Catalytic reductions of nitroaromatic compounds over heterogeneous catalysts with rhenium sub-nanostructures.

Nitroaromatic compounds (NACs) are key contaminants of anthropogenic origin and pose a severe threat to human and animal lives. Although the catalytic activities of Re nanostructures (NSs) are significantly higher than those of other heterogeneous catalysts containing NSs, few studies have been reported on the application of Re-based nanocatalysts for NAC hydrogenation. Accordingly, herein, catalytic reductions of nitrobenzene (NB), 4-nitrophenol (4-NP), 2-nitroaniline (2-NA), 4-nitroaniline (4-NA), and 2,4,6-trinitrophenol (2,4,6-TNP) over new Re-based heterogeneous catalysts were proposed. The catalytic materials were designed to enable effective syntheses and stabilisation of particularly small Re structures over them. Accordingly, catalytic hydrogenations of NACs under mild conditions were significantly enhanced by Re sub-nanostructures (Re-sub-NSs). The highest pseudo-first-order rate constants for NB, 4-NP, 2-NA, 4-NA, and 2,4,6-TNP reductions over the catalyst acquired by stabilising Re using bis(3-aminopropyl)amine (BAPA), which led to Re-sub-NSs with Re concentrations of 16.7 wt%, were 0.210, 0.130, 0.100, 0.180, and 0.090 min-1, respectively.

Rhenium Nanostructures Loaded into Amino-Functionalized Resin as a Nanocomposite Catalyst for Hydrogenation of 4-Nitrophenol and 4-Nitroaniline.

The present work presents a new nanocomposite catalyst with rhenium nanostructures (ReNSs) for the catalytic hydrogenation of 4-nitrophenol and 4-nitroaniline. The catalyst, based on an anion exchange resin with functionality derived from 1,1'-carboimidazole, was obtained in the process involving anion exchange of ReO4- ions followed by their reduction with NaBH4. The amino functionality present in the resin played a primary role in the stabilization of the resultant ReNSs, consisting of ≈1% (w/w) Re in the polymer mass. The synthesized and capped ReNSs were amorphous and had the average size of 3.45 ± 1.85 nm. Then, the obtained catalyst was used in a catalytic reduction of 4-nitrophenol (4-NP) and 4-nitroaniline (4-NA). Following the pseudo-first-order kinetics, 5 mg of the catalyst led to a 90% conversion of 4-NP with the mass-normalized rate constant (km1) of 6.94 × 10-3 min-1 mg-1, while the corresponding value acquired for 4-NA was 7.2 × 10-3 min-1 mg-1, despite the trace amount of Re in the heterogenous catalyst. The obtained material was also conveniently reused.

Plant Extracts Activated by Cold Atmospheric Pressure Plasmas as Suitable Tools for Synthesis of Gold Nanostructures with Catalytic Uses.

Because cold atmospheric pressure plasma (CAPP)-based technologies are very useful tools in nanomaterials synthesis, in this work we have connected two unique in their classes approaches-a CAPP-based protocol and a green synthesis method in order to obtain stable-in-time gold nanoparticles (AuNPs). To do so, we have used an aqueous Gingko biloba leave extract and an aqueous Panax ginseng root extract (untreated or treated by CAPP) to produce AuNPs, suitable for catalytical uses. Firstly, we have adjusted the optical properties of resulted AuNPs, applying UV/Vis absorption spectrophotometry (UV/Vis). To reveal the morphology of Au nanostructures, transmission electron microscopy (TEM) in addition to energy dispersive X-ray scattering (EDX) and selected area X-ray diffraction (SAED) was utilized. Moreover, optical emission spectrometry (OES) in addition to a colorimetric method was used to identify and determine the concentration of selected RONS occurring at the liquid-CAPP interface. Additionally, attenuated total reflectance Fourier transform-infrared spectroscopy (ATR FT-IR) was applied to reveal the active compounds, which might be responsible for the AuNPs surface functionalization and stabilization. Within the performed research it was found that the smallest in size AuNPs were synthesized using the aqueous P. ginseng root extract, which was activated by direct current atmospheric pressure glow discharge (dc-APGD), generated in contact with a flowing liquid cathode (FLC). On the contrary, taking into account the aqueous G. biloba leave extract, the smallest in size AuNPs were synthesized when the untreated by CAPP aqueous G. biloba leave extract was involved in the Au nanostructures synthesis. For catalytical studies we have chosen AuNPs produced using the aqueous P. ginseng root extract activated by FLC-dc-APGD as well as AuNPs synthesized using the aqueous G. biloba leave extract also activated by FLC-dc-APGD. Those NPs were successfully used as homogenous catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).

Tuning Optical and Granulometric Properties of Gold Nanostructures Synthesized with the Aid of Different Types of Honeys for Microwave-Induced Hyperthermia.

Size-controlled gold nanoparticles (AuNPs) were synthesised with solutions of three types of Polish honeys (lime, multiflower, honeydew) and used in microwave-induced hyperthermia cancer treatment. Optical and structural properties of nanostructures were optimized in reference to measurements made by using UV/Vis absorption spectrophotometry (UV/Vis), transmission electron microscopy (TEM) supported by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and attenuated total reflectance Fourier transformation infrared spectroscopy (ATR FT-IR). In addition, concentrations of reducing sugars and polyphenols of honeys applied were determined to reveal the role of these chemical compounds in green synthesis of AuNPs. It was found that the smallest AuNPs (20.6 ± 23.3 nm) were produced using a 20% (w/v) multiflower aqueous honey solution and 25 mg·L-1 of Au(III) ions. These AuNPs were then employed in microwave-induced hyperthermia in a system simulating metastatic tissues. This research illustrated that AuNPs, as produced with the aid of a multiflower honey solution, could be suitably used for microwave-induced heating of cancer. A fluid containing resultant Au nanostructures, as compared to water, revealed facilitated heating and the ability to maintain a temperature of 45 °C required for hyperthermia treatment.

Molecular reactors for synthesis of polymeric nanocomposites with noble metal nanoparticles for catalytic decomposition of 4-nitrophenol.

HYPOTHESIS: A new, facile in-situ method for synthesis of polymeric nanocomposites (NCs) with nanoparticles (NPs) of Au, Pt and Pd is proposed. The method involves reduction-coupled sorption of Au(III), Pt(VI), and Pd(II), which avoids diffusion limitations, allowing the precipitation and stabilization of the NPs directly in the polymeric matrix. EXPERIMENTS: The obtained nanomaterials were characterized by transmission electron microscopy (TEM), and Fourier-transformation infrared spectroscopy (FT-IR). NPs loaded into polymers were also investigated using X-ray diffraction (XRD). FINDINGS: Based on the results, it was concluded that the amino functionalities simultaneously reduced noble metals ions and capped the NPs. The average diameter of the obtained AuNPs ranged from 25 to 109 nm, while reduction-coupled sorption was carried out in 1 and 3 mol L-1 HCl solutions, respectively. Applying a 0.1 mol L-1 HCl solution containing Au(III), Pd(II) and Pt(VI), a NC with AuNPs and cubic-like PdNPs was fabricated, while using a solution of the same composition, but in 3 mol L-1 HCl, resulted in formation of a NC with flower-like PtNPs. Ultimately, the selected NC based on a resin with functionalities derived from 1-(2-aminoethyl)piperazine and with bi-metallic active sites, i.e. AuNPs and PdNPs, revealed catalytic activity in the reduction of 4-nitrophenol.

Atmospheric Pressure Plasma-Mediated Synthesis of Platinum Nanoparticles Stabilized by Poly(vinylpyrrolidone) with Application in Heat Management Systems for Internal Combustion Chambers.

Poly(vinylpyrrolidone)-stabilized Pt nanoparticles (PVP-PtNPs) were produced in a continuous-flow reaction-discharge system by application of direct current atmospheric pressure glow discharge (dc-APGD) operated between the surface of a flowing liquid anode (FLA) and a pin-type tungsten cathode. Synthesized PVP-PtNPs exhibited absorption across the entire UV/Vis region. The morphology and elemental composition of PVP-PtNPs were determined with transmission electron microscopy (TEM) and energy dispersive X-ray scattering (EDX), respectively. As assessed by TEM, PVP-PtNPs were approximately spherical in shape, with an average size of 2.9 ± 0.6 nm. EDX proved the presence of Pt, C, and O. Dynamic light scattering (DLS) and attenuated total reflectance Fourier transform-infrared spectroscopy (ATR FT-IR) confirmed PtNPs functionalization with PVP. As determined by DLS, the average size of PtNPs stabilized by PVP was 111.4 ± 22.6 nm. A fluid containing resultant PVP-PtNPs was used as a heat conductive layer for a spiral radiator managing heat generated by a simulated internal combustion chamber. As compared to water, the use of PVP-PtNPs enhanced efficiency of the system, increasing the rate of heat transfer by 80% and 30% during heating and cooling, respectively.

Polymerization-Driven Immobilization of dc-APGD Synthesized Gold Nanoparticles into a Quaternary Ammonium-Based Hydrogel Resulting in a Polymeric Nanocomposite with Heat-Transfer Applications.

A new method for the production of nanocomposites, composed of gold nanoparticles (AuNPs) and (vinylbenzyl)trimethylammonium chloride-co-N,N-methylene bisacrylamide (VBTAC-co-MBA) hydrogel, is described. Raw-AuNPs of defined optical and granulometric properties were synthesized using direct current atmospheric pressure glow discharge (dc-APGD) generated in contact with a solution of HAuCl4. Different approaches to the polymerization-driven synthesis of Au/VBTAC-co-MBA nanocomposites were tested. It was established that homogenous dispersion of AuNPs in this new nanomaterial with was achieved in the presence of NaOH in the reaction mixture. The new nanocomposite was found to have excellent heat-transfer properties.

An Assessment of a New Synthetic Procedure for Core-shell Polymeric Supports Based on the Amberlite XAD-4 Adsorbent.

In pursuit for new reactive materials designed for synthesis of functional resins, the novel core-shell type polymeric supports with accessible chloromethyl groups were synthesized. The commercial Amberlite XAD-4 adsorbent was impregnated with different mixtures of vinylbenzylchloride and divinylbenzene, that were further polymerized in the structure of the polymer carrier. The syntheses have been evaluated by recording FT-IR spectra, capturing SEM micrographs as well as analyzing the sorption and desorption of nitrogen at 77 K. The amount of the introduced functionalities has been estimated by chlorine content determination. Based on the obtained results, the reactive chloromethyl groups were successfully introduced into XAD-4 structure. Captured SEM micrographs revealed that VBC/DVB copolymer has covered initial polymeric matrix of XAD-4 adsorbent. Based on the results we have determined conditions of the synthesis that allow us to receive that effect.

Polymer resins for recovery of valuable metals.

Vinylbenzyl chloride/divinylbenzene gel copolymer beads have been modified using piperidine, hexamethyleneimine, piperazine, 1-(2-aminoethyl)piperazine, and N-cyclohexyl-1,3-propanediamine. These resins were then tested for the sorption of noble metal ions, namely, Re(VII), Pd(II), Pt(IV), and Au(III), from a 0.1 M HCl solution. The effect of these resins on the sorption of other coexisting ions, such as Cu, Ni and Fe, was also studied. Of the resins tested, resin 4 [1-(2-aminoethyl)piperazine groups] showed the highest sorption capacity for Pt(IV) and Re(VII) from single and multicomponent solutions, with the sorption of Pt(IV) from the multicomponent solution (Re, Au, Pd, Pt, Cu, Ni Fe) in 0.1 M HCl reaching 68 mg Pt/g.