Correction: The role of ion solvation in lithium mediated nitrogen reduction.

[This corrects the article DOI: 10.1039/D2TA07686A.].

The role of ion solvation in lithium mediated nitrogen reduction.

Since its verification in 2019, there have been numerous high-profile papers reporting improved efficiency of lithium-mediated electrochemical nitrogen reduction to make ammonia. However, the literature lacks any coherent investigation systematically linking bulk electrolyte properties to electrochemical performance and Solid Electrolyte Interphase (SEI) properties. In this study, we discover that the salt concentration has a remarkable effect on electrolyte stability: at concentrations of 0.6 M LiClO4 and above the electrode potential is stable for at least 12 hours at an applied current density of -2 mA cm-2 at ambient temperature and pressure. Conversely, at the lower concentrations explored in prior studies, the potential required to maintain a given N2 reduction current increased by 8 V within a period of 1 hour under the same conditions. The behaviour is linked more coordination of the salt anion and cation with increasing salt concentration in the electrolyte observed via Raman spectroscopy. Time of flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy reveal a more inorganic, and therefore more stable, SEI layer is formed with increasing salt concentration. A drop in faradaic efficiency for nitrogen reduction is seen at concentrations higher than 0.6 M LiClO4, which is attributed to a combination of a decrease in nitrogen solubility and diffusivity as well as increased SEI conductivity as measured by electrochemical impedance spectroscopy.

Mapping internal temperatures during high-rate battery applications.

Electric vehicles demand high charge and discharge rates creating potentially dangerous temperature rises. Lithium-ion cells are sealed during their manufacture, making internal temperatures challenging to probe1. Tracking current collector expansion using X-ray diffraction (XRD) permits non-destructive internal temperature measurements2; however, cylindrical cells are known to experience complex internal strain3,4. Here, we characterize the state of charge, mechanical strain and temperature within lithium-ion 18650 cells operated at high rates (above 3C) by means of two advanced synchrotron XRD methods: first, as entire cross-sectional temperature maps during open-circuit cooling and second, single-point temperatures during charge-discharge cycling. We observed that a 20-minute discharge on an energy-optimized cell (3.5 Ah) resulted in internal temperatures above 70 °C, whereas a faster 12-minute discharge on a power-optimized cell (1.5 Ah) resulted in substantially lower temperatures (below 50 °C). However, when comparing the two cells under the same electrical current, the peak temperatures were similar, for example, a 6 A discharge resulted in 40 °C peak temperatures for both cell types. We observe that the operando temperature rise is due to heat accumulation, strongly influenced by the charging protocol, for example, constant current and/or constant voltage; mechanisms that worsen with cycling because degradation increases the cell resistance. Design mitigations for temperature-related battery issues should now be explored using this new methodology to provide opportunities for improved thermal management during high-rate electric vehicle applications.

The origin of overpotential in lithium-mediated nitrogen reduction.

The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO4, 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was -3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms.

Terahertz magnetoplasmon resonances in coupled cavities formed in a gated two-dimensional electron gas.

We report on both experiments and theory of low-terahertz frequency range (up to 400 GHz) magnetoplasmons in a gated two-dimensional electron gas at low (<4K) temperatures. The evolution of magnetoplasmon resonances was observed as a function of magnetic field at frequencies up to ∼400 GHz. Full-wave 3D simulations of the system predicted the spatial distribution of plasmon modes in the 2D channel, along with their frequency response, allowing us to distinguish those resonances caused by bulk and edge magnetoplasmons in the experiments. Our methodology is anticipated to be applicable to the low temperature (<4K) on-chip terahertz measurements of a wide range of other low-dimensional mesoscopic systems.

A novel fuel cell design foroperandoenergy-dispersive x-ray absorption measurements.

A polymer electrolyte fuel cell has been designed to allowoperandox-ray absorption spectroscopy (XAS) measurements of catalysts. The cell has been developed to operate under standard fuel cell conditions, with elevated temperatures and humidification of the gas-phase reactants, both of which greatly impact the catalyst utilisation. X-ray windows in the endplates of the cell facilitate collection of XAS spectra during fuel cell operation while maintaining good compression in the area of measurement. Results of polarisation curves and cyclic voltammograms showed that theoperandocell performs well as a fuel cell, while also providing XAS data of suitable quality for robust XANES analysis. The cell has produced comparable XAS results when performing a cyclic voltammogram to an establishedin situcell when measuring the Pt LIII edge. Similar trends of Pt oxidation, and reduction of the formed Pt oxide, have been presented with a time resolution of 5 s for each spectrum, paving the way for time-resolved spectral measurements of fuel cell catalysts in a fully-operating fuel cell.

Data for an Advanced Microstructural and Electrochemical Datasheet on 18650 Li-ion Batteries with Nickel-Rich NMC811 Cathodes and Graphite-Silicon Anodes.

The data presented here were collected from a commercial LG Chem cylindrical INR18650 MJ1 lithium-ion (Li-ion) battery (approximate nominal specifications: 3.5 Ah, 3.6 V, 12.2 Wh). Electrochemical and microstructural information is presented, the latter collected across several length scales using X-ray computed tomography (CT): from cell to particle. One cell-level tomogram, four assembly-level and two electrode/particle-level 3D datasets are available; all data was collected in the pristine state. The electrochemical data consists of the full current and voltage charge-discharge curves for 400 operational cycles. All data has been made freely available via a repository [10.5522/04/c.4994651] in order to aid in the development of improved computational models for commercially-relevant Li-ion battery materials.

Data on the theoretical X-Ray attenuation and transmissions for lithium-ion battery cathodes.

This article reports the data required for planning attenuation-based X-ray characterisation e.g. X-ray computed tomography (CT), of lithium-ion (Li-ion) battery cathodes. The data reported here is to accompany a co-submitted manuscript (10.1016/j.matdes.2020.108585 [1]) which compares two well-known X-ray attenuation data sources: Henke et al. and Hubbell et al., and applies methodology reported by Reiter et al. to extend this data towards the practical characterisation of prominent cathode materials. This data may be used to extend beyond the analysis reported in the accompanying manuscript, and may aid in the applications for other materials, not limited to Li-ion batteries.

Prevalence of chronic viral hepatitis in people of south Asian ethnicity living in England: the prevalence cannot necessarily be predicted from the prevalence in the country of origin.

The prevalence of hepatitis B and hepatitis C in immigrant communities is unknown. Immigrants from south Asia are common in England and elsewhere, and the burden of viral hepatitis in these communities is unknown. We aimed to determine the prevalence of viral hepatitis in immigrants from south Asia living in England, and we therefore undertook a community-based testing project in such people at five sites in England. A total of 4998 people attending community centres were screened for viral hepatitis using oral fluid testing. The overall prevalence of anti-hepatitis C virus (HCV) in people of south Asian origin was 1.6% but varied by country of birth being 0.4%, 0.2%, 0.6% and 2.7% in people of this ethnic group born in the UK, India, Bangladesh and Pakistan, respectively. The prevalence of hepatitis B surface antigen was 1.2%-0.2%, 0.1%, 1.5% and 1.8% in people of this ethnic group born in the UK, India, Bangladesh and Pakistan, respectively. Analysis of risk factors for HCV infection shows that people from the Pakistani Punjab and those who have immigrated recently are at increased risk of infection. Our study suggests that migrants from Pakistan are at highest risk of viral hepatitis, with those from India at low risk. As prevalence varies both by country and region of origin and over time, the prevalence in migrant communities living in western countries cannot be easily predicted from studies in the country of origin.

Comparison between urban Toronto PM and selected materials: aerosol characterization using laser ablation/ionization mass spectrometry (LAMS).

Laser ablation/ionization mass spectrometry (LAMS) of particulate matter (PM) was undertaken on-line in order to extend and contrast PM characterization. Qualitative on-line LAMS results for certified materials and Toronto source materials demonstrated the versatility and limitations of the technique. The observation of organic and inorganic components of certified materials verified the proper working condition of the in-house on-line LAMS. Organic and inorganic components of Toronto source materials were also observed with the on-line LAMS. Common components identified from both types of materials were Na, Al, Ca, Fe, and K. Other recognized components were compared with marker elements reported for some common PM emission sources. An in-house off-line LAMS was used to analyze urban Toronto PM deposited on glass substrates, while the on-line LAMS analyzed individual urban Toronto PM particles that were introduced directly into the instrument. Scanning electron microscopy (SEM), X-ray spectrometry and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used for confirmatory purposes. Organic and inorganic components of urban Toronto PM at their typical ng/m3 concentrations were successfully observed in mass spectra using both off-line LAMS and on-line LAMS. Identified ions unique to each analyzed material were compared to identified ions of urban Toronto PM. The ability of LAMS to analyze individual respirable PM particles (viz. < 2 microns), both for inorganic trace elements and for organic components, greatly extended our capability to characterize PM and also to achieve estimates of concentration contributions of each material.

Measurement of PM10/2.5 fractionated respirable particles in urban Toronto by INAA, PIXE, ICP-AES, and LAMS. A comparison.

The chemical analysis of urban Toronto airborne particulate matter (PM), size segregated into respirable PM10/2.5, is presented. The characterization of PM by use of proton-induced X-ray emission analysis (PIXE), and inductively coupled plasma-atomic emission spectrometry revealed elemental information; a newer laser ablation-ionization mass spectrometry approach has the potential to expand the chemical information from PM by analyzing both the inorganic and organic species. These PM analytical approaches will be continued in the future for studying (1) emission source identification, (2) inhalation health hazards, and (3) urban smog chemistry.

A nuclear mass spectrometer for studying radon progeny clusters.

A Nuclear Mass Spectrometer (NMS) system was developed and used to investigate the cluster formation of radon progeny (218Po) in gaseous H2O and H2O-SO2 environments. This NMS combines the mass-separation ability of a mass spectrometer and the low detection limit of a surface barrier detector for alpha particles and enables the detection of individual radon progeny cluster ions of defined mass at the molecular level. Clusters in the form of 218Po+(H2O)n were experimentally observed for 218Po at a relative humidity of 0.1%. The number n ranged from 1 to 7 with 4 being the most abundant peak under these conditions. No charged cluster of 218Po was detected when the relative humidity was 90%, possibly due to a neutralization process. On addition of SO2 at a low relative humidity, 218Po+(H2O)n (H2SO4)m clusters were experimentally detected for the first time by the NMS system in this study with n from 0-4 and m from 0-3. The maximum distribution occurs at a radius of about 3.65 angstrom or a mobility of about 2.00 cm2 V-1 s-1. These maximum clusters correspond to a composition of 218Po+(H2SO4)2 or 218Po+(H20)2 (H2SO4)1.

The smooth muscle alpha-actin gene promoter is differentially regulated in smooth muscle versus non-smooth muscle cells.

To identify potential regulators of smooth muscle cell (SMC) differentiation, we studied the molecular mechanisms that control the tissue-specific transcriptional expression of SM alpha-actin, the most abundant protein in fully differentiated SMCs. A construct containing the region from -1 to -125 of the promoter (p125CAT) had high transcriptional activity in SMCs (57-fold > promoterless) and endothelial cells (ECs) (18-fold) but not in skeletal myoblasts or myotubes. Mutation of either of two highly conserved CC(AT-rich)6GG (CArG) motifs at -62 and -112 abolished the activity of p125CAT in SMCs but had no effect in ECs. In contrast, high transcriptional activity in skeletal myotubes, which also express SM alpha-actin, required at least 271 base pairs of the promoter (-1 to > or = -271). Constructs containing 547 base pairs or more of the promoter were transcriptionally active in SMCs and skeletal myotubes but had no activity in skeletal myoblasts or ECs, cell types that do not express SM alpha-actin. Electrophoretic mobility shift assays provided evidence for binding of a unique serum response factor-containing complex of factors to the CArG box elements in SMCs. Results indicate that: 1) transcriptional expression of SM alpha-actin in SMCs requires the interaction of the CArG boxes with SMC nucleoprotein(s); 2) expression of SM alpha-actin in skeletal myotubes requires different cis-elements and trans-factors than in SMCs; and 3) negative-acting cis-elements are important in restricting transcription in cells that do not express SM alpha-actin.

Nuclear analytical techniques in environmental studies.

Nuclear analytical techniques are particularly suitable for measuring trace components in a wide variety of environmental samples, and for that reason, the techniques have made a significant contribution to environmental research. Presently, at a time when biosphere contamination and threats of global change in the atmosphere are of widespread concern, there exist an impressive array of specialized instrumental methods available to life scientists engaged in environmental studies; however, the nuclear techniques will probably continue to play a useful role in the future, notwithstanding the decreasing availability of necessary facilities, such as research reactors and accelerators. Reasons for the particular suitability of radionanalytical techniques are reviewed and illustrated by examples of recent applications to solid wastes, biomonitoring, and urban aerosol source identification in this laboratory.

Studies of incinerator ashes and environmental effects using radioanalytical techniques.

We have studied solid waste incinerator ashes to understand the leaching mechanism and speciation of toxic and other elements in them. Leaching media, such as water and acetate buffer, at various pHs were used. Incinerator ashes generally contain concentrations of many toxic elements, such as Cd, As, Hg, and Se. These elements are leached out rather easily. Many of the elements are leached within the first few minutes to an hour, and the majority of the elements reach peak equilibrium concentrations within 200 h. The pH and nature of the leaching medium are important factors in the leaching of the elements.

Hair trace elements in kidney dialysis patients by INAA.

INAA was used to determine selected trace elements--Ca, Al, P, and S--in 104 cleaned scalp hair samples from kidney dialysis patients (n = 54) and healthy controls (n = 50) in order to explore any differences in these elements that might be related to prolonged dialysis and/or associated medication in comparison with blood serum levels of Al and P measured in the same clinic at the time of hair sampling. After correction for P (and Si) interference in Al content, it was observed that there were no significant differences (at 95% confidence level) in hair Al and Ca, which had been expected, whereas while there were definite increases in P and S. Multivariant factor analysis applied to the same data set, however, showed some multiple correlations among four variables: serum Al, duration of dialysis, medication, and hair Al.