Synthesis, Self-Aggregation, Surface Characteristics, Electrochemical Property, Micelle Size, and Antimicrobial Activity of a Halogen-Free Picoline-Based Surface-Active Ionic Liquid.

We present a new approach toward the design of a halogen-free picoline-based surface-active ionic liquid (SAIL) (1-octyl-4-methyl pyridinium dodecyl sulfate) [C8γPic]DS consisting of long dodecyl sulfate (DS) as an anion. The surface properties, micellization behavior, and antimicrobial activity in an aqueous solution were investigated using tensiometry, conductometry, and ultraviolet (UV) spectroscopy. Incorporating the DS group in SAIL leads to lower critical micellar concentration (CMC) and enhanced adsorption at the air/water interface of the functionalized ionic liquid compared to the C8-alkyl chain-substituted pyridine ionic liquids. The antimicrobial activity was evaluated against a representative Gram-negative and Gram-positive bacteria panel. Antibacterial activities increased with the alkyl chain length, C8 being the homologous most effective antimicrobial agent. The micelle size of [C8γPic]DS was determined by the dynamic light-scattering (DLS) study. Cyclic voltammetry (CV) measurements have been employed to evaluate the interaction between the SAIL micelle and working electrode, diffusion coefficient, and micelle size of the SAIL solution. The diffusion coefficient explored the correlation of surface properties and the antimicrobial activity of [C8γPic]DS. This halogen-free SAIL is the future of wetting agents and emulsion studies in agriculture due to its small micelle size and surface characteristics.

Real-time photovoltaic parameters assessment of carbon quantum dots showing strong blue emission.

The need for replacing conventional sources of energy with renewable ones has been on a swift rise since the last couple of decades. In this context, the progress in third-generation solar cells has taken a good leap in the last couple of years with increasing prospects of high efficiency, stability, and lifetime. Quite recently, a new form of carbon has been discovered accidentally in the form of carbon quantum dots (C QD), which is being pursued actively owing to its chemical stability and luminescent properties. In the current work, we report highly luminescent C QD prepared via a simple hydrothermal route. Transmission electron microscopy revealed an average particle size of 3.4 nm. The prepared C QD were used in a co-sensitized solar cell, where an improvement in the device characteristics was observed. The enhancement in the device characteristics is supported by impedance and electron life-time analysis. Further, the time-dependent analysis of the current and voltage revealed the functioning of the solar cell in real-time condition.

Synergistic 2D MoSe2@WSe2 nanohybrid heterostructure toward superior hydrogen evolution and flexible supercapacitor.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) heterostructure is a new age strategy to achieve high electrocatalytic activity and ion storage capacity. The less complex and cost-effective applicability of the large-area TMDC heterostructure (HS) for energy applications require more research. Herein, we report the MoSe2@WSe2 nanohybrid HS electrocatalyst prepared using liquid exfoliated nanocrystals, followed by direct electrophoretic deposition (EPD). The improved catalytic activity is attributed to the exposure of catalytic active sites on the edge of nanocrystals after liquid exfoliation and the synergistic effect arises at HS interfaces between the MoSe2 and WSe2 nanocrystals. As predicted, the HS catalyst achieves a lower overpotential of 158 mV, a smaller Tafel slope of 46 mV dec-1 for a current density of 10 mA cm-2, and is stable for a long time. The flexible symmetric supercapacitor (FSSC) based on the HS catalyst demonstrates the excellent specific capacitance (Csp) of 401 F g-1 at 1 A g-1, 97.20% capacitance retention after 5000 cycles and high flexible stability over 1000 bending cycles. This work presents a less complex and solution-processed efficient catalyst for future electrochemical energy applications.

Hierarchically Porous Metal-Organic Gel Hosting Catholyte for Limiting Iodine Diffusion and Self-Discharge Control in Sustainable Aqueous Zinc-I2 Batteries.

Rechargeable aqueous zinc-iodine batteries (AZIBs) represent excellent zinc-iodine redox chemistry and emerged as a promising aspirant due to their high safety, low cost, ease of fabrication, and high energy density. Nevertheless, the high-dissolution-induced iodide diffusion toward the zinc anode brings the self-discharge, which governs the capacity fading and poor cycling life of the battery. Herein, a multipurpose sponge-like porous matrix of a metal-organic gel to host a substantial amount of an iodine-based catholyte and uniform distribution of iodine with controlled iodide diffusion is introduced. Limiting the iodine diffusion due to increased viscosity provides superior electrochemical performance of this promising cathode for solid-state AZIBs. As a result, AZIBs delivering high performance and long-term stability are fabricated with a capacity of 184.9 mA h g-1 with a superior capacity retention of 95.8% even after 1500 cycles at 1 C rate. The unique concept of self-discharge protection is successfully evaluated. Prototype flexible band-aid-type AZIBs were fabricated, which delivered 166.4 mA h g-1 capacity in the bending state, and applied to real-scale wearable applications.

Immobilization of Agrobacterium tumefaciensd-psicose 3-epimerase onto titanium dioxide for bioconversion of rare sugar.

d-Psicose (d-ribo-2-hexulose or d-allulose) is the Carbon-3 epimer of d-fructose sugar and considered as an unnatural (rare) sugar found in low amount in nature. It has about 70% of the relative sweetness but 0.3% of the energy of sucrose, which is suggested as the most suitable sucrose substitute for food additives. Enzymatic biosynthesis using ketose 3-epimerases is a necessary procedure for the production of d-Psicose from d-fructose. However, significant drawbacks in the application of ketose 3-epimerases at industrial scale observe lower thermal stability as well as bioconversion efficiency, reusability and recovery of the enzyme. We have attempted immobilization of ketose 3-epimerases from Agrobacterium tumefaciens (agtu) d-psicose 3-epimerase (DPEase) on titanium dioxide. Further, Scanning electron microscopy (SEM), inverted microscopy, Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy showed that the enzyme was successfully immobilized on the titanium dioxide (TiO2) surface. Titanium dioxide immobilized agtu-DPEase (TiO2-agtu-DPEase) shows pH optima at 6.0 and 60 °C as a higher working temperature. TiO2-agtu-DPEase showed a half-life of 180 min at 60 °C, which is higher as compared to Agrobacterium tumefaciens (agtu) DPEase (3.99 min at 50 °C). At equilibrium, 36:64 (D-psicose: d-fructose), the bioconversion efficiency was accounted for titanium dioxide immobilized DPEase, which is higher than the agtu-DPEase. Titanium dioxide immobilized DPEase showed bioconversion efficiency up to 9 cycles of reusability.

Above 800 mV Open-Circuit Voltage in Solid-State Photovoltaic Devices Using Phosphonium Cation-Based Solid Ionic Conductors.

Here, we report phosphonium-based two solid ionic conductors (SICs), namely, triphenylphosphonium methyl iodide (TPPMeI) and triphenylphosphonium iodide (TPPHI), prepared via simple protocol at room temperature and were used as an electrolyte for solid-state photovoltaic devices (ss-PVDs) with open-circuit voltage (Voc) exceeding 800 mV. Here, for the first time, detailed electrochemical investigations with theoretical aspects of phosphonium electrolytes were conducted, where PVDs prepared from these SICs, TPPMeI, showed the highest power conversion efficiency (PCE) of 4.08% with a Voc of 810 mV. However, this performance was further improved up to the PCE of 6.71% with 824 mV of Voc in the presence of additives like LiI and tert-butyl pyridine. This work leads to find the best alternative of liquid and quaternary ammonium ion-based electrolytes that suffers from problems like lower Voc (<800 mV) and stability, leakage, etc.

Electrophoretically Deposited MoSe2/WSe2 Heterojunction from Ultrasonically Exfoliated Nanocrystals for Enhanced Electrochemical Photoresponse.

The solar response ability and low-cost fabrication of the photoanode are important factors for the effective output of the photoelectrochemical system. Modification of the photoanode by which its ability to absorb irradiation can be manipulated has gained tremendous attention. Here, we demonstrated the MoSe2, WSe2, and MoSe2/WSe2 nanocrystal thin films prepared by the liquid-phase exfoliated and electrophoresis methods. Atomic force microscopy and high-resolution transmission electron microscopy show that the liquid exfoliated nanocrystals have a few layered dimensions with good crystallinity. Scanning electron microscopy demonstrated uniform distribution and randomly oriented nanocrystals, having a homogeneous shape and size. X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectra confirm the equal contribution of MoSe2 and WSe2 nanocrystals in the formation of the MoSe2/WSe2 heterojunction. Because of superior absorption of MoSe2/WSe2 heterojunction in the visible region and type-II heterojunction band alignment, in situ measurement of heterojunction electrode shows almost 1.5 times incident photo-to-current conversion efficiency and photoresponsivity in comparison to individual material electrodes. Our result clearly indicates the influence of heterojunction formation between liquid exfoliated nanocrystals on effective separation of photogenerated exciton and enhances charge carrier transfer, which leads to the improvement in photoelectrochemical performance. Liquid exfoliated nanosheet-based heterojunction is attractive as efficient photoanodes for the photoelectrochemical systems.

A Smart Flexible Solid State Photovoltaic Device with Interfacial Cooling Recovery Feature through Thermoreversible Polymer Gel Electrolyte.

Quasi-solid-state dye-sensitized solar cells (DSSCs) fabricated with lightweight flexible substrates have a great potential in wearable electronic devices for in situ powering. However, the poor lifespan of these DSSCs limits their practical application. Strong mechanical stresses involved in practical applications cause breakage of the electrode/electrolyte interface in the DSSCs greatly affecting their performance and lifetime. Here, a mechanically robust, low-cost, long-lasting, and environment-friendly quasi-solid-state DSSC using a smart thermoreversible water-based polymer gel electrolyte with self-healing characteristics at a low temperature (below 0 °C) is demonstrated. When the performance of the flexible DSSC is hindered by strong mechanical stresses (i.e., from multiple bending/twisting/shrinking actions), a simple cooling treatment can regenerate the electrode/electrolyte interface and recover the performance close to the initial level. A performance recovery as high as 94% is proven possible even after 300 cycles of 90° bending. To the best of our knowledge, this is the first aqueous DSSC device with self-healing behavior, using a smart thermoreversible polymer gel electrolyte, which provides a new perspective in flexible wearable solid-state photovoltaic devices.

Iodine induced 1-D lamellar self assembly in organic ionic crystals for solid state dye sensitized solar cells.

A novel saturated heterocyclic organic ionic crystal, piperidinium iodide (PiHI), is synthesized by a facile route and applied as a solid electrolyte in Dye Sensitized Solar Cells (ss-DSSCs). Upon addition of a small quantity of iodine, PiHI self-assembles into a 1D lamellar micro crystalline structure that shows anisotropic conductivity. The two-component PiHI was characterized by using electrochemical impedance spectroscopy, cyclic voltammetry, steady state voltammetry, FT-IR, and Raman spectroscopy. Wide angle X-ray diffraction (XRD) measurement confirms the presence of long range 1D lamellar channels that pave the way for the diffusion of the redox couple I-/I3- and exhibit high anisotropic conductivity. The ionic conductivity of 1D PiHI (with I2) aligned perpendicular to the electrode, σ⊥ (15.46 mS cm-1), is 1.5 times higher than that aligned parallel to the electrode σ∥ = 10.32 mS cm-1. The ss-DSSC devices with these self-assembled ordered ionic crystals with a carbazole based sensitizer (SK1) achieved a power conversion efficiency (PCE) of 4.2% and 5.2% for ∥al and ⊥ar arrangement, respectively. The reported PCEs are better than that obtained from a classical liquid electrolyte with SK1 sensitizers. The electron kinetics at various interfaces of ss-DSSC devices was evaluated using Electrochemical Impedance Spectroscopy (EIS) measurements. The presence of a saturated cyclic structure promotes close packing through H-bonding and electrostatic interactions, which make ss-DSSC devices more stable up to 600 h under illumination of 1 sun.

Effect of fluorine substitution and position on phenylene spacer in carbazole based organic sensitizers for dye sensitized solar cells.

The preparation of a series of organic dyes having a carbazole donor, cyanoacrylic acid as an acceptor, and phenylene ring as a spacer with the difference in the positions of fluorine substitution is reported. Due to its unique properties of small size and high electronegativity, fluorine is now being extensively used to control the optoelectronic properties of organic conjugated materials. In this study, the results revealed that the specific position and number of fluorine substitution were very crucial to control the optical as well as the electrochemical properties of organic dyes. It was found that fluorine substitution led to a redshift in the absorption spectra of the dyes and reduced the band gap. The injection rate of photoexcited electrons was measured using time-resolved photoluminescence and the o-fluoro substituted dye MA1F-o showed the best electron injection dynamics. As a result of broad absorption and high electron injection rate, the dye MA1F-o outperformed other dyes with a power conversion efficiency of 4.02% (Jsc = 8.3 mA cm-2, Voc = 0.75 V and FF = 0.64). The non-fluorinated dye MA0F exhibited a power conversion efficiency of 3.23% (Jsc = 6.8, Voc = 0.72 and FF = 0.67). The dye MA1F-m exhibited the least molar absorption coefficient and a lower power conversion efficiency because of the meta inductive effect.

A Smart Flexible Zinc Battery with Cooling Recovery Ability.

Flexible batteries are essential for wearable electronic devices. To meet practical applications, they need to be mechanically robust and stable. However, strong or multiple bending may sever the interfacial contact between electrode and electrolyte, causing capacity fading or even battery failure. Herein we present a new cooling-recovery concept for flexible batteries, which involves a temperature-sensitive sol-gel transition behavior of the thermoreversible polymer hydrogel electrolyte. Once a battery has suffered from strong mechanical stresses, a simple cooling process can refresh the electrode-electrolyte interface. The energy-storage capability can be recovered with a healing efficiency higher than 98 %. It is believed that this study not only offers new valuable insights, but also opens up new perspectives to develop functional wearable devices.

Design, synthesis and DSSC performance of o-fluorine substituted phenylene spacer sensitizers: effect of TiO2 thickness variation.

The influence of TiO2 film thickness on the performance of DSSCs with a new series of dyes having ortho-fluorine substituted phenyl spacers and different donor moieties is reported. Optical, electrochemical, molecular orbital and photovoltaic properties were studied by varying the TiO2 thickness (9 and 12 µm) using these dyes. The thickness variation of TiO2 films had a significant effect on the open circuit voltage (Voc), short circuit current (Jsc) and efficiency. The Jsc and Voc of dye 1b with a TiO2 film thickness of 12 µm (8.91 mA cm-2 and 0.63 V) were larger than those of the 9 µm film thickness device (8.40 mA cm-2 and 0.57 V). This could be due to the variation in the thickness of the TiO2 film. However, at an optimized thickness of the TiO2 film (12 µm), 1b exhibited the highest power conversion efficiency (η) of 4.0% (average 3.6%). This highest efficiency value for 1b from 3.3% to 4.0% without using any co-absorbents was solely based on changing the thickness of the TiO2 film. In addition 1b had a planar structure, whereas dyes 2b and 3b had three and two dimensional structures. The optimized geometry calculation of o-fluoro phenyl π-spacer dyes was ascertained by density functional theory (DFT) using the B3LYP/631G(d,p) basis set. These results reveal that dye 1b has higher efficiency due to the deeper HOMO level and it exhibited better charge transfer from donor to acceptor, compared to the other dyes.

Humic Acid as a Sensitizer in Highly Stable Dye Solar Cells: Energy from an Abundant Natural Polymer Soil Component.

Humic acid (HA), a natural polymer and soil component, was explored as a photosensitizer in dye-sensitized solar cells (DSSCs). Photophysical and electrochemical properties show that HA covers a broad visible range of the electromagnetic spectrum and exhibits a quasi-reversible nature in cyclic voltammetry (CV). Because of its abundant functionalities, HA was able to bind onto the nano-titania surface and possessed good thermal stability. HA was employed as a sensitizer in DSSCs and characterized by various photovoltaic techniques such as I-V, incident-photo-to-current conversion efficiency (IPCE), electrochemical impedance spectroscopy (EIS), and Tafel polarization. The HA-based device shows a power conversion efficiency (PCE) of 1.4% under 1 sun illumination. The device performance was enhanced when a coadsorbent, chenodeoxycholic acid (CDCA), along with HA was used and displayed 2.4% PCE under 0.5 sun illumination. The DSSCs employing HA with CDCA showed excellent stability up to 1000 h. The reported efficiency of devices with HA is better than that of devices with all natural sensitizers reported so far.

Microbial Selenium Nanoparticles (SeNPs) and Their Application as a Sensitive Hydrogen Peroxide Biosensor.

The cell-free extract, a crude enzyme (cytosolic and membrane fraction) obtained from an environmental isolate, Bacillus pumilus sp. BAB-3706 worked as excellent in reducing as well as stabilizing agent and facilitated the formation of stable colloidal selenium nanoparticles (SeNPs). Resulting nanoparticles were characterized using UV-vis spectrophotometer, TEM, EDAX, FT-IR and XRD, respectively. A working electrode was modified by coating the surface of indium tin oxide (ITO) with colloidal SeNPs. Successive additions of H2O2 (100 to 600 µM) in conventional three electrodes system, cyclic voltammeter with potential scan rate 25.0 mV/s, in 0.1 M phosphate buffer solution (PBS) yielded increase in current. A perpetual amperometric response at fixed potential (-1.0 V) and at selected time interval of 100 s showed different magnitude of current at every addition of H2O2. The linear range of detection of H2O2 was from 5 to 600 mM (R(2) = 0.9965), while the calculated limit of detection was found to be 3.00 µM. The current study suggested that microbial SeNPs can be used for fabrication of low cost, sensitive H2O2 biosensor.

Influence of N-alkylpyridinium halide based ionic liquids on micellization of P123 in aqueous solutions: a SANS, DLS, and NMR study.

The isotropic micellar state of Pluronic P123 in the presence and absence of N-alkylpyridinium halide ionic liquids (ILs) is investigated using SANS, DLS, and (1)H NMR studies. The micellar structural parameters are obtained as a function of variation in alkyl chain length, anions, and concentrations of ILs by fitting the SANS scattering data with a model composed of core-shell form factor and a hard sphere structure factor of interaction. Addition of ILs decreases the micellar core, aggregation number, and hard sphere radius of P123 micelles. From quantitative analysis, we determined the amount of solvent (D2O + IL) present inside the core and the core-shell interface along with cationic head groups. This is further supported by monitoring interaction between ILs and polymer micelle using (1)H NMR spectroscopy. The results are discussed and explained as a function of concentration of C8PyCl, alkyl chain length, and anions of N-alkylpyridinium halides.

Highly efficient one-dimensional ZnO nanowire-based dye-sensitized solar cell using a metal-free, D-π-A-type, carbazole derivative with more than 5% power conversion.

Hydrothermally grown one-dimensional ZnO nanowire (1D ZnO NW) and a newly synthesized metal-free, D-π-A type, carbazole dye (SK1) sensitizer-based photovoltaic device with a power conversion efficiency (PCE) of more than 5% have been demonstrated by employing the cobalt tris(2,2'-bipyridyl) redox shuttle. A short-circuit current density (Jsc) of ∼12.0 mA/cm(2), an open-circuit voltage (Voc) of ∼719 mV, and a fill factor (FF) of ∼65% have been afforded by the 1D ZnO NW-based dye-sensitized solar cell (DSSC) incorporating [Co(bpy)3](3+/2+) complex as the one-electron redox mediator. In contrast, the identical DSSC with traditional I3(-)/I(-) electrolyte has shown a Jsc ≈ 12.2 mA/cm(2), a Voc ≈ 629 mV, and a FF ≈ 62%, yielding a PCE of ∼4.7%. The persuasive role of the inherent superior electron transport property of 1D ZnO NWs in enhancing the device efficiency is evidenced from the impoverished performance of the DSSCs with photoanodes fabricated using ZnO nanoparticles (NPs). The DSSCs having ZnO NP-based photoanodes have achieved the PCEs of ∼3.6% and ∼3.2% using cobalt- and iodine-based redox electrolytes, respectively. The electronic interactions between the SK1 sensitizer and ZnO (NWs and NPs) to induce the photogenerated charge transfer from SK1 to the conduction band (CB) of ZnO are evidenced from the significant quenching of photoluminescence and exciton lifetime decay of SK1, when it is anchored onto the ZnO architectures. The energetics of the SK1 dye molecule are estimated by combining the spectroscopic and electrochemical techniques. The electronic distributions of SK1 dye molecule in its HOMO and LUMO energy levels are interpreted using density functional theory (DFT)-based calculations. The electron donor-π linker-acceptor (D-π-A) configuration of SK1 dye provides an intramolecular charge transfer within the molecule, prompting the electron migration from the carbazole donor to cyanoacrylic acceptor moiety via the oligo-phenylenevinylene linker group. The D-π-A-mediated electron movement witnesses the favorable photoexcited electron transfer from the LUMO of SK1 dye to the CB of ZnO through the carboxyl anchoring group.

Aggregation behavior of pyridinium based ionic liquids in water--surface tension, 1H NMR chemical shifts, SANS and SAXS measurements.

The aggregation behavior of short alkyl chain ionic liquids (ILs), namely 1-butyl, or 1-hexyl or 1-octylpyridinium and 1-octyl-2-, or -3-, or -4-methylpyridinium chlorides, in water has been assessed using surface tension, electrical conductance, (1)H NMR, small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS) measurements. Critical aggregation concentrations (CACs), adsorption (at air/water interface) and thermodynamic parameters of aggregation have been reported. The values of CAC and area per adsorbed molecule decrease with the number of carbon atoms in the alkyl chain. The aggregation process is driven by both favorable enthalpy and entropy contributions. An attempt was made to examine the morphological features of the aggregates in water using SANS and SAXS methods. SANS and SAXS curves displayed diffuse structural peaks that could not be model fitted, and therefore, we calculated the mean aggregation numbers from the Q(max) assuming that IL molecules typically order into cubic type clusters.

Ionic conductivity through thermoresponsive polymer gel: ordering matters.

Thermoreversible polymer gel has been prepared using PEO-PPO-PEO block copolymer (Pluronic F77) which self-assembles into different microcrystalline phases like cubic, 2D-hexagonal, and lamellar. Addition of electrolyte (LiI/I(2)) converts the gel into a polymer gel electrolyte (PGE) which exhibits microphase-dependent ionic conductivity. The crystalline phases have been identified by SAXS as a function of the polymer concentration. It is found that the optimum value for the ionic conductivity (≈1 × 10(-3) S x cm(-1)) is achieved in the Im3m phase due to faster diffusion of ions through the 3D-interconnected micellar nanochannels. This fact is further supported by FTIR study, ionic transference number, and diffusion coefficient measurements.