Au-Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core-shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-step strategy for the controlled growth of monodisperse Au-Pd alloy and core-shell IH with terraced shells by turning an ionic switch between [Br(-)]/[Cl(-)] in the coreduction process. The core-shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (<2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. This strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis.
Excess nitrite (NO2
-) concentrations in water supplies is considered detrimental to the environment and human health, and is associated with incidence of stomach cancer. In this work, the authors describe a nitrite detection system based on the synthesis of gold nanoparticles (AuNPs) on reduced graphene oxide (rGO) using an aqueous solution of chitosan and succinic acid. The AuNPs-rGO nanocomposite was confirmed by different physicochemical characterization methods including transmission electron microscopy, elemental analysis, X-ray diffraction, UV-visible (UV-vis) and Fourier transform infrared spectroscopy. The AuNPs-rGO nanocomposite was applicable to the sensitive and selective detection of NO2
− with increasing concentrations quantifiable by UV–vis spectroscopy and obvious to the naked eye. The color of the AuNPs-rGO nanocomposite changes from wine red to purple with the addition of different concertation of NO2
−. Therefore, nitrite ion concentrations can be quantitatively detected using AuNPs-rGO sensor with UV-vis spectroscopy and estimated with the naked eye. The sensor is able to detect NO2
− in a linear response ranging from 1 to 20 μM with a detection limit of 0.1 μM by spectrophotometric method. The as-prepared AuNPs-rGO nanocomposite shows appropriate selectivity towards NO2
− in the presence of potentially interfering metal anions.
A 0D discrete molecule [Co(3,5-pdc)(H2O)5].2H2O (1) was obtained in quantitative yield from the reaction of CoCl2.6H2O and pyridine-3,5-dicarboxylate (3,5-pdc) in pure water solvent at ambient temperature. While a 1D zigzag chain species, [{Co(3,5-pdc)(H2O)4}.H2O]n (2), was produced in a water-rich environment, a 2D layer compound, [Co(3,5-pdc)(H2O)2]n (3), with a 6(3) topology was generated under a water-reduced condition and a 2D sheet structure, [{Cu(3,5-pdc)(py)2}.H2O.EtOH]n (4), was formed under a water-poor condition. Compounds 1, 2, and 4 were characterized by single-crystal X-ray diffraction analysis. The 1D zigzag chain 2 shows a recoverable collapsing property. Compound 4 adopts a 2D sheet structure with a 4.8(2) topology, observed for the first time for the 3,5-pdc-related metal-organic frameworks. Water content was found to be an important factor in determining the topologies of the products in the self-assembly of divalent metal ions (Co2+, Cu2+) and pyridine-3,5-dicarboxylate under mild conditions.
Three novel triosmium complexes with unusual coordination characteristics are reported. Treatment of the hydridotriosmium cluster (mu-H)2Os3(CO)10 with CNNPPh3 in CH2Cl2 gave complexes (mu-H)Os3(CO)(10)(mu2-eta2-C(H)NNPPh3) (1) and (mu-H)Os3(CO)10(mu2-eta1-CHPPh3) (2). Complex 1 represents the first example of the existence of a coordinated phosphinazine ligand. An in-situ 1H NMR study showed that the reaction of (mu-H)2Os3(CO)10 with CNNPPh3 produced complex 1 as the initial product in 100% conversion. The latter is not stable in solution and slowly eliminates nitrogen to form an unusual ylide complex 2 in quantitative yield. The thermolysis of 2 in refluxing toluene afforded (mu-H)3Os3(CO)9(mu3-eta1-CCO2CH2Ph) (3) as a colorless compound. Complexes 1-3 were characterized by spectroscopic methods and single-crystal X-ray diffraction analysis. The interesting feature of structure 3 is the presence of a mu3-alkylidyne ligand where the symmetrically triply bridged CCO2CH2Ph fragment lies perpendicular to and above the triosmium triangle.
The band profiles of ZnMgO/ZnO heterostructures were confirmed through surface potential measurements by Kelvin probe force microscopy. A simple model for the band profile was proposed and the various band parameters were evaluated experimentally and theoretically based on the band model. The band profile was calculated and validated with experimental results using the Schrödinger–Poisson equation. The energy level of the ZnMgO surface donor state, which serves as the source of the two-dimensional electron gas in ZnMgO/ZnO heterostructures, was estimated from the band parameters; nearly identical energy levels around 0.8 eV were obtained for Zn1−xMgxO layers with Mg compositions x ranging from 0.12 to 0.42 and the corresponding charge densities were estimated to be 8×1012 cm−2.
A simple and facile green process was used for the synthesis of iron nanoparticles (FeNPs) decorated reduced graphene oxide (rGO) nanocomposite by using Ipomoea pes-tigridis leaf extract as a reducing and stabilizing agent. The as-prepared rGO/FeNPs nanocomposite was characterized by transmission electron microscopy, X-ray spectroscopy and Fourier transform infrared spectroscopy. The nanocomposite was further modified on the glassy carbon electrode and used for non-enzymatic sensing of hydrogen peroxide (HO). Cyclic voltammetry results reveal that rGO/FeNPs nanocomposite has excellent electro-reduction behavior to HO when compared to the response of FeNPs and rGO modified electrodes. Furthermore, the nanocomposite modified electrode shows 9 and 6 folds enhanced reduction current response to HO than that of rGO and FeNPs modified electrodes. Amperometric method was further used to quantify the HO using rGO/FeNPs nanocomposite, and the response was linear over the concentration ranging from 0.1μM to 2.15mM. The detection limit and sensitivity of the sensor were estimated as 0.056μM and 0.2085μAμMcm, respectively. The fabricated sensor also utilized for detection of HO in the presence of potentially active interfering species, and found high selectivity towards HO.
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