Zero-dimensional methylammonium iodo bismuthate solar cells and synergistic interactions with silicon nanocrystals

This work was supported by EPSRC (EP/K022237/1 and EP/M024938/1) and by the New Energy and Industrial Technology Development Organization (NEDO).Organometal trihalide perovskite solar cells have attracted monumental attention in recent years. Today's best devices, based on a three-dimensional perovskite structure of corner-sharing PbI6 octahedra, are unstable, toxic, and display hysteresis in current-voltage measurements. We present zero-dimensional organic-inorganic hybrid solar cells based on methylammonium iodo bismuthate (CH3NH3)3(Bi2I9) (MABI) comprising a Bi2I9 bioctahedra and observe very low hysteresis for scan rates in the broad range of 150 mV s-1 to 1500 mV s-1 without any interfacial layer engineering. We confirm good stability for devices produced and stored in open air without humidity control. The MABI structure can also accommodate silicon nanocrystals, leading to an enhancement in the short-circuit current. Through the material MABI, we demonstrate a promising alternative to the organometal trihalide perovskite class and present a model material for future composite third-generation photovoltaics.PostprintPeer reviewe

Synthesis of 2,6-trans- and 3,3,6-Trisubstituted Tetrahydropyran-4-ones from Maitland-Japp Derived 2H-Dihydropyran-4-ones: A Total Synthesis of Diospongin B

6-Substituted-2H-dihydropyran-4-one products of the Maitland-Japp reaction have been converted into tetrahydropyrans containing uncommon substitution patterns. Treatment of 6-substituted-2H-dihydropyran-4-ones with carbon nucleophiles led to the formation of tetrahydropyran rings with the 2,6-trans-stereochemical arrangement. Reaction of the same 6-substituted-2H-dihydropyran-4-ones with l-Selectride led to the formation of 3,6-disubstituted tetrahydropyran rings, while trapping of the intermediate enolate with carbon electrophiles in turn led to the formation 3,3,6-trisubstituted tetrahydropyran rings. The relative stereochemical configuration of the new substituents was controlled by the stereoelectronic preference for pseudo-axial addition of the nucleophile and trapping of the enolate from the opposite face. Application of these methods led to a synthesis of the potent anti-osteoporotic diarylheptanoid natural product diospongin B

QuantPipe: Applying Adaptive Post-Training Quantization for Distributed Transformer Pipelines in Dynamic Edge Environments

Pipeline parallelism has achieved great success in deploying large-scale transformer models in cloud environments, but has received less attention in edge environments. Unlike in cloud scenarios with high-speed and stable network interconnects, dynamic bandwidth in edge systems can degrade distributed pipeline performance. We address this issue with QuantPipe, a communication-efficient distributed edge system that introduces post-training quantization (PTQ) to compress the communicated tensors. QuantPipe uses adaptive PTQ to change bitwidths in response to bandwidth dynamics, maintaining transformer pipeline performance while incurring limited inference accuracy loss. We further improve the accuracy with a directed-search analytical clipping for integer quantization method (DS-ACIQ), which bridges the gap between estimated and real data distributions. Experimental results show that QuantPipe adapts to dynamic bandwidth to maintain pipeline performance while achieving a practical model accuracy using a wide range of quantization bitwidths, e.g., improving accuracy under 2-bit quantization by 15.85\% on ImageNet compared to naive quantization

Synthesis and electrochemical study of CoNi2S4 as a novel cathode material in a primary Li thermal battery

The authors acknowledge support and contribution from AWE Plc for this work, and thank the STFC for neutron diffraction beam-time.In this work CoNi2S4 was investigated as a candidate cathode material for Li thermal batteries. The CoNi2S4 was synthesized by a solid state reaction at 550◦C in a sealed quartz tube. Neutron powder diffraction was utilized to confirm normal spinel structure up to 200◦C, however, there was cation disorder above this temperature. The electrochemical properties of the batteries were investigated at 500◦C by galvanostatic discharge to elucidate the mechanism and the products NiS, Co3S4 and Co9S8 of the discharge mechanism were confirmed using powder X-ray diffraction. CoNi2S4 exhibits two voltage plateaus vs Li13Si4 at 500◦C, one at 1.75 V and the second at 1.50 V. CoNi2S4 has an overall capacity of 318 mA h g−1 from OCV 2.58 V to 1.25 V vs Li13Si4 which is comparable to that of the well-known metal disulfidesPublisher 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

Can the Use of an External: Internal Ratio During Standardised Small-Sided Games be a Detector of Fatigue in Professional Adolescent Soccer Players?

The aim of the investigation was to explore whether the external: internal(E: I) ratio during a standardised small-sided game (SSG) was impacted by fatigue monitoring methods in professional adolescent soccer players. Ten professional male soccer players (Mean ± SD; Age: 19.6 ± 1.4 years) data from seven standardised SSG’s (6v6+GK, 2x4 min, 40 x 35m) were analysed during the study. Total distance (TD):Heart rate exertion (HRe), PlayerLoadTM(PL): HReand Explosive distance (ED): HRewere the E: Iratio’s analysed from the SSG’s. Morning perceived wellness score, using a customised self-report questionnaire (energy levels, sleep and muscle soreness), and Flight time: Contraction time (FT:CT), taken from a counter-movement jump (CMJ) performed prior totraining, were used as markers of fatigue in the study. A Z-score of -1 was considered ‘fatigued’. Mixed-effect linear models revealed a significant effect for perceived wellness Z-score on TD: HRe, PL: HReand ED: HRe, which resulted in a small increase in allE: Iratios. FT: CTZ-score resulted in a non-significant, trivial effect on TD: HRe, PL: HReand ED: HRe. The results suggest E:I ratiosare influenced by subjective fatigue, thus, E: Iratio’s may be a non-invasive tool for fatigue detection. However, caution should be taken when interpreting an increase in E:I ratio, and, therefore, the use of E: Iratio’s as a means for fatigue detection requires further investigation

Carrier extraction from metallic perovskite oxide nanoparticles

This work was supported by EPSRC (EP/K022237/1, EP/M024938/1 and EP/R023638/1), the EPSRC Supergen SuperSolar Hub, the Department for Employment and Learning (DEL) of Northern Ireland Studentship, and by the New Energy and Industrial Technology Development Organization (NEDO).We observe the extraction of carriers excited between two types of bands in the perovskite oxide, Sr-deficient strontium niobate (Sr0.9NbO3). Sr0.9NbO3 exhibits metallic behaviour and high conductivity, whilst also displaying broad absorption across the ultraviolet, visible, and near-infrared spectral regions, making it an attractive material for solar energy conversion. Furthermore, the optoelectronic properties of strontium niobate can easily be tuned by varying the Sr fraction or through doping. Sr-deficient strontium niobate exhibits a split conduction band, which enables two types of optical transitions: intraband and interband. However, whether such carriers can be extracted from an unusual material as such remains unproven. In this report, we have overcome the immense challenge of photocarrier extraction by fabricating an extremely thin absorber layer of Sr0.9NbO3 nanoparticles. These findings open up great opportunities to harvest a very broad solar spectral absorption range with reduced recombination losses.Publisher PDFPeer reviewe

Zirconium trisulfide as a promising cathode material for Li primary thermal batteries

In this work ZrS3 has been synthesized by solid state reaction in a sealed quartz tube and investigated as a candidate cathode material in Li thermal batteries. The structure of ZrS3 before and after cell testing has been studied using powder X-ray diffraction. A new spinel related material, LiZr2S4, has been identified as the product of the electrochemical process, which can be indexed to a = 10.452(8) Å cubic unit cell. The electrochemical properties of the batteries were investigated at 500 °C against Li13Si4 by galvanostatic discharge and galvanostatic intermittent titration technique (GITT). In a thermal Li cell at 500 °C a single voltage plateau of 1.70 V at a current density of 11 mA/cm2 was achieved with capacity of 357 mA h g-1. Therefore ZrS3 material has some promise as a cathode for Li thermal batteries.Publisher PDFPeer reviewe

Quantitative Analysis of Planar Laser-Induced Fluorescence Measurements in a Hypersonic Boundary Layer

Several quantitative measurements extracted from nitric oxide (NO) planar laser-induced fluorescence (PLIF) data obtained in a hypersonic boundary layer are reported: (a) off-body NO mole fraction; (b) surface heat flux; and (c) near-wall static temperature. The experimental data was obtained at NASA Langley Research Centers 31 in. Mach 10 air tunnel. NO was seeded into the flow through a spanwise slot on the surface of the 10 degree half-angle wedge model. An ultraviolet planar laser sheet was positioned perpendicular to the wedge surface, downstream of the seeding slot, to excite six fluorescence transitions. A method for extracting the relative NO mole fraction, based on spatial variations of the J= 0.5 PLIF signal, is presented. Combined with the principle of mass conservation, the absolute NO mole fraction is determined. These measurements were used to assess CFD diffusion modelling, correct previously reported PLIF thermometry results, and develop methods for NO-PLIF heat transfer measurements