data.ncl.ac.uk/articles/Tracking_the_evolution_of_a_single_composite_particle_during_redox_c...
 
Description DIFFER Institute - electro-chem 
Organisation Dutch Institute for Fundamental Energy Research
Country Netherlands 
Sector Public 
PI Contribution Provision of ex-solved material samples.
Collaborator Contribution Electrochemical experiments on ex-solved materials.
Impact Publications.
Start Year 2020
 
Description IC - XPS/electron microcopy 
Organisation Imperial College London
Country United Kingdom 
Sector Academic/University 
PI Contribution Provision of material samples.
Collaborator Contribution XPS and electron microscopy of ex-solved materials.
Impact Publications
Start Year 2020
 
Description St Andrews - material synthesis and magnetic studies 
Organisation University of St Andrews
Country United Kingdom 
Sector Academic/University 
PI Contribution Tests on functional capabiliites of ex-solved materials.
Collaborator Contribution Synthesis of novel ex-solved materials (Prof Irvine's group) and magnetic studies ( Prof Lee's group)
Impact Publications
Start Year 2019
 
Description Strathclyde - ex-solved materials 
Organisation University of Strathclyde
Country United Kingdom 
Sector Academic/University 
PI Contribution Continuation of research methods and topics with previous member of research group.
Collaborator Contribution Continued links on materials development and testing methods.
Impact Publcations
Start Year 2020
 
Description University of Ulster - plasma 
Organisation Ulster University
Country United Kingdom 
Sector Academic/University 
PI Contribution Tests on properties of exsolved materials created by plasma activation.
Collaborator Contribution Prof Marriotta's group provided samples of exsolved materials created by plasma activation.
Impact Publications
Start Year 2020
 
Description Anatolia College - STEM themes 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Undergraduate students
Results and Impact Organised seminar with 'Greek women in STEM' and Anatolia College to introduce students to STEM themes and sectors- Oral, Virtual
Year(s) Of Engagement Activity 2020
 
Description CAM-IES Annual meeting - 3 Nov 2020 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact CAM-IES Annual meeting Online Webinar 3 Nov 20 - Oral, Virtual - 'Straining materials with endoparticles'
Year(s) Of Engagement Activity 2020
 
Description Chemop - University of W Macedonia 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Chemop, University of Western Macedonia - Invited Talk, Virtual - 'Research in a UK University' aiming to help early career researchers choose an academic path- Oral, Virtual
Year(s) Of Engagement Activity 2020
 
Description H2FC Supergen Hydrogen Research Conference 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Poster presentation - Leonidas Bekris, H2FC Supergen Hydrogen Research Conference 2020, Nottingham University (Feb 2020) Poster Competition Award Winner
Year(s) Of Engagement Activity 2020