Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size.
Size-controlled and monodispersed silver nanoparticles were synthesized from an aqueous solution containing silver nitrate as a metal precursor, polyvinyl alcohol as a capping agent, isopropyl alcohol as hydrogen and hydroxyl radical scavengers, and deionized water as a solvent with a simple radiolytic method. The average particle size decreased with an increase in dose due to the domination of nucleation over ion association in the formation of the nanoparticles by gamma reduction. The silver nanoparticles exhibit a very sharp and strong absorption spectrum with the absorption maximum λmax blue shifting with an increased dose, owing to a decrease in particle size. The absorption spectra of silver nanoparticles of various particle sizes were also calculated using a quantum physics treatment and an agreement was obtained with the experimental absorption data. The results suggest that the absorption spectrum of silver nanoparticles possibly derived from the intra-band excitations of conduction electrons from the lowest energy state (n = 5, l = 0) to higher energy states (n ≥ 6; Δl = 0, ±1; Δs = 0, ±1), allowed by the quantum numbers principle. This demonstrates that the absorption phenomenon of metal nanoparticles based on a quantum physics description could be exploited to be added into the fundamentals of metal nanoparticles and the related fields of nanoscience and nanotechnology.
Gamma radiolytic synthesis was used to produce size-controlled spherical platinum nanoparticles from an aqueous solution containing platinum tetraammine and polyvinyl pyrrolidone. The structural characterizations were performed using X-ray diffraction, and transmission electron microscopy. The transmission electron microscopy was used to determine the average particle diameter, which decreased from 4.4nm at 80kGy to 2.8nm at 120kGy. The UV-visible absorption spectrum was measured and found that platinum nanoparticles exhibit two steady absorption maxima in UV regions due to plasmonic excitation of conduction electrons, which blue shifted to lower wavelengths with a decrease in particle size. We consider the conduction electrons of platinum nanoparticles to follow Thomas-Fermi-Dirac-Weizsacker atomic model that they are not entirely free but weakly bounded to particles at lower-energy states {n = 5, l = 2 or 5d} and {n = 6, l = 0 or 6s}, which upon receiving UV photon energy the electrons make intra-band quantum excitations to higher-energy states allowed by the principles of quantum number that results the absorption maxima. We found an excellent agreement between the experimental and theoretical results, which suggest that the optical absorption of metal nanoparticles could be fundamentally described by a quantum mechanical interpretation, which could be more relevant to photo-catalysis and heterogeneous catalysis.
Platinum nanoparticles were synthesized using the gamma radiolytic technique in an aqueous solution containing Platinum tetraammine chloride in presence of poly vinyl pyrrolidone, isopropanol, tetrahydrofuran and deionized water. The gamma irradiation was carried out in a60Co gamma source chamber and the particle size was found to decrease from 4.88 to 3.14 nm on increasing the gamma radiation dose from 80 to 120 kGy. UV-visible absorption spectra were measured and revealed two steady absorption maxima at 216 and 264 nm in the UV region, which was blue shifted (i.e. toward lower wavelength) with decreasing particle size. By taking the conduction electrons of an isolated particle that are not entirely free, but instead bound to their respective quantum levels, the optical absorption of platinum nanoparticles can be calculated via intra-band quantum excitation for particle sizes similar to those measured experimentally. We found that the calculated absorption maxima of electronic excitations matched the measured absorption maxima well. This finding suggests that the optical absorption of metal nanoparticles commonly applied in nanoscience and nanotechnology can be described accurately by the quantum excitation of conduction electrons.
The modified thermal treatment method via alternate oxygen and nitrogen flow was successfully employed to synthesize very narrow and pure Ag nanoparticles. The structural and optical properties of the obtained metal nanoparticles at different calcination temperatures between 400 and 800 °C were studied using various techniques. The FTIR and EDX confirmed the formation of Ag nanoparticles without a trace of impurities. The XRD spectra revealed that the amorphous sample at 30 °C had transformed into the cubic crystalline nanostructures at the calcination temperature of 400 °C and higher. The TEM images showed the formation of spherical Ag nanoparticles in which the average particle size decreased with increasing calcination temperature from 7.88 nm at 400 °C to 3.29 nm at 800 °C. The optical properties were determined by UV-vis absorption spectrophotometer, which showed an increase in the conduction band of Ag nanoparticles with increasing calcination temperature from 2.75 eV at 400 °C to 3.04 eV at 800 °C. This was due to less attraction between conduction electrons and metal ions as the particle size decreases in corresponding to fewer numbers of atoms that made up the metal nanoparticles.
Very narrow and pure silver nanoparticles were synthesized by modified thermal treatment method via oxygen and nitrogen flow in succession. The structural and optical properties of the calcined silver nanoparticles at 600°C with diverse Poly(vinylpyrrolidone) concentrations varied from 2% to 4% were studied by means of different techniques. Fourier transform infrared spectroscopy was used to monitor the production of pure Ag nanoparticles at a given Poly(vinylpyrrolidone) concentration. The X-ray powder diffraction spectra are evidence for the transformation of the amorphous sample at 30°C to the cubic crystalline nanostructures at the calcination temperatures for all Poly(vinylpyrrolidone) concentrations. The transmission electron microscopy images showed the creation of spherical silver nanoparticles with the average particle size decreased by increasing Poly(vinylpyrrolidone) concentrations from 4.61 nm at 2% to 2.49 nm at 4% Poly(vinylpyrrolidone). The optical properties were investigated by means of UV-vis absorption spectrophotometer, which showed an increase in the conduction band of Ag nanoparticles with increasing Poly(vinylpyrrolidone) concentrations from 2.83 eV at 2% Poly(vinylpyrrolidone) to 2.94 eV at 4% Poly(vinylpyrrolidone) due to decreasing particle size. This was due to less attraction between conduction electrons and metal ions for smaller particle size corresponding to fewer atoms that made up the metal nanoparticles.
A study was carried out on the concentration of REEs (Dy, Sm, Eu,Yb, Lu, La and Ce) that are present in the core marine sediments of East Malaysia from three locations at South China Sea and one location each at Sulu Sea and Sulawesi Sea. The sediment samples were collected at a depth of between 49 and 109 m, dried, and crushed to powdery form. The entire core sediments prepared for Instrumental Neutron Activation Analysis (INAA) were weighted approximately 0.0500 g to 0.1000 g for short irradiation and 0.1500 g to 0.2000 g for long irradiation. The samples were irradiated with a thermal neutron flux of 4.0×10(12) cm(-2) s(-1) in a TRIGA Mark II research reactor operated at 750 kW. Blank samples and standard reference materials SL-1 were also irradiated for calibration and quality control purposes. It was found that the concentration of REEs varies in the range from 0.11 to 36.84 mg/kg. The chondrite-normalized REEs for different stations suggest that all the REEs are from similar origins. There was no significant REEs contamination as the enrichment factors normalized for Fe fall in the range of 0.42-2.82.
A study was carried out on the distribution and enrichment of trace elements in the core marine sediments of East Malaysia from three stations at South China Sea and one station each at Sulu Sea and Sulawesi Sea. Five stations of sediment cores were recovered and the vertical concentration profiles of six elements namely Br, Cs, Hf, Rb, Ta, and V were determined using the instrumental neutron activation analysis. The enrichment factor, geoaccumulation index and the modified degree of contamination were used to calculate the anthropogenic and pollution status of the elements in the samples. Except for Cs and Hf, which by the enrichment factor are categorized from minimum enrichment to moderate enrichment in all stations and for V and Rb in Sulu Sea and Sulawesi Sea, which are categorized minimum enrichment, other elements are found to be no enrichment at all stations. The geoaccumulation index of Hf in one station shows moderately polluted and for other elements are unpolluted. However, the modified degree values of all samples are less than 1, suggesting very low contamination of elements found in all the stations.
Fifty-five core marine sediments from three locations at South China Sea and one location each at Sulu Sea and Sulawesi Sea of coastal East Malaysia were analyzed for heavy metals by instrumental neutron activation analysis and inductively coupled plasma mass spectroscopy. The enrichment factor and the modified degree of contamination were used to calculate the anthropogenic and pollution status of the elements in the samples. The enrichment factor of As, Cd, Cr, Cu, Ni, Pb, and Zn varied from 0.42-4.26, 0.50-2.34, 0.31-0.82, 0.20-0.61, 0.91-1.92, 0.23-1.52, and 0.90-1.28, respectively, with the modified degree of contamination values below 0.6. Comparative data showed that coastal East Malaysia has low levels of contamination.