Electrocatalytic Glycerol Oxidation with Concurrent Hydrogen Evolution Utilizing an Efficient MoOx /Pt Catalyst.

Glycerol electrolysis affords a green and energetically favorable route for the production of value-added chemicals at the anode and H2 production in parallel at the cathode. Here, a facile method for trapping Pt nanoparticles at oxygen vacancies of molybdenum oxide (MoOx ) nanosheets, yielding a high-performance MoOx /Pt composite electrocatalyst for both the glycerol oxidation reaction (GOR) and the hydrogen evolution reaction (HER) in alkaline electrolytes, is reported. Combined electrochemical experiments and theoretical calculations reveal the important role of MoOx nanosheets for the adsorption of glycerol molecules in GOR and the dissociation of water molecules in HER, as well as the strong electronic interaction with Pt. The MoOx /Pt composite thus significantly enhances the specific mass activity of Pt and the kinetics for both reactions. With MoOx /Pt electrodes serving as both cathode and anode, two-electrode glycerol electrolysis is achieved at a cell voltage of 0.70 V to reach a current density of 10 mA cm-2 , which is 0.90 V less than that required for water electrolysis.

Employer-sponsored behavioral health program impacts on care utilization and cost.

OBJECTIVES: To examine the impact of an employer-sponsored behavioral health (BH) program on all-cause health care utilization and cost. STUDY DESIGN: Retrospective analysis of health insurance claims data obtained from a large employer in western New York covering a 25-month period between 2016 and 2018. Those employees treated by the employer-sponsored BH program were compared against a contemporaneous comparison group of employees of the same employer who had eligible BH diagnoses for the program but were treated elsewhere. METHODS: A difference-in-differences method was used to estimate the program's impact on all-cause care utilization (physician office visits and acute care utilization) and total cost of care, including prescription drug costs. RESULTS: Program participation was associated with a reduction of approximately 28% in total cost of care including prescription drug costs (P = .043) over an 18-month period following the initial program encounter, as well as 27% reductions in primary care provider (PCP) visits (P = .001) and non-BH specialist visits (P = .005). No significant impacts were observed for acute care utilization and BH specialist visit rates. CONCLUSIONS: The results suggest that the employer-sponsored BH program implementation may have shifted treatments of certain BH conditions away from PCPs and non-BH specialists who may not have the proper training or resources to manage such conditions. Therefore, these results are consistent with the expectation that improved access to BH care is likely to improve efficiency in the health care system via provision of more appropriate care for those who need it.

Structure-Reactivity Effects of Biomass-based Hydroxyacids for Sustainable Electrochemical Hydrogen Production.

Biomass electro-oxidation is a promising approach for the sustainable generation of H2 by electrolysis with simultaneous synthesis of value-added chemicals. In this work, the electro-oxidation of two structurally different organic hydroxyacids, lactic acid and gluconic acid, was studied comparatively to understand how the chemical structure of the hydroxyacid affects the electrochemical reactivity under various conditions. It was concluded that hydroxyacids such as gluconic acid, with a considerable density of C-OH groups, are highly reactive and promising for the sustainable generation of H2 by electrolysis at low potentials and high conversion rates (less than -0.15 V vs. Hg/HgO at 400 mA cm-2 ) but with low selectivity to specific final products. In contrast, the lower reactivity of lactic acid did not enable H2 generation at very high conversion rates (<100 mA cm-2 ), but the reaction was significantly more selective (64 % to pyruvic acid). This work shows the potential of biomass-based organic hydroxyacids for sustainable generation of H2 and highlights the importance of the chemical structure on the reactivity and selectivity of the electro-oxidation reactions.

Feasibility of Chemically Modified Cellulose Nanofiber Membranes as Lithium-Ion Battery Separators.

Chemical modification of cellulose is beneficial to produce highly porous lithium-ion battery (LIB) separators, but introduction of high charge density adversely affects its electrochemical stability in a LiNi1/3Mn1/3Co1/3O2 (NMC)/graphite full cell. In this study, the influence of carboxylate functional groups in 2,2,6,6-tetramethylpiperidine-1-oxyl-mediated oxidized cellulose nanofibers (TOCNs) on the electrochemical performances of the LIB separator was investigated. X-ray photoelectron spectroscopy and in operando mass spectrometry measurements were used to elucidate the cause of failure of the batteries containing TOCN separators in the presence and absence of sodium counterions in the carboxylate groups and additives. For the TOCN separator with sodium carboxylate functional groups, it seems that Na deposition is the dominant reason for poor electrochemical stability of the cell thereof. The poor performance of the protonated TOCN separator, attributed to a high amount of gas evolution, is dramatically improved by adding 2 wt % of vinylene carbonate (VC) because of suppressed gas evolution. Unveiling the failure mechanism of the TOCN separators and successively implementing the strategies to improve performance, for example, removing Na, adding VC, and adjusting cycling rates, enable a remarkable cycling performance in the NMC/graphite full cell at ≈2 C (3 mA/cm2) of a fast discharging rate. Despite the aforementioned efforts and compromises required, an increased charge density of the TOCN is beneficial to acquire a mechanically stronger separator. In conclusion, the manufacturing process of cellulose nanofibers needs to be carefully adjusted to acquire a desired separator property. To the best of our knowledge, it is first reported to perform operando gas evolution measurements to systematically investigate the electrochemical stability of nanocellulose as an LIB separator material. The results elucidate not only the challenges for extensive applications of hygroscopic biomaterials for commercial LIBs but also the practical solutions to achieve high electrochemical stability of the materials.

In situ catalyst reactivation for enhancing alcohol electro-oxidation and coupled hydrogen generation.

A novel method exploiting the in situ reactivation of a PdNi catalyst to enhance the electro-oxidation of alcohols is reported. The periodic regeneration of the catalyst surface leads to significant gains in terms of conversion rate, energy requirements and stability compared to the conventional potentiostatic method.

Utilization of an Employee Behavioral Health Program and Its Effects on Outcomes for Depression and Anxiety Disorders.

OBJECTIVE: To examine the impact of an employer-sponsored behavioral health program on depression and anxiety by assessing dose effect of psychotherapy. METHODS: A retrospective data analysis of patients with baseline scores more than or equal to 10 on the Patient Health Questionnaire (PHQ9) or the Generalized Anxiety Disorder 7-item scale (GAD7). Survival analyses were conducted to assess whether those with a higher number of therapy sessions per episode (dose) achieved faster response (score reduction by 50% or below 10). RESULTS: Patients with medium (8 to 12 visits) or high (more than 12 visits) dose achieved faster response than those with low dose (less than eight visits; hazard ratios more than 1.5, P < 0.05). No significant difference was found between the medium and high dose. CONCLUSION: Higher dose of psychotherapy is correlated with improved behavioral health outcomes, although there appears to be no incremental benefit beyond a certain level.

Effects of Different Manufacturing Processes on TEMPO-Oxidized Carboxylated Cellulose Nanofiber Performance as Binder for Flexible Lithium-Ion Batteries.

Carboxylated cellulose nanofibers (CNF) prepared using the TEMPO-route are good binders of electrode components in flexible lithium-ion batteries (LIB). However, the different parameters employed for the defibrillation of CNF such as charge density and degree of homogenization affect its properties when used as binder. This work presents a systematic study of CNF prepared with different surface charge densities and varying degrees of homogenization and their performance as binder for flexible LiFePO4 electrodes. The results show that the CNF with high charge density had shorter fiber lengths compared with those of CNF with low charge density, as observed with atomic force microscopy. Also, CNF processed with a large number of passes in the homogenizer showed a better fiber dispersibility, as observed from rheological measurements. The electrodes fabricated with highly charged CNF exhibited the best mechanical and electrochemical properties. The CNF at the highest charge density (1550 µmol g-1) and lowest degree of homogenization (3 + 3 passes in the homogenizer) achieved the overall best performance, including a high Young's modulus of approximately 311 MPa and a good rate capability with a stable specific capacity of 116 mAh g-1 even up to 1 C. This work allows a better understanding of the influence of the processing parameters of CNF on their performance as binder for flexible electrodes. The results also contribute to the understanding of the optimal processing parameters of CNF to fabricate other materials, e.g., membranes or separators.

Flexible Paper Electrodes for Li-Ion Batteries Using Low Amount of TEMPO-Oxidized Cellulose Nanofibrils as Binder.

Flexible Li-ion batteries attract increasing interest for applications in bendable and wearable electronic devices. TEMPO-oxidized cellulose nanofibrils (TOCNF), a renewable material, is a promising candidate as binder for flexible Li-ion batteries with good mechanical properties. Paper batteries can be produced using a water-based paper making process, avoiding the use of toxic solvents. In this work, finely dispersed TOCNF was used and showed good binding properties at concentrations as low as 4 wt %. The TOCNF was characterized using atomic force microscopy and found to be well dispersed with fibrils of average widths of about 2.7 nm and lengths of approximately 0.1-1 µm. Traces of moisture, trapped in the hygroscopic cellulose, is a concern when the material is used in Li-ion batteries. The low amount of binder reduces possible moisture and also increases the capacity of the electrodes, based on total weight. Effects of moisture on electrochemical battery performance were studied on electrodes dried at 110 °C in a vacuum for varying periods. It was found that increased drying time slightly increased the specific capacities of the LiFePO4 electrodes, whereas the capacities of the graphite electrodes decreased. The Coulombic efficiencies of the electrodes were not much affected by the varying drying times. Drying the electrodes for 1 h was enough to achieve good electrochemical performance. Addition of vinylene carbonate to the electrolyte had a positive effect on cycling for both graphite and LiFePO4. A failure mechanism observed at high TOCNF concentrations is the formation of compact films in the electrodes.

Selectivity between Oxygen and Chlorine Evolution in the Chlor-Alkali and Chlorate Processes.

Chlorine gas and sodium chlorate are two base chemicals produced through electrolysis of sodium chloride brine which find uses in many areas of industrial chemistry. Although the industrial production of these chemicals started over 100 years ago, there are still factors that limit the energy efficiencies of the processes. This review focuses on the unwanted production of oxygen gas, which decreases the charge yield by up to 5%. Understanding the factors that control the rate of oxygen production requires understanding of both chemical reactions occurring in the electrolyte, as well as surface reactions occurring on the anodes. The dominant anode material used in chlorate and chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high, the fundamental reasons for this high selectivity are just now becoming elucidated. This review summarizes the research, since the early 1900s until today, concerning the selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions, electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.

Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries.

The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO4 positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAh·g-1 for the positive electrode and 305 mAh·g-1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g-1 and the negative electrode with 160 mAh·g-1 at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries.

Hospital to home: a geriatric educational program on effective discharge planning.

There has been increased attention on the needs of the burgeoning older adult population, with focus on the limited education and training experiences available in geriatric care. Older adults transitioning between levels of care often require increased attention, and the American Geriatrics Society (AGS) Task Force on the Future of Geriatric Medicine has encouraged greater training opportunities be provided to better understand the needs of this population. The Hospital to Home Program is one model of geriatric training emphasizing many of the AGS recommendations. Through qualitative analyses of 51 internal medicine residents' reflections, the authors report how this educational program is meeting the above need and share how Hospital to Home is enhancing residents' skills in creating a safe discharge for geriatric patients and their families.