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Metal telluride (MTe)-based nanomaterials have emerged as a potential alternative for efficient, highly conductive, robust, and durable electrodes in energy storage/conversion applications. Significant progress in the material development of MTe-based electrodes is well-sought, from the synthesis of its nanostructures, integration of MTes with supporting materials, synthesis of their hybrid morphologies, and their implications in energy storage/conversion systems. Herein, an extensive exploration of the recent advancements and progress in MTes-based nanomaterials is reviewed. This review emphasizes elucidating the fundamental properties of MTes and providing a systematic compilation of its wet and dry synthesis methods. The applications of MTes are extensively summarized and discussed, particularly, in energy storage and conversion systems including batteries (Li-ion, Zn-ion, Li-S, Na-ion, K-ion), supercapacitor, hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and CO2 reduction. The review also emphasizes the future prospects and urgent challenges to be addressed in the development of MTes, providing knowledge for researchers in utilizing MTes in energy storage and conversion technologies.
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The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster-based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au3 triangular units can be successfully introduced into the double-stranded helical kernel of Au44 (TBBT)28 , where TBBT=4-tert-butylbenzenethiolate, resulting in the formation of two atomically precise defective Au44 nanoclusters. Along with the regular face-centered-cubic (fcc) nanocluster, the first series of mixed-ligand cluster homologues is identified, with a unified formula of Au44 (PPh3 )n (TBBT)28-2n (n=0-2). The Au44 (PPh3 )(TBBT)26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the rate-determining step in the whole catalytic process.
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The advances in determining the total structure of atomically precise metal nanoclusters have prompted extensive exploration into the origins of chirality in nanoscale systems. While chirality is generally transferrable from the surface layer to the metal-ligand interface and kernel, we present here an alternative type of gold nanoclusters (138 gold core atoms with 48 2,4-dimethylbenzenethiolate surface ligands) whose inner structures are not asymmetrically induced by chiral patterns of the outermost aromatic substituents. This phenomenon can be explained by the highly dynamic behaviors of aromatic rings in the thiolates assembled via π - π stacking and C - H···π interactions. In addition to being a thiolate-protected nanocluster with uncoordinated surface gold atoms, the reported Au138 motif expands the size range of gold nanoclusters having both molecular and metallic properties. Our current work introduces an important class of nanoclusters with intrinsic chirality from surface layers rather than inner structures and will aid in elucidating the transition of gold nanoclusters from their molecular to metallic states.
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Polyphosphazenes are an inorganic molecular hybrid family with multifunctional properties due to their wide range of organic substitutes. This review intends to propose the basics of the synthetic chemistry of polyphosphazene, describing for researchers outside the field the basic knowledge required to design and prepare polyphosphazenes with desired properties. A special emphasis is placed on recent advances in chemical synthesis, which allow not only the synthesis of polyphosphazenes with controlled molecular weights and polydispersities but also the synthesis of novel branched designs and block copolymers. We also investigated the synthesis of polyphosphazenes using various functional materials. This review aims to assist researchers in synthesizing their specific polyphosphazene material with unique property combinations, with the hope of stimulating further research and even more innovative applications for these highly interesting multifaceted materials.
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We reported a study on the preparation of bimetallic Ag-Cu nanoparticles (NPs) impregnated on PZS poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) nanotubes via a facile and efficient reduction method. Herein, PZS nanotubes consisting of enriched hydroxyl groups are fabricated through an in situ template method, and then, fluctuating the amount ratios of Cu and Ag precursors, bimetallic NPs can be fabricated on readily prepared PZS nanotubes using NaBH4 as a reductant, which results in a series of bimetallic catalysts having tunable catalytic activity. The characterization investigations of scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy results show that Ag-Cu bimetallic NPs are well-dispersed, ultrasmall in size, and well-anchored on the surface of PZS nanotubes. In addition, to examine the catalytic activity and reusability of these nanocomposites, reduction of 4-nitrophenol to 4-aminophenol is utilized as a prototype reaction. The optimized Ag-Cu NPs with a copper ratio of 0.3% are well-stabilized by the organic-inorganic poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) nanotubes. The obtained results show that bimetallic NPs have remarkably higher catalytic ability than that of their monometallic counterparts with maximum catalytic activity. These results are even better than those of noble metal-based bimetallic catalysts and pave the avenue to utilize the polyphosphazene polymer as a substrate material for highly effective bimetallic catalysts.
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While the formation of superatomic nanoclusters by the three-dimensional assembly of icosahedral units was predicted in 1987, the synthesis and structural determination of such clusters have proven to be incredibly challenging. Herein, we employ a mixed-ligand strategy to prepare phosphinous acid-phosphinito gold nanocluster Au52(HOPPh2)8(OPPh2)4(TBBT)16 with a tetra-icosahedral kernel. Unlike expected, each icosahedral Au13 unit shares one vertex gold atom with two adjacent units, resulting in a "puckered" ring shape with a nuclearity of 48 in the kernel. The phosphinous acid-phosphinito ligand set, which consists of two phosphinous acids and one phosphinito motif, has strong intramolecular hydrogen bonds; the π-π stacking interactions between the phosphorus- and sulfur-based ligands provide additional stabilization to the kernel. Highly stable Au52(HOPPh2)8(OPPh2)4(TBBT)16 serves as an effective electrocatalyst in the oxygen reduction reaction. Density functional theory calculations suggest that the phosphinous acid-phosphinito ligands provide the most active sites in the electrochemical catalysis, with O* formation being the rate-determining step.
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The development of excellent drug adsorbents and clarifying the interaction mechanisms between adsorbents and adsorbates are greatly desired for a clean environment. Herein, we report that a reduced graphene oxide modified sheeted polyphosphazene (rGO/poly (cyclotriphosphazene-co-4,4'-sulfonyldiphenol)) defined as PZS on rGO was used to remove the tetracycline (TC) drug from an aqueous solution. Compared to PZS microspheres, the adsorption capacity of sheeted PZS@rGO exhibited a high adsorption capacity of 496 mg/g. The adsorption equilibrium data well obeyed the Langmuir isotherm model, and the kinetics isotherm was fitted to the pseudo-second-order model. Thermodynamic analysis showed that the adsorption of TC was an exothermic, spontaneous process. Furthermore, we highlighted the importance of the surface modification of PZS by the introduction of rGO, which tremendously increased the surface area necessary for high adsorption. Along with high surface area, electrostatic attractions, H-bonding, π-π stacking and Lewis acid-base interactions were involved in the high adsorption capacity of PZS@rGO. Furthermore, we also proposed the mechanism of TC adsorption via PZS@rGO.
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OBJECTIVES: Escherichia coli is the key pathogen in the family producing ESBL (extended spectrum ß-lactamase) and associated with community-acquired infections. Therefore, this study was planned to determine the antibiotic susceptibility pattern of uropathogenic E. coli, prevalence of the ESBL gene group and class 1 integrons. MATERIALS AND METHODS: Clinical isolates of uropathogenic E. coli were isolated from different hospitals of Karachi. Antibiotic susceptibility test was performed by Kirby-Bauer Methods. Presence of ß- lactamases genes (CTX, TEM, and SHV) and integron 1 were identified by polymerase chain reaction (PCR). RESULTS: Out of 500, 105 isolates were identified as multi-drug resistant (MDR) uropathogenic E. coli. The subject MDR isolates showed the highest resistance to aztreonam, amoxil/ clavulanic acid, ampicillin, cotrimoxazole, ceftriaxone, cefipime, and cefuroxime. Genetic analysis showed that the majority of the MDR E. coli carry CTX M1 (57.1%) followed by TEM (33.3%) and SHV (9.5%). Moreover, 79% of MDR E. coli harbored class 1 integrons, whereas all three conserved genes for class 1 integrons were present in 58% of MDR E. coli. CONCLUSION: This study is helpful to provide information regarding the antibiotic susceptibility pattern, distribution ESBLs and class 1 integrons among uropathogenic E. coli.