Evaluation of novel ZnO–Ag cathode for CO2 electroreduction in solid oxide electrolyser

CO₂ and steam/CO₂ electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnO_mix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnO_inf –Ag cathode). ZnO_mix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO₂ and H₂/CO₂ (4:1 v/v). A maximum overall CO₂ conversion of 48% (in H₂/CO₂) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO₂ electroreduction. It was further revealed that for ZnO_inf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnO_mix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO₂ electrolysis. Although ZnO_inf –Ag cathode produced trace amount of methane at higher voltages, with ZnO_mix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.

     

Synthesis,characterizations, and electrochemical studies of ZnO/reduced graphene oxide nanohybrids for supercapacitor application

Herein the present article reports the fabrication of ZnO/reduced graphene oxide (ZnG) nanohybrid following a reduction-based process using a non-hazardous material, i.e., ascorbic acid. The morphology, structure, and bonding in the nanohybrid were analyzed using different techniques. Atomic force microscopy and scanning electron microscopy images show spherical particles of ZnO distributed over reduced graphene oxide (rGO). The X-ray diffraction analysis gives calculated values of crystallite size for ZnO as 15.62 nm. The successful incorporation of ZnO nanoparticles into rGO was confirmed using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analyses. The electrochemical studies were performed using an electrolyte (0.5 M H₂SO₄). The calculated value of specific capacitance for the nanohybrid was 345 Fg^-1, which was found to be almost double as compared to that of rGO, which is having a value of only 190.5 Fg^-1 at the same scan rate. The nanohybrid also showed excellent capacitance retention after 1,000 cycles.     

Poly(Pyridinium Salt)s Containing 2,7-Diamino-9,9′-Dioctylfluorene Moieties with Various Organic Counterions Exhibiting Both Lyotropic Liquid-Crystalline and Light-Emitting Properties

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (¹H), and fluorine 19 (¹⁹F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (M_ns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λ_em peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λ_em peaks were blue shifted.     

Synthesis and biological evaluation of novel 4-(6-substituted quinolin-4-yl)-N-aryl thiazol-2-amine derivatives as potential antimicrobial agents

Cyclocondensation reaction of 4-(2-bromoacetyl)quinolin-1-ium bromide ( 4a–d ) with substituted arylthiourea, ( 5a–g ) afforded 4-(6-substituted quinolin-4-yl)-N-aryl/pyridyl thiazol-2-amine ( 6a-ab ). These newly synthesized derivatives were evaluated for in vitro antibacterial activity against Escherichia coli (NCIM 2574), Proteus mirabilis (NCIM 2388) (Gram-negative strains), Bacillus subtilis (NCIM 2063), Staphylococcus albus (NCIM 2178) (Gram-positive strains) and in vitro antifungal activity against Aspergillus niger (ATCC 504) and Candida albicans (NCIM 3100). Compounds 6a , 6b , 6d , 6f , 6k , and 6l showed moderate to good antibacterial activity against S. albus. Ten derivatives 6c , 6q , 6r , 6s , 6t , 6v , 6w , 6x , 6y , and 6aa , showed moderate to good activity against A. niger. N-[4-(Quinolin-4-yl)-1,3-thiazol-2-yl]pyridin-2-amine presented comparable activity against A. niger with respect to standard drug Rouconazole.     

Studies on morphology of polyaniline films formed at liquid–liquid and solid–liquid interfaces at 25 and 5 °C,respectively, and effect of doping

It is well accepted that the morphology of the nanomaterials has great effect on the properties and hence their applications. Therefore, morphology of materials has become a focus of research in the scientific world. The present study shows that interfacial polymerization and subsequent self-assembly provides a control over the morphology, nanorod/nanosheet, of polyaniline (PANI) films synthesized by liquid–liquid interface reaction technique and solid–liquid interface reaction technique. The synthesized PANI films and its particulate structure are characterized by using various spectroscopic techniques such as UV–visible, ATR-IR, Raman and XPS. The study confirmed the formation, the structure, the size and shape of particles and morphology of PANI by using analytical techniques namely, SAED, SEM and TEM. An important observation is that doping with HCl significantly improves the nanorod formation at the interface. The doped PANI electrode exhibits a higher area with rectangular shape in CV cycle and better cycle stability when compared with the performance of undoped PANI films. We believe that the results of these studies can give valuable leads to manoeuvre formation of PANI films with desired morphology for various applications.

Efficient Chemical Protein Synthesis using Fmoc-Masked N-Terminal Cysteine in Peptide Thioester Segments

We report an operationally simple method to facilitate chemical protein synthesis by fully convergent and one-pot native chemical ligations utilizing the fluorenylmethyloxycarbonyl (Fmoc) moiety as an N-masking group of the N-terminal cysteine of the middle peptide thioester segment(s). The Fmoc group is stable to the harsh oxidative conditions frequently used to generate peptide thioesters from peptide hydrazide or o-aminoanilide. The ready availability of Fmoc-Cys(Trt)-OH, which is routinely used in Fmoc solid-phase peptide synthesis, where the Fmoc group is pre-installed on cysteine residue, minimizes additional steps required for the temporary protection of the N-terminal cysteinyl peptides. The Fmoc group is readily removed after ligation by short exposure (<7 min) to 20 % piperidine at pH 11 in aqueous conditions at room temperature. Subsequent native chemical ligation reactions can be performed in presence of piperidine in the same solution at pH 7.     

Density functional theory investigation of structure,stability, and glycerol/hydrogen adsorption on Cu,Cu?Zn,and Cu?ZnO clusters

Extensive density functional theory calculations are performed to analyze the structure and activity of Cu and Cu Zn/Cu ZnO clusters containing up to 10 Cu/Zn atoms. The minimum-energy structures of Cu Zn and Cu ZnO clusters are found by doping minimum-energy pure Cu clusters with Zn atom(s) and ZnO molecule(s), respectively, followed by energy minimization of the resultant clusters. Odd-even alteration in properties that determine cluster stability/activity is observed with cluster size, which may be attributed to the presence/absence of unpaired electrons. The difference in behavior between Zn/ZnO doping can be interpreted in terms of charge transfer between atoms. Charge transfers from Zn to Cu in the Cu Zn clusters and from Cu and Zn atoms to O atom in Cu-ZnO clusters, which implies that the Cu atom acts as an electron acceptor in the Cu Zn clusters but not in the Cu ZnO clusters. Finally, the adsorption energies of glycerol and hydrogen on Cu Zn/Cu ZnO clusters are computed in the context of the use of Cu Zn/Cu ZnO catalysts in glycerol hydrogenolysis. Glycerol adsorption is generally found to be more energetically favorable than hydrogen adsorption. Dual-site glycerol adsorption is also observed in some of the planar clusters. Fundamental insights obtained in this study can be useful in the design of Cu Zn/Cu ZnO catalysts.     

Acetic acid catalysed solvent-free synthesis of spiro-isoxazolo[5,4-b]pyridines/quinolines by mechano-chemical grinding

A simple and efficient three-component procedure has been developed for the synthesis of a series of spiro-isoxazolo[5,4-b]pyridines/quinolines by one-pot condensation of isatins, 3-methylisoxazol-5-amine and enolizable cyclic carbonyl compounds. The protocol has been accomplished under solvent-free conditions by grinding the components at room temperature in presence of catalytic CH₃COOH. The described process offers environmentally benign reaction conditions for the synthesis of pharmacologically important spirooxindole fused heterocycles with the advantages ofoperational simplicity, short reaction time and good to excellent yields of isolated pure product.