The mineral manaksite, KNaMnSiO, as a supercapattery-type electrochemical energy storage material.

The manaksite mineral KNaMnSiO was synthesized and used to fabricate electrodes, which were investigated for electrochemical energy storage (EES) application using cyclic voltammetry (CV), galvanostatic charge and discharge (GCD), and electrochemical impedance spectroscopy (EIS). Optimum weight percentages (wt%) of electrode components were established as 10 wt% polytetrafluoroethylene (PTFE) binder, 15 wt% RuO and 5 wt% carbon black. RuO was added to improve electrical conductivity.

A CaCuSiO/GCE electrochemical sensor for detection of norfloxacin in pharmaceutical formulations.

This study reports on a calcium copper tetrasilicate (CaCuSiO)/glassy carbon electrode (GCE) electrochemical sensor developed for rapid sensing and quantification of an antibacterial drug, norfloxacin, using both cyclic voltammetry and differential pulse voltammetry. The sensor was fabricated by modifying a glassy carbon electrode with the CaCuSiO. Electrochemical impedance spectroscopy was performed and the Nyquist plot showed that the CaCuSiO/GCE had a lower charge transfer resistance of 22.

polymerization and electrical conductivity of polypyrrole/cellulose nanocomposites using Schweizer's reagent.

Cellulose-based composites have attracted interest given the shift towards 'green' materials, but achieving uniform dispersions of cellulose in polymer matrices and/or enhancement of interfacial interactions between components remains challenging. Herein we report the preparation of polypyrrole/cellulose nanocomposites in [Cu(NH)(HO)](OH) (Schweizer's reagent/cuoxam)-based reaction media polymerization. The effect of cellulose template morphology and reaction media on the microstructure, electrical conductivity, and surface wettability was studied.

Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol.

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties.

Interstitial Hydrides in Nanoclusters can Reduce M(I) (M=Cu, Ag, Au) to M(0) and Form Stable Superatoms.

High-nuclearity clusters resemble the closest model between the determination of atomically precise chemical species and the bulk metallic version thereof, and both impacts on a variety of applications, including catalysis, optics, sensors, and new energy sources. Our interest lies with the nanoclusters of the Group 11 (Cu, Ag, Au) metals stabilized by dichalcogenido and hydrido ligands. Herein, we describe superatoms formed by the clusters and their relationship with precursor hydrido clusters.

Synergistically enhanced performance of transition-metal doped NiP for supercapacitance and overall water splitting.

Cost-effective and readily available catalysts applicable for electrochemical conversion technologies are highly desired. Herein, we report the synthesis of dithiophosphonate complexes of the type [Ni{SP(OH)(4-CHOCH)}] (1), [Co{SP(OCH)(4-CHOCH)}] (2) and [Fe{SP(OH)(4-CHOCH)}] (3) and employed them to prepare NiP, Co-NiP and Fe-NiP nanoparticles. NiP was formed by a facile hot injection method by decomposing complex 1 in tri-octylphosphine oxide/tri-n-octylphosphine at 300 °C.

Triphenylphosphine-Assisted Transformation of NiS to NiP through a Solvent-Less Pyrolysis Route: Synthesis and Electrocatalytic Performance.

Straightforward synthetic routes to the preparation of transition metal phosphides or their chalcogenide analogues are highly desired due to their widespread applications, including catalysis. We report a facile and simple route for the preparation of a pure phase nickel phosphide (NiP) and phase transformations in the nickel sulfide (NiS) system through a solvent-less synthetic protocol. Decomposition of different sulfur-based complexes (dithiocarbamate, xanthate, and dithiophosphonate) of nickel(II) was investigated in the presence and absence of triphenylphosphine (TPP).

[Cu{SC(O)OPr}]: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis.

The hierarchical self-organization of structurally complex high-nuclearity metal clusters with metallosupramolecular wheel architectures that are obtained from the self-assembly of smaller solvated cluster units is rare and unique. Here, we use the potentially heteroditopic monothiocarbonate ligand and demonstrate for the first time the synthesis and structure of a solvated non-cyclic hexadecanuclear cluster [Cu{SC(O)OPr}]·2THF () that can simultaneously desolvate and self-assemble in solution and subsequently form a giant metallaring, [Cu{SC(O)OPr}] (). We also demonstrate a luminescent precursor to cluster () can be achieved through a solventless and rapid mechanochemical synthesis.

A construction guide for high-nuclearity (≥50 metal atoms) coinage metal clusters at the nanoscale: bridging molecular precise constructs with the bulk material phase.

Synthesis remains a major strength in chemistry and materials science and relies on the formation of new molecules and diverse forms of matter. The construction and identification of large molecules poses specific challenges and has historically lain in the realm of biological (organic)-type molecules with evolved synthesis methods to support such endeavours. But with the development of analytical tools such as X-ray crystallography, new synthesis methods toward large metal-based (inorganic) molecules and clusters have come to the fore, making it possible to accurately determine the precise distribution of hundreds of atoms in large clusters.

Synthesis and structures of divalent Co, Ni, Zn and Cd complexes of mixed dichalcogen and dipnictogen ligands with corrosion inhibition properties: experimental and computational studies.

The structural and corrosion inhibition properties of four different transition-metal complexes of heteroleptic S-donor atom dithiophosphonate and N-donor atom phenanthroline ligands are reported. Full structural characterization of the Co, Ni, Zn and Cd complexes was achieved with the aid of single-crystal X-ray crystallography. Structural elucidation revealed the formation of a 4-coordinate Zn(ii) complex, and 6-coordinate Ni(ii) and Cd(ii), as well as a novel dithiophosphonato Co(ii) complex.

Formation of dialysis-free Kombucha-based bacterial nanocellulose embedded in a polypyrrole/PVA composite for bulk conductivity measurements.

The preparation of dialysis-free bacterial nanocrystalline cellulose (BNCC) combined with a suitable polymer to form a robust conducting material remains a challenge. In this work, we developed a polypyrrole@BNCC/PVA nanocomposite that avoids the time-consuming dialysis step and which exhibits bulk electrical conductivity. The nanocellulose (NC) was derived from bacterial cellulose (BC) that was grown from a symbiotic colony of bacteria and yeast (SCOBY) starting from Kombucha tea, and then subjected to sulfuric acid hydrolysis that led to isolable bacterial nanocrystalline cellulose (BNCC) product and subsequently utilized as a stabilizer and support.

Four-Component Fusion Protocol with NiO/ZrO as a Robust Recyclable Catalyst for Novel 1,4-Dihydropyridines.

Nickel oxide loaded on zirconia (NiO/ZrO) as an expedient catalyst is reported for the synthesis of 18 unsymmetrical 1,4-dihydropyridine derivatives. The Lewis acidic nature of the catalyst proved an excellent choice for the one-pot, four-component fusion reaction with excellent yields of 89-98% and a completion time of 20-45 min. Mechanistic studies show that enamine and imine functionalities are the two possible pathways for the formation of 1,4-dihydropyridines with high selectivity.

Flexible Molecular Precursors for Selective Decomposition to Nickel Sulfide or Nickel Phosphide for Water Splitting and Supercapacitance.

Herein, the synthesis of three nickel(II) dithiophosphonate complexes of the type [Ni{S P(OR)(4-C H OMe)} ] [R=H (1), C H (2)] and [Ni{S P(OR)(4-C H OEt} ] [R=(C H ) CH (3)] is described; their structures were confirmed by single-crystal X-ray studies. These complexes were subjected to surfactant/solvent reactions at 300 °C for one hour as flexible molecular precursors to prepare either nickel sulfide or nickel phosphide particles. The decomposition of complex 2 in tri-octylphosphine oxide/1-octadecene (TOPO/ODE), TOPO/tri-n-octylphosphine (TOP), hexadecylamine (HDA)/TOP, and HDA/ODE yielded hexagonal NiS, Ni P, Ni P , and rhombohedral NiS, respectively.

Aqueous Route to Stable Luminescent Tetranuclear Copper(I) Dithiophosphonate Clusters.

A series of seven luminescent copper(I) dithiophosphonate (dtp) clusters of the type CuL (L = SPR(OR')) were formed from CuCl·2HO precursor in aqueous medium under ambient conditions. The dtp ligand serves the dual function of acting as a sacrificial reducing agent and cluster core stabilizer. The new clusters were characterized by H and P NMR and ESI-MS, and the single-crystal X-ray structures for two representative clusters [Cu{(SP(1,4-CHOMe)(OR')}] (R' = OCH(CH); CHCH) were determined.

Copper hydride clusters in energy storage and conversion.

Hydrogen is seen as an increasingly important clean and sustainable energy source going into the future. There are a host of materials being investigated for the storage of hydrogen. In this frontier, we provide an overview of hydride clusters derived from Earth-abundant copper being used for the storage and conversion of hydrides into hydrogen, and the reaction of CO2 with hydride sources to produce the formic acid/formate pairing, which are considered excellent hydrogen carriers.

Ag₂O on ZrO₂ as a Recyclable Catalyst for Multicomponent Synthesis of Indenopyrimidine Derivatives.

We describe the synthesis of silver loaded on zirconia and its use as an efficient catalyst for a one-pot three-component reaction to synthesize 11 indenopyrimidine derivatives, of which 7 are new compounds. The procedure involves substituted benzaldehydes, indane-1,3-dione, and guanidinium hydrochloride, with ethanol as solvent. The proposed green protocol at room temperature is simple and efficient, giving excellent yields (90⁻96%) in short reaction times (<30 min).

An efficient and green approach for the synthesis of 2,4-dihydropyrano[2,3-]pyrazole-3-carboxylates using BiO/ZrO as a reusable catalyst.

A novel material of bismuth loaded on zirconia (BiO/ZrO) is synthesized by simple wet-impregnation method and characterized by several techniques (P-XRD, TEM, SEM, BET, ). BiO/ZrO proved to be a good catalyst for the four-component, one-pot reaction to produce a new series of 2,4-dihydropyrano[2,3-]pyrazole-3-carboxylate derivatives with excellent yields (91 to 98%) under mild conditions at RT with short reaction times (≈20 min). The structures of the target molecules were confirmed by H NMR, C NMR, N NMR, HRMS and FT-IR.

Nanocrystalline cellulose isolated from discarded cigarette filters.

We report the isolation of nanocrystalline cellulose (NCC) produced from discarded cigarette filters (DCF). The DCF were processed into cellulose via ethanolic extraction, hypochlorite bleaching, alkaline deacetylation, and then converted into NCC by sulfuric acid hydrolysis. The morphological structures of the isolated NCC established with TEM showed that the nanocrystals were needle-like with a mean length of 143nm.

Ceria-Vanadia/Silica-Catalyzed Cascade for C-C and C-O Bond Activation: Green One-Pot Synthesis of 2-Amino-3-cyano-4H-pyrans.

We designed a ceria-vanadia/silica (Ce-V/SiO2) heterogeneous catalyst and used it for the green and efficient synthesis of 2-amino-3-cyano-4H-pyran derivatives. The green reaction was a multicomponent one-pot condensation of 5,5-dimethylcyclohexane-1,3-dione, aromatic aldehyde, and malononitrile in an eco-compatible solvent (ethanol). The catalyst was synthesized and fully characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis.

Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion.

Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs).

[Cu32 (H)20 {S2 P(OiPr)2 }12 ]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction.

An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu32 (H)20 {S2 P(OiPr)2 }12 ] (1H ) was synthesized and structurally characterized. The molecular structure of 1H exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2×9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes.

Heteroditopic P,N ligands in gold(I) complexes: synthesis, structure and cytotoxicity.

New heteroditopic, bi- and multidentate imino- and aminophosphine ligands were synthesised and complexed to [AuCl(THT)] (THT=tetrahydrothiophene). X-ray crystallography confirmed Schiff base formation in three products, the successful reduction of the imino-group to the sp(3)-hybridised amine in several instances, and confirmed the formation of mono-gold(I) imino- and aminophosphine complexes for four Au-complexes. Cytotoxicity studies in cancerous and non-cancerous cell lines showed a marked increase in cytotoxicity upon ligand complexation to gold(I).

Anion templating from a silver(i) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and decanuclear silver(i) clusters.

We report on a Ag5 coordination polymer and discrete Ag8 and Ag10 dithiophosphate clusters. The cluster formation and structures were affected by the stoichiometric control of the M : L molar ratios used. The cluster [Ag5{S2P(O(i)Pr)2}4]n(PF6)n, , is a monomeric unit within a coordination polymer formed through the reaction between [Ag(CH3CN)4]PF6 and the dithiophosphate ligand, [S2P(O(i)Pr)2](-), used in a M : L molar ratio of 5 : 4.

Phosphinogold(I) dithiocarbamate complexes: effect of the nature of phosphine ligand on anticancer properties.

The reactions of potassium salts of the dithiocarbamates L {where L = pyrazolyldithiocarbamate (L1), 3,5-dimethylpyrazolyldithiocarbamate (L2), or indazolyldithiocarbamate (L3)} with the gold precursors [AuCl(PPh3)], [Au2Cl2(dppe)], [Au2Cl2(dppp)], or [Au2Cl2(dpph)] lead to the new gold(I) complexes [AuL(PPh3)] (1-3), [Au2L2(dppe)] (4-6), [(Au2L2)(dppp)] (7-9), and [Au2(L)2(dpph)] (10-12) {where dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, and dpph = 1,6-bis(diphenylphosphino)hexane}. These gold compounds were characterized by a combination of NMR and infrared spectroscopy, microanalysis, and mass spectrometry; and in selected cases by single-crystal X-ray crystallography. Compounds 4-6, which have dppe ligands, are unstable in solution for prolonged periods, with 4 readily transforming to the Au18 cluster [Au18S8(dppe)6]Cl2 (4a) in dichloromethane.

Dinuclear gold(I) dithio- and diselenophosph(in)ate complexes forming mononuclear gold(III) oxidative addition complexes and reversible chemical reductive elimination products.

Dinuclear gold(i) dithio- and diselenophosph(in)ate complexes were prepared to serve as precursors for subsequent oxidative addition (OA) chemistry following reaction with mild oxidant iodine, I2. The new OA products circumvented the formation of the expected dinuclear Au(ii) complexes, but instead formed novel chelating mononuclear square-planar gold(iii) products of the type [AuI2{E2PR2}] (R = (CH2)2Ph; E = S, 2; E = Se, 3) and [AuI2{Se2P(OR)2}] (R = Et, 4; (i)Pr, 5) directly. We further demonstrate that this process is chemically reversible as all the Au(iii) complexes undergo chemical reductive elimination to the starting dinuclear Au(i) complexes in the presence of SnI2 as determined by (119)Sn and (31)P NMR.