Self-Assembled Conjugated Coordination Polymer Nanorings: Role of Morphology and Redox Sites for the Alkaline Electrocatalytic Oxygen Evolution Reaction.

Electrocatalytic water splitting provides a sustainable method for storing intermittent energies, such as solar energy and wind, in the form of hydrogen fuel. However, the oxygen evolution reaction (OER), constituting the other half-cell reaction, is often considered the bottleneck in overall water splitting due to its slow kinetics. Therefore, it is crucial to develop efficient, cost-effective, and robust OER catalysts to enhance the water-splitting process. Transition-metal-based coordination polymers (CPs) serve as promising electrocatalysts due to their diverse chemical architectures paired with redox-active metal centers. Despite their potential, the rational use of CPs has faced obstacles including a lack of insights into their catalytic mechanisms, low conductivity, and morphology issues. Consequently, achieving success in this field requires the rational design of ligands and topological networks with the desired electronic structure. This study delves into the design and synthesis of three novel conjugated coordination polymers (CCPs) by leveraging the full conjugation of terpyridine-attached flexible tetraphenylethylene units as electron-rich linkers with various redox-active metal centers [Co(II), Ni(II), and Zn(II)]. The self-assembly process is tuned for each CCP, resulting in two distinct morphologies: nanosheets and nanorings. The electrocatalytic OER performance efficiency is then correlated with factors such as the nanostructure morphology and redox-active metal centers in alkaline electrolytes. Notably, among the three morphologies studied, nanorings for each CCP exhibit a superior OER activity. Co(II)-integrated CCPs demonstrate a higher activity between the redox-active metal centers. Specifically, the Co(II) nanoring morphology displays exceptional catalytic activity for OER, with a lower overpotential of 347 mV at a current density of 10 mA cm-2 and small Tafel slopes of 115 mV dec-1. The long-term durability is demonstrated for at least 24 h at 1.57 V vs RHE during water splitting. This is presumably the first proof that links the importance of nanostructure morphologies to redox-active metal centers in improving the OER activity, and it may have implications for other transdisciplinary energy-related applications.

Plastic Chip Electrode: An Emerging Multipurpose Electrode Platform.

The properties of electrodes play a crucial role in the processes occurring on them. Therefore, a variety of materials have been tried as electrodes. Carbon composite materials are among the most admired ones. Use of composites as electrode material dates back to the mid of the last century when polymer-carbon composites were tried as general-purpose electrode platforms and epoxy impregnated graphite paste/ solid electrodes were tried in polarography. Later the composite electrodes have seen several phases of development. Plastic Chip Electrode (PCE) is a class of polymer composite electrode developed by our group. This monographic review gives a bird's eye account of polymer composite electrodes and appurtenant work, followed by elaborating on various aspects and state-of-the-art plastic chip electrodes.

A Highly Sensitive Luminescent Upconversion Nanosensor for Turn-On Detection of As3.

A luminescent nanoprobe (NP), MnO2-modified Er3+/Yb3+-codoped Ag2MoO4 upconversion nanoparticles (UCNPs; cod-AMO-3/MnO2), was constructed for rapid, sensitive, and selective "turn-on" detection of trace As3+. Herein, two kinds of luminescent NPs were developed based on luminescence resonance energy transfer (LRET) between cod-AMO-3 as the energy donor and MnO2 as the energy acceptor. By using MnO2 as the matrix in cod-AMO-3/MnO2 fluorometric assay, the upconversion luminescence (UCL) intensity (IUCL) of the cod-AMO-3 probe was quenched significantly through LRET, illustrating MnO2 as an efficient quencher for UCL. With the addition of As3+, a stable bidentate binuclear (BB) corner-sharing bridged complex (As5+-MnO2) was probably formed, which alters the surface of the upconversion NP, leading to gradual separation between UCNPs and MnO2 and subsequent recovery of IUCL. Interestingly, it possessed superior sensitivity, reaction kinetics, and also high selectivity toward As3+ in aqueous solution. Our optimized cod-AMO-3/MnO2 nanocomposite (NComp) demonstrated a linear range of 0-150 ppb and an ultrasensitive detection limit of 0.028 ppb for As3+, which is extremely below the regulatory level, signifying the promising practical usage of this system. To the best of our knowledge, such a surface-modified Ln3+-codoped Ag-based nanosensor being applied for As3+ detection probably has not been reported yet, and it is rather unexplored. In a nutshell, the ability to monitor the As3+ concentration may enable the rational design of a convenient platform for a diverse range of environmental monitoring applications.

Tetraphenylporphyrin Decorated Bi2MoO6 Nanocomposite: Its Twin Affinity of Oxygen Reduction Reaction and Electrochemical Detection of 4-Nitrophenol.

A selective electrode for oxygen reduction reaction (ORR) and electrocatalytic reduction of 4-nitrophenol (p-NP) was fabricated on a glassy carbon electrode using organic-inorganic Bi2MoO6/H2TPP nanocomposites with different weight percentages of tetraphenylporphyrin, synthesized by the solvothermal process. Materials thus synthesized were characterized through UV-Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) analysis. The electrocatalytic performance of the modified electrode toward ORR in the 0.1 M KOH solution, the onset potential Eonset (0.942 V), E1/2 (0.704 V) vs RHE, Jd (-5.545 mA cm-2), and n = 4 physicochemical parameters were well appreciable. It exhibits good catalytic activity toward ORR through a four-electron pathway with excellent stability and high active site density, and thus, the in situ Porphy-decorated metal oxide system facilitates the electron transport process. High selectivity and efficacy for the oxygen reduction reaction (ORR) are a significant measure for several energy-converting applications. The decorated electrode, glassy carbon electrode (GCE)/Bi2MoO6/3 wt % Porphy, serves as an electrochemical sensor that exhibited good sensitivity (0.4683 µAµM-1 cm-2), good reproducibility, a low detection limit (0.0940 µM), and long-term stability in the aqueous phase without any appreciable effect in the presence of some common organic and inorganic interferences for the detection of p-NP in a linear concentration range of 0.5-350 µM. Therefore, the material performs as an effective electrode for both the ORR and the electrocatalytic reduction of p-NP with real matrix samples at room conditions.

Photosensitive electrocatalysts based on Ni-WS2nanohybrids for hydrogen evolution reaction.

Efficient hydrogen evolution by electrolysis plays an indispensable role for hydrogen fuel generation in green energy devices. In order to implement high-performance electrocatalytic activity, it is usually necessary to design economically viable, effective and stable electrocatalysts to reduce activation potential barriers. Herein, we report the photosensitive Ni-WS2nanohybrids for enhanced electrocatalytic hydrogen evolution reaction (HER). Optimisation of chemical composition in catalysts has resulted in the rapid water electrolysis which was further promoted by illumination of 532 nm light. Obvious HER has been achieved at over potential of as low as -210 mV versus RHE without and -190 mV versus RHE (at -10 mA cm-2) with illumination. Being a photosensitive electrocatalysts, Ni-WS2Nanohybrids have demonstrated stable time-resolved photoresponse with photocurrent of 12.7 mA cm-2at -250 mV V versus RHE as well as self-powered photodetection with current 0.68 mA cm-2. Finally, HER with improvement under visible light illumination has shown considerable development in clean energy generation by using renewable energy sources.

Picomolar detection of retinol binding protein 4 for early management of type II diabetes.

Type (II) diabetes is one of the major threats to mankind as it causes insulin resistance in human body and Retinol Binding Protein 4 (RBP4) is currently considered as a potential biomarker for early management of this disease. Hence a low-level detection of RBP4 is a very important task and for this purpose, a novel RBP4 biosensor has been developed using homemade plastic chip electrodes (PCEs) as a platform for self-assembled monolayer (SAM) of 4-ATP and further functionalization with glutaraldehyde. Anti RBP4 is used as biorecognition species and electrochemical impedance spectroscopy has been performed to detect different RBP4 concentrations plotted against charge transfer resistance. A wide concentration range from 100 fg/mL to 1 ng/mL has been tested and a low limit of detection (LOD) of 100 fg/mL has been achieved. This is the first report for fabrication of electrochemical biosensor of RBP4 using Ag-Ab interaction having such low LOD. The sensor is characterized by various physico-chemical techniques. Excellent reproducibility and quick measurement make this biosensor extremely useful for the biomedical industry.

Amperometric Glucose Sensing at Nanomolar Level Using MOF-Encapsulated TiO2 Platform.

A new synthetic approach is established where both TiO2 nanoparticles and glucose oxidase (GO x ) are together encapsulated into the cavity of ZIF-8 metal-organic framework (MOF) to fabricate a mediator-free glucose sensor in aqueous media. ZIF-8 possesses high stability both physically and chemically. Moreover, its large surface area and tunable cavity size are supportive to encapsulate both nanoparticles (TiO2) and enzymes (GO x ). The as-synthesized nanocomposite is methodically characterized by various advanced analytical techniques, which suggests that TiO2 is uniformly distributed within the cavity of ZIF-8 MOF. High surface area and double-layer capacitance of nanostructured TiO2 jointly enhance the catalytic biosensor activity. The as-synthesized nanocomposite exhibits commendable stability and is able to detect low-level concentration (80 nM) of glucose in aqueous media by utilizing very low concentration of GO x (62 µg in 1 mL).

Correlating growth mechanism and morphology in Cu-TCNQ organometallic complex: A microscopic study.

The structure-property correlation in the Cu-TCNQ organometallic complex is very important for explaining its unusual electrical, optical and magnetic properties. Consequently several morphological studies and their correlation with the properties of these materials can be found in the literature, although no systematic study of various morphologies with growth conditions and their correlation has been reported to the best of our knowledge. Therefore in this manuscript the interconversion of various morphologies is reported using electron and probe microscopies. A conventional Cu TEM grid acted as the copper source to form a Cu-TCNQ complex and the complex, which formed at the surface of the TEM grid. The complex thus prepared was characterized by FTIR and Raman spectroscopic techniques. The shifting of ̵-CN from 2221 cm-1 (TCNQ) to 2201 cm-1 indicates formation of a complex and the identical nature of IR spectra in two phases indicates that they are polymorphs. The morphologies of Cu-TCNQ were followed through FE-SEM and TEM studies. Various morphologies such as needle, square tube, platelet etc. were observed as a function of time. A distinct transition from needle to platelet morphology was observed as the complex grew. The conductance of various morphologies in phase-I as well as phase-II were also measured and compared by Spreading Resistance Imaging (SRI) at different bias voltage i.e. 1 V, 3 V and 5 V.

Fabrication of a Cu(II)-Selective Electrode in the Polyvinyl Chloride Matrix Utilizing Mechanochemically Synthesized Rhodamine 6g as an Ionophore.

A Cu(II)-selective electrode has been fabricated by utilizing a mechanochemically synthesized copper-specific ionophore "L" embedded in a poly(vinyl chloride) membrane. 2-Nitrophenyloctylether and sodium tetraphenylborate have been used as a plasticizer and as a solvent mediator, respectively, and found to be enhancing the sensitivity of the fabricated ion-selective electrode (ISE). A range of membranes (S1-S7) with varying compositions were casted and investigated in ISE. Results revealed an excellent Nernstian response of 29.38 ± 0.55 mV/dec for the ISE S6. The fabricated ISE operates well in the pH window 4.0-7.5, and the limit of detection was found to be 5 µM (0.3 ppm). Quick response time (15 s), long shelf-life, and selectivity (on the order of 10-4 and 10-5) over a number of interfering cations enabled S6 promising for real off laboratory sample analysis and can be employed to detect copper ion in various industrial as well as biological and environmental samples. To demonstrate the practical application of these ISE, the Cu concentration in the digested printed circuit board has been estimated using the standard calibration plot. The fabricated ISE has been regenerated through extracting copper by chelating with ethylenediaminetetraacetic acid.

Semi-Interpenetrating Network-Type Cross-Linked Amphoteric Ion-Exchange Membrane Based on Styrene Sulfonate and Vinyl Benzyl Chloride for Vanadium Redox Flow Battery.

Clean energy is the main requirement for human life. Redox flow battery may be an alternative to fossil fuels. An ion-exchange membrane is the heart of the redox flow battery. In the present study, we synthesize semi-interpenetrating cross-linked copolymer amphoteric ion-exchange membranes (AIEMs) with a partially rigid backbone. The styrene sulfonate and vinyl benzyl chloride monomers are used as the cationic and anionic moieties into the AIEMs. Three different types of quaternizing agents are used to convert a primary amine into a quaternary amine group. Here, we avoid the use of the carcinogenic chemical CMME, commonly used for the synthesis of anion-exchange membranes. The prepared membranes exhibit good electrochemical and physicochemical properties with a high acidic stability. The membranes also show moderate water uptake and dimensional change. The ZWMO membrane shows better properties among the AIEMs, with an ionic conductivity of 3.12 × 10-2 S cm-1 and 5.49 water molecules per functional group. The anion and cation-exchange capacities of the ZWMO membranes are calculated to be 1.11 and 0.62 mequiv/g. All AIEMs show good thermal and mechanical stabilities, calculated by differential scanning calorimetry, dynamic mechanical analysis, and universal testing machine analysis. The membranes show low vanadium ion permeability than the commercial membrane Nafion for their use in vanadium redox flow batteries. Further, the AIEMs are applied in redox flow batteries as separators and deliver good results with the charging and discharging phenomena, with 87% voltage efficiency and 91% current efficiency.

Development of high-performance supercapacitor electrode derived from sugar industry spent wash waste.

This study aims at developing supercapacitor materials from sugar and distillery industry wastes, thereby mediating waste disposal problem through reuse. In a two-step process, biomethanated spent wash (BMSW) was acid treated to produce solid waste sludge and waste water with significantly reduced total organic carbon (TOC) and biological oxygen demand (BOD) content. Further, waste sludge was directly calcined in presence of activating agent ZnCl2 in inert atmosphere resulting in high surface area (730-900m2g-1) carbon of unique hexagonal morphology. Present technique resulted in achieving two-faceted target of liquid-solid waste remediation and production of high-performance carbon material. The resulted high surface area carbon was tested in both three and two electrode systems. Electrochemical tests viz. cyclic voltammetry, galvanostatic charge-discharge and impedance measurement were carried out in aqueous KOH electrolyte yielding specific capacitance as high as 120Fg-1, whereas all solid supercapacitor devised using PVA/H3PO4 polyelectrolyte showed stable capacitance of 105Fg-1 at 0.2Ag-1. The presence of transition metal particles and hetero-atoms on carbon surface were confirmed by XPS, EDX and TEM analysis which enhanced the conductivity and imparted pseudocapacitance to some extent into the working electrode. The present study successfully demonstrated production of high-performance electrode material from dirtiest wastewater making process green, sustainable and economically viable.

Enhanced photocatalytic performance of morphologically tuned Bi2S3 NPs in the degradation of organic pollutants under visible light irradiation.

Here in, morphologically tuned Bi2S3 NPs were successfully synthesized from a single-source precursor complex [Bi(ACDA)3] [HACDA=2-aminocyclopentene-1-dithiocarboxylic acid] by decomposing in various solvents using a simple solvothermal method. The as-obtained products were characterized by XRD, TEM, UV-vis spectroscopy and BET surface area measurements. Structural analyses revealed that the as-prepared Bi2S3 NPs can be tuned to different morphologies by varying various solvents and surfactants. The interplay of factors that influenced the size and morphology of the nanomaterials has been studied. Moreover, mastery over the morphology of nanoparticles enables control of their properties and enhancement of their usefulness for a given application. These materials emerged as a highly active visible light-driven photocatalyst towards degradation of methylene blue dye and the efficiencies are dependent on size and surface area of the NPs. In addition, photocatalytic degradation of highly toxic dichlorodiphenyltrichloroethane was studied using synthesized Bi2S3 NPs as catalyst and the rate of degradation has been found to be much better compared to that exhibited by commercial WO3. We believe that this new synthesis approach can be extended to the synthesis of other metal sulfide nanostructures and open new opportunities for device applications.

Ultrasensitive electrochemical immunoassay for surface array protein, a Bacillus anthracis biomarker using Au-Pd nanocrystals loaded on boron-nitride nanosheets as catalytic labels.

Bacillus anthracis, the causative agent of anthrax, is a well known bioterrorism agent. The determination of surface array protein (Sap), a unique biomarker for B. anthracis can offer an opportunity for specific detection of B. anthracis in culture broth. In this study, we designed a new catalytic bionanolabel and fabricated a novel electrochemical immunosensor for ultrasensitive detection of B. anthracis Sap antigen. Bimetallic gold-palladium nanoparticles were in-situ grown on poly (diallyldimethylammonium chloride) functionalized boron nitride nanosheets (Au-Pd NPs@BNNSs) and conjugated with the mouse anti-B. anthracis Sap antibodies (Ab2); named Au-Pd NPs@BNNSs/Ab2. The resulting Au-Pd NPs@BNNSs/Ab2 bionanolabel demonstrated high catalytic activity towards reduction of 4-nitrophenol. The sensitivity of the electrochemical immunosensor along with redox cycling of 4-aminophenol to 4-quinoneimine was improved to a great extent. Under optimal conditions, the proposed immunosensor exhibited a wide working range from 5 pg/mL to 100 ng/mL with a minimum detection limit of 1 pg/mL B. anthracis Sap antigen. The practical applicability of the immunosensor was demonstrated by specific detection of Sap secreted by the B. anthracis in culture broth just after 1h of growth. These labels open a new direction for the ultrasensitive detection of different biological warfare agents and their markers in different matrices.

Electrochemical loading of TEM grids used for the study of potential dependent morphology of polyaniline nanofibres.

An electrochemical method for loading electroactive materials over the TEM grid is reported. The protocol has been demonstrated using polyaniline as an example. The electroactive polymer was directly deposited over the Au TEM grid, used as working electrode in a 3 electrode electrochemical cell. The undisturbed as-deposited morphologies under the influence of various counter ions and ex situ electrochemical states have been studied and compared. Contrary to behaviour in bulk the individual polyaniline fibre was found thinner at anodic potentials. The movement of counter ions as a function of the electrochemical state of the polymer was studied using STEM-EDX elemental mapping.

A fluorescent probe for bisulfite ions: its application to two-photon tissue imaging.

A benzoxazinone based fluorescent probe for the specific and efficient detection of bisulfite ions in aqueous medium is described. The probe formed a bisulfite/sulphite adduct with an associated turn-on fluorescence response in the red wavelength region. No interference was observed in the detection process from all possible competing anions and molecules, including cyanide ion, cysteine, homocysteine and glutathione. In addition, the probe showed a fast response time, low detection limit, and cell membrane permeability. Furthermore, the probe was two-photon excitable, enabling imaging of endogenous bisulfite ions in HeLa cells as well as in deep tissues from different organs of mouse.

A rapid conductometric sensor for the analysis of cyanide using imidazole based receptor.

A specific and efficient hydrogen bonding interaction between cyanide and the HN-H [imidazole] in an aqueous medium has been utilized for the selective recognition of cyanide under physiological conditions. The possibility of utilizing such an interaction for developing any practical device for the specific detection of cyanide in an aqueous environment has not been explored to date. We now report a simple dip and read conductometric sensor for cyanide ions using a tailored electrode in aqueous media. The purpose built reagent, 2-phenyl-1H-anthra-[2,3-d]-immidazole-5,10 dione was immobilized in a polyaniline matrix to fabricate this conductometric device. The homogeneous immobilization of the receptor in polyaniline was confirmed by FT-IR mapping. The proposed transduction mechanism is charge neutralization on the polyaniline moiety, which ultimately inhibits the protonation resulting in a decrease in the conductance of polyaniline. The sensor response was measured in three ranges of cyanide concentration (10(-10) M to 10(-8) M; 10(-8) M to 10(-6) M and 10(-6) M to 10(-3) M). Whereas the device is found insensitive in the first range, it acts as a detector in the second range and as a proportional sensor in the third range. The minimum detection limit of this device was found to be 10 nmol L(-1) (2.6 ppt), which is significantly less than the WHO guideline values. The responses have been investigated under various conditions such as different pH and the electrochemical state of the polymer. The current device has been found to be better close to neutral pH and at a 400 mV vs. Ag/AgCl potential. The reproducibility and repeatability of the sensor was investigated and interference studies were performed.

Efficient photocatalytic selective nitro-reduction and C-H bond oxidation over ultrathin sheet mediated CdS flowers.

We report here a visible light driven selective nitro-reduction and oxidation of saturated sp(3) C-H bonds using ultrathin (0.8 nm) sheet mediated uniform CdS flowers as catalyst under a household 40 W CFL lamp and molecular oxygen as oxidant. The CdS flowers were synthesized using a simple surfactant assisted hydrothermal method.

Polymer-graphite composite: a versatile use and throw plastic chip electrode.

We report an efficient plastic chip electrode (PCE) fabricated from a composite of graphite and poly(methyl methacrylate) by a simple solution casting method and promoted as an economically inexpensive, multipurpose disposable electrode for various applications. The TEM images of the filler (graphite) show that the material consists of single, as well as multi-layers. Thus, the self-standing and arid electrodes prepared were characterized for their material properties such as, microscopy (SEM and AFM), as well as thermal properties (TGA), mechanical (tensile strength) and electrical properties. A set of physical parameters were derived from these characterizations for sustainability of these electrodes in harsh off-laboratory conditions. The utility of these mechanically stable, bulk-conducting and high surface area electrodes were demonstrated in various well understood electrochemical protocols, such as cyclic voltammetry, stripping voltammetry, electropolymerization, electrowinning and amperometric sensing. The voltammetry data were compared with the data recorded on a conventional glassy carbon electrode.

Effective management of passive layers using composite cathodes in solid state magnesium batteries.

A simple and effective method for the management of the passive layer in solid state batteries is reported. The success is achieved using a composite cathode with embedded channels of polyaniline allowing smooth charge transfer across the passive layer. The composite cathode manifested better performance in terms of the cell characteristics and shelf life.

Electrocatalytic activity of silver nanoparticles modified glassy carbon electrode as amperometric sensor for hydrogen peroxide.

A simple chemical route has been applied for the preparation of quasi-spherical silver (Ag) nanoparticles (NPs) with average diameter of 265 and 8 nm. The as prepared products were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis absorption spectroscopy. Ag NPs immobilized on glassy carbon (GC) electrode showed a superior electrocatalytic activity for the reduction of hydrogen peroxide (H2O2) in aqueous medium. The fabricated electrode was also applied for the amperometric detection of H2O2 and showed a favorable response at an applied potential of -0.5 V (vs. Ag/AgCl). The results demonstrate that the fabricated electrode has potential application for hydrogen peroxide sensor.