Pt Nanophase supported catalysts and electrode systems for water electrolysis

Doctor Scientiae - DScIn this study novel composite electrodes were developed, in which the catalytic components were deposited in nanoparticulate form. The efficiency of the nanophase catalysts and membrane electrodes were tested in an important electrocatalytic process, namely hydrogen production by water electrolysis, for renewable energy systems. The activity of electrocatalytic nanostructured electrodes for hydrogen production by water electrolysis were compared with that of more conventional electrodes. Development of the methodology of preparing nanophase materials in a rapid, efficient and simple manner was investigated for potential application at industrial scale. Comparisons with industry standards were performed and electrodes with incorporated nanophases were characterized and evaluated for activity and durability.South Afric

Treatment of Acid Mine Drainage with Coal Fly Ash: Exploring the Solution Chemistry and Product Water Quality

A treatment process for Acid mine drainage (AMD) using coal fly ash (CFA) was developed. AMD was treated with CFA as the alkaline agent at different CFA: AMD ratios and pH, electrical conductivity (EC) evolution monitored over time. In a separate experiment two AMD sources with differing chemistry were treated with the same CFA to evaluate the impact of AMD chemistry on the treatment process and product water quality. Various CFA: AMD ratios were stirred in a beaker for a pre-set time and the process water chemistry determined. pH was observed to increase in a stepwise manner with buffer zones observed at 4-4.5, 4.5-7 and 6-8. AMD with low concentration of Al3+, Fe2+, Fe3+ and Mn2+ didn’t exhibit these buffer zones. Two competing processes were observed to control the evolving pH of process water: dissolution of basic oxides (CaO, MgO) from CFA led to pH increase and hydrolysis of AMD species such as Al3+, Fe2+, Fe3+ and Mn2+ led to pH decrease. These processes initiated mechanisms such as precipitation, adsorption and ion exchange that led to decrease in inorganic contaminants as the treatment progressed. Inorganic contaminants removal was directly related to amount of CFA in reaction media. Precipitation of insoluble hydroxides and Al, Fe-oxyhydroxysulphates contributed to removal of major and minor chemical species. Precipitation of gypsum contributed to removal of sulphate. Na, K and Mg remained largely in solution after initial decrease. Significant leaching of B, Sr, Ba, and Mo from CFA was observed and was directly linked to amount of CFA in the reaction media. This will be a shortcoming of the treatment process since other processes may be required to polish up the product water. The treatment of AMD with CFA was observed to depend on CFA, AMD chemistry, treatment time and might therefore be site specific

Hydrothermal Conversion of South African Coal Fly Ash into Pure Phase Zeolite Na‐P1

South African coal combustion power utilities generate huge amounts of coal fly ash that can be beneficiated into zeolitic products. This chapter reports on the optimization of the presynthesis and synthesis conditions for a pure‐phase zeolite Na‐P1 from selected South African coal fly ashes. The hydrothermal treatment time, temperature, and molar quantities of water during the hydrothermal treatment step were successfully optimized. The optimum hydrothermal treatment time and temperature were 48 h and 140°C, respectively. Pure‐phase zeolite Na‐P1 was obtained with a molar regime of 1 SiO2:0.36 Al2O3:0.59 NaOH:0.49 H2O at an aging temperature of 47°C for 48 h. The optimized conditions were applied to two fly ashes from two coal‐fired power utilities, and high‐purity zeolite Na‐P1 was obtained. The third coal fly ash with a different chemical composition gave a low‐quality Na‐P1 under the optimized conditions. The cation exchange capacity for the high‐purity zeolite phase was 4.11 mEq/g, indicating that the adjustment of reactant composition and presynthesis or synthesis parameters leads to yields of high‐quality zeolite Na‐P1. The results also show that conversion of the coal fly ash into high‐purity zeolite also depends on the chemical and mineralogical composition of the coal fly ash

The steric influence of extra-framework cations on framework flexibility:An LTA case study

The theoretical extent of framework flexibility of Zeolite A (LTA) in response to the steric and geometric effects of different Si/Al compositions and extra-framework cation content has been explored using GASP software. Flexibility windows and compression mechanisms for siliceous LTA and aluminosilicate Na-LTA, Ca-LTA and K-LTA have been modelled. As expected, relatively small cations in the zeolite pores have little effect on the range of flexibility observed. Aluminosilicate LTA, Na-LTA and Ca-LTA frameworks exhibit identical flexibility windows and these frameworks also follow the same compression mechanisms. The introduction of larger K+ ions, however, results in greater steric hindrance. This restricts the flexibility of the framework and alters the compression mechanism to accommodate these larger cations. It is shown that the limits of the flexibility window of Zeolite A are dependent on framework aluminium content and extra-framework cation size.</p

Synthesis of oxygen deficient tio2 for improved photocatalytic efficiency in solar radiation

The photocatalytic activities of TiO2 have been limited mainly to absorbing in the ultraviolet spectrum which accounts for only 5% of solar radiation. High energy band gap and electron recombination in TiO2 nanoparticles are responsible for its limitations as a photocatalyst. An oxygen deficient surface can be artificially created on the titanium oxide by zero valent nano iron through the donation of its excess electrons. A visible light active TiO2 nanoparticle was synthesized in the current investigation through simple chemical reduction using sodium boro-hydride. The physical and textural properties of the synthesized oxygen deficient TiO2 photocatalyst was measured using scanning/ transmission electron microscopy while FTIR, XRD and nitrogen sorption methods (BET) were employed for its further characterizations. Photochemical decoloration of orange II sodium dye solution in the presence of the synthesized TiO2 was measured using an UV spectrophotometer. The resulting oxygen deficient TiO2 has a lower energy band-gap, smaller pore sizes, and enhanced photo-catalytic properties

Environmental evaluation and nano-mineralogical study of fresh and unsaturated weathered coal fly ashes

Coal combustion and the disposal of combustion wastes emit enormous quantities of nano-sized particles that pose significant health concerns on exposure, particularly in unindustrialized countries. Samples of fresh and weathered class F fly ash were analysed through various techniques including X-ray fluorescence (XRF), X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), field-emission gun scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM) coupled with energy dispersive x-ray spectroscopy (EDS), and Raman Spectroscopy. The imaging techniques showed that the fresh and weathered coal fly ash nanoparticles (CFA-NPs) are mostly spherical shaped. The crystalline phases detected were quartz, mullite, ettringite, calcite, maghemite, hematite, gypsum, magnetite, clay residues, and sulphides. The most abundant crystalline phases were quartz mixed with Al-Fe-Si-K-Ti-O-amorphous phases whereas mullite was detected in several amorphous phases of Al, Fe, Ca, Si, O, K, Mg, Mn, and P. The analyses revealed that CFANPs are 5–500 nm in diameter and encapsulate several potentially hazardous elements (PHEs). The carbon species were detected as 5–50 nm carbon nanoballs of graphitic layers and massive fullerenes. Lastly, the aspects of health risks related to exposure to some detected ambient nanoparticles are also discussed

Binderless zeolite monoliths production with sacrificial biopolymers

3D printing has emerged as an attractive way of formulating structured adsorbents, as it imparts lower manufacturing costs compared to hydraulic extrusion while also allowing for unprecedented geometric control. However, binderless structures have not been fabricated by 3D printing, as ink formulation has previously required clay binders which cannot be easily removed. In this study, we report the development of a facile approach to shape engineer binderless zeolites. 3D-printed inks comprised of 13X, 5A, ZSM-5, and experimental South African zeolites were prepared using gelatin and pectin as binding agents along with dropwise addition of various solvents. After printing, the dried monoliths were calcined to remove the biopolymers and form 100% pure zeolite structures. From N2 physisorption and CO2 adsorption measurements at 0 °C, all monoliths showed narrowing below 1 nm from their powders, which was attributed to pore malformation caused by intraparticle bridging during calcination

Synthesis of zeolites from coal fly ash using mine waters

In this study mine waters obtained from coal mining operations in South Africa were used as a substitute for pure water during the synthesis of zeolites from South African coal fly ash. Procedures that had been optimized to produce single phase zeolite Na-P1 and X using pure water were employed independently. The use of circumneutral mine water resulted in similar quality zeolite Na-P1 and X whereas the use of acidic mine drainage led to the formation of a single phase hydroxysodalite zeolite. Since these two wastes (fly ash and mine waters) are found in close proximity to each other, this study demonstrates that they can be used to ameliorate each other and at the same time produce saleable zeolitic products that can be used to offset their costs of disposal and treatment.Web of Scienc

Synthesis of an ordered mesoporous carbon with graphitic characteristics and its application for dye adsorption

An ordered mesoporous carbon (OMC) was prepared by a chemical vapor deposition technique using liquid petroleum gas (LPG) as the carbon source. During synthesis, LPG was effectively adsorbed in the ordered mesopores of SBA-15 silica and converted to a graphitic carbon at 800 °C. X-ray diffraction and nitrogen adsorption/desorption data and high-resolution transmission electron microscopy (HRTEM) of the OMC confirmed its ordered mesoporous structure. The OMC was utilized as an adsorbent in the removal of dyes from aqueous solution. A commercial powder activated carbon (AC) was also investigated to obtain comparative data. The efficiency of the OMC for dye adsorption was tested using acidic dye acid orange 8 (AO8) and basic dyes methylene blue (MB) and rhodamine B (RB). The results show that adsorption was affected by the molecular size of the dye, the textural properties of carbon adsorbent and surface-dye interactions. The adsorption capacities of the OMC for acid orange 8 (AO8), methylene blue (MB) and rhodamine B (RB) were determined to be 222, 833, and 233 mg/g, respectively. The adsorption capacities of the AC for AO8, MB, and RB were determined to be 141, 313, and 185 mg/ g, respectively. The OMC demonstrated to be an excellent adsorbent for the removal of MB from wastewater.Web of Scienc