Electrochemical Wastewater Refining: A Vision for Circular Chemical Manufacturing.

Wastewater is an underleveraged resource; it contains pollutants that can be transformed into valuable high-purity products. Innovations in chemistry and chemical engineering will play critical roles in valorizing wastewater to remediate environmental pollution, provide equitable access to chemical resources and services, and secure critical materials from diminishing feedstock availability. This perspective envisions electrochemical wastewater refining─the use of electrochemical processes to tune and recover specific products from wastewaters─as the necessary framework to accelerate wastewater-based electrochemistry to widespread practice. We define and prescribe a use-informed approach that simultaneously serves specific wastewater-pollutant-product triads and uncovers a mechanistic understanding generalizable to broad use cases. We use this approach to evaluate research needs in specific case studies of electrocatalysis, stoichiometric electrochemical conversions, and electrochemical separations. Finally, we provide rationale and guidance for intentionally expanding the electrochemical wastewater refining product portfolio. Wastewater refining will require a coordinated effort from multiple expertise areas to meet the urgent need of extracting maximal value from complex, variable, diverse, and abundant wastewater resources.

A lithium-oxygen battery based on lithium superoxide.

Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

A Validation of Six Wearable Devices for Estimating Sleep, Heart Rate and Heart Rate Variability in Healthy Adults.

The primary aim of this study was to examine the validity of six commonly used wearable devices, i.e., Apple Watch S6, Garmin Forerunner 245 Music, Polar Vantage V, Oura Ring Generation 2, WHOOP 3.0 and Somfit, for assessing sleep. The secondary aim was to examine the validity of the six devices for assessing heart rate and heart rate variability during, or just prior to, night-time sleep. Fifty-three adults (26 F, 27 M, aged 25.4 ± 5.9 years) spent a single night in a sleep laboratory with 9 h in bed (23:00-08:00 h). Participants were fitted with all six wearable devices-and with polysomnography and electrocardiography for gold-standard assessment of sleep and heart rate, respectively. Compared with polysomnography, agreement (and Cohen's kappa) for two-state categorisation of sleep periods (as sleep or wake) was 88% (κ = 0.30) for Apple Watch; 89% (κ = 0.35) for Garmin; 87% (κ = 0.44) for Polar; 89% (κ = 0.51) for Oura; 86% (κ = 0.44) for WHOOP and 87% (κ = 0.48) for Somfit. Compared with polysomnography, agreement (and Cohen's kappa) for multi-state categorisation of sleep periods (as a specific sleep stage or wake) was 53% (κ = 0.20) for Apple Watch; 50% (κ = 0.25) for Garmin; 51% (κ = 0.28) for Polar; 61% (κ = 0.43) for Oura; 60% (κ = 0.44) for WHOOP and 65% (κ = 0.52) for Somfit. Analyses regarding the two-state categorisation of sleep indicate that all six devices are valid for the field-based assessment of the timing and duration of sleep. However, analyses regarding the multi-state categorisation of sleep indicate that all six devices require improvement for the assessment of specific sleep stages. As the use of wearable devices that are valid for the assessment of sleep increases in the general community, so too does the potential to answer research questions that were previously impractical or impossible to address-in some way, we could consider that the whole world is becoming a sleep laboratory.

Correction: Bellenger et al. Wrist-Based Photoplethysmography Assessment of Heart Rate and Heart Rate Variability: Validation of WHOOP. Sensors 2021, 21, 3571.

The authors wish to correct the following errors in the original paper [...].

Evaluating the Typical Day-to-Day Variability of WHOOP-Derived Heart Rate Variability in Olympic Water Polo Athletes.

Heart rate (HR) and HR variability (HRV) can be used to infer readiness to perform exercise in athletic populations. Advancements in the photoplethysmography technology of wearable devices such as WHOOP allow for the frequent and convenient measurement of HR and HRV, and therefore enhanced application in athletes. However, it is important that the reliability of such technology is acceptable prior to its application in practical settings. Eleven elite male water polo players (age 28.8 ± 5.3 years [mean ± standard deviation]; height 190.3 ± 3.8 cm; body mass 95.0 ± 6.9 kg; international matches 117.9 ± 92.1) collected their HR and HRV daily via a WHOOP strap (WHOOP 3.0, CB Rank, Boston, MA, USA) over 16 weeks ahead of the 2021 Tokyo Olympic Games. The WHOOP strap quantified HR and HRV via wrist-based photoplethysmography during overnight sleep periods. The weekly (i.e., 7-day) coefficient of variation in lnRMSSD (lnRMSSDCV) and HR (HRCV) was calculated as a measure of day-to-day variability in lnRMSSD and HR, and presented as a mean of the entire recording period. The mean weekly lnRMSSDCV and HRCV over the 16-week period was 5.4 ± 0.7% (mean ± 95% confidence intervals) and 7.6 ± 1.3%, respectively. The day-to-day variability in WHOOP-derived lnRMSSD and HR is within or below the range of day-to-day variability in alternative lnRMSSD (~3-13%) and HR (~10-11%) assessment protocols, indicating that the assessment of HR and HRV by WHOOP does not introduce any more variability than that which is naturally present in these variables.

Wrist-Based Photoplethysmography Assessment of Heart Rate and Heart Rate Variability: Validation of WHOOP.

Heart rate (HR) and HR variability (HRV) infer readiness to perform exercise in athletic populations. Technological advancements have facilitated HR and HRV quantification via photoplethysmography (PPG). This study evaluated the validity of WHOOP's PPG-derived HR and HRV against electrocardiogram-derived (ECG) measures. HR and HRV were assessed via WHOOP and ECG over 15 opportunities. WHOOP-derived pulse-to-pulse (PP) intervals were edited with WHOOP's proprietary filter, in addition to various filter strengths via Kubios HRV software. HR and HRV (Ln RMSSD) were quantified for each filter strength. Agreement was assessed via bias and limits of agreement (LOA), and contextualised using smallest worthwhile change (SWC) and coefficient of variation (CV). Regardless of filter strength, bias (≤0.39 ± 0.38%) and LOA (≤1.56%) in HR were lower than the CV (10-11%) and SWC (5-5.5%) for this parameter. For Ln RMSSD, bias (1.66 ± 1.80%) and LOA (±5.93%) were lowest for a 200 ms filter and WHOOP's proprietary filter, which approached or exceeded the CV (3-13%) and SWC (1.5-6.5%) for this parameter. Acceptable agreement was found between WHOOP- and ECG-derived HR. Bias and LOA in Ln RMSSD approached or exceeded the SWC/CV for this variable and should be interpreted against its own level of bias precision.

Exercise before bed does not impact sleep inertia in young healthy males.

Sleep inertia is the transitional state marked by impaired cognitive performance and reduced vigilance upon waking. Exercising before bed may increase the amount of slow-wave sleep within the sleep period, which has previously been associated with increased sleep inertia. Healthy males (n = 12) spent 3 nights in a sleep laboratory (1-night washout period between each night) and completed one of the three conditions on each visit - no exercise, aerobic exercise (30 min cycling at 75% heart rate), and resistance exercise (six resistance exercises, three sets of 10 repetitions). The exercise conditions were completed 90 min prior to bed. Sleep was measured using polysomnography. Upon waking, participants completed five test batteries every 15 min, including the Karolinska Sleepiness Scale, a Psychomotor Vigilance Task, and the Spatial Configuration Task. Two separate linear mixed-effects models were used to assess: (a) the impact of condition; and (b) the amount of slow-wave sleep, on sleep inertia. There were no significant differences in sleep inertia between conditions, likely as a result of the similar sleep amount, sleep structure and time of awakening between conditions. The amount of slow-wave sleep impacted fastest 10% reciprocal reaction time on the Psychomotor Vigilance Task only, whereby more slow-wave sleep improved performance; however, the magnitude of this relationship was small. Results from this study suggest that exercise performed 90 min before bed does not negatively impact on sleep inertia. Future studies should investigate the impact of exercise intensity, duration and timing on sleep and subsequent sleep inertia.

A validation study of the WHOOP strap against polysomnography to assess sleep.

The aim of the study was to compare the WHOOP strap - a wearable device that estimates sleep based on measures of movement and heart rate derived from actigraphy and photoplethysmography, respectively. Twelve healthy adults (6 females, 6 males, aged 22.9 ± 3.4 years) participated in a 10-day, laboratory-based protocol. A total of 86 sleeps were independently assessed in 30-s epochs using polysomnography and WHOOP. For WHOOP, bed times were entered by researchers and sleeps were scored by the company based on proprietary algorithms. WHOOP overestimated total sleep time by 8.2 ± 32.9 minutes compared to polysomnography, but this difference was non-significant. WHOOP was compared to polysomnography for 2-stage (i.e., wake, sleep) and 4-stage categorisation (i.e., wake, light sleep [N1 or N2], slow-wave sleep [N3], REM) of sleep periods. For 2-stage categorisation, the agreement, sensitivity to sleep, specificity for wake, and Cohen's kappa were 89%, 95%, 51%, and 0.49, respectively. For 4-stage categorisation, the agreement, sensitivity to light sleep, SWS, REM, and wake, and Cohen's kappa were 64%, 62%, 68%, 70%, 51%, and 0.47, respectively. In situations where polysomnography is impractical (e.g., field settings), WHOOP is a reasonable method for estimating sleep, particularly for 2-stage categorisation, if accurate bedtimes are manually entered.

In Situ Formed Ir3Li Nanoparticles as Active Cathode Material in Li-Oxygen Batteries.

Lithium-oxygen (Li-O2) batteries are a promising class of rechargeable Li batteries with a potentially very high achievable energy density. One of the major challenges for Li-O2 batteries is the high charge overpotential, which results in a low energy efficiency. In this work size-selected subnanometer Ir clusters are used to investigate cathode materials that can help control lithium superoxide formation during discharge, which has good electronic conductivity needed for low charge potentials. It is found that Ir particles can lead to lithium superoxide formation as the discharge product with Ir particle sizes of ∼1.5 nm giving the lowest charge potentials. During discharge these 1.5 nm Ir nanoparticles surprisingly evolve to larger ones while incorporating Li to form core-shell structures with Ir3Li shells, which probably act as templates for growth of lithium superoxide during discharge. Various characterization techniques including DEMS, Raman, titration, and HRTEM are used to characterize the LiO2 discharge product and the evolution of the Ir nanoparticles. Density functional calculations are used to provide insight into the mechanism for formation of the core-shell Ir3Li particles. The in situ formed Ir3Li core-shell nanoparticles discovered here provide a new direction for active cathode materials that can reduce charge overpotentials in Li-O2 batteries.

Toward Highly Efficient Electrocatalyst for Li-O2 Batteries Using Biphasic N-Doping Cobalt@Graphene Multiple-Capsule Heterostructures.

For the promotion of lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity, and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electroactive zones possible; furthermore, the colander-like porous electrode facilitates the oxygen diffusion, catalytic reaction, and stable deposition of discharge products. As a result, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.

Excess Li-Ion Storage on Reconstructed Surfaces of Nanocrystals To Boost Battery Performance.

Because of their enhanced kinetic properties, nanocrystallites have received much attention as potential electrode materials for energy storage. However, because of the large specific surface areas of nanocrystallites, they usually suffer from decreased energy density, cycling stability, and effective electrode capacity. In this work, we report a size-dependent excess capacity beyond theoretical value (170 mA h g-1) by introducing extra lithium storage at the reconstructed surface in nanosized LiFePO4 (LFP) cathode materials (186 and 207 mA h g-1 in samples with mean particle sizes of 83 and 42 nm, respectively). Moreover, this LFP composite also shows excellent cycling stability and high rate performance. Our multimodal experimental characterizations and ab initio calculations reveal that the surface extra lithium storage is mainly attributed to the charge passivation of Fe by the surface C-O-Fe bonds, which can enhance binding energy for surface lithium by compensating surface Fe truncated symmetry to create two types of extra positions for Li-ion storage at the reconstructed surfaces. Such surface reconstruction nanotechnology for excess Li-ion storage makes full use of the large specific surface area of the nanocrystallites, which can maintain the fast Li-ion transport and greatly enhance the capacity. This discovery and nanotechnology can be used for the design of high-capacity and efficient lithium ion batteries.

Insight into the Catalytic Mechanism of Bimetallic Platinum-Copper Core-Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions.

The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt-Cu core-shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li-O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt-Cu core-shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

Insight into the Capacity Fading Mechanism of Amorphous Se2S5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes.

In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component was gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.

Tuning of Photoluminescence by Cation Nanosegregation in the (CaMg)(x)(NaSc)(1-x)Si2O6 Solid Solution.

Controlled photoluminescence tuning is important for the optimization and modification of phosphor materials. Herein we report an isostructural solid solution of (CaMg)x(NaSc)1-xSi2O6 (0 < x < 1) in which cation nanosegregation leads to the presence of two dilute Eu(2+) centers. The distinct nanodomains of isostructural (CaMg)Si2O6 and (NaSc)Si2O6 contain a proportional number of Eu(2+) ions with unique, independent spectroscopic signatures. Density functional theory calculations provided a theoretical understanding of the nanosegregation and indicated that the homogeneous solid solution is energetically unstable. It is shown that nanosegregation allows predictive control of color rendering and therefore provides a new method of phosphor development.

Local X-ray magnetic circular dichroism study of Fe/Cu(111) using a tunneling smart tip.

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

Growth of Au on Pt icosahedral nanoparticles revealed by low-dose in situ TEM.

A growth mode was revealed by an in situ TEM study of nucleation and growth of Au on Pt icosahedral nanoparticles. Quantitative analysis of growth kinetics was carried out based on real-time TEM data, which shows the process involves: (1) deposition of Au on corner sites of Pt icosahedral nanoparticles, (2) diffusion of Au from corners to terraces and edges, and (3) subsequent layer-by-layer growth of Au on Au surfaces to form Pt@Au core-shell nanoparticles. The in situ TEM results indicate diffusion of Au from corner islands to terraces and edges is a kinetically controlled growth, as evidenced by a measurement of diffusion coefficients for these growth processes. We demonstrated that in situ electron microscopy is a valuable tool for quantitative study of nucleation and growth kinetics and can provide new insight into the design and precise control of heterogeneous nanostructures.

Interfacial effects on lithium superoxide disproportionation in Li-O2 batteries.

During the cycling of Li-O2 batteries the discharge process gives rise to dynamically evolving agglomerates composed of lithium-oxygen nanostructures; however, little is known about their composition. In this paper, we present results for a Li-O2 battery based on an activated carbon cathode that indicate interfacial effects can suppress disproportionation of a LiO2 component in the discharge product. High-intensity X-ray diffraction and transmission electron microscopy measurements are first used to show that there is a LiO2 component along with Li2O2 in the discharge product. The stability of the discharge product was then probed by investigating the dependence of the charge potential and Raman intensity of the superoxide peak with time. The results indicate that the LiO2 component can be stable for possibly up to days when an electrolyte is left on the surface of the discharged cathode. Density functional calculations on amorphous LiO2 reveal that the disproportionation process will be slower at an electrolyte/LiO2 interface compared to a vacuum/LiO2 interface. The combined experimental and theoretical results provide new insight into how interfacial effects can stabilize LiO2 and suggest that these interfacial effects may play an important role in the charge and discharge chemistries of a Li-O2 battery.

Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery.

Uniformly dispersed Pd nanoparticles on ZnO-passivated porous carbon were synthesized via an atomic layer deposition (ALD) technique, which was tested as a cathode material in a rechargeable Li-O2 battery, showing a highly active catalytic effect toward the electrochemical reactions-in particular, the oxygen evolution reaction. Transmission electron microscopy (TEM) showed discrete crystalline nanoparticles decorating the surface of the ZnO-passivated porous carbon support in which the size could be controlled in the range of 3-6 nm, depending on the number of Pd ALD cycles performed. X-ray absorption spectroscopy (XAS) at the Pd K-edge revealed that the carbon-supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The ZnO-passivated layer effectively blocks the defect sites on the carbon surface, minimizing the electrolyte decomposition. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports for Li-O2 batteries.

Determining the resolution limits of electron-beam lithography: direct measurement of the point-spread function.

One challenge existing since the invention of electron-beam lithography (EBL) is understanding the exposure mechanisms that limit the resolution of EBL. To overcome this challenge, we need to understand the spatial distribution of energy density deposited in the resist, that is, the point-spread function (PSF). During EBL exposure, the processes of electron scattering, phonon, photon, plasmon, and electron emission in the resist are combined, which complicates the analysis of the EBL PSF. Here, we show the measurement of delocalized energy transfer in EBL exposure by using chromatic aberration-corrected energy-filtered transmission electron microscopy (EFTEM) at the sub-10 nm scale. We have defined the role of spot size, electron scattering, secondary electrons, and volume plasmons in the lithographic PSF by performing EFTEM, momentum-resolved electron energy loss spectroscopy (EELS), sub-10 nm EBL, and Monte Carlo simulations. We expect that these results will enable alternative ways to improve the resolution limit of EBL. Furthermore, our approach to study the resolution limits of EBL may be applied to other lithographic techniques where electrons also play a key role in resist exposure, such as ion-beam-, X-ray-, and extreme-ultraviolet lithography.