Synthesis and characterization of pt-sn/c cathode catalysts via polyol reduction method for use in direct methanol fuel cell

Philosophiae Doctor - PhDDirect methanol fuel cells (DMFCs) are attractive power sources as they offer high conversion efficiencies with low or no pollution. One of the major advantages DMFCs has over PEMFCs is that methanol is a liquid and can be easily stored where in the case for PEMFCs storing hydrogen requires high pressures and low temperatures. However, several challenging factors especially the sluggish oxygen reduction reaction (ORR) and the high cost of Pt catalysts, prolong their commercialization. With the aim to search for more active, less expensive more active ORR catalysts and methanol tolerant catalysts than pure Pt, this dissertation focuses on the development of low loading Pt electrocatalyst and the understanding of their physical and electrochemical properties. Pt-Sn/C electrocatalsyts have been synthesized by a modified polyol reduction method. The effect of temperature, pH, water, sonication and addition of carbon form were studied before a standard polyol method was established. From XRD patterns, the Pt-Sn/C peaks shifted slightly to lower 2Ө angles when compared with commercial Pt/C catalyst, suggesting that Sn is alloying with Pt. Based on HRTEM data, the Pt-Sn/C nanoparticles showed small particle sizes well-dispersed onto the carbon support with a narrow particle distribution. The particle sizes of the different as-prepared catalysts were found to be between 2-5 nm. The Pt-Sn/C HA Slurry pH3 catalysts was found to be the best asprepared catalyst and was subjected to heat-treatment in a reducing atmosphere at 250-600 °C which led to agglomeration yielding nanoparticles of between 5-10 nm. The Methanol Oxidation Reaction (MOR) on the as-prepared Pt-Sn/C HA Slurry pH3 catalyst appeared at lower currents (+7.11 mA at 860 mV vs. NHE) compared to the commercial Pt/C (+8.25 mA at +860 mV vs. NHE) suggesting that the Pt-Sn/C catalyst has „methanol tolerance capabilities‟. Pt-Sn/C HA Slurry pH3 and Pt-Sn/C 250 °C catalysts showed better activity towards the ORR than commercial Pt/C with specific and mass activities higher than Pt/C at +0.85 V vs NHE. The Tafel slopes of Pt-Sn/C HA Slurry pH3 catalyst was -62 and -122 mV dec-1 for the low and high current regions respectively and suggests that the ORR mechanism is similar to that of commercial Pt/C indicating that the ORR kinetics was not negatively influenced by the addition of tin. It was found that the electrochemical oxidation reduction reaction follows first order kinetics of a multi-electronic (n=4ē) charge transfer process producing water. All the Pt-Sn/C catalysts showed resistance towards MOR and it was found for the heat-treated catalysts that an increase in temperature resulted in an increase in methanol tolerance. The synthesized Pt-Sn/C HA Slurry pH3 catalysts were also tested in a fuel cell environment. Electrodes were prepared by either spraying on Toray carbon paper with the Asymtek machine or by VI spraying directly on the membrane with a hand spray gun the catalysts coated membrane (CCM) technique. Polarization curves obtained in DMFC with CCM showed superior performance than electrode prepared by spraying on the carbon paper with the machine. In our study, the Pt-Sn/C catalyst appears to be a promising methanol tolerant catalyst with activity towards the ORR in the DMFC

El Niño-Southern Oscillation influence on tropospheric mercury concentrations

The El Nino-Southern Oscillation (ENSO) affects the tropospheric concentrations of many trace gases. Here we investigate the ENSO influence on mercury concentrations measured in the upper troposphere during Civil Aircraft for the Regular Investigation of the atmosphere Based on an instrumented Container flights and at ground at Cape Point, South Africa, and Mace Head, Ireland. Mercury concentrations cross-correlate with Southern Oscillation Index (SOI) with a lag of 8 +/- 2 months. Highest mercury concentrations are always found at the most negative SOI values, i.e., 8 months after El Nino, and the amplitude of the interannual variations fluctuates between similar to 5 and 18%. The time lag is similar to that of CO whose interannual variations are driven largely by emissions from biomass burning (BB). The amplitude of the interannual variability of tropospheric mercury concentrations is consistent with the estimated variations in mercury emissions from BB. We thus conclude that BB is a major factor driving the interannual variation of tropospheric mercury concentrations

Multi-model study of mercury dispersion in the atmosphere : Atmospheric processes and model evaluation

Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air-surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM=GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM=GEM ratios from spring to summer. O3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere

Methods to Investigate the Global Atmospheric Microbiome

The interplay between microbes and atmospheric physical and chemical conditions is an open field of research that can only be fully addressed using multidisciplinary approaches. The lack of coordinated efforts to gather data at representative temporal and spatial scales limits aerobiology to help understand large scale patterns of global microbial biodiversity and its causal relationships with the environmental context. This paper presents the sampling strategy and analytical protocols developed in order to integrate different fields of research such as microbiology, –omics biology, atmospheric chemistry, physics and meteorology to characterize atmospheric microbial life. These include control of chemical and microbial contaminations from sampling to analysis and identification of experimental procedures for characterizing airborne microbial biodiversity and its functioning from the atmospheric samples collected at remote sites from low cell density environments. We used high-volume sampling strategy to address both chemical and microbial composition of the atmosphere, because it can help overcome low aerosol and microbial cell concentrations. To account for contaminations, exposed and unexposed control filters were processed along with the samples. We present a method that allows for the extraction of chemical and biological data from the same quartz filters. We tested different sampling times, extraction kits and methods to optimize DNA yield from filters. Based on our results, we recommend supplementary sterilization steps to reduce filter contamination induced by handling and transport. These include manipulation under laminar flow hoods and UV sterilization. In terms of DNA extraction, we recommend a vortex step and a heating step to reduce binding to the quartz fibers of the filters. These steps have led to a 10-fold increase in DNA yield, allowing for downstream omics analysis of air samples. Based on our results, our method can be integrated into pre-existing long-term monitoring field protocols for the atmosphere both in terms of atmospheric chemistry and biology. We recommend using standardized air volumes and to develop standard operating protocols for field users to better control the operational quality

Electrochemistry and electrophoresis of mercury cysteine and ditizone complexes

Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008.There are various mercury species in the environment and their toxicity and availability relies on their chemical form and oxidation states. Inorganic and organic mercury is found to co-exist in water and body tissue of some organisms. Among them inorganic mercury has a lower toxicity than the organic mercury. Methyl mercury (CH3Hg+) is the most toxic species found in the environment because it can enter the food chain accumulating and contaminating humans. Hence the total mercury concentration does not reflect the important information and thus the needs for the development of methods for the simultaneously separating and determination of mercury species. A study of the electrochemistry of mercury and organo mercury complexes with cysteine and dithizone indicated the formation of stable complexes, which can be utilized for the determination of the species in environmental matrices. Cyclic voltammetry is used to determine the electrochemical properties of the complexes. A technique based on capillary electrophoresis and amperometric detection (CE-AD) has been developed for the speciation of mercury. This technique has the capability to detect mercury species that are electrochemically active. Using capillary electrophoresis in combination with electrochemical detection makes speciation of the complexes possible at lower than normal concentrations. For CE-AD the detection limits were 0.005 μg/L for Hg2+ and 0.4 μg/L for MeHg+. These detection sensitivities are attractive for environmental monitoring

Investigation of BTX Concentrations and Effects of Meteorological Parameters in the Steelpoort Area of Limpopo Province, South Africa

It has been demonstrated that benzene, toluene, and xylene are carcinogens. Its combined effects with other contaminants have the potential to harm several ecosystem components. Since most human benzene exposure takes place inside, it is important to understand how outdoor benzene emissions from traffic and industry affect interior concentrations. However, this area of study has not received enough attention to date. Herein, we examine the outdoor concentrations of benzene, toluene, and xylene (BTX) in a Steelpoort mining area. BTX pollutants were passively sampled on the first seven days of the month, from January to December 2021 using Radiello samplers. The effects of meteorological parameters such as temperature, relative humidity, wind speed, and solar radiation on BTX concentrations were also statistically tested. For all seasons, BTX concentrations were greater in the winter than in the summer with concentrations of 0.69 µg/m3, 2.97 µg/m3 and 0.80 µg/m3 for benzene, toluene and xylene, respectively. In addition, toluene was the most common BTX compound with the highest concentrations when compared to benzene and xylene. Benzene, toluene and xylene, had yearly average concentrations of 0.61 µg/m3, 1.48 µg/m3 and 0.64 µg/m3, respectively. The benzene and xylene concentrations were below international exposure limits (annual, 5 µg/m3 for benzene; weekly, 260 µg/m3 for toluene), as in comparison to the World Health Organization, as well as within South African exceedance limits. Both positive and negative correlations between BTX and meteorological parameters were demonstrated by statistical models. Temperature, wind speed, and relative humidity depicted a weak negative correlation with benzene of 0.003, 0.019 and 0.006, respectively. Toluene showed a positive correlation with wind speed (1.90) and relative humidity (0.041). Overall, the concentration of benzene is of major concern since it is an agent of cancer and it is there in the atmosphere

Chitosan-Based Polymer Nanocomposites for Environmental Remediation of Mercury Pollution

Mercury is a well-known heavy metal pollutant of global importance, typically found in effluents (lakes, oceans, and sewage) and released into the atmosphere. It is highly toxic to humans, animals and plants. Therefore, the current challenge is to develop efficient materials and techniques that can be used to remediate mercury pollution in water and the atmosphere, even in low concentrations. The paper aims to review the chitosan-based polymer nanocomposite materials that have been used for the environmental remediation of mercury pollution since they possess multifunctional properties, beneficial for the adsorption of various kinds of pollutants from wastewater and the atmosphere. In addition, these chitosan-based polymer nanocomposites are made of non-toxic materials that are environmentally friendly, highly porous, biocompatible, biodegradable, and recyclable; they have a high number of surface active sites, are earth-abundant, have minimal surface defects, and are metal-free. Advances in the modification of the chitosan, mainly with nanomaterials such as multi-walled carbon nanotube and nanoparticles (Ag, TiO2, S, and ZnO), and its use for mercury uptake by batch adsorption and passive sampler methods are discussed

Atmospheric mercury in the Southern Hemisphere – Part 1: Trend and inter-annual variations in atmospheric mercury at Cape Point, South Africa, in 2007–2017, and on Amsterdam Island in 2012–2017

International audienceThe Minamata Convention on Mercury (Hg) entered into force in 2017, committing its 116 parties (as of January 2019) to curb anthropogenic emissions. Monitoring of atmospheric concentrations and trends is an important part of the effectiveness evaluation of the convention. A few years ago (in 2017) we reported an increasing trend in atmospheric Hg concentrations at the Cape Point Global Atmosphere Watch (GAW) station in South Africa (34.3535∘ S, 18.4897∘ E) for the 2007–2015 period. With 2 more years of measurements at Cape Point and the 2012–2017 data from Amsterdam Island (37.7983∘ S, 77.5378∘ E) in the remote southern Indian Ocean, a more complex picture emerges: at Cape Point the upward trend for the 2007–2017 period is still significant, but no trend or a slightly downward trend was detected for the period 2012–2017 at both Cape Point and Amsterdam Island. The upward trend at Cape Point is driven mainly by the Hg concentration minimum in 2009 and maxima in 2014 and 2012. Using ancillary data on 222Rn, CO, O3, CO2, and CH4 from Cape Point and Amsterdam Island, the possible reasons for the trend and its change are investigated. In a companion paper this analysis is extended for the Cape Point station by calculations of source and sink regions using backward-trajectory analysis

A synthesis of mercury research in the Southern Hemisphere, part 2: Anthropogenic perturbations

Environmental mercury (Hg) contamination is a global concern requiring action at national scales. Scientific understanding and regulatory policies are underpinned by global extrapolation of Northern Hemisphere Hg data, despite historical, political, and socioeconomic differences between the hemispheres that impact Hg sources and sinks. In this paper, we explore the primary anthropogenic perturbations to Hg emission and mobilization processes that differ between hemispheres and synthesize current understanding of the implications for Hg cycling. In the Southern Hemisphere (SH), lower historical production of Hg and other metals implies lower present-day legacy emissions, but the extent of the difference remains uncertain. More use of fire and higher deforestation rates drive re-mobilization of terrestrial Hg, while also removing vegetation that would otherwise provide a sink for atmospheric Hg. Prevalent Hg use in artisanal and small-scale gold mining is a dominant source of Hg inputs to the environment in tropical regions. Meanwhile, coal-fired power stations continue to be a significant Hg emission source and industrial production of non-ferrous metals is a large and growing contributor. Major uncertainties remain, hindering scientific understanding and effective policy formulation, and we argue for an urgent need to prioritize research activities in under-sampled regions of the SH