Alex T. Kuvarega

Stabilisation of silver and copper nanoparticles in a chemically modified chitosan matrix

This work describes the stabilisation of silver and copper nanoparticles in chemically modified chitosan colloidal solution. Chitosan-N-2-methylidene-hydroxy-pyridine-6-methylidene hydroxy thiocarbohydrazide (CSPTH) was used as a stabilising and reducing agent for silver and copper nanoparticles. The modified chitosan derivatives and the synthesised nanoparticles were characterised by Fourier transform infrared (FT-IR) spectroscopy, Ultraviolet-visible (UV-Vis) spectroscopy and X-ray diffraction (XRD). Particle size, morphology and segregation of the nanoparticles were determined by transmission electron microscopy (TEM). The size of the nanoparticles was found to be less than 20 nm and 50 nm for silver and copper nanoparticles, respectively. These nanoparticles were stabilised in a chemically modified chitosan solution and their properties were studied using fluorescence spectroscopy, photoluminescence spectroscopy and surface-enhanced Raman scattering (SERS). The optical properties of silver nanoparticles in surface plasmon band (SPB) were enhanced at 407 nm compared to those of copper nanoparticles. Fluorescence (400 nm and 756 nm), photoluminescence (450 and 504 nm) and Raman scattering (1382 and 1581 cm(-1)) properties for the copper nanoparticles were superior to those of the silver nanoparticles.

Enhanced visible-light photocatalytic activity of multi-elements-doped ZrO2 for degradation of indigo carmine

Abstract In this study, C,N,S-doped ZrO 2 and a series of Eu doped C,N,S-ZrO 2 photocatalysts were synthesized by a coprecipitation method using thiourea as the source of C, N and S and Eu(NO 3 )·6H 2 O as source of Eu. The materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), UV-visible diffuse reflectance spectroscopy, scanning electron microscopy (SEM)/energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). Indigo carmine (IC) was chosen as a model for organic pollutants and used to evaluate the photocatalytic performance of the photocatalysts under simulated solar light. Commercial ZrO 2 was used as a reference material. XRD and Raman results indicated the formation of both tetragonal and monoclinic phase ZrO 2 with particle size ranging from 8-30 nm. Multi-element doping had a great influence on the optical responses manifested as red shift in the absorption edge. The highest photocatalytic activity towards IC was observed for the Eu,C,N,S-doped ZrO 2 (0.6 mol.% Eu) sample ( k =1.09×10 −2 min −1 ). The commercial ZrO 2 showed the lowest photodegradation activity ( k =5.83×10 −4 min −1 ). The results showed that the control of Eu doping in the C,N,S-ZrO 2 was very important in reducing electron-hole recombination. The synergistic effect of Eu, C, N, and S in the ZrO 2 matrix led to enhanced utilization of simulated solar energy for the degradation of IC through narrowing of bandgaps.

Mixed Matrix PVDF Membranes With in Situ Synthesized PAMAM Dendrimer-Like Particles: A New Class of Sorbents for Cu(II) Recovery from Aqueous Solutions by Ultrafiltration

Advances in industrial ecology, desalination, and resource recovery have established that industrial wastewater, seawater, and brines are important and largely untapped sources of critical metals and elements. A Grand Challenge in metal recovery from industrial wastewater is to design and synthesize high capacity, recyclable and robust chelating ligands with tunable metal ion selectivity that can be efficiently processed into low-energy separation materials and modules. In our efforts to develop high capacity chelating membranes for metal recovery from impaired water, we report a one-pot method for the preparation of a new family of mixed matrix polyvinylidene fluoride (PVDF) membranes with in situ synthesized poly(amidoamine) [PAMAM] particles. The key feature of our new membrane preparation method is the in situ synthesis of PAMAM dendrimer-like particles in the dope solutions prior to membrane casting using low-generation dendrimers (G0 and G1-NH2) with terminal primary amine groups as precursors and epichlorohydrin (ECH) as cross-linker. By using a combined thermally induced phase separation (TIPS) and nonsolvent induced phase separation (NIPS) casting process, we successfully prepared a new family of asymmetric PVDF ultrafiltration membranes with (i) neutral and hydrophilic surface layers of average pore diameters of 22-45 nm, (ii) high loadings (∼48 wt %) of dendrimer-like PAMAM particles with average diameters of ∼1.3-2.4 μm, and (iii) matrices with sponge-like microstructures characteristics of membranes with strong mechanical integrity. Preliminary experiments show that these new mixed matrix PVDF membranes can serve as high capacity sorbents for Cu(II) recovery from aqueous solutions by ultrafiltration.

TiO2-based Photocatalysis: Toward Visible Light-Responsive Photocatalysts Through Doping and Fabrication of Carbon-based Nanocomposites

ABSTRACT Elimination of toxic organic compounds from wastewater and provision of safe, clean, and cheap water to communities is currently one of the most important global topics in water-pollution control. TiO2 has emerged as one of the most fascinating material in the modern era due to its potential catalytic properties. In spite of extensive efforts to apply TiO2 for environmental remediation, photocatalytic activity in the visible region has remained quite low hence the need to fabricate highly photoactive catalysts through modification of TiO2 and to apply them for water remediation using the abundantly available solar radiation. Carbon materials are promising candidates for application as functional materials due to their superior physico-chemical properties. This has prompted investigations into their possible application in environmental clean-up. Nanocomposite assemblies composed of different types and proportions of carbon based materials (i.e., carbon nanotubes, graphene, fullerenes, activated carbon, carbon nanofibers) and TiO2 have also found widespread applicability in water decontamination studies using UV or visible light. This article surveys the literature and highlights recent progress in the development of TiO2 and nanocarbon/TiO2 photocatalysts for water decontamination. The nitty-gritties, on-going challenges, areas of controversy, “hotspots” and possible new directions are outlined in this article.

Comparison between base metals and platinum group metals in nitrogen, m codoped TiO 2 (M = Fe, Cu, Pd, Os) for photocatalytic removal of an organic dye in water

The photocatalytic performance of a number of nonmetal and metal codoped TiO2 for the degradation of eosin yellow under simulated solar radiation was investigated. The synthesised materials were characterised by FTIR, Raman spectroscopy, XRD, DRUV-Vis, SEM, and TEM. The N, metal codoped TiO2 containing 0.5 wt.% of the metal consisted mainly of the anatase phase, with a particle size range of 15-28 nm. The particles were largely spherical and shifted the absorption edge well into the visible region. Band gap reduction was more pronounced for the N, PGM codoped TiO2 compared to N, base metal codoped samples. Codoping led to an enhancement in the photocatalytic activity of the materials for the degradation of eosin yellow. N, Pd codoped TiO2 was the most effective photocatalyst (99.9% dye removal) while N, Cu codoped TiO2 showed the least activity (25.5% removal). The mechanism for the photocatalytic enhancement was proposed on the basis of formation of an electron deficient Schottky barrier at the semiconductor-metal interface, which acts as an electron sink and thus retards electron-hole recombination. It was shown that the ability of the photocatalyst to degrade the dye depends on the nature and type of themetal dopant in the codoped TiO2 system.

Double Walled Carbon Nanotube/TiO2 Nanocomposites for Photocatalytic Dye Degradation

Double walled carbon nanotube DWCNT/N,Pd codoped TiO2 nanocomposites were prepared by a modified sol-gel method and characterised using FTIR, Raman spectroscopy, TGA, DRUV-Vis, XRD, SEM, and TEM analyses. TEM images showed unique pearl-bead-necklace structured morphologies at higher DWCNT ratios. The nanocomposite materials showed characteristic anatase TiO2 Raman bands in addition to the carbon nanotube D and G bands. Red shifts in the UV-Vis absorption edge were observed at low DWCNT percentages. The photocatalytic activity of DWCNT/N,Pd TiO2 nanocomposite was evaluated by the photocatalytic degradation of eosin yellow under simulated solar light irradiation and the 2% DWCNT/N,Pd TiO2 nanocomposite showed the highest photoactivity while the 20% DWCNT/N,Pd TiO2 hybrid was the least efficient. The photocatalytic enhancement was attributed to the synergistic effects of the supporting and electron channeling role of the DWCNTs as well as the electron trapping effects of the platinum group metal. These phenomena favour the separation of the photogenerated electron-hole pairs, reducing their recombination rate, which consequently lead to significantly enhanced photoactivity.

Facile Synthesis of Nitrogen Doped Graphene Oxide from Graphite Flakes and Powders: A Comparison of Their Surface Chemistry

Nitrogen-doped graphene oxide (NGO) nanosheets were prepared via a facile one-pot modified Hummers approach at low temperatures using graphite powder and flakes as starting materials in the presence of a nitrogen precursor. It was found that the morphology, structure, composition and surface chemistry of the NGO nanosheets depended on the nature of the graphite precursor used. GO nanosheets doped with nitrogen atoms exhibited a unique structure with few thin layers and wrinkled sheets, high porosity and structural defects. NGO sheets made from graphite powder (NGOp) exhibited excellent thermal stability and remarkably high surface area (up to 240.53 m2 ·g-1) compared to NGO sheets made from graphite flakes (NGOf) which degraded at low temperatures and had an average surface area of 24.70 m2 ·g-1. NGOf sheets had a size range of 850 to 2200 nm while NGOp sheets demonstrated obviously small sizes (460-1600 nm) even when exposed to different pH conditions. The NGO nanosheets exhibited negatively charged surfaces in a wide pH range (1 to 12) and were found to be stable above pH 6. In addition, graphite flakes were found to be more suitable for the production of NGO as they produced high N-doping levels (0.65 to 1.29 at.%) compared to graphite powders (0.30 to 0.35 at.%). This study further demonstrates that by adjusting the amount of N source in the host GO, one can tailor its thermal stability, surface morphology, surface chemistry and surface area.

Template-free preparation of TiO2 microspheres for the photocatalytic degradation of organic dyes

TiO2 microspheres were successfully synthesised by simple solution phase method by using various amount of titanium butoxide as precursor. The prepared TiO2 were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance absorption spectra (UV-DRS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XRD analysis revealed that the as-synthesized TiO2 microsphere poses an anatase phase. The photocatalytic degradation experiments were carried out with three different dyes, such as methylene blue, brilliant black, reactive red-120 for four hours under UV light irradiation. The results show that TiO2 morphology had great influence on photocatalytic degradation of organic dyes. The experimental results of dye mineralization indicated the concentration was reduced by a high portion of up to 99% within 4 hours. On the basis of various characterization of the photocatalysts, the reactions involved to explain the photocatalytic activity enhancement due to the concentration of titanium butoxide and morphology include a better separation of photogenerated charge carriers and improved oxygen reduction inducing a higher extent of degradation of aromatics.

A Facile and Scalable Route to the Preparation of Catalytic Membranes with in Situ Synthesized Supramolecular Dendrimer Particle Hosts for Pt(0) Nanoparticles Using a Low-Generation PAMAM Dendrimer (G1-NH2) as Precursor

Since the first reports of Cu dendrimer-encapsulated nanoparticles (DENs) published in 1998, the dendrimer-templating method has become the best and most versatile method for preparing ultrafine metallic and bimetallic nanoparticles (1-3 nm) with well-defined compositions, high catalytic activity, and tunable selectivity. However, DENs have remained for the most part model systems with limited prospects for scale up and integration into high-performance and reusable catalytic modules and systems for industrial-scale applications. Here, we describe a facile and scalable route to the preparation of catalytic polyvinylidene fluoride (PVDF) membranes with in situ synthesized supramolecular dendrimer particles (SDPs) that can serve as hosts and containers for Pt(0) nanoparticles (2-3 nm). These new catalytic membranes were prepared using a reactive encapsulation process similar to that utilized to prepare Pt DENs by addition of a reducing agent (sodium borohydride) to aqueous complexes of Pt(II) + G4-OH/G6-OH polyamidoamine (PAMAM) dendrimers. However, the SDPs (2.4 μm average diameter) of our new mixed matrix PVDF-PAMAM membranes were synthesized in the dope dispersion without purification prior to film casting using (i) a low-generation PAMAM dendrimer (G1-NH2) as particle precursor and (ii) epichlorohydrin, an inexpensive functional reagent, as cross-linker. In addition, the membrane PAMAM particles contain secondary amine groups (∼1.9 mequiv per gram of dry membrane), which are more basic and thus have higher Pt binding affinity than the tertiary amine groups of the G4-OH and G6-OH PAMAM dendrimers. Proof-of-concept experiments show that our new PVDF-PAMAM-G1-Pt/membranes can serve as highly active and reusable catalysts for the hydrogenation of alkenes and alkynes to the corresponding alkanes using (i) H2 at room temperature and a pressure of 1 bar and (ii) low catalyst loadings of ∼1.4-1.6 mg of Pt. Using cyclohexene as model substrate, we observed near quantitative conversion to cyclohexane (∼98%). The regeneration studies showed that our new Pt/membrane catalysts are stable and can be reused for five consecutive reaction cycles for a total duration of 120 h including 60 h of heating at 100 °C under vacuum for substrate, product, and solvent removal with no detectable loss of cyclohexene hydrogenation activity. The overall results of our study point to a promising, versatile, and scalable path for the integration of catalytic membranes with in situ synthesized SDP hosts for Pt(0) nanoparticles into high-throughput modules and systems for heterogeneous catalytic hydrogenations, an important class of reactions that are widely utilized in industry to produce pharmaceuticals, agrochemicals, and specialty chemicals.

Hybrid Ceramic Materials for Environmental Applications

Ceramics and ceramic nanocomposites have attracted a lot of interest in the recent past due to their relatively easy and well understood fabrication techniques as well as an array of commercial applications ranging from structural to environmental. Their properties have been tailored to suit the desired applications through nano-structuring of mono-, di-, tri- and even multi-phasic systems. This chapter highlights some of the current state of knowledge on synthesis, processing, mechanical properties and environmental applications of nanoceramics.