High-throughput, combinatorial synthesis of multimetallic nanoclusters.

Multimetallic nanoclusters (MMNCs) offer unique and tailorable surface chemistries that hold great potential for numerous catalytic applications. The efficient exploration of this vast chemical space necessitates an accelerated discovery pipeline that supersedes traditional "trial-and-error" experimentation while guaranteeing uniform microstructures despite compositional complexity. Herein, we report the high-throughput synthesis of an extensive series of ultrafine and homogeneous alloy MMNCs, achieved by 1) a flexible compositional design by formulation in the precursor solution phase and 2) the ultrafast synthesis of alloy MMNCs using thermal shock heating (i.e., ∼1,650 K, ∼500 ms). This approach is remarkably facile and easily accessible compared to conventional vapor-phase deposition, and the particle size and structural uniformity enable comparative studies across compositionally different MMNCs. Rapid electrochemical screening is demonstrated by using a scanning droplet cell, enabling us to discover two promising electrocatalysts, which we subsequently validated using a rotating disk setup. This demonstrated high-throughput material discovery pipeline presents a paradigm for facile and accelerated exploration of MMNCs for a broad range of applications.

The role of emotional sensitivity to probability in the decision to choose genetic testing.

While the availability of genetic testing is rapidly increasing, many opt out of testing. The decision to test or not is emotionally charged, and both clinical research and theoretical work in psychology show that in emotional decisions, people often struggle to interpret and utilize risk information. Clinical research on genetic testing uptake also shows that feeling overwhelmed by numeric information may be a deterrent to testing. However, recent psychological research indicates that some portion of the population has greater emotional sensitivity to probability, (i.e., the extent to which emotional reactions to risk depend on probabilities) than others. We hypothesize that participants high in emotional sensitivity to probability will be more interested in genetic testing as an opportunity to seek greater precision in risk estimates and that this relationship is moderated by the testing context itself. In an online survey of a nationally representative sample (not recruited as patients), participants were presented with a hypothetical scenario describing a suspected diagnosis with an option for genetic testing. The scenario experimentally varied the pre-test probability estimate of the diagnosis (low or high) and whether the test results would result in certainty (ruling in or ruling out the diagnosis), or reduced uncertainty (providing a more precise individual risk estimate). Results indicated that emotional sensitivity to probability was a strong predictor of intention to test, particularly when the test allowed participants to rule out a diagnosis, reducing an already low probability to zero. These results highlight the way patients' individual characteristics interact with the testing context to guide decision-making and provide important insight into the way patients integrate risk probability information into intensely emotional decisions.

Cellulose ionic conductors with high differential thermal voltage for low-grade heat harvesting.

Converting low-grade heat into useful electricity requires a technology that is efficient and cost effective. Here, we demonstrate a cellulosic membrane that relies on sub-nanoscale confinement of ions in oxidized and aligned cellulose molecular chains to enhance selective diffusion under a thermal gradient. After infiltrating electrolyte into the cellulosic membrane and applying an axial temperature gradient, the ionic conductor exhibits a thermal gradient ratio (analogous to the Seebeck coefficient in thermoelectrics) of 24 mV K-1-more than twice the highest value reported until now. We attribute the enhanced thermally generated voltage to effective sodium ion insertion into the charged molecular chains of the cellulosic membrane, which consists of type II cellulose, while this process does not occur in natural wood or type I cellulose. With this material, we demonstrate a flexible and biocompatible heat-to-electricity conversion device via nanoscale engineering based on sustainable materials that can enable large-scale manufacture.

Stable Multimetallic Nanoparticles for Oxygen Electrocatalysis.

Nanostructured catalysts often face an important challenge: poor stability. Many factors contribute to catalytic degradation, including parasitic chemical reactions, phase separation, agglomeration, and dissolution, leading to activity loss especially during long-term catalytic reactions. This challenge is shared by a new family of catalysts, multimetallic nanoparticles, which have emerged owing to their broad tunability and high activity. While significant synthesis-based advances have been made, the stability of these nanostructured catalysts, especially during catalytic reactions, has not been well addressed. In this study, we reveal the critical influence of a synthetic method on the stability of nanostructured catalysts through aprotic oxygen catalysis (Li-O2 battery) demonstrations. In comparison to the conventional wet impregnation (WI) method, we show that the carbothermal shock (CTS) method dramatically improves the overall structural and chemical stability of the catalyst with the same elemental compositions. For multimetallic compositions (4- and 8-elements), the overall stability of the electrocatalysts as well as the battery lifetime can be further improved by incorporating additional noncatalytically active elements into the individual nanoparticles via CTS. The results offer a new synthetic path toward the stabilization of nanostructured catalysts, where additional reaction schemes beyond oxygen electrocatalysis are foreseeable.

Ultrahigh-Capacity Lithium-Oxygen Batteries Enabled by Dry-Pressed Holey Graphene Air Cathodes.

Lithium-oxygen (Li-O2) batteries have the highest theoretical energy density of all the Li-based energy storage systems, but many challenges prevent them from practical use. A major obstacle is the sluggish performance of the air cathode, where both oxygen reduction (discharge) and oxygen evolution (charge) reactions occur. Recently, there have been significant advances in the development of graphene-based air cathode materials with a large surface area and catalytically active for both oxygen reduction and evolution reactions, especially with additional catalysts or dopants. However, most studies reported so far have examined air cathodes with a limited areal mass loading rarely exceeding 1 mg/cm2. Despite the high gravimetric capacity values achieved, the actual (areal) capacities of those batteries were far from sufficient for practical applications. Here, we present the fabrication, performance, and mechanistic investigations of high-mass-loading (up to 10 mg/cm2) graphene-based air electrodes for high-performance Li-O2 batteries. Such air electrodes could be easily prepared within minutes under solvent-free and binder-free conditions by compression-molding holey graphene materials because of their unique dry compressibility associated with in-plane holes on the graphene sheet. Li-O2 batteries with high air cathode mass loadings thus prepared exhibited excellent gravimetric capacity as well as ultrahigh areal capacity (as high as ∼40 mAh/cm2). The batteries were also cycled at a high curtailing areal capacity (2 mAh/cm2) and showed a better cycling stability for ultrathick cathodes than their thinner counterparts. Detailed post-mortem analyses of the electrodes clearly revealed the battery failure mechanisms under both primary and secondary modes, arising from the oxygen diffusion blockage and the catalytic site deactivation, respectively. These results strongly suggest that the dry-pressed holey graphene electrodes are a highly viable architectural platform for high-capacity, high-performance air cathodes in Li-O2 batteries of practical significance.

Universal, In Situ Transformation of Bulky Compounds into Nanoscale Catalysts by High-Temperature Pulse.

The synthesis of nanoscale metal compound catalysts has attracted much research attention in the past decade. The challenges of preparation of the metal compound include the complexity of the synthesis process and difficulty of precise control of the reaction conditions. Herein, we report an in situ synthesis of nanoparticles via a high-temperature pulse method where the bulk material acts as the precursor. During the process of rapid heating and cooling, swift melting, anchoring, and recrystallization occur, resulting in the generation of high-purity nanoparticles. In our work, the cobalt boride (Co2B) nanoparticles with a diameter of 10-20 nm uniformly anchored on the reduced graphene oxide (rGO) nanosheets were successfully prepared using the high temperature pulse method. The as-prepared Co2B/rGO composite displayed remarkable electrocatalytic performance for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). We also prepared molybdenum disulfide (MoS2) and cobalt oxide (Co3O4) nanoparticles, thereby demonstrating that the high-temperature pulse is a universal method to synthesize ultrafine metal compound nanoparticles.

Tuning two-dimensional nanomaterials by intercalation: materials, properties and applications.

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results in terms of tunable properties and device performance. Among all modification methods, intercalation of 2D materials has emerged as a particularly powerful tool: it provides the highest possible doping level and is capable of (ir)reversibly changing the phase of the material. Intercalated 2D materials exhibit extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. The recent progress on host 2D materials, various intercalation species, and intercalation methods, as well as tunable properties and potential applications enabled by intercalation, are comprehensively reviewed.

Rapid, in Situ Synthesis of High Capacity Battery Anodes through High Temperature Radiation-Based Thermal Shock.

High capacity battery electrodes require nanosized components to avoid pulverization associated with volume changes during the charge-discharge process. Additionally, these nanosized electrodes need an electronically conductive matrix to facilitate electron transport. Here, for the first time, we report a rapid thermal shock process using high-temperature radiative heating to fabricate a conductive reduced graphene oxide (RGO) composite with silicon nanoparticles. Silicon (Si) particles on the order of a few micrometers are initially embedded in the RGO host and in situ transformed into 10-15 nm nanoparticles in less than a minute through radiative heating. The as-prepared composites of ultrafine Si nanoparticles embedded in a RGO matrix show great performance as a Li-ion battery (LIB) anode. The in situ nanoparticle synthesis method can also be adopted for other high capacity battery anode materials including tin (Sn) and aluminum (Al). This method for synthesizing high capacity anodes in a RGO matrix can be envisioned for roll-to-roll nanomanufacturing due to the ease and scalability of this high-temperature radiative heating process.

Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte.

All-solid-state Li-batteries using solid-state electrolytes (SSEs) offer enhanced safety over conventional Li-ion batteries with organic liquid electrolytes due to the nonflammable nature of SSEs. The superior mechanical strength of SSEs can also protect against Li dendrite penetration, which enables the use of the highest specific capacity (3861 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) anode: Li metal. However, contact between the Li metal and SSEs presents a major challenge, where a large polarization occurs at the Li metal/SSE interface. Here, the chemical properties of a promising oxide-based SSE (garnet) changed from "super-lithiophobicity" to "super-lithiophilicity" through an ultrathin coating of amorphous Si deposited by plasma-enhanced chemical vapor deposition (PECVD). The wettability transition is due to the reaction between Li and Si and the in situ formation of lithiated Si. As a result, symmetric cells composed of a Si-coated garnet-structured SSE and Li metal electrodes exhibited much smaller impedance and excellent stability upon plating/stripping cycles compared to cells using bare garnet SSE. Specifically, the interfacial resistance between Li and garnet dramatically decreased from 925 to 127 Ω cm(2) when lithiated Si was formed on the garnet. Our discovery of switchable lithiophobic-lithiophilic surfaces to improve the Li metal/SSE interface opens opportunities for improving many other SSEs.

Atomic force microscopy studies on molybdenum disulfide flakes as sodium-ion anodes.

A microscale battery comprised of mechanically exfoliated molybdenum disulfide (MoS2) flakes with copper connections and a sodium metal reference was created and investigated as an intercalation model using in situ atomic force microscopy in a dry room environment. While an ethylene carbonate-based electrolyte with a low vapor pressure allowed topographical observations in an open cell configuration, the planar microbattery was used to conduct in situ measurements to understand the structural changes and the concomitant solid electrolyte interphase (SEI) formation at the nanoscale. Topographical observations demonstrated permanent wrinkling behavior of MoS2 electrodes upon sodiation at 0.4 V. SEI formation occurred quickly on both flake edges and planes at voltages before sodium intercalation. Force spectroscopy measurements provided quantitative data on the SEI thickness for MoS2 electrodes in sodium-ion batteries for the first time.

Transient Rechargeable Batteries Triggered by Cascade Reactions.

Transient battery is a new type of technology that allows the battery to disappear by an external trigger at any time. In this work, we successfully demonstrated the first transient rechargeable batteries based on dissoluble electrodes including V2O5 as the cathode and lithium metal as the anode as well as a biodegradable separator and battery encasement (PVP and sodium alginate, respectively). All the components are robust in a traditional lithium-ion battery (LIB) organic electrolyte and disappear in water completely within minutes due to triggered cascade reactions. With a simple cut-and-stack method, we designed a fully transient device with an area of 0.5 cm by 1 cm and total energy of 0.1 J. A shadow-mask technique was used to demonstrate the miniature device, which is compatible with transient electronics manufacturing. The materials, fabrication methods, and integration strategy discussed will be of interest for future developments in transient, self-powered electronics. The demonstration of a miniature Li battery shows the feasibility toward system integration for all transient electronics.

Coherent plasmon-exciton coupling in silver platelet-J-aggregate nanocomposites.

Hybrid nanostructures that couple plasmon and exciton resonances generate hybridized energy states, called plexcitons, which may result in unusual light-matter interactions. We report the formation of a transparency dip in the visible spectra of colloidal suspensions containing silver nanoplatelets and a cyanine dye, 1,1'-diethyl-2,2'-cyanine iodide (PIC). PIC was electrostatically adsorbed onto the surface of silver nanoplatelet core particles, forming an outer J-aggregate shell. This core-shell architecture provided a framework for coupling the plasmon resonance of the silver nanoplatelet core with the exciton resonance of the J-aggregate shell. The sizes and aspect ratios of the silver nanoplatelets were controlled to ensure the overlap of the plasmon and exciton resonances. As a measure of the plasmon-exciton coupling strength in the system, the experimentally observed transparency dips correspond to a Rabi splitting energy of 207 meV, among the highest reported for colloidal nanoparticles. The optical properties of the silver platelet-J-aggregate nanocomposites were supported numerically and analytically by the boundary-element method and temporal coupled-mode theory, respectively. Our theoretical predictions and experimental results confirm the presence of a transparency dip for the silver nanoplatelet core J-aggregate shell structures. Additionally, the numerical and analytical calculations indicate that the observed transparencies are dominated by the coupling of absorptive resonances, as opposed to the coupling of scattering resonances. Hence, we describe the suppressed extinction in this study as an induced transparency rather than a Fano resonance.

Characterization of size-specific particulate matter emission rates for a simulated medical laser procedure--a pilot study.

Prior investigation on medical laser interaction with tissue has suggested device operational parameter settings influence laser generated air contaminant emission, but this has not been systematically explored. A laboratory-based simulated medical laser procedure was designed and pilot tested to determine the effect of laser operational parameters on the size-specific mass emission rate of laser generated particulate matter. Porcine tissue was lased in an emission chamber using two medical laser systems (CO2, λ = 10,600 nm; Ho:YAG, λ = 2100 nm) in a fractional factorial study design by varying three operational parameters (beam diameter, pulse repetition frequency, and power) between two levels (high and low) and the resultant plume was measured using two real-time size-selective particle counters. Particle count concentrations were converted to mass emission rates before an analysis of variance was used to determine the influence of operational parameter settings on size-specific mass emission rate. Particle shape and diameter were described for a limited number of samples by collecting particles on polycarbonate filters, and photographed using a scanning electron microscope (SEM) to examine method of particle formation. An increase in power and decrease in beam diameter led to an increase in mass emission for the Ho:YAG laser at all size ranges. For the CO2 laser, emission rates were dependent on particle size and were not statistically significant for particle ranges between 5 and 10 µm. When any parameter level was increased, emission rate of the smallest particle size range also increased. Beam diameter was the most influential variable for both lasers, and the operational parameters tested explained the most variability at the smallest particle size range. Particle shape was variable and some particles observed by SEM were likely created from mechanical methods. This study provides a foundation for future investigations to better estimate size-specific mass emission rates and particle characteristics for additional laser operational parameters in order to estimate occupational exposure, and to inform control strategies.

Application of a two-zone model to estimate medical laser-generated particulate matter exposures.

We estimated particulate matter exposures for two simulated medical laser procedures using a near-field/far-field model. Size-specific mass emission rates obtained from a laboratory-based emission chamber study were used with estimated room size, air exchange rate, and interflow between zones to demonstrate the potential exposure range. Modeled steady-state concentrations for the near-field ranged between 80 and 2140 µg/m(3) and between 40 and 1650 µg/m(3) in the far-field. Results indicate concentrations in the simulated scenarios are similar to those obtained from limited field assessments conducted in hospital operating rooms. Since new medical laser technologies and applications continue to grow, modeled occupational exposures of medical laser-generated particulate matter can be useful in better understanding these exposures in the clinical environment, and to inform control strategies.

Groundwater arsenic in Chimaltenango, Guatemala.

In the Municipality of Chimaltenango, Guatemala, we sampled groundwater for total inorganic arsenic. In total, 42 samples were collected from 27 (43.5%) of the 62 wells in the municipality, with sites chosen to achieve spatial representation throughout the municipality. Samples were collected from household faucets used for drinking water, and sent to the USA for analysis. The only site found to have a concentration above the 10 µg/L World Health Organization provisional guideline for arsenic in drinking water was Cerro Alto, where the average concentration was 47.5 µg/L. A health risk assessment based on the arsenic levels found in Cerro Alto showed an increase in noncarcinogenic and carcinogenic risks for residents as a result of consuming groundwater as their primary drinking water source. Using data from the US Geological Survey and our global positioning system data of the sample locations, we found Cerro Alto to be the only site sampled within the tertiary volcanic rock layer, a known source of naturally occurring arsenic. Recommendations were made to reduce the levels of arsenic found in the community's drinking water so that the health risks can be managed.

Modeled occupational exposures to gas-phase medical laser-generated air contaminants.

Exposure monitoring data indicate the potential for substantive exposure to laser-generated air contaminants (LGAC); however the diversity of medical lasers and their applications limit generalization from direct workplace monitoring. Emission rates of seven previously reported gas-phase constituents of medical laser-generated air contaminants (LGAC) were determined experimentally and used in a semi-empirical two-zone model to estimate a range of plausible occupational exposures to health care staff. Single-source emission rates were generated in an emission chamber as a one-compartment mass balance model at steady-state. Clinical facility parameters such as room size and ventilation rate were based on standard ventilation and environmental conditions required for a laser surgical facility in compliance with regulatory agencies. All input variables in the model including point source emission rates were varied over an appropriate distribution in a Monte Carlo simulation to generate a range of time-weighted average (TWA) concentrations in the near and far field zones of the room in a conservative approach inclusive of all contributing factors to inform future predictive models. The concentrations were assessed for risk and the highest values were shown to be at least three orders of magnitude lower than the relevant occupational exposure limits (OELs). Estimated values do not appear to present a significant exposure hazard within the conditions of our emission rate estimates.

Plasticizer contamination of firefighter personal protective clothing--a potential factor in increased health risks in firefighters.

Chemical exposures may be responsible for firefighters' elevated incidences of cancer and cardiovascular disease. This study characterized semivolatile chemical contamination on firefighter personal protective clothing to assess exposure of firefighters to these chemicals. Samples from used firefighter protective clothing, including gloves, hood, and one coat wristlet, were extracted with methylene chloride and analyzed by EPA method 8270 for semivolatile contaminants, including 20 polycyclic aromatic hydrocarbons (PAHs) and 6 phthalate diesters. Twenty-two of the chemicals of interest were found on at least one clothing swatch. Only di-(2-ethylhexyl) phthalate (DEHP), a plasticizer, added to polyvinyl chloride (PVC) to increase flexibility, was found on every swatch. DEHP concentrations were the highest of any chemical measured, and were 52 to 875 times higher than any PAH concentration measured. DEHP was also detected on most items of unused firefighter personal protective clothing, although at much lower levels. These findings suggest that firefighters are exposed to high levels of DEHP, a probable human carcinogen, and at levels much higher than PAHs, the semivolatile toxic combustion products most extensively studied historically. Firefighter exposure to DEHP and other phthalate diesters therefore merits further study.

A pilot study to determine medical laser generated air contaminant emission rates for a simulated surgical procedure.

The U.S. Occupational Safety and Health Administration (OSHA) estimates that half a million health-care workers are exposed to laser surgical smoke each year. The purpose of this study was to establish a methodology to (1) estimate emission rates of laser-generated air contaminants (LGACs) using an emission chamber, and to (2) perform a screening study to differentiate the effects of three laser operational parameters. An emission chamber was designed, fabricated, and assessed for performance to estimate the emission rates of gases and particles associated with LGACs during a simulated surgical procedure. Two medical lasers (Holmium Yttrium Aluminum Garnet [Ho:YAG] and carbon dioxide [CO2]) were set to a range of plausible medical laser operational parameters in a simulated surgery to pyrolyze porcine skin generating plume in the emission chamber. Power, pulse repetition frequency (PRF), and beam diameter were evaluated to determine the effect of each operational parameter on emission rate using a fractional factorial design. The plume was sampled for particulate matter and seven gas phase combustion byproduct contaminants (benzene, ethylbenzene, toluene, formaldehyde, hydrogen cyanide, carbon dioxide, and carbon monoxide): the gas phase emission results are presented here. Most of the measured concentrations of gas phase contaminants were below their limit of detection (LOD), but detectable measurements enabled us to determine laser operation parameter influence on CO2 emissions. Confined to the experimental conditions of this screening study, results indicated that beam diameter was statistically significantly influential and power was marginally statistically significant to emission rates of CO2 when using the Ho:YAG laser but not with the carbon dioxide laser; PRF was not influential vis-a-vis emission rates of these gas phase contaminants.

Context Matters: Emotional Sensitivity to Probabilities and the Bias for Action in Cancer Treatment Decisions.

BACKGROUND: Past studies have shown a commission bias for cancer treatment, a tendency to choose active treatment even when watchful waiting is less risky. This bias suggests motivations for action beyond mortality statistics, but recent evidence suggests that individuals differ in their emotional sensitivity to probabilities (ESP), the tendency to calibrate emotional reactions to probability. The current study aims to examine the role of ESP in the commission bias, specifically whether those higher in ESP are more likely to choose watchful waiting when risk probabilities align with that choice. METHODS: Participants (N = 1,055) read a scenario describing a hypothetical cancer diagnosis and chose between surgery and watchful waiting, with random assignment between versions where the mortality rate was either lower for surgery or for watchful waiting. We modeled choice using the Possibility Probability Questionnaire (PPQ), a measure of ESP, and several other individual differences in a logistic regression. RESULTS: We observed a commission bias as in past studies with most participants choosing surgery both when surgery was optimal (71%) and when watchful waiting was optimal (58%). An ESP × Condition interaction indicated that the predictive role of ESP depended on condition. Those higher in ESP were more likely to choose surgery when probabilities favored surgery, ß = 0.57, P < 0.001, but when probabilities favored watchful waiting, ESP had a near-zero relationship with choice, ß = 0.05, P < 0.99. CONCLUSIONS: The role of ESP in decision making is context specific. Higher levels of ESP predict choosing action when that action is warranted but do not predict a shift away from surgery when watchful waiting offers better chances of survival. ESP does not overcome the commission bias. HIGHLIGHTS: Past studies have identified a "commission bias," a tendency to choose active treatment over watchful waiting, even when mortality rate is lower for waiting.Evaluation of risk probabilities is related to individual differences in emotional sensitivity to probabilities (ESP) and has been shown to predict reactions to and decisions about health risk situations.ESP appears to be selectively factored into decision making. ESP was a robust predictor of choosing surgery when probability information supported surgery but did not predict decisions when probability information supported watchful waiting.Those who are most emotionally attuned to probabilities are just as susceptible to the commission bias as those who are less attuned.

Integration of Li4Ti5O12 Crystalline Films on Silicon Toward High-Rate Performance Lithionic Devices.

The growth of crystalline Li-based oxide thin films on silicon substrates is essential for the integration of next-generation solid-state lithionic and electronic devices including on-chip microbatteries, memristors, and sensors. However, growing crystalline oxides directly on silicon typically requires high temperatures and oxygen partial pressures, which leads to the formation of undesired chemical species at the interface compromising the crystal quality of the films. In this work, we employ a 2 nm gamma-alumina (γ-Al2O3) buffer layer on Si substrates in order to grow crystalline thin films of Li4Ti5O12 (LTO), a well-known active material for lithium-ion batteries. The ultrathin γ-Al2O3 layer enables the formation of a stable heterostructure with sharp interfaces and drastically improves the LTO crystallographic and electrochemical properties. Long-term galvanostatic cycling of 50 nm LTO films in liquid-based half-cells demonstrates a high capacity retention of 91% after 5000 cycles at 100 C. Rate capability tests showcase a specific charge of 56 mA h g-1 at an exceptional C-rate of 5000 C (15 mA cm-2). Moreover, with sub-millisecond current pulse tests, the reported thin-film heterostructure exhibits rapid Li-ion (de)intercalation, which could lead to fast switching timescales in resistive memory devices and electrochemical transistors.