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A series of new thiophene amides containing a pyridine ring has been synthesized and characterized. Single crystal X-ray structures have been determined for four of the new substances which show two distinct patterns of hydrogen-bonding. The crystal structure of the copper (II) complex of one of the ligands shows that the bonding is O,N in a square planar geometry with perchlorate ions in the axial positions. The new compounds do not undergo electropolymerization due to primary oxidation of the amide function but tuning of the amide group by introduction of an electron-withdrawing group on the pyridine ring allows electropolymerization to occur.
Tin phosphide (Sn4P3) has a high theoretical specific capacity as anode material for lithium-ion batteries, nevertheless the large volumetric expansion during lithium insertion and Li-Sn alloying suppresses its application. Herein, we design sandwiched hollow spherical graphene-wrapping Sn4P3 nanoparticles composite by in-situ solvothermal phosphorization from nano-sized tetragonal-Sn. The product perfectly inherits the sandwich hollow spherical structure from the Sn precursor, a stable and high content COP covalent bond is formed between the Sn4P3 active substrate and graphene skeleton to improve the binding force and electrical conductivity. More importantly, the layer-structure Sn4P3 nanoparticles (20–50 nm) are inserted in the loosely stacking graphene shells, thus the radial volume expansion along c-axis and Sn aggregation can be effectively buffered. The synergy effect provides the transformed product with fewer structural changes comparing with metal Sn anodes, lithiation-generated Li3P and Sn can inter-support for each other to promote the conversion reaction with high reversibility. Thus, the sandwich-Sn4P3/spherical graphene composite exhibits excellent structural integrity and cycling stability, a high reversible capacity of 606.4 mAh g−1 is preserved at a rate of 0.1C over 100 cycles.
Polymer electrolyte films have been prepared by solution casting techniques from precursor solutions of a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), lithium-bis(trifluoromethane) sulfonimide (LiTFSI), and propylene carbonate (PC). Arrays of graded composition were characterised by electrochemical impedance spectroscopy (EIS), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) using high throughput techniques. Impedance analysis showed the resistance of the films as a function of LiTFSI, PC and polymer content. The ternary plot of conductivity shows an area that combines a solid-like mechanical stability with high conductivity, 1×10−5 Scm−1 at the composition 0.55/0.15/0.30wt% PVdF-HFP/LiTFSI/PC, increasing with PC content. In regions with less than a 50wt% fraction of PVdF-HFP the films were too soft to give meaningful results by this method. The DSC measurements on solvent free, salt-doped polymers show a reduced crystallinity, and high throughput XRD patterns show that non-polar crystalline phases are suppressed by the presence of LiTFSI and PC.
Theoretical models of Attention deficit/hyperactivity disorder (ADHD) have long implicated executive function (EF) skills as contributing to the etiology, maintenance, and changes in ADHD symptomatology over time. Although there is interest making within-person inferences (i.e., deficits in EF skills give rise to ADHD behaviors), most of the evidence has been derived from studies that conflated between- and within-person sources of variance. Here, we use repeated-measures data to test within-person association between EF skills and ADHD behaviors. Participants included 1160 children from the Family Life Project, an ongoing prospective longitudinal study of child development in low-income, nonmetropolitan communities. We tested the magnitude of the association between EF skills and ADHD behaviors when children were 3, 4, and 5 years old. Consistent with meta-analyses, unadjusted bivariate associations between EF and ADHD (which reflect combined between- and within-person variation) were of moderate magnitude (rs = −0.20 to −0.30). However, after controlling for all time-invariant, between-person sources of variation, the within-person associations between EF skills and ADHD behaviors were weak (βs − 0.04 to −0.05, ps = 0.01). These results suggest that EF skills may contribute less prominently to ADHD behaviors in early childhood than is commonly assumed and provoke broader questions about developmental models of ADHD.
ABSTRACT Great challenge for the fabrication of free-standing three-dimensional electrode still remains to simultaneously achieve high specific capacitance, rate performance and cycle stability. The paper reprted a new three-dimensional (3D) electrode of Ni/Co layered double hydroxide@NiCo2S4@graphene@Ni foam (Ni/Co-LDH@NiCo2S4@G) for supercapacitors. The as-prepared 3D electrode offers an unique architecture, which create an efficient conduction network and maximum utilization of space and interface. The graphene acts as well-knit and conductive skin coated on the skeleton of Ni foam for growing NiCo2S4. The conductive NiCo2S4 array serves as bridge between Ni/Co-LDH and graphene, leading to ultrafast electron transfer and electrolyte transport. A slew of splits and holes existing in the NiCo2S4 array play one role as the ion-reservoir to contain host of electrolyte ions. To evaluate the feasibility of 3D electrode’s application in supercapacitors, the electrochemical performance was investigated by using the three-electrodes test system and two-electrodes test system, respectively. The 3D electrode exhibits high specific capacitance (2001.2Fg−1), big areal capacitance (15.21Fcm−2), high rate capability (1645.6Fg−1 at the current density of 8Ag−1) and prominent synergetic effect (more than 1.6-fold that of the theoretical capacitance) in a three-electrode test system with 3M KOH electrolyte. Interestingly, the addition of K3Fe(CN)6 into the KOH electrolyte further enhances the pseudocapacitance via both directly contributing pseudocapacitance to the Ni/Co-LDH@NiCo2S4@G and promoting electron gain and loss of Co and Ni ions. The specific capacitance increases to 6282.6Fg−1 at the current density of 6Ag−1. The asymmetric supercapacitor of Ni/Co-LDH@NiCo2S4@G/activated carbon provides the energy density of 102.8Whkg−1 at the power density of 800Wkg−1 in the two-electrodes test system, which is close to that of lithium ion battery. Such a large capacitive performance make it can be used as promising electrode materials for next-generation high-performance supercapacitors.
As the fraction of electricity generated from intermittent renewable sources (such as solar and wind) grows, developing reliable energy storage technologies to store electrical energy in large scale is of increasing importance. Redox flow batteries are now enjoying a renaissance and regarded as a leading technology in providing a well-balanced solution for current daunting challenges. In this article, state-of-the-art studies of the complex multicomponent transport phenomena in aqueous redox flow batteries, with a special emphasis on all-vanadium redox flow batteries, are reviewed and summarized. Rather than elaborating on the details of previous experimental and numerical investigations, this article highlights: i) the key transport issues in each battery's component that need to be tackled so that the rate capability and cycling stability of flow batteries can be significantly improved, ii) the basic mechanisms that control the active species/ion/electron transport behaviors in each battery's component, and iii) the key experimental and numerical findings regarding the correlations between the multicomponent transport processes and battery performance.
Anxiety is a common neuropsychiatric symptom in Parkinson’s disease (PD). Until now, anxiety has been consistently related to cognitive deficits and severity of motor symptoms, whereas the association between anxiety and motor subtypes (TD-PD, tremor dominant and PIGD-PD, postural instability/gait disturbances dominant) revealed contrasting results. The present study aims to investigate the relationship between PD motor subtypes and anxiety and to explore whether the relationship between anxiety and cognitive deficits occurs in a specific PD motor subtype. Consecutive PD outpatients were recruited and divided into TD-PD and PIGD-PD groups according to Jankovic et al.’s criteria. All participants underwent a neuropsychological battery to evaluate anxiety, apathy, the global cognitive functioning, memory abilities, executive and visuo-constructional functions. Thirty-six patients with TD-PD and 35 patients with PIGD-PD were enrolled. The two groups did not differ on demographical and clinical variables. As for the severity of anxiety, no significant difference between the two groups was found. Regression analysis revealed that higher anxiety score was associated with poorer performance on constructional visuospatial test in both TD-PD and PIGD-PD. Clinical variables were not associated with anxiety in the two groups. Our findings indicated that the severity of anxiety was not associated with any PD motor subtypes. Moreover, regression analysis revealed that impaired visuo-constructional abilities are related to anxiety independently of PD motor subtypes. Since altered fronto-parietal network might be one of the pathogenetic mechanisms underpinning anxiety and constructional visuospatial deficits, the treatment of cognitive dysfunctions might reduce anxious symptoms.
Catalytic self-ignition of methanol over platinum supported on anodized alumina in a microburner is demonstrated. The effects of air flow rate and air/methanol ratio on the system start-up time and steady state temperature have been studied. The air flow rate strongly affects the system start-up time. However, at the same flow rate, the start-up time is not affected by the air/methanol ratio over the range studied. Computational fluid dynamics simulations confirm these experimental findings. It is proposed that high flow rates and relatively lower fuel content can lead to attaining steady state faster with minimal fuel utilization. Transient axial temperature profiles showed that the hot spot of the reaction started at the inlet of the burner and did not shift downstream with time under most reaction conditions. The burner effective thermal conductivity was increased using copper thermal spreaders on the burner outer walls, allowing for thermally uniform walls. The uniform temperature profile allowed for optimal integration of the microburner with a thermoelectric device. The integrated microburner/thermoelectric device was shown to self-start from room temperature. The maximum power generated with the thermoelectric was 0.65W and the maximum thermal efficiency was 1.1%.
Coal still remains an important source of power generation world over. Along with its usage, comes unwanted generation of noxious gas emissions, toxic metal releases into wastewater and other pollutants which ultimately lead to environmental concerns. So cleaning of coal through physical or chemical processes becomes utmost important. There are several coals which cannot be cleaned by physical beneficiation techniques to produce low ash cleaner coals. Such coals can be cleaned only through chemical cleaning techniques. The present paper reviews the chemical demineralisation and desulphurisation of coals over the years using various inorganic and organic acids, alkalis, oxidants, leachants and various acids and alkali-acid combinations to reduce the ash and sulphur contents in coals. As high as 90% demineralisation and desulfurization could be achieved with the use of these cheap inorganic acids as compared to the expensive solvents used for solvent extraction processes, a parallel approach of cleaning and refining coals.
ABSTRACT Various nanostructured materials, namely, multi-walled carbon nanotube (MWNT), graphene, Vulcan XC-72 carbon, lead oxide nanorods and ball milled lead oxide nanospheres have been incorporated as additives in the negative paste mix of lead acid battery negative electrodes. Charge/discharge cycling has been performed at room temperature on 9 Ah cells with 2 (+) ve/1 (−) ve cells assembled from these negative electrodes and their performances have been compared. It has been noticed that the graphene and MWNT additives introduced negative electrodes give 11 and 12% improved specific capacity and active material utilization (a.m.u), respectively, than those of the electrodes without additive. The reasons for this improvement is attributed to integration of these additives into the skeleton structure of the negative active mass of the electrodes that forms uniform rectangular beads of size < 200nm during the course of charge/discharge cycling.
The electro-oxidation of iodide has been investigated as a function of concentration using steady-state microelectrode voltammetry, transient cyclic voltammetry and linear-sweep semi-integral voltammetry on platinum, glassy carbon and boron-doped diamond electrodes in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. Two oxidation processes are observed on all of the investigated electrode materials, with the first being assigned to the oxidation of iodide to triiodide (confirmed by UV/visible spectroscopy) and the second being attributed to the oxidation of triiodide to iodine. Iodide oxidation is kinetically more facile on platinum compared to glassy carbon or boron-doped diamond. At elevated bulk iodide concentrations, the nucleation and growth of sparingly soluble electrogenerated iodine at the electrode surface was observed and imaged in situ using optical microscopy. The diffusion coefficient of iodide was determined to be 2.59 (±0.04)×10−7 cm2 s−1 and independent of the bulk concentration of iodide. The steady-state iodide oxidation current measured at a platinum microelectrode was found to be a linear function of iodide concentration, as expected if there are no contributions from non-Stokesian mass-transport processes (electron hopping and/or Grotthuss-type exchange) under the investigated conditions.
Growing concerns about energy conservation and the environmental impacts of greenhouse gas emissions over the world have promoted the development of the electric vehicles (EVs) market. However, one of the biggest barriers in the development of the EV market is the lack of the public charging infrastructure. This paper reviews the factors that can directly and indirectly influence the economics of the public charging infrastructure. The knowledge gaps, barriers and opportunities in the development of the charging infrastructure have been identified and analyzed. In order to promote the development of the public charging infrastructure, more research efforts should be paid on the impacts of psychological factors of customers and the technical development of charging infrastructures and EV batteries. The government support has been proved to play an important role, so that how the government policy can be tailored for the development of the charging infrastructure market should receive more attentions. In addition, the charging price as an endogenous factor should be considered more carefully in modelling the charging infrastructure market. New business models are also urgently needed to accelerate the future development of the public charging infrastructure.
Social cognitive impairments are common, detectable across a wide range of tasks, and appear to play a key role in explaining poor outcome in schizophrenia and related psychotic disorders. However, little is known about the underlying factor structure of social cognition in people with psychotic disorders due to a lack of exploratory factor analyses using a relatively comprehensive social cognitive assessment battery. In a sample of 85 outpatients with psychosis, we examined the factor structure and clinical/functional correlates of eight indexes derived from five social cognition tasks that span the domains of emotional processing, social perception, attributional style, and Theory of Mind. Exploratory factor analysis revealed three factors with relatively low inter-correlations that explained a total of 54% of the variance: (1) Hostile attributional style, (2) Lower-level social cue detection, and (3) Higher-level inferential and regulatory processes. None of the factors showed significant correlations with negative symptoms. Factor 1 significantly correlated with clinical symptoms (positive, depression-anxiety, agitation) but not functional outcome, whereas Factors 2 and 3 significantly correlated with functional outcome (functional capacity and real-world social and work functioning) but not clinical symptoms. Furthermore, Factor 2 accounted for unique incremental variance in functional capacity, above and beyond non-social neurocognition (measured with MATRICS Consensus Cognitive Battery) and negative symptoms. Results suggest that multiple separable dimensions of social cognition can be identified in psychosis, and these factors show distinct patterns of correlation with clinical features and functional outcome.
Lithium-ion cells are presently being considered for use in a wide range of aerospace applications. Cells for these aerospace applications, such as F-16 and JSF aircraft, are required to operate at rates up to 15C and at temperatures from −40 to 71°C. To address these requirements, a series of experiments has been undertaken to empirically determine those factors that limit performance. The first experiment compares three different electrode weight loadings and two different anode particle sizes. A chemistry identified from this experiment was able to increase room temperature rate capability by >500%. Pulse discharge rates as high as 70C and continuous discharge rates of 20C were demonstrated. Furthermore, cell performance of 1C at −40°C and 4C at −30°C has been demonstrated. A second experiment evaluated the use of non-solid/electrolyte interface (SEI) forming conductive diluents in the anode. This experiment did not identify any advantages to the conductive diluent at temperatures above −20°C. However, at a discharge rate of 1C at −40°C, the group with the highest level of diluent offers 300% more capacity than the baseline experimental group with no non-SEI forming diluent.
As a high-theoretical-capacity (782mA hg-1), low-cost and low-toxicity material, SnO2 has attracted intense interest for use as an anode electrode for lithium-ion batteries (LIBs). Despite intensive study, the practical use of SnO2-based anodes is hindered by their poor capacity retention and low rate capacity resulting from their large specific-volume changes and kinetic limitations in ion/electron transfer during the lithium ion insertion/extraction process. Improving the performance of SnO2-based electrodes has become one of the most popular scientific and industrial efforts. Herein, we present a type of SnO2-graphene composite anode in which SnO2 nanoparticles are uniformly anchored on both sides of vertically aligned graphene nanosheets (SnO2-VAGN-SnO2). The VAGNs sandwiched by the nanoparticles can supply rapid ion and electron transport pathways for Li+ and e-. Such integrated electrodes exhibit high specific capacity and excellent cycling stability, even at high current densities. The cells can cycle more than 5,000 times and retain a reversible capacity of 210mA h g-1 at 9 A g-1. A high current density of up to 20 A g-1 is achieved, and the power and energy density can reach 1576.75W kg-1 and 110.14 Wh kg-1, respectively. These performances indicate that the composite could offer the advantages of both LIBs (high energy density) and supercapacitors (high power density).
We investigate the relationship between building energy efficiency and the probability of mortgage default. To this end, we construct a novel panel data set by combining Dutch loan-level mortgage information with provisional building energy ratings provided by the Netherlands Enterprise Agency. Using the logit regression and the extended Cox model, we find that building energy efficiency is associated with a lower probability of mortgage default. There are three possible channels that might drive the results: (i) personal borrower characteristics captured by the choice of an energy-efficient building, (ii) improvements in building performance that could help to free-up the borrower’s disposable income, and (iii) improvements in dwelling value that lower the loan-to-value ratio. We address all three channels. In particular, we find that the default rate is lower for borrowers with less disposable income. The results hold for a battery of robustness checks. This suggests that the energy efficiency ratings complement borrowers’ credit information and that a lender using information from both sources can make superior lending decisions than a lender using only traditional credit information. These aspects are not only crucial for shaping future energy policy, but also have implications for the risk management of European financial institutions.
Mercury-bearing material has been placed in municipal landfills from a wide array of sources including fluorescent lights, batteries, electrical switches, thermometers, and general waste. Despite its known volatility, persistence, and toxicity in the environment, the fate of mercury in landfills has not been widely studied. The nature of landfills designed to reduce waste through generation of methane by anaerobic bacteria suggests the possibility that these systems might also serve as bioreactors for the production of methylated mercury compounds. The toxicity of such species mandates the need to determine if they are emitted in municipal landfill gas (LFG). In a previous study, we had measured levels of total gaseous mercury (TGM) in LFG in the μg/m3 range in two Florida landfills, and elevated levels of monomethyl mercury (MMM) were identified in LFG condensate, suggesting the possible existence of gaseous organic Hg compounds in LFG. In the current study, we measured TGM, Hg0, and methylated mercury compounds directly in LFG from another Florida landfill. Again, TGM was in the μg/m3 range, MMM was found in condensate, and this time we positively identified dimethyl mercury (DMM) in the LGF in the ng/m3 range. These results identify landfills as a possible anthropogenic source of DMM emissions to air, and may help explain the reports of MMM in continental rainfall.
Poor rate capability and cycling performance are the major barriers to the application of lithium rich layered oxides as the next generation cathodes for lithium-ion batteries. In this paper, a novel tactics is applied to enhance the rate property and low temperature performance of lithium rich layered oxides materials by using graphene and multi-walled carbon nanotubes as the building blocks to form a hybrid 3D conductive network in the synthesized composites. Spray pyrolysis method is employed to obtain the target material. The hybrid 3D conductive network can decrease the reaction overpotential greatly, as well as reduce the cell resistance and enhance the lithium ion transportation in the bulk material, which are confirmed by cyclic voltammetry measurement and electrochemical impedance spectroscopy. The conductivity of the obtained composite is so high that no additional conductive agent is needed in the fabrication of electrodes. Our investigation further demonstrates that the conducting framework can efficiently alleviate the polarization of pristine lithium rich layered oxides material, leading to an outstanding enhancement in rate capability, low temperature performance and cycling stability.