17 November 2022, London, UK Materials chemistry poster symposium
MATERIALS CHEMISTRY COMMUNITY
17 November 2022, London, UK Materials chemistry poster symposium
Book of Abstracts
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Introduction
Dear Colleagues, Welcome to the 2022 Royal Society of Chemistry Materials Chemistry Community Poster Symposium, designed to celebrate the breadth and strength of materials chemistry research by researchers in the early stages of their careers. We hope you enjoy the day and take advantage of the opportunities to network and learn about the best in materials chemistry research. The presenters of two posters, selected by our panel of judges, will receive a free registration to MC16, the 16th International Conference in Materials Chemistry. This is the Materials Chemistry Community’s flagship event and will take place in Dublin next year. You will also be able to vote for your favourite poster, which will win a prize, sponsored by the Journal of Materials Chemistry, of a gift voucher for an RSC Materials Science book. I am delighted that our panel of judges includes this year’s Materials Chemistry Prize winners, Dr Lucy Clark, Professor Andrew Beale and Professor Paul Attfield. I am also pleased to welcome Dr Marie-Beatrice Madec, Dr Ataulla Shegiwal, Dr Simon Foxon and Mr George Garratt to the meeting today to participate in the careers panel. I look forwards to hearing more from them throughout the day. It only remains for me to welcome you once again, to thank you all for travelling here, and to wish you an enjoyable and stimulating time at the symposium. Magda Titirici President, Materials Chemistry Community
Meeting information
The Materials Chemistry poster symposium is organised by the Materials Chemistry Community. This book contains abstracts of the 60 posters presented at the symposium. All abstracts are produced directly from typescripts supplied by authors. Copyright reserved. Posters Posters have been numbered consecutively: P01-P60 Poster prizes Our judges will recognise the two best posters, who will win free registration to the 16th International conference on materials chemistry (MC16). You can also vote for your favourite poster, which will win a prize, sponsored by the Journal of Materials Chemistry, of a gift voucher of £200 to be applied against RSC Materials Science book. Please use the voting slips and box in the Science Room. Flash poster presentations These will take place in the library on the 1st floor. Posters Will be on display in the Science and Fish Rooms (ground floor). Career Panel Discussion This will take place in the library. Invited speakers from industry and academia will give a brief overview of their careers to date, followed by a panel discussion and a short question and answer session led by Laura Woodward. Career Consultations For those that have booked an appointment they will take place in the Hinshelwood Room (1st floor). If you would like the opportunity to have a 15 minute consultation with a qualified career and professional development adviser for the Royal Society of Chemistry please check with the registration desk if there are any appointments available. Catering Refreshments and lunch will be served in the Science and Fish room (ground floor), the drinks reception at the end of the day will be held in the Council room (1st floor). Wi-Fi Access Network – RSC_Guest_Temp Password – platinum-794 Sponsor We would like to thank Journal of Materials Chemistry A, B &C for sponsoring a poster prize.
Scientific Committee
Magda Titirici (Chair) Imperial College London, UK
Jan-Willem Bos Heriot Watt University, UK
Emma McCabe Durham University, UK
Ben Xu Northumbria University, UK
Materials Chemistry Community
The Materials Chemistry Community supports the study and dissemination of materials chemistry in all its forms. We support networking and community building among materials chemists across academic and industrial research, advance scientific knowledge through conferences, events and scientific activities, and act as an advocate for the field of Materials Chemistry. We organise a range of activities including the series of Materials Chemistry conferences, support regional meetings, and support our community through our scientific meetings grant and travel grant schemes. For more information on the Materials Chemistry Community please contact Dr Philip Stackhouse (stackhousep@rsc.org)
Programme
Thursday 17 November 2022 (GMT)
Registration
10:15
Flash presentations session 1
11:00
Poster / judging session 1
11:45
LUNCH
13:00
Flash presentations session 2
14:00
Poster / judging session 2
14:45
16:00 Afternoon refreshment break
Careers Panel Presentation of Prizes
16:30
Reception
17:30
18:30 CLOSE
Please note these timings are subject to change
Poster presentations
Tuneable naphthalene-based porous polyimide networks for CO 2 capture and conversion Basiram Brahma Narzary University of Bristol, UK Nanocarbon functionalised micro and nanoelectrodes for electrochemical hydrogen peroxide sensing Rachel Bocking University of Leeds, UK Lithiophilic nanowire hosts for dendrite inhibition in Li-metal anodes Syed Abdul Ahad University of Limerick, Ireland Synthesis and characterisation of asymmetric perylene-based supramolecular polymers Helal Alharbi University of Bristol, UK Application of molten flux sintering for half-heusler thermoelectric materials Blair Kennedy Heriot-Watt University, UK Synthesis of chiral copper (II) oxide nanosheets via treatment of layered double hydroxides Áine Coogan Trinity College Dublin, Ireland Understanding the phase stability of BaZrS 3 using ab-initio thermodynamics Prakriti Kayastha Northumbria University, UK Investigating the effects of post-synthetic treatments of MAPbI 3 on its lattice structure and cation dynamics using X-ray diffraction and
P01
P02
P03
P04
P05
P06
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P08
solid-state NMR Jessica Dawber University of Kent, UK
A deep convolutional neural network for real-time analysis of big powder diffraction data Hongyang Dong University College London, UK Design self-assembling peptide hydrogel for targeted cancer drug delivery Siyuan Dong University of Manchester, UK Hansen solubility parameter toolkits for the design and control of functional materials Xue Fang University of Bristol, UK A first-principle approach to a spin-polarised metal oxide surface Fei Gao Imperial College London, UK
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P10
P11
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Controlling functionality and self-assembly of pdi-based supramolecular polymers by targeted modification
P13
Maximilian Hagemann University of Bristol, UK
Thermal and hydrolytic degradation of regenerated cellulose fibres relative to their crystallinity Louise Garner University College London, UK Tuning the phase fraction of multiphase Na 0.9 Fe 0.5 Mn 0.5 O 2 cathode by biotemplating for Na-ion batteries Rebecca Huang University of Sheffield, UK Tuning electron affinity by heteroannulation of benzothiadiazole in organic semiconductors Xiantao Hu Imperial College London, UK
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Hydrothermal synthesis of carbon dots from Irish seaweed and seaweed derivatives Karlijn Hertsig Trinity College Dublin, Ireland Towards novel organic semiconductor-based contrast agents for targeting matrix metalloproteinases and the tumour microenvironment Ana-Maria Ivanus University College London, UK Designing peg-peptide copolymer hydrogel for biomedical applications Andong Liu The University of Manchester, UK Hydrothermal synthesis and analysis of porous zno-chitosan composites Kanako Kimura University of Leeds, UK Excellent long-range charge-carrier mobility in 2D perovskites Manuel Kober-Czerny University of Oxford, UK Luminescent waveguide-encoded lattices for indoor photovoltaics Takashi Lawson University of Cambridge, UK Characterisation of doped honeycomb-like multiferroics MnAMo 3 O 8 (A2+ = Fe, Co and Zn) Holly McPhillips University of Kent, UK Electrospray pyrolysis as an effective way to synthesis porous photoelectrodes to drive useful organic reactions Ayman Mohammed University of York, UK
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P19
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Templated iron single atoms in nitrogen-doped carbon O 2 reduction electrocatalysts: towards 100% active site utilisation? Angus Pedersen Imperial College London, UK Synthesis of degradable linear and bottlebrush thioester- functional copolymers through atom transfer radical ring-opening copolymerization of a thionolactone Qamar Nisa University of Surrey, UK Manipulation of charge carrier flow in a Bi 4 NbO 3 Cl nanoplate with metal loading for water splitting photocatalysis Kanta Ogawa Imperial College London, UK Rational design of carbon nitride photoelectrodes with high activity toward organic oxidations Carolina Pulignani University of Cambridge, UK High-throughput materials design of quaternary sodium halide electrolytes, Na 6 M’M’’X 12 , for all-solid-state sodium batteries Anthony Onwuli Imperial College London, UK Surface modification of transitional metal dichalcogenides for intrinsically self-healing hydrogels Chirag R Ratwani Bournemouth University, UK Insertion of degradable thioester linkages into styrene and methacrylate polymers Matthew Rix University of Surrey, UK Modulating the self-assembly, gelation and antimicrobial properties of β-sheet forming ultra-short de novo ionic-complementary peptides via charge distribution Mohamed Ahmed Naseef Soliman De Montfort University, UK
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Polymer-POSS composites as hosts for Luminescent Solar Downshifters Helen Tunstall-Garcia University of Cambridge, UK Photocatalytic hydrogen production using recombinant escherichia coli-conjugated polymer nanoparticle biohybrid systems Ying Yang University of Liverpool, UK Device-scale atomistic modelling of phase-change memory materials using a machine-learned interatomic potential Yuxing Zhou University of Oxford, UK Redox-active porous materials for CO 2 capture and conversion Ulzhalgas Karatayeva University of Bristol, UK Bismuth based panchromatic solar light absorption complexes Harsh Bhatia University College London, UK Controlling the microstructure of metal and polymer foams via microfluidic approaches Thomas Moore University of Leeds, UK Design for recycle: alternative binders for optimising recyclability Sean Scott University of Leicester, UK An electrochemical perspective of solar redox flow batteries Gengyu Tian Queen Mary University of London, UK
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Understanding biofilm formation on aircraft materials Martin Warburton Swansea University, UK
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A facile continuous approach for the high throughput synthesis of functionalised 2D derived nanocomposites Conor Davids London South Bank University, UK Anticancer co-assembling ultra-short ionic complementary peptide hydrogels for localised therapy of malignant glioblastoma Abdulwahhab Khedr De Montfort University, UK Upscalable and semi-transparent organic photovoltaics for energy-generating windows Brendan Coles Swansea University, UK The role of colloidal stability in graphene oxide/nanoparticle hybrid synthesis Alex Massey University of Leeds, UK Sulfur encapsulated in single-walled carbon nanotubes for improved hydrogen storage Charles Brewster University of Bristol, UK
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Designing a Li-N-H based solid electrolyte Jeremy Lowen University of Birmingham, UK
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Synthesis and anisotropic growth of metastable wurtzite cuins 2 nanostructures Aoife Kavanagh Trinity College Dublin, Ireland Structures and thermoelectric properties of co-doped quaternary chalcogenides of Cu 2 FeGeSe 4 Alaa Aldowiesh University of Reading, UK
P48
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Catalytic studies of imide–transition-metal composites for ammonia decomposition Caitlin Brooker-Davis University of Birmingham, UK Influence of sodium precursor on the cubic to monoclinic phase transformation and controlled colloidal synthesis of nasbs 2 nanoparticles Maria Zubair University of Limerick, Ireland Relationship between Reactivity, Energy-Gap and Absorption Spectra Study of Armchair-, Zigzag- and Chiral-Edged Hexagonal Graphene Quantum Dots Tristan Stephens-Jones King’s College London, UK
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The influence of Al and Ga doping on the chemical and electrochemical cycling of T-LiFeO 2 Suraj Mahato University of Oxford, UK
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Evaluation of carbon felts functionalized with deep eutectic solvents as electrodes for all-vanadium redox flow batteries Mauricio Murillo Queen Mary University of London, UK Synthesis and characterisation of dense ferroic frameworks Thomas Hitchings University of Kent, UK
P54
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LiFe2-xInxSbO 6 oxides as Li-ion electrode materials Xabier Martinez de Irujo Labalde University of Oxford, UK
P56
Biomass-derived carbon quantum dots via continuous hydrothermal flow synthesis for nano-sensing applications Kiem Nguyen London South Bank University, UK
P57
Electron spin selective electrodes for oxygen evolution reaction Carlos Mingoes Queen Mary University of London, UK Removal is removal; or is it? Towards decoupling physisorption from true degradation on carbon-supported Fenton-like composite catalysts Bence Solymosi University of Leeds, UK Heteroatom doped lignin-derived carbon fibres from electrospinning for electrode materials in flow batteries Michael Thielke Queen Mary University of London, UK
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Tuneable naphthalene-based porous polyimide networks for CO 2 capture and conversion Basiram Brahma Narzary 2 , Jerry Mintah 1 , Dr. Benjamin C. Baker 1 , Dr. Jie Chen 3 and Prof. Charl FJ Faul 1 1 School of Chemistry, University of Bristol, UK, 2 University of Bristol, UK, 3 Fuzhou University, China Climate change is a significant global challenge and a serious threat to the planet. Several strategies have been proposed to reduce the emission of anthropogenic CO 2 (carbon dioxide) and to explore the use of CO 2 as an abundant feedstock to produce sustainable fuels. Capturing CO 2 using porous polymers and converting it into valuable chemical feedstocks is a promising solution to this problem. Crosslinked porous polyimides (pPIs), a type of porous organic polymer (POP), offer great potential for CO 2 capture and conversion, owing to their porous nature and excellent chemical and thermal stabilities. 1, 2 However, incompatibility of solvents during the condensation of the material can yield into lower surface areas and by that limits the total gas uptake. The Bristol-Xian-Jiaotong (BXJ) approach to tune solvent-polymer compatibility can be employed to optimise the synthesised pPIs and their resulting functionality. 3, 4 In this approach inorganic salts are used to tune the porosity and enhance the surface area by tuning the compatibility of the reaction solvent and the growing porous polymer. By implementing the BXJ approach, pPIs were optimised to enable CO 2 capture of up to 14 wt%. Additionally, the pPIs were successfully utilised to electrocatalytically reduce CO 2 to methanol and formate with Faradaic efficiencies of up to 85% and 95%, respectively. Further investigation shows that pPIs can incorporate CO 2 into epoxides (epichlorohydrin) to form cyclic carbonates ((chloromethyl)ethylene carbonate) with 98% conversion. References 1. Y. Liao, J. Weber and C. F. J. Faul, Macromolecules , 2015 , 48, 2064-2073. 2. B. B. Narzary, B. C. Baker, N. Yadav, V. D'Elia and C. F. J. Faul, Polymer Chemistry , 2021 , 12, 6494-6514. 3. J. Chen, W. Yan, E. J. Townsend, J. Feng, L. Pan, V. Del Angel Hernandez and C. F. J. Faul, A ngew Chem Int Ed Engl , 2019 , 58, 11715-11719. 4. J. Chen, T. Qiu, W. Yan and C. F. J. Faul, Journal of Materials Chemistry A , 2020, 8, 22657-22665.
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© The Author(s), 2022
Nanocarbon functionalised micro and nanoelectrodes for electrochemical hydrogen peroxide sensing Rachel Bocking 1 , Prof Helen Picton 2 , Dr Paolo Actis 3 , Dr Robert Menzel 1 1 School of Chemistry, University of Leeds, UK, 2 School of Medicine, University of Leeds, UK 3 School of ElectricalEngineering, University of Leeds, UK This work investigates the modification of micro and nanoscale electrodes with electro-catalytic nanomaterials for enhanced electrochemical sensing of hydrogen peroxide in the context of embryonic development monitoring. Dynamic and quantitative monitoring of hydrogen peroxide around individual blastocysts is key to understanding embryo health and metabolism, but it remains extremely challenging. 1 While carbon nanoelectrodes and ultra- microelectrodes have been utilised for minimally invasive sensing in tissue 2 , their use in single cell studies remains underexplored due to poor signal-to-noise and selectivity issues. Tuning of electrochemical sensors with electro-catalytic nanomaterials can improve the sensitivity and selectivity of the sensor towards specific chemical species of interest. 3 Electrophoretic functionalisation of electrodes with high-surface-area metal-nanoparticle/ nanocarbon composite coatings is investigated here, alongside molecular functionalisation of nanocarbons with enzymes. Using a macro-electrode model system, a range of nanoparticle/nanocarbon coatings were screened and optimised towards H 2 O 2 sensing in a complex, biologically relevant medium. The macroscale study was then used as a platform to transpose electrode functionalisation to the microscale and nanoscale to substantially improve sensitivity and limit of detection. The resulting enhancements in H 2 O 2 sensing are key milestones for the ultimate project goal of in-situ metabolite sensing at the single cell level, through integration of functionalised nanoelectrodes into existing cell imaging technologies. References 1. M. A. Riaz and Y. Chen, Nanoscale Horizons , 2022, 7 , 463-479. 2. P. Actis, S. Tokar, J. Clausmeyer, B. Babakinejad, S. Mikhaleva, R. Cornut, Y. Takahashi, A. L. Cordoba, P. Novak, A. I. Shevchuck, J. A. Dougan, S. G. Kazarian, P. V. Gorelkin, A. S. Erofeev, I. V. Yaminsky, P. R. Unwin, W. Schuhmann, D. Klenerman, D. A. Rusakov, E. V. Sviderskaya and Y. E. Korchev, ACS Nano , 2014, 8 , 875–884. 3. H. Yu, J. Yu, L. Li, Y. Zhang, S. Xin, X. Ni, Y. Sun and K. Song, Frontiers in Chemistry , 2021, 9 , 677876.
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© The Author(s), 2022
Lithiophilic nanowire hosts for dendrite inhibition in Li-metal anodes Syed Abdul Ahad 1 , Shayon Bhattacharya 3 , Seamus Kilian 1 , Michela Ottaviani 1 , Kevin M. Ryan 1 , Tadhg Kennedy 1 , Damien Thompson 2 , Hugh Geaney 1 1 Department of Chemical Sciences, University of Limerick, Ireland 2 Department of Physics, University of Limerick, Ireland Lithium-ion batteries (LIBs) remain the most popular rechargeable battery of our era, but currently facing challenges in meeting the rising energy density demands, for applications like electric vehicles (EVs) [1,2]. To overcome energy density issues in LIBs, Lithium metal batteries (LMBs) are gaining renewed interest due to its ability to provide enhanced energy density as compared to the current state-of-the-art LIBs. Li metal is considered the ‘holy grail’ of battery materials specifically due to its high theoretical capacity (3860 mAh g -1 ) and low electrochemical potential (-3.07 V vs. standard hydrogen electrode (SHE)) [3,4]. However, several issues plague the commercialization of LMBs. Some notable problems include the loss of active material (Li), unstable solid electrolyte interface (SEI) formation, excessive Li dendrite growth causing short-circuits and hazardous fires during battery operation [5]. To overcome the issue of dendrite formation, we will present the design of a hierarchical nanowire (NW) – carbon fiber (CF) host for dendrite-free cycling in LMBs. These lithiophilic nanowires (NWs) were grown on CF hosts via a vapour-liquid-solid (VLS) approach, followed by Li infusion. The NW morphology played a significant role in reducing the local current density on the surface of NW-CF host, thereby inhibiting the dendrite formation. Extensive symmetric cell and full cell testing conducted against LiFePO 4 (LFP) and sulfur cathodes demonstrated superior performance in Li infiltrated NW-CF hosts as compared to pristine Li metal anode. In-depth material and electrochemical characterization, supported by density functional theory (DFT) calculations, was conducted to examine the role of various lithiated phases in dendrite suppression during electrochemical cycling. The post- mortem imaging of metal anodes shed light on the influence of changing NW composition in achieving long-term cycling characteristics in LMBs. Our findings provide new avenues for the use of lithiophilic NWs to suppress Li dendrite formation, enabling uniform Li deposition for high energy density LMBs. References
1. J. -M. Tarascon, M. Armand, Nature, 2001, 414, 359–367 2. D. Lin, Y. Liu, Y. Cui, Nat. Nanotechnol. 2017, 12, 194. 3. X. B. Cheng, R. Zhang, C. Z. Zhao, Q. Zhang, Chem. Rev. 2017, 117, 10403. 4. J. W. Choi, D. Aurbach, Nat. Rev. Mater. 2016, 1. 5. Y. Guo, H. Li, T. Zhai, Adv. Mater. 2017, 29
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© The Author(s), 2022
Synthesis and characterisation of asymmetric perylene-based supramolecular polymers Helal Alharbi and Prof. Charl F. J. Faul University of Bristol, UK Supramolecular polymers (SMPs) are a unique class of materials, which are held together by non-covalent and highly directional interactions. SMPs and conventional polymers possess common properties, such as low viscosity. However, owing to the reversibility of non-covalent interactions, SMPs exhibit significantly more dynamic behaviour, enabling them to display various properties such as self-healing, processability, and stimuli- responsiveness. 1 Perylene diimides (PDIs) have attracted attention as building blocks for SMPs through solution self-assembly. PDIs feature a range of attractive properties, including optoelectronic properties, that enables the investigation of their self-assembly, thermal and photochemical stability, easy chemical modification, and widespread potential applications. 2 Modification on the imide position is one of the strategies for designing novel functional PDIs. 3 Asymmetric PDIs with different substituents at each imide position are an essential subgroup within this class of compounds owing to their substantial synthetic versatility, 4 and have not been explored in great details for their self-assembly behaviour. In this work, we aim to explore the formation of SMPs based on asymmetric PDIs by targeting the imide positions on perylene tetracarboxylic dianhydrides. To facilitate the synthetic process, we applied a recently developed one- step technique developed by Hawker and co-workers, which uses a stoichiometric mixture of various amines in a one-step reaction. 5 Different asymmetric PDIs have been successfully synthesised using a variety of hydrophilic/ hydrophobic amines. We expect to design novel SMPs based on asymmetric PDIs and explore their self- assembly mode, behaviour and resulting supramolecular structures. References 1. T. F. A. De Greef, M. M. J. Smulders, M. Wolffs, A. P. H. J. Schenning, R. P. Sijbesma and E. W. Meijer, Chem. Rev., 2009, 109, 5687–5754. 2. C. Jarrett-Wilkins, X. He, H. E. Symons, R. L. Harniman, C. F. J. Faul and I. Manners, Chem. - A Eur. J., 2018, 24, 15556– 15565. 3. R. S. Wilson-Kovacs, X. Fang, M. J. L. Hagemann, H. E. Symons and C. F. J. Faul, Chem. – A Eur. J., 2022, 28, e202103443. 4. H. Wang, H. Liu, J. Wang, Z. He, Z. Zhang, E. He, R. Zhang and H. Zhang, Tetrahedron, 2016, 72, 7076–7080. 5. M. J. Robb, B. Newton, B. P. Fors and C. J. Hawker, J. Org. Chem., 2014, 79, 6360–6365.
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© The Author(s), 2022
Application of molten flux sintering for half-heusler thermoelectric materials Jan-Willem Bos and Blair Kennedy Heriot-Watt University, UK Half Heusler alloys are a key family of compounds for thermoelectric waste heat recovery. The alloys possess good electrical properties, wide operating temperature ranges and abundant, low toxicity precursors. The significant issue facing these alloys is the inherently high thermal conductivity that lowers the thermoelectric performance (zT = (S 2 σ/κ)T). The reduction of κ has been the focus of the last two decades of Half-Heusler alloy research. 1 Isovalent alloying of these compounds, resulting in mass and bond disorder, is the primary strategy for reducing κ. Atomic size mismatch and high enthalpy of mixing, however, result in a non-ideal solid solution, with phase segregation reducing point defect disorder. In previous work, we have observed the effect of a Cu based mineralizer reducing this effect, with the best performance occurring with a Cu-Sn based phase present. 2 Here we present our findings from investigating this mineralizing flux in a prominent n-type Half-Heusler alloy composition Ti 0.5 Zr 0.5 NiCu y Sn (y = 0.025, 0.1). In a variable temperature study, the phase behaviour of these compositions are examined through a combination of X-ray powder diffraction and scanning electron microscopy, with complementary energy dispersive X-ray spectroscopy. This poster will discuss the observed phase behaviour of these Half-Heusler alloys in the presence of the Cu mineralizer, in comparison to models based on lattice solubility. Thermoelectric analysis shows a direct correlation between the phase behaviour and thermal
conductivity. References
1. R. J. Quinn and J. W. G. Bos, Mater. Adv. , 2021, 2 , 6246-6266 2. S. A. Barczak et al , J. Mater. Chem. A , 2019, 7 , 27124-27134
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© The Author(s), 2022
Synthesis of chiral copper (II) oxide nanosheets via treatment of layered double hydroxides Áine Coogan 1 , Lucia Hughes 1,2, Finn Purcell-Milton 1,3 , Seán Cardiff 1,4 , Valeria Nicolosi 1,2 and Yurii Gun'ko 1
1 Trinity College Dublin, Ireland, 2 CRANN and AMBER Research Centres, Trinity College Dublin, Ireland, 3 Technological University Dublin, Ireland, 4 School of Physics, Trinity College Dublin, Ireland
In recent years, much research has focused on the development of new chiral inorganic nanostructures, including a wide variety of materials, such as spherical quantum dots, nanowires, and tetrapods, among others. 1-3 However, the induction of chirality in 2D materials is minimally explored. 4 Layered double hydroxides (LDHs) are a class of ionic 2D nanomaterials that are known for their porous laminar structures and anion-exchange properties. As such, they can host a wide variety of species in their interlayer – including chiral molecules.Despite this unique property, to the best of our knowledge there are minimal reports on the effect of chiral ligands on the properties of LDHs, and the potential for chirality induction. In addition, chiral copper (II) oxide (CuO) is a material of significant interest due to its potential applications in non-linear optics and the treatment of Parkinson's disease. 5,6 However, the synthesis often requires moderate-to-high temperatures, as well as additional surfactants and symmetry- breaking agents. 7 To the best of our knowledge, no reports exist on the synthesis of chiral CuO at room temperature, or by using LDHs as precursors. In this work, we report the synthesis and investigation of chiral copper (II) oxide nanosheets by post-synthetic treatment of copper-aluminium LDHs. The initial LDH nanomaterials have been synthesised by a simple, scalable co-precipitation procedure. Then, the resultant 2D nanomaterials were treated with L- and D-Phenylalanine at room temperature in aqueous, basic conditions, resulting in materials with induced chirality, and circular dichroism (CD) response in the visible region, far beyond the onset of the CD signal from the original ligand. Time- dependent CD and powder X-Ray diffraction (pXRD) studies demonstrate a gradual transformation from achiral LDH nanosheets, to chiral CuO nanosheet clusters, exhibiting g-factors of up to 0.0035. We anticipate that these materials could have potential future applications in enantiomeric separation and asymmetric catalysis. References 1. M. P. Moloney, Y. K. Gun’ko and J. M. Kelly, Chemical Communications , 2007, 3900–3902. 2. D. Kehoe, E. Mates-Torres, P. Samokhvalov, M. García-Melchor and Y. K. Gun’ko, Journal of Physical Chemistry C , 2022, 126 , 434–443. 3. J. E. Govan, E. Jan, A. Querejeta, N. A. Kotov and Y. K. Gun’ko, Chemical Communications , 2010, 46 , 6072–6074. 4. F. Purcell-Milton, R. McKenna, L.J. Brennan, et. al.ACS Nano , 2018, 12 , 954–964. 5. G.S. Boltaev, R.A. Ganeev, P.S. Krishnendu, K.Zhang and C. Guo, Scientific Reports 2019 9:1 , 2019, 9 , 1–8. 6. C. Hao, A. Qu, L. Xu, M. Sun, H. Zhang, C. Xu and H. Kuang, J Am Chem Soc , 2019, 141 , 1091–1099. 7. Y. Duan, X. Liu, L. Han, S. Asahina, D. Xu, Y. Cao, Y. Yao and S. Che, J Am Chem Soc , 2014, 136 , 7193–7196.
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Understanding the phase stability of BaZrS 3 using ab-initio thermodynamics Prakriti Kayastha, Giulia Longo and Lucy D. Whalley Northumbria University, UK Chalcogenide perovskites are a non-toxic, lead-free alternative to halide perovskites for photovoltaics applications. BaZrS 3 is particularly promising as it is chemically stable and earth abundant with an ideal band gap for applications in a tandem solar cell architecture 1,2 . Synthesis routes at the low to moderate temperatures required for successful device fabrication are under-developed, and there is no systematic study of the phase stability against all competing phases in the Ba-Zr-S system. Understanding the stability of these new materials can provide insight into the reaction pathways that are feasible under certain processing conditions. Although there is some first-principles data available through materials databases, this is not sufficient for predictions of thermodynamic stability across a range of temperatures and synthesis conditions. We will present state-of-the-art DFT and lattice dynamics data for predicting the Gibbs free energy of BaZrS 3 and its competing ternary and binary phases, as a function of temperature and sulphur partial pressure. We will use this to locate the conditions under which there is a thermodynamic driving force towards perovskite formation, in particular highlighting the important role that sulphur partial pressure plays in phase formation. We will also introduce the ThermoPot package used to analyze our first-principles data 3 , which can be applied by other researchers to their systems of interest. References
1. Tiwari et al , J Phys. Energy (2021) 3 034010 2. Sophia et al , Adv. Opt. Mater. (2021) 10 2101704 3. https://github.com/NU-CEM/ThermoPot/
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© The Author(s), 2022
Investigating the effects of post-synthetic treatments of MAPbI 3 on its lattice structure and cation dynamics using X-ray diffraction and solid-state NMR Jessica Dawber 1, 2 , Julien Trébosc 3 , Mark Green 1 , Olivier Lafon 2 1 University of Kent, UK, 2 Univ. Lille, CNRS, UMR 8181-UCCS-Unité de Catalyse et Chimie de Solide, France, 3 Univ. Lille, CNRS, FR 2638 – IMEC – Fédération Chevreul, France Hybrid perovskites, consisting of an organic cation inside a metal halide scaffold, arose in 2009 1 as low-cost photovoltaic devices. Methylammonium lead iodide (MAPbI 3 ) is one of the most extensively studied hybrid perovskite materials since it exhibits high photovoltaic conversion efficiencies (> 25%), while substantially reducing production costs over existing technologies. 2-4 However, thermal and moisture stability issues, along with structural variability over the general operating temperatures of a perovskite solar cell (15 – 70 °C) 5 , affect their overall photovoltaic performance. 6 Our research involves developing post-synthetic annealing treatments the material structure in the bulk. We show that post-treatment of MAPbI 3 under various conditions alters the motions of the cation (measured by solid-state NMR), which correlate to the change in tilting of the PbI 6 octahedra observed in X-ray diffraction. This exhibits the importance of using a combination of techniques to characterise the structural modifications in the treated phases, while also demonstrating the synergy between the structure and dynamics in these systems. This allows for the opportunity of a range of new related hybrid perovskite materials through topotactic transformations, that can have properties tuned according to the requirements of their application. References 1. Kojima, et al., JACS 2009, 131, 6050.H. Im, et al., Nanoscale, 2011 2. Chen, et al., ACS Energy Lett., 2019, 4, 6, 1258–1259 3. M. Lee, et al., Scientific Reports , 2012, 2, 59
4. 1T. Weller, et al., Chem. Commun. , 2015, 51, 4180—4183 5. Slonopas, et al., Journal of Applied Physics , 2016, 119, 074101
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A deep convolutional neural network for real-time analysis of big powder diffraction data Hongyang Dong 1 , K. Butler 2 , R. Khatry 3 , S. D. M. Jacques 4 , A. M. Beale 1,4 , A. Vamvakeros 1,4 1 University College London, UK, 2 Rutherford Appleton Laboratory, UK 3 National Physical Laboratory, UK, 4 Finden Limited, UK We present the first regression deep convolutional neural network, termed PQ-Net, providing quantitative analysis of powder X-ray diffraction patterns from multi-phase systems. The network is tested against simulated and experimental datasets of increasing complexity with the last one being X-ray diffraction computed tomography dataset of a multi-phase Ni-Pd/CeO2-ZrO2/Al2O3 catalytic material system consisting of ca. 50,000 diffraction patterns. It is shown that the network predicts accurate scale factor, lattice parameter, and crystallite size maps for all phases, which are comparable to those obtained using full profile analysis using the Rietveld method. The main advantage of PQ-Netis its ability to yield these results orders of magnitude faster, showing its potential as a new tool for real-time diffraction data analysis during in situ/operando experiments. References 1. Dong, H., Butler, K.T., Matras, D.et al.A deep convolutional neural network for real-time full profile analysis of big powder diffraction data.npj Comput Mater7,74 (2021). https://doi.org/10.1038/s41524-021-00542-4
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Design self-assembling peptide hydrogel for targeted cancer drug delivery Siyuan Dong 1 , Aline F. Miller 1,2 , Alberto Saiani 2 1 Manchester Institute of Biotechnology, The University of Manchester, UK 2 School of Engineering, The University of Manchester, UK Introduction Self-assembling peptide based hydrogels have attracted considerable attention in the past decade in the drug delivery field [1]. One family of self-assembling peptide which has shown great promise as far as hydrogel design is concerned are β-sheet forming peptides [2]. In order to design and formulate hydrogels loaded drugs composites it is essential to understand how the drug and the peptide network interact and how the drug diffusion can be controlled. For this purpose we designed two novel peptides, E(FKFE) 2 (-1) and K(FEFK) 2 (+1) that form hydrogels at pH7. As a model drug compound we chose a series of fluorescein labelled polymers (dextran and poly-l-lysine) with varying molecular weights and charges allowing us to probe the effect of guest molecule hydrodynamic size and electrostatic interaction on its diffusion. Interleukin 21 was loaded into two different charge of peptide hydrogels to investigate the release profile and applied on peripheral blood mononuclear cell (PBMC) to study the cell marker expression. Results and discussion The formation of β-sheet rich fibres was confirmed in both peptide hydrogels by FTIR. The size of fibres was measured by TEM and SAXS. The dextran was anionic and poly-l-lysine was cationic. As a result, very different release profiles were observed in the two peptide hydrogel systems. Dextran probes released faster from E(FKFE) 2 hydrogel but they were trapped in K(FEFK) 2 which could anticipate that the electrostatic interaction existed between peptide hydrogel and probe. Poly-L-Lysine with 28kDa presented a slow release process form K(FEFK) 2 hydrogel who carried the same charge molecules. However, it cannot release out from E(FKFE) 2 hydrogel. Further, K(FEFK) 2 hydrogel loaded with poly-L-Lysine was found to swell significantly. This is thought to be due to the strong electrostatic repulsion existing between the poly-L-Lysine and the peptide fibres resulting in the overall hydrogel fibres being pushed apart and leading to swelling. The good cell viability results indicated the peptide hydrogels present good biocompatibility and IL21 performed good control release kinetics in E(FKFE) 2 gel. Conclusion Our work clearly shows the potential of using rational design to create hydrogel suitable for the delivery of large drug molecules for specific needs. IL21 loaded into our peptide hydrogel prolong the half live of drug, enlarge the therapeutic window and might activate CD4+, CD8+ and CD56+ cell marker which is able to apply into immune cancer therapy. References 1. R. Huang, W. Qi, L. Feng, R. Su, and Z. He, ‘‘Self-assembling peptide-polysaccharide hybrid hydrogel as a potential carrier for drug delivery,’’ Soft Matter, 2011. 2. D. Roberts, C. Rochas, A. Saiani, and A. F. Miller, “Effect of peptide and guest charge on the structural, mechanical and release properties of β-sheet forming peptides,’’ Langmuir, 2012
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Hansen solubility parameter toolkits for the design and control of functional materials Xue Fang 1 , Ulzhalgas Karatayeva 2 , Charl FJ Faul 3 1 University of Bristol, China, 2 University of Bristol, Kazakhstan 3 University of Bristol, UK/South Africa Solvent–solute interactions are critical to control chemical reactions and materials properties. Determining the appropriate solvent system to process a new material usually relies on empirical approaches and trial-and-error methods. Optimising the solvent environment can cost a large amount of time, effort and money, especially when multi-solvent systems are involved – developing quantitative solvent-selection methods is urgently needed. Among various solubility parameters, Hansen solubility parameters (HSP) 1 have been found to show great potential to support solvent selection for use with functional materials. 2 HSP decomposes molecular interactions into dispersion (δ D ), dipolar (δ P ) and H-bonding (δ H ) components, which allows researchers to interpret solvent- dependent properties by understanding the contribution of each sub-component. We hereby report two open-source HSP toolkits, Solvent Predictor and M Locator . These toolkits can predict multi-solvent combinations from a target HSP or predict HSP of the as-studied material based on a solubility score, for example, from UV-Vis spectroscopic features. With Solvent Predictor , each HSP sub-parameter can be independently modified. Solvent replacement options based on personalised conditions can be realised accordingly, which suggests potential opportunities in green chemistry and reaction design, amongst other. By applying the M Locator toolkit, we have managed to predict HSPs of conjugated microporous polymers (CMP), whose performance for CO 2 uptake can be optimised by carefully tuning HSPs of reaction solvents. 3 With these toolkits in hand, we can now efficiently design reaction conditions and control functionalities of materials utilising a bottom-up rationally designed approach. References 1. C. M. Hansen, Hansen solubility parameters: a user’s handbook , CRC press, 2nd edn., 2007. 2. J. Chen, W. Yan, E. J. Townsend, J. Feng, L. Pan, V. Del Angel Hernandez and C. F. J. Faul, Angew. Chem. Int. Ed. , 2019, 58 , 11715–11719. 3. J. Chen, T. Qiu, W. Yan and C. F. J. Faul, J. Mater. Chem. A , 2020, 8 , 22657–22665.
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A first-principle approach to a spin-polarised metal oxide surface Fei Gao 1 , Nicholas Harrison 1 , Patrick Keil 2 1 Imperial College London, UK, 2 BASF Coatings GmbH, Germany First principle calculation plays an essential role in surface chemistry, which brings us an atomistic point of view of interpreting the chemistry and physics of material surfaces. There is a great deal of current interest in the molecular level understanding of the interfaces involved in catalysis and corrosion. This is hard to obtain experimentally and for strongly interactingsystemsis hard to model with empirical force fields. The advent of large scale ab initio molecular dynamics (AIMD) as a practical approach to these systems is therefore of great importance. We present the geometry and electronic structure of spin-polarised Fe x O y . As a description of strong on- siteelectroniccorrelation is essential results obtained with different approximations to electronic exchange and correlation are compared along with the computational cost. Specifically the geometry, thermodynamics and electronic structure obtained with thegeneralised gradient approximation (GGA), generalised gradient approximation with Hubbard-like correction (GGA+U), and global hybrid functionals (PBE0) are compared. The predicted lattice constants and magnetic moments, along with the projected density of states (PDOS) are compared with the available diffraction and spectroscopic measurements. Calculations were performed using localGaussianbasis sets in the CP2K and CRYSTAL codes.
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© The Author(s), 2022
Controlling functionality and self-assembly of PDI-Based supramolecular polymers by targeted modification Maximilian Hagemann , Dr. Henry E. Symons, Prof. Charl F. J. Faul University of Bristol, UK Supramolecular polymers (SMPs) are an exciting class of materials with a wide range of new properties owing to their dynamic behaviour. A current challenge in the field is to fully control self-assembly behaviour and properties of the resulting SMPs. The self-assembly behaviour of SMPs can be influenced by a variety of external forces, including by selective chemical modification of the monomers. [1] Thionation of the monomers has been studied as an interesting tool to control the properties of SMPs. [2,3] Previous investigations suggest stronger binding between thionated perylene diimides (PDIs), paired with changes in assembly due to steric effects of the sulphur. Initial work in our group has shown how low degrees of thionation can lead to careful control of the supramolecular polymerisation process. [2] Here we show the initial steps towards the synthesis of various perylene SMP monomers thionated to different degrees. Multiple routes were attempted, including approaches to directly thionate the perylene anhydride with subsequent addition of the synthesized trialkoxy amine, as well as the synthesis of a variety of well-soluble PDIs for a more efficient thionation. The thionation has been optimized using a modified microwave-assisted literature route. Following this approach, we are optimistic to obtain novel SMPs, based on thionated PDIs for further analysis and studies, with control over structure and function. References 1. S. Wilson-Kovacs, X. Fang, M. J. L. Hagemann, H. E. Symons, Prof. C. F. J. Faul, Chem. Eur. J. 2022, 28, e2021034. 2. H. E. Symons, M. J. L. Hagemann, R. L. Harniman, C. F. J. Faul, J. Mater. Chem. C, 2022, 10, 2828–2837. 3. A. J. Tilley, R. D. Pensack, T. S. Lee, B. Djukic, G. D. Scholes, D. S. Seferos, J. Phys. Chem. C 2014, 118, 9996–10004.
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Thermal and hydrolytic degradation of regenerated cellulose fibres relative to their crystallinity Louise Garner 2 and Katherine Curran 1 1 Barlette School of Environment Energy and Resources, UK and 2 UCL, UK This study investigates the degradation of regenerated-cellulose fibres in relation to textiles to provide insight on how the crystallinity of the fibres impact it’s interaction with environmental drivers. Adopting a dual focus, this work sits across two different spheres of research. Firstly, investigation of the degradation of cellulosic fibres disposed in the environment is relevant to textile waste management. This work will facilitate our understanding of appropriate waste disposal strategies and determine the relative impact of these different cellulosic fibres on the environment. Secondly, the preservation of cellulosic fibres in the context of heritage through understanding which environmental conditions are most damaging for cellulosic textiles; this will help guide long-term preservation strategies offering clarity on the lifetime of these fibres in collections. Through understanding how regenerated cellulosic fibres degrade we can both facilitate their preservation and expedite their degradation by understanding the fibres' interactions with various environmental drivers relative to their crystal properties. The primary objectives of this study were to establish how different degrees of crystallinity found in cellulose fibres impact their degradation. In addition, we also explore how the relative crystallinity of cellulose fibres changes as it degrades. Accelerated aging was conducted on four types of cellulosic fibres with different ratios of crystalline to amorphous regions. These were aged at 80°C and 75% relative humidity for 3 months to induce thermal and hydrolytic degradation. Fibres were monitored for chemical change using FTIR spectroscopy focusing on changes in peaks representative of the glycosidic link to establish potential breakdown of the polymer backbone. To monitor crystallinity, XRD was used to establish changes in the cellulose’s crystallinity index (CrI) to determine if degradation in the crystalline region is preceded by the amorphous region. These changes were correlated with physical degradation of thefibres using colorimetry, microscopy and visual observations. This work provides a more complete understanding of how chemical and structural changes manifest physically as the material degrades.These results provide an initial understanding of how crystallinity of these fibres provokes different interactions with their environments despite having the same fundamental chemical composition. References 1. Lionetto, F.; Del Sole, R.; Cannoletta, D.; Vasapollo, G.; Maffezzoli, A. Materials 2012, Vol. 5, Pages 1910-1922 2012, 5, 1910–1922. 2. Quye, A. Polymer Degradation and Stability 2014, 107, 210–218. 3. Park, C. H.; Kang, Y. K.; Im, S. S. Journal of Applied Polymer Science 2004, 94, 248–253. 4. Sülar, V.; Devrim, G. Fibres and Textiles in Eastern Europe 2019, 27, 100–111. 5. Ju, X.; Bowden, M.; Brown, E. E.; Zhang, X. Carbohydrate Polymers 2015, 123, 476–481.
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Tuning the phase fraction of multiphase Na 0.9 Fe 0.5 Mn 0.5 O 2 cathode by biotemplating for Na-ion batteries Rebecca Huang, Rebecca Boston University of Sheffield, UK Sodium ion batteries (SIBs) are considered to be promising alternatives to lithium ion batteries for energy grid-scale applications. [1] Layered structures have been extensively studied as cathode materials for sodium ion batteries due to their relatively high specific capacity and facile synthesis route. [2] One such material, Na y Fe x Mn 1-x O 2 isenvironmentally benign, composed of abundant raw materials which are low cost, making this a good candidate for future batteries. Although single P2 and O3 phases are the most common polymorphs for Na y Fe x Mn 1-x O 2 , [3] research recently has been more interested in investigating the synergetic effect of multiphase materials.[4] However, there is little control of the phase fraction during synthesis, and some synthesis processes consume vast amounts of energy by calcining at high temperatures for long periods of time. Here we report a systematic study of phase fraction with different calcination temperatures for Na 0.9 Fe 0.5 Mn 0.5 O 2 .Using a biotemplating synthesis method, layered structures with O3 and P3 biphase (ca. 1:1) were produced at 600 °C for 2 hours, while the P2 phase was present at 620 °C and higher. When increasing the calcination temperature, the O3 phase became dominant in the crystal structure and the P3 phase fully converted at 900 °C. A reversible transition between the P3 and O3 phase was detected after a second heat treatment at 500 °C for 2 hours. The best electrochemical results exhibit high specific discharge capacity, almost 140 mAh/g and still remain 82% of capacity after 50 cycles. References 1. N. Yabuuchi, K. Kubota, M. Dahbi, and S. Komaba, “Research development on sodium-ion batteries,” Chem. Rev. , 114, 11636-11682, 2014 . DOI: 10.1021/cr500192f 2. P.-F. Wang, Y. You, Y.-X. Yin, and Y.-G. Guo, “Layered oxide cathodes for sodium-ion batteries: phase transition, air stability, and performance,” Adv. Energy Mater. , 8, 1701912, 2018 . DOI: 10.1002/aenm.201701912 3. Yabuuchi, N., Kajiyama, M., Iwatate, J. et al. P2-type Na x [Fe 1/2 Mn 1/2 ]O 2 made from earth-abundant elements for rechargeable Na batteries. Nature Mater. , 11, 512–517, 2012 . DOI: 10.1038/nmat3309 4. Q. Wang, S. Chu, and S. Guo, “Progress on multiphase layered transition metal oxide cathodes of sodium ion batteries,” Chinese Chem. Lett. , 31, 2167-2178, 2020 . DOI: 10.1016/j.cclet.2019.12.008
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© The Author(s), 2022
Tuning electron affinity by heteroannulation of benzothiadiazole in organic semiconductors Xiantao Hu 1 , Aniruddha Basu 2 , Datt Ram 3 , Qiao He 1 Thomas D. Anthopoulos 2 , Wing Chung Tsoi 3 and Martin Heeney 1 1 Imperial College London, UK, 2 King Abdullah University of Science and Technology, Saudi Arabia 3 Swansea University, UK Remarkable progress has been made in the development of organic semiconductors for flexible electronics like organic field-effect transistor, organic photovoltaics since the initial proposal of alternating donor-acceptor (D-A) systems. In D-A type materials, the energetics can be tuned by rational choice of the D and A components, with the LUMO (lowest unoccupied molecular orbital) largely determined by the acceptor unit. Here we report our effort to develop novel electron-deficient units based on the extensively investigated acceptor unit benzothiadiazole (BT). Different from changing the heteroatom in thiadiazole ring or functionalising the benzo ring to modify the energetics, we adopt an expedient one-step reaction to heteroannulate additional rings to the BT core, extending the conjugation by appending an electron-withdrawing 2-(1,3-dithiol-2-ylidene)malonitrile group. We report the influence of appending the ring to the 5,6-positions, as well as the 4,5-positions. In the former case, a variety of co-polymers are reported which exhibit thermochromic behaviour, ambipolar charge transport and reasonable performance as the semiconducting layer in organic field-effect transistor. 1 In the latter case, small molecule acceptors are synthesized with the modified BT as end-group. The resulting medium band gap materials are examined in blends with various donor polymers and showed good performance in organic photovoltaics. 2 Our findings demonstrate that heteroannulating additional rings by appending the 2-(1,3-dithiol-2-ylidene) malonitrile group is a useful approach to construct electron-deficient units in organic semiconductors. References 1. Synergistic Interaction of Heteroannulation and Fluorination in n-Type Semiconducting Polymers for Organic Field-effect Transistor. X. Hu, A. Basu, Q. He, T. D. Anthopoulus and M. Heeney. (In Preparation) 2. Facile synthesis of annulated benzothiadiazole derivatives and their application as medium band gap acceptors in organic photovoltaic devices. X. Hu, R. Datt, Q. He, P. Kafourou, H. Ka Hin Lee, A. J. P. White, W. C. Tsoi and M. Heeney, Journal of Materials Chemistry C , 2022 , 10, 9249-9256.
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