Manipulating O3/P2 phase ratio in bi-phasic sodium layered oxides via ionic radius control

Funding: This work was supported by the Faraday Institution (Grant number FIRG018). The authors would like to thank Dr. David Rochester at Lancaster University for conducting the ICP-OES experiments. A.B.N. would like to acknowledge funding by the Engineering and Physical Sciences Research Council under grant numbers EP/L017008/1, EP/R023751/1, and EP/T019298/1 for the electron microscopy analysis.Bi-phasic O3/P2 sodium layered oxides have emerged as leading candidates for the commercialisation of next-generation sodium-ion batteries. However, beyond simply altering the sodium content, rational control of the O3/P2 ratio in these materials has proven particularly challenging despite being crucial for the realization of high-performance electrode materials. Here, using abundant elements, we manipulate the O3/P2 ratio using the average ionic radius of the transition metal layer and different synthesis conditions. These methods allow deterministic control over the O3/P2 ratio, even for constant Na contents. In addition, tuning the O3/P2 ratio yields high-performing materials with different performance characteristics, with a P2-rich material achieving high rate capabilities and excellent cycling stability (92% retention, 50 cycles), while an O3-rich material displayed an energy density up to 430 Wh kg−1, (85%, 50 cycles). These insights will help guide the rational design of future high-performance materials for sodium-ion batteries.Publisher PDFPeer reviewe

Influence of electrode processing and electrolyte composition on multiwall carbon nanotube negative electrodes for sodium ion batteries

Dr. A. Fuente Cuesta would like to thank Agency for Green Technology (AGT), Dr. S. A. M. Dickson would like to thank the Faraday Institution NEXGENNA project (FIRG018), and C. Lonsdale would like to thank the Faraday Institution FUSE Internship Programme for funding. The authors also acknowledge the EPSRC (grant codes EP/L017008/1, EP/T019298/1, and EP/R023751/1).Nanostructured one-dimensional multiwall-carbon nanotubes have a variety of advantageous properties including good electrical conductivity and mechanical strength, and thus have been widely investigated for use in lithium-ion battery electrodes as conductive and microstructural additives, though also possess some electrochemical activity. Their application to sodium-ion batteries has been less extensively researched, and therefore a greater understanding of the electrochemical reaction with sodium, and effects of slurry composition and electrolyte formulation is warranted. Here, we report the fabrication of aqueous and organic multi-wall carbon nanotube negative electrodes processed by ball milling. The binder of choice is noted to greatly affect the electrochemical performance, both in terms of capacity retention and rate capability over a range of current densities from 25 to 500 mA g-1. Switching from a carbonate- to diglyme-based electrolyte considerably improves initial coulombic efficiencies (~10 to 60%), attributed to less extensive formation of solid electrolyte interphase, and enables a reversible mechanism with capacities up to 150 mAh g-1 over 100 cycles depending upon the binder used.Publisher PDFPeer reviewe

Enhanced CO2 electrolysis through Mn substitution coupled with Ni exsolution in lanthanum calcium titanate electrodes

Funding: This work was financially supported by the Industrial Decarbonisation Research and Innovation Centre. Further support was kindly provided by EPSRC, under research grant numbers EP/L017008/1, EP/R023751/1 and EP/T019298/1.In this study, perovskite oxides La0.3Ca0.6Ni0.05MnxTi0.95−xO3−γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 – 3% H2O. The performance of La0.3Ca0.6Ni0.05Ti0.95O3−γ is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.Peer reviewe

Characterising the HLA-I Immunopeptidome of plasma-derived extracellular vesicles in patients with melanoma

This work was funded by grants from Breast Cancer Now UK (2018JulPR1086), and the Melville Trust for the Care and Cure of Cancer UK (XCT014). We also gratefully acknowledge funding from the EPSRC via EP/L017008/1 for TEM imaging infrastructure, and EP/R023751/1 and EP/T019298/1.Extracellular vesicles (EVs) frequently express human leukocyte antigen class I (HLA-I) molecules. The immunopeptidomes presented on EV HLA-I are being mapped to provide key information on both specific cancer-related peptides, and for larger immunopeptidomic signatures associated with disease. Utilizing HLA-I immunoisolation and mass spectrometry, we characterised the HLA-I immunopeptidome of EVs derived from the melanoma cancer cell line, ESTDAB-026, and the plasma of 12 patients diagnosed with advanced stage melanoma, alongside 11 healthy controls. The EV HLA-I immunopeptidome derived from melanoma cells features T cell epitopes with known immunogenicity and peptides derived from known tumour associated antigens (TAAs). Both T cell epitopes with known immunogenicity and peptides derived from known TAAs were also identifiable in the melanoma patient samples. Patient stratification into two distinct groups with varying immunological profiles was also observed. The data obtained in this study suggests for the first time that the HLA-I immunopeptidome of EVs derived from blood may aid in the detection of important diagnostic or prognostic biomarkers and also provide new immunotherapy targets.Peer reviewe

Silicon redistribution, acid site loss and the formation of a core-shell texture upon steaming SAPO-34 and their impact on catalytic performance in the methanol-to-olefins (MTO) reaction

IBM has received funding from the Engineering and Physical Sciences Research Council (EPSRC, Centre for Doctoral Training in Critical Resource Catalysis, EP/I017008/1) and Scotland's Chemistry departments (ScotCHEM). IBM also received a scholarship from the SCI and Santander. Johnson Matthey is thanked for in-kind contributions and hosting IBM in their R&D labs. ABN gratefully acknowledges support from the EPSRC (grants EP/L017008/1 and EP/R023751/1). The research data supporting this publication can be accessed at: https://doi.org/10.17630/09ddc03e-f121-4e79-9b55-674f64d9c8c4 [62].SAPO-34 is a commercially-implemented silicoaluminophosphate catalyst for selective high yield production of ethene and propene from methanol, but high temperature regeneration in the presence of steam leads to its deactivation. A comprehensive investigation of the effect of prolonged hydrothermal treatment on the structure and properties of SAPO 34 explains the changes in its catalytic methanol-to-olefins (MTO) performance. Microcrystalline powdered SAPO-34 (ca. 3 µm crystals, Al17.1P15.6Si3.3O72) and two batches of larger single crystals of SAPO-34 of different Si concentration (20-100 µm; Al17.3P14.7Si4.0O72 and Al17.7P12.3Si5.9O72 ) were steamed (pH2O = 0.95 atm) at 873–1023 K for up to 240 h. The acidity (NH3-TPD), crystallinity (PXRD), framework cation environment (solid-state 27Al, 29Si and 31P MAS NMR) and porosity were followed for all materials; larger crystals were amenable to single crystal X-ray diffraction, FIB-SEM and synchrotron IR microspectroscopy, including operando study during methanol and dimethyl ether conversions. Some level of steaming improved the lifetime of all SAPO-34 materials in MTO catalysis without affecting their olefin selectivity, although more severe conditions led to the formation of core-shell structures, microporosity loss and eventually at 1023 K, recrystallization to a dense phase. All these irreversible changes occurred faster in crystals with higher Si contents. The initial increase in catalytic lifetime results from an activated reduction in acid site density (Eact = 146(18) kJ mol⁻1), a result of redistribution of Si within the SAPO framework without porosity loss. Operando IR with online product analysis during methanol conversion suggests similar reaction pathways in calcined and steamed crystals, but with greatly reduced methoxy group densities in the latter. The gradual development of optically dark crystal cores upon progressive steaming was shown by FIB-SEM to be due to the formation of regions with meso- and macropores, and these were shown by IR mapping to possess low hydroxyl densities.PostprintPostprintPeer reviewe

Enhanced cycling stability in the anion redox material P3-type Zn-substituted sodium manganese oxide

Funding: Faraday Institution (Grant Number(s): FIRG018), Diamond Light Source (Grant Number(s): SP14239), Engineering and Physical Sciences Research Council (Grant Number(s): EP/L017008/1, EP/R023751/1, EP/T019298/1), SPRing8 (Grant Number(s): 2021A1425).Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‑ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‑doping on the electrochemical properties of P3-type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‑Na 0.67 Mn 0.9 Zn 0.1 O 2 and Oxy‑Na 0.67 Mn 0.9 Zn 0.1 O 2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96% of their initial capacity after 30 cycles, where Mn 3+ /Mn 4+ redox dominates. Increasing the voltage range to 1.8‑4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‑capacity and structurally stable oxygen redox‑based materials for SIBs.Publisher PDFPeer reviewe

Atomic ordering and bond relaxation in optical spectra of self-organized InP/GaInP2 Wigner molecule structures

A.M.M., D.V.L., and A.S.V. acknowledge the support of the Russian Science Foundation Grant No. 19-19-00246. K.G.B., M.V.R., and A.A.T. acknowledge the financial support of the Russian Foundation for Basic Research (Project No. 18-02-01212). This research was also enabled by the Science Foundation Ireland under Grant Nos. 15/IA/2864, 12/RC/2276, 12/RC/2276-P2, and 18/US/3512, and the Northern Ireland Department for the Economy (Grant No. USI-140). A.B.N. acknowledges support from EPSRC grant no. EP/R023751/1.We used transmission electron microscopy, Raman, and photoluminescence spectroscopy to identify the effect of CuPt-type GaP-InP atomic ordering (AO) on the structural and emission properties of self-organized (SO) InP/GaInP2 Wigner molecule (WM) quantum dot (QD) structures. We found that the correlation of AO and SO growth results in the formation of InP/GaInP2 QD/AO-domain (QD/AOD) core-shell composites. This observation shows that intrinsic WMs in this system emerge due to a strong piezoelectric field generated by AODs, which induces QD doping and a built-in magnetic field. We found that the bond relaxation of AODs leads to a decrease in the emission energy of WMs of 80 meV. The photoluminescence spectra of single WMs having an emission energy ∼1.53 eV are presented here, the lowest one reported for this system.Publisher PDFPeer reviewe