Faculty of Science (ETDs)

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Mapping and monitoring the impacts of climate variability on rainfed agriculture in Semi-arid North Darfur, Sudan
(University of the Witwatersrand, Johannesburg, 2024-02) Altoom, Mohammed Bashar Adam; Adam, Elhadi
Rainfed agriculture is vital to food security and income in most parts of the world. However, one-third of the population of developing countries population lives in the less favoured rainfed agricultural regions. Around 75-82% of the total cropland areas in the world are under rainfed agriculture and produce more than 60% of the globe’s cereal grains. However, rainfed agriculture is most prominent in some regions of Africa, such as Sub-Saharan Africa, where more than 95% of the cropland is rainfed. This crucial agriculture sector usually depends on the physical environment and, most importantly, the variability and distribution of rainfall. Therefore, rainfed farming is vulnerable to climate-related hazards, and the crop yield is unreliable and difficult to predict. For instance, the spatio-temporal variability of precipitation extreme events often subjects crops to short-term water deficits, causing crop losses. Sudan heavily depends on rainfed agriculture—about 90% of arable land dominates rainfed cultivation, contributing one-third of the country’s gross domestic product (GDP). Rainfed agriculture is the primary source of livelihood for 65% of the population. Unfortunately, agriculture in North Darfur of the west Sudan is characterised by environmental hazards, e.g., frequent droughts and unpredictable low, poorly distributed, and highly variable monthly/seasonal rainfall. Therefore, using various Earth observation data, this study aimed to monitor the impacts of rainfall variability on rainfed agriculture in North Darfur State in Sudan. Firstly, the study aimed to determine the feasibility of estimating rainfall variability across North Darfur State at daily, monthly and annual timescales using six satellite precipitation products (SPPs), i.e., the Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA), African Rainfall Climatology (ARC), and Climate Hazards Group Infrared Precipitation with Station Data (CHIRPS) were evaluated using four categorical indices, i.e., probability of detection (POD), probability of false alarm (POFA), bias in detection (BID) and Heidke skill score (HSS), and four continuous indices, i.e., Pearson correlation coefficient (r), root mean square error (RMSE), per cent bias (Pbias), and Nash-Sutcliffe model efficiency coefficient (NSE) against ground rain-gauge observations. The other SPPs were Integrated Multi-satellitE Retrievals for Global Precipitation Measurements (GPM) Final Run (GPMIMERG), Precipitation Estimation from Remote Sensing Information using Artificial Neural Networks-Climate Data Record (PERSIANN-CDR), and the Tropical Applications of Meteorology using SATellite and ground-based observations (TAMSAT). Results of the statistical analysis demonstrated that 1) at the daily timescale, the SPPs underestimate daily rainfall by 6.53–17.61%, and CHIRPS was the best for detecting rainy days, while PERSIANN-CDR performed poorly; 2) monthly and annual scales performed better than daily timescale, and TAMSAT and CHIRPS portrayed better performance than the ther SPPs. Secondly, the study assessed the capability of optical Earth Observation Data (EOD), i.e., Sentinel-2 multispectral dataset, to map crop types in the heterogeneous semi-arid environment of North Darfur using machine learning classifiers in Google Earth Engine (GEE) platform. Five datasets were compared against random forest (RF) and support vector machine (SVM) classification algorithms: (1) 10 Sentinel-2 bands (comprising visible, near-infrared and shortwave infrared bands), (2) Sentinel-2 (10 bands) + 8 vegetation indices, (3) visible bands and near-infrared bands only, (4) visible and shortwave infrared bands only, and (5) 8 vegetation indices. The eight vegetation indices were normalised difference vegetation index (NDVI), enhanced vegetation index (EVI), soil-adjusted vegetation index (SAVI), green normalised difference vegetation index (GNDVI, weighted difference vegetation index (WDVI), red edge NDVI (NDVIre), ratio-vegetation index (RVI) and normalised difference infrared index (NDII). Results showed that the RF algorithm produced the highest classification overall accuracy (OA), i.e., 97% and Kappa coefficient (κ), 0.96, using 10 Sentinel-2 bands dataset. Producer’s (PA) and user’s accuracies (UA) were in the range of 40-97% and 40-100%, respectively. Thirdly, the spatiotemporal trend of drought events and their impact on millet production in North Darfur from 1981 to 2020 was analyzed using standardized precipitation index (SPI) and reconnaissance drought index (RDI) by employing different timescales, i.e., 3- month (June-August), 6-month (June-November), and 9-month (June-February) timescales. Drought-yield relationships were assessed using Pearson correlation coefficients (r). Results indicated that RDI is more sensitive to rainfall variabilities than SPI in detecting drought trends. Results revealed that drought events affected North Darfur over broad spatial extents, particularly in 1989, 1990, 1992, 1999, and 2001—an extreme drought event was in 2003. Correlation analysis between the SPI and RDI and the standardized variable of crop yield (SVCY) for millet grain yield showed a strong agreement between them. Moderate to extreme reductions in millet crop yield occurred in 1992, 1999, 2001, and 2003, corresponding to the moderate to extreme drought indicated by RDI. Severe crop losses were in Kabkabiya and Umm Kadadda. Fourthly, this study aimed to map and monitor spatio-temporal dynamics of rainfed agriculture in North Darfur State from 1984 to 2019 using multitemporal Landsat observation data using random forest (RF) classification algorithm. Overall, Landsat Operational Landsat Imageries (OLI) outperformed Landsat Multispectral Scanner (MSS), Landsat Thematic Mapper (TM), Landsat Enhanced Thematic Mapper Plus (ETM+) in monitoring change in agricultural land and other land use land cover (LULC) classes. Overall accuracies ranged between 94.7% and 96.9%, while kappa statistics were greater than 0.90. Results showed that Goz land used for rainfed agriculture increased by 889,622.46 ha between 1994 and 999, while it decreased by 658,568.61 ha between 2004 and 2009. Rainfed cultivation of wadi lands expanded significantly by 580,515.03 ha over the 2014–2019 period and decreased by 182,701.8 ha over the 1994–1999 period. Overall, this study enhances the understanding of spatio-temporal rainfall patterns and current drought trends, aiding in developing more effective policies and resource management strategies. Additionally, it offers crucial spatial data that is currently scarce due to ongoing conflicts, empowering decision-makers to establish sustainable land use monitoring systems. The methodologies used in this study have proved successful in mapping crop types in a fragmented highly heterogeneous fine agricultural semi-arid landscape; such mapping approaches can be applied in other environments with similar characteristics.
Studies on the chemistry and biochemistry of gold(III) carboxamide pincer chelates
(University of the Witwatersrand, Johannesburg, 2024-06) Razuwika, Rufaro; Nowakowska, Monika; Mathura, adhna
Cancer, a group of diseases characterised by the uncontrollable growth of abnormal or mutated cells within an organ, is a global concern. Metallodrugs have emerged as promising solutions to this pandemic, leading to intense research on different metal complexes. In this study, gold(III) carboxamide pincer complexes were evaluated as potential chemotherapeutic agents. The novel NNN-type carboxamide pincer molecules (ligands) effectively stabilising the gold(III) metal centre. The strong σ-donor properties of both the anionic and pyridine N groups further enhanced this stability. Ligands 1a-1f exhibited atropisomerism, a common feature in drug discovery, and containing special heterocycles such as quinolones, indazole, benzophenone, and phenanthroline, which are particularly relevant in drug development. Atropisomerism, however, was lost upon metalation of the ligands. Three complexes, 2d, 2e, and 2f, were successfully synthesised and isolated. Complex 2d was subjected to biochemical property testing and in vitro analysis due to its superior stability and solubility compared to 2e (poor stability) and 2f (poor solubility in the buffer solution used in the study). Speciation studies, combined with computational studies, suggested that 2d exists as a neutral complex under physiological conditions. This inert complex demonstrated stability against the reducing agent glutathione, indicating resilience to reduction under physiological conditions. DNA spectroscopic titration studies revealed that 2d exhibited intensive interaction with ct-DNA, with binding constants Ka1 = 1.48 x109 M-1 and Ka2 = 6.59 x105 M-1. This interaction resulted in a notable increase in the DNA melting point by 4 °C and an enhancement in viscosity in a dose-responsive manner. The DNA titrations, melting point, and viscosity studies suggested a dual binding mode of 2d to ct-DNA, involving base binding with a nearly equal preference for A, T, G, and C bases, and groove binding. Complex 2d exhibited a high affinity towards the transport protein HSA (Ka values were 1.57 x104 M-1), suggesting that it can be transported in the body by means of the HSA-mediated pathway, enhancing its efficacy and stability. In comparison to its affinity towards DNA, there is a significant difference allowing for the successful transfer of 2d from HSA to DNA. The poor solubility of complex 2d in aqueous environments may have hindered its cellular uptake, but binding to HSA could mitigate this, ensuring minimal interference with its cytotoxicity towards different cancer cell lines. MTT studies demonstrated that 2d has comparable cytotoxicity towards the breast cancer cell line MCF-7 with an IC50 of 9 µM. The IC50 for HT-29 was, however, too high to measure accurately (>100 µM). In conclusion, complex 2d exhibits promising anticancer properties based on its DNA binding studies and cytotoxicity evaluations. This suggests that this class of compounds can be applied in cancer treatments, with potential modifications to compounds 2e and 2f to improve their solubility and stability.
Nutrient and Salinity Loading Based On The Temporal And Spatial Water Quality Data In The Upper Crocodile River Basin
(University of the Witwatersrand, Johannesburg, 2024-03) Mistry, Nikhil Jayant; Ali, K. Adam; Abiye, Tamiru
The Upper Crocodile River Basin has undergone a drastic change through anthropogenic factors such as rapid urban growth, industrial activities, agriculture and mining in the past thirty-eight years. This has led to an increase in nutrient and salinity loads with decreasing water quality. The Upper Crocodile River Basin wastewater treatment works struggle to maintain loading rates, causing partially treated wastewater to enter the river systems that increased the salinity loads. Water chemistry and discharge data from the DWS were collected, cleaned and processed; data were summated across the necessary river channels in which they are located to determine the nutrient and salinity loads in all rivers in the Upper Crocodile River Basin. The results indicated that the Hennops, Jukskei and Crocodile Rivers are responsible for the largest nutrient and salinity loading rates. Changes in land use activities and climate over the past thirty-eight years, since 1980, have drastically impacted the rate at which nutrient and salinity loads enter into the UCRB. During the early 1980s to 1990s a significant drop was observed in nutrient and salinity loading rates, spiking in the late 1990s and early 2000s, influenced by changes in water management and climatic events like the La Niña and the El Niño phenomena. The inter-basin transfer in the early 2000s and subsequent two decades have led to an overall rise in nutrient and salinity loading rates, posing serious water quality and health risks to people in the UCRB area. Mining activities, poor landfill management and leaking tailing storage facilities have resulted in increased sulphate loading rates into the UCRB. Nitrogen loading has risen due to uncontrolled waste disposal from informal settlements, industrial activities and sewage spills in the Johannesburg region. Phosphorus loading rates have risen due to agricultural fertiliser runoff, with the Jukskei River being the largest contributor to these loads in the Upper Crocodile River Basin. The loads entering the Hartbeespoort dam during summer and winter seasons in the 2016-2018 period for sulphate is 6819.24 kg/hr, 4873.62kg/hr; for nitrogen 4179.24 kg/hr, 4021.55 kg/hr and for phosphorus 40.08 kg/hr, 34.724 kg/hr, respectively. Salinity loads entering the Hartbeespoort dam during summer and winter are 42952.87 kg/hr and 27548.39 kg/hr, respectively. According to the findings, water resource management must act quickly to improve the overall quality of the water; in the upcoming ten years, as loading rates are expected to rise exponentially as a result of increased demand and stressed water use, which will lead to poor water quality. This will pose serious health and economic risks to the people of the Upper Crocodile River Basin and the populace of South Africa.
High entropy spinel oxides and iron-cobalt based electrocatalysts for rechargeable zinc-air batteries
(University of the Witwatersrand, Johannesburg, 2024-08) Mongwe, Agnes Monosi; Ozoemena, Kenneth Ikechukwu; Haruna, Aderemi B.
The development of effective and stable rechargeable zinc-air batteries (RZABs) using noble-metal free bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) has been a key challenge to its practical applications. This MSc research work strategically investigated some synthetic methods aimed at tuning the physicochemistry and electrochemical properties of two electrocatalysts (i.e., noble-metal free high entropy spinel oxide (HESOx) ((CoCuFeMnNi)3O4) and spinel Fe2CoO4 for rechargeable zinc-air batteries). For HESOx, a simple and reproducible Pechini method was used to synthesize a homogeneous nanosized electrocatalyst HESOx-550. The HESOx-550 was thereafter supported on onion-like carbon (OLC) in (1) an acidic environment to produce HESOx-550/OLCAT (where AT stands for acid-treated) and (2) a nonacidic environment to produce HESOx-550/OLC. The effects of the different synthesis environments on these three samples were thoroughly investigated using different analytical techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, thermogravimetric analysis (TGA) and Nitrogen Gas Adsorption analysis. The Nitrogen Gas Adsorption analysis results show that the HESOx-550/OLCAT has the largest surface area and more volume. The electron paramagnetic resonance (EPR) and O1s XPS data consistently proved that HESOx-550/OLCAT has improved oxygen vacancies which are essential in improving conductivity and offering abundant reaction sites. The HESOx-550/OLCAT shows the best bifunctional ORR and OER electrocatalytic performance with a bifunctionality index (ΔE) of 0.70 V in 1 M KOH. In addition, the RZAB air electrode with HESOx 550/OLCAT exhibits high areal capacity (60 mAh cm-2) and areal energy density (73.2 mWh cm-2) with a long-term cycle stability over 112 h in 6.0 M KOH and 0.2 M zinc acetate. The HESOx-550/OLCAT RZAB shows better electrochemical performance than 10wt.% Pt/C- IrO2 when cycled over 315 h under 27% depth of discharge condition. For Fe2CoO4, iron cobalt-based electrocatalysts on Vulcan carbon support were synthesized using a simple reduction method to produce two composites (FeCo-Fe2CoO4/CAnnealed), and (FeCo Fe2CoO4/CMicrowave). The physicochemical analytical methods such as XRD, XPS, Raman, TGA and Nitrogen Gas Adsorption analysis were used to investigate the samples. The electrochemical analysis showed that the FeCo-Fe2CoO4/CAnn had a very low “bifunctionality index” (ΔE) of 0.76 V and the FeCo-Fe2CoO4/CAnn air cathode RZAB demonstrated good stability for over 50 h under harsh DOD conditions (35.2%). The assembled RZABs have areal energy densities of 48.4 mWhcm-2 and 60.5 mWhcm-2 which are higher than the minimum recommended areal energy density of 35 mWhcm-2 (and better than most electrocatalysts reported in the literature). This study has significant contributions to the progress of practical applications of RZABs.
Spatiotemporal characteristics of surface water in Sua Pan, Botswana, using Earth Observation data: 1992–2022
(University of the Witwatersrand, Johannesburg, 2024-10) Peplouw, Muchelene Tiara; Adam, Elhadi; Grab, Stefan
Surface water is a critical resource for sustaining both human and ecological health. However, climate change and human actions threaten its availability in semi-arid regions like Botswana. In addition, current research on monitoring and understanding surface water dynamics in Botswana lacks the application of remote sensing and machine learning. This highlights a crucial gap in knowledge that this study aims to address. This study investigates the spatiotemporal dynamics of land use/land cover (LULC) and surface water extent changes in Sua Pan, Botswana, from 1992 to 2022. Employing remote sensing, machine learning, and statistical techniques, the research offers valuable insights into the intricate relationships between land cover modifications, surface water variations, and climatic variables. Google Earth Engine (GEE) facilitated efficient analysis of Landsat imagery for LULC mapping. Random Forest (RF) effectively classified several land cover types within Sua Pan. To address the challenges of saline environments, a novel water index, the Saline Water Index (SWI), was developed specifically for Sua Pan. The McNemar statistical test compared the performance of SWI to established indices like the Modified Normalised Difference Water Index (MNDWI) and the Normalised Difference Salinity Index (NDSI). Surface water variations were analysed using homogeneity tests and the Mann-Kendall trend test. The relationships between hydro climatic data (rainfall, evapotranspiration, land surface temperature) retrieved from GEE and surface water area for both wet and dry seasons were evaluated using Pearson correlation coefficients and visualised by line and area graphs. Additionally, the influence of the El Niño Southern Oscillation (ENSO) on rainfall and surface water area was assessed using Analysis of Variance (ANOVA) to identify the specific ENSO phases that exert an influence. The findings demonstrate the effectiveness of GEE for LULC mapping with the RF algorithm, achieving moderate to high classification accuracy (65.2% - 90.69%) and Kappa coefficients (0.54 - 0.85). Surface water and bare area exhibited increasing trends (coefficients: 13.017 and 9.0609, respectively), whereas vegetation and salt hard pan showed decreasing trends (-16.786 and -5.3081, respectively). The newly developed SWI outperformed MNDWI and NDSI in detecting surface water, achieving the highest overall accuracy (94%) compared to MNDWI (64%) and NDSI (59%). The McNemar test confirmed no significant statistical difference between the SWI map and the validation dataset (p = 0.2673), while both MNDWI and NDSI maps showed significant differences (p < 0.0001). Utilising SWI, the study revealed that surface water was most prevalent in central and northeastern regions, with an average coverage of 33%. Seasonal homogeneity tests indicated a non-homogenous distribution of surface water area in wet seasons, with abrupt changes in 1994 and 2003. Conversely, dry seasons exhibited a homogenous distribution. The Mann-Kendall trend test identified a statistically significant (p-value = 0.01) but weak positive trend (tau = 0.329) for surface water areas in wet seasons. In contrast, the dry seasons displayed a non-significant (p-value = 0.734) and a very weak positive trend (tau = 0.043). Surface water area, rainfall, evapotranspiration, and temperature consistently increase during the wet seasons compared to the dry seasons. Notably, increased evapotranspiration significantly impacted surface water presence. ENSO exhibited no significant influence on either rainfall or surface water extent (p-value > 0.05 for both). These findings highlight the potential of earth observation data for real-time surface water monitoring in salt pans. The developed techniques offer valuable insights for policy decisions regarding environmental management and conservation efforts in Sua Pan. In addition, the study emphasises the importance of cost-effective approaches for water change assessment, particularly appropriate for under-resourced regions.
A systematic study on the use of the sol-gel synthetic method for lithium manganese oxide-based cathode materials
(University of the Witwatersrand, Johannesburg, 2024-09) Muntswu, Zwivhuya; Billing, Caren; Ferg, Ernst E.; Billing, David G.
This dissertation investigated the synthesis of two lithium manganese oxide-based cathode materials (Li1.03Mn1.97O4 and LiAl0.4Mn1.6O4) using the sol-gel method and probing the phase transitions during the synthesis. The sol-gel synthetic method involved dissolving stoichiometric amounts of lithium nitrate, manganese nitrate hydrate, and citric acid in distilled water forming an aqueous solution. The starting precursor materials were dried at 140 °C which formed a crystalline phase of -Aqua-S-citrato (2-)-manganese(II) with an orthorhombic crystal system and P222 space group. The thermal behaviour of the precursor was explored to understand the effects of calcination/annealing temperatures. Thermal analysis of precursors prepared using nitrate salts with a 1:1 total metal ion to citric acid ratio displayed thermal stability to temperatures higher than 380 °C with the formation of a final metal oxide after 70% mass loss due to the decomposition of the organic and nitrate materials. However, when increasing the concentration of the complexing agent, an increase in material decomposition due to an increase in organic material is seen. The precursor materials prepared with a lower complexing agent concentration result in materials that have thermal instability when exposed to high temperatures. Thermal analysis of Li1.03Mn1.97O4 and LiAl0.4Mn1.6O4 prepared using acetate salts as starting materials shows material decomposition at high temperature of ~600 °C Calcining both undoped and Al-doped nitrate precursors at moderate temperatures (380 °C to 500 °C) resulted in the formation of Li1.03Mn1.97O4 and LiAl0.4Mn1.6O4 with a pure cubic spinel structure and an Fd-3m space group, however, increasing the calcining temperature to 800 °C for the undoped nitrate-based precursor revealed an impurity phase formation relating to dilithium manganese oxide with a monoclinic crystal system. On the other hand, calcining acetate-based precursors at moderate temperatures (380 °C to 500°C) results in metal oxides with low crystallinity compared to metal oxides prepared with nitrate-based precursors. Calcining acetate-based precursors at 800 °C was more favourable since they form the desired metal oxides without any impurities which might imply structural phase stability at high temperatures. The local and average crystallographic structures (via PDF and XRD respectively) of various nitrate-based metal oxides were investigated, where a good agreement between collected data and a calculated structural model revealed the formation of a cubic spinel structure of space group Fd-3m. Li1.03Mn1.97O4 and LiAl0.4Mn1.6O4 metal oxides were achieved from calcining precursors at moderate temperatures of 380 °C and 450 °C. The PDF high r-value signal displays a good fit which confirms to the average structure data information where the r-value signal which correspond to the local structure refinements have a minor discrepancy when fitted with a cubic spinel of space group Fd-3m.
Double-diffusive convection in rotating fluids under gravity modulation
(University of the Witwatersrand, Johannesburg, 2024-09) Mathunyane, Alfred Ntobeng; Duba, C. Thama; Mason, D.P.
This study employs the method of normal modes and linear stability analysis to investigate double-diffusive convection in a horizontally layered, rotating fluid, specifically focusing on its application to oceanic dynamics. Double diffusive convection arises when opposing gradients of salinity and temperature interact within a fluid, a phenomenon known as thermohaline convection, and it is crucial for the understanding of ocean circulation and its role in climate change. With the increasing mass of water due to glaciers melting, fluid pressure variations occur, leading to slight fluctuations in gravity. We conduct both stationary and oscillatory stability analyses to determine the onset of double-diffusive convection under gravity modulation. Our analysis reveals that time-dependent periodic modulation of gravitational fields can stabilize or destabilize thermohaline convection for both stationary and oscillatory convection, with amplitude stabilizing and frequency destabilizing. The wavenumber in the y- direction also affects convection in the equatorial regions. This wavenumber exhibits destabilizing effects for large values and stabilizing effects for small values for both stationary and oscillatory convection. Rotation along with gravity modulation tends to destabilize the system for both stationary and oscillatory convection. The key difference between stationary and oscillatory convection is that oscillatory convection exhibits large values of the Rayleigh number, thus susceptible to overstability while stationary convection tends to have relatively smaller Rayleigh numbers and thus more stable. This research provides insights into the complex interplay between gravity modulation and thermohaline convection, contributing to our understanding of ocean dynamics and their implications for climate change.
Palaeoclimate Reconstruction Using Charcoal from a Mid-Holocene Stratum 4b, Wonderwerk Cave, South Africa
(University of the Witwatersrand, Johannesburg, 2024-06-18) Hlophe, Busisiwe; Bamford, Marion
Caves are often sources for palaeoenvironmental information in the dry interior regions of southern Africa. The Wonderwerk Cave, located in Northern Cape, is a national heritage site with a well-preserved, nearly complete record of the local Holocene LSA techno-complexes and past environmental indicators. Hence, it has the potential to provide valuable insights into past human behaviour as well as the local palaeoclimate and vegetation. This study examined wood charcoal from stratum 4b, Excavation 1 of the Wonderwerk Cave. The aim was to evaluate the taxonomic composition and the physiognomy of the charcoal to understand the environment around the cave 6.9-5.9 ka. The study also investigated the modern uses of the vegetation to infer how humans may have utilized the woody plants around them during that period. The results indicate the landscape cover included woody plants adapted to dry conditions and summer rainfall. However, the archaeological taxa identified also included two species that thrive in moist environments, Halleria lucida and Olinia ventosa, suggesting fluctuations in climate. The taxonomic composition also suggests an environment similar to the modern bushveld found near the cave. The low conductivity capacity as well as vulnerability and mesomorphy indices of the woods support the implication that the vegetation was adapted to low water availability or aridity. The cave's inhabitants likely used the identified plants for firewood, magical and medicinal purposes, and more between 6.9 and 5.9 ka.
Synthesis and electrochemical properties of high-entropy spinel oxides, cobalt atomic clusters and zinc oxide as electrode materials for rechargeable zinc-air batteries
(University of the Witwatersrand, Johannesburg, 2024-07) Gaolatlhe, Lesego; Ozoemena, Kenneth Ikechukwu
This thesis investigated cathode and anode electrode materials for application in rechargeable zinc-air battery (RZAB). Two types of cathode materials were strategically studied in RZAB applications: (a) cobalt carbon composites of (i) cobalt atomic clusters (Co AC@CBPDC) and (ii) cobalt nanoparticles (Co NP@CBPDC), and (b) high-entropy spinel oxide (HESOx, containing five transition metals – Cu, Mn, Fe, Ni, and Co). The activities of these materials toward oxygen reduction reaction (ORR and oxygen evolution reaction (OER) were investigated in both half- and full-cell configurations as a proof-of-concept in RZAB cells in alkaline electrolyte. Considering that conventional zinc plate has several short-comings as an anode for RZAB, a new material, polydopamine-derived carbon-coated zinc oxide (ZnO@PDA-DC), was also synthesised and applied in RZAB as a possible alternative anode to the popular zinc plate. First, Co AC@CBPDC and Co NP@CBPDC were prepared using the metal-organic framework (MOF) route through the microwave-assisted solvothermal method and acid treatment. From the XRD results, the spectra showed dominant {111} and {200} phases, characteristic of metallic cobalt with a face-centred cubic (fcc). There were trace amounts of CoO observed indicating the coexistence of Co/CoO. From TEM imaging, Co AC@CBPDC was highly defective with a visible porous carbon structure than its counterpart (Co NP@CBPDC) and showed dispersed atomic clusters. BET data showed that Co AC@CBPDC had a higher surface area (144.8 m2/g) than the Co NP@CBPDC (33.25 m2/g). The improved physicochemical merits of the Co AC@CBPDC allowed for better ORR and OER activities than the Co NP@CBPDC in terms of low halfway potential (E1/2), onset potential (Eonset), overpotential at 10 mA/cm2 (ƞ10), potential gap (∆E) between the overpotential of OER and the halfway potential, and a higher kinetic current density (jk). The enhanced electrochemistry of the Co AC@CBPDC was attributed to the defects created by the acid treatment. As proof of real-life applicability, the Co AC@CBPDC electrocatalyst delivered an excellent air cathode in a parallel plate RZAB cell with notable OCV (1.23 V), peak power density (49.9 mW/cm2), a real energy density (477 mAh/cm2), long-term stability for 210 h, enhanced voltage retention, Coulombic efficiency (ca. 100 %) and DOD (51.3%), comparable to literature. In addition, an all-solid-state RZAB based on the Co AC@CBPDC catalyst gave a higher and constant OCV (1.73 V) at varied bending angles (0 – 180 degrees) and excellent stability. Second, new HESOx materials were prepared via the Pechini method at two different annealing temperatures of 500 and 750 oC (abbreviated herein as HESOx-500 and HESOx-750). P-XRD results showed that these are inverse spinel oxides, with {311} as the dominant phase. HR-TEM images proved that they are single nanocrystalline materials. XRD and BET data showed that the HESOx-500 is smaller in size, more porous, and has a higher surface area than its counterpart (HESOx-750). HESOx-500 showed superior ORR performance with an onset potential of 0.93 V and a E1/2 of 0.88 mV. The OER performance also showed improved ƞ10 compared to IrO2 with an overpotential of 340 mV at a current density of 10 mA/cm2, and a 45 ± 5.0 mV/dec Tafel slope, above the performance of IrO2 (66 ± 6.1 V/dec). The ∆E of HESOx-500 was 0.69 V. The material was further tested as a cathode material in a RZAB cell. The optimised RZAB cell showed remarkable performance with a theoretical potential of 1.67 V and long-term stability of 375 h at 10 mA/cm2. The performance was attributed to the high-entropy compositional design with a high number of surface oxygen vacancies and different metal oxidation states. Finally, having dealt with the issue of bifunctionality in RZAB, a new ZnO@C anode material was also considered. The ZnO@PDA-DC (where PDA-DC means polydopamine-derived carbon) was used due to its ability to form Zn2+ pathways. Electrochemical potentiodynamic polarisation tests were performed to understand and compare the corrosion inhibition effects in an alkaline medium (6 M KOH). The ZnO@PDA-DC showed better corrosion inhibition properties than the zinc plate and other samples: low corrosion current (icorr = 0.107 uA/cm2) and corrosion potential (Ecorr = 1.077 V), and a mixed inhibition effect, indicating reduced hydrogen evolution reaction and zinc dissolution. Due to the excellent corrosion inhibition properties of the ZnO@PDA-DC, it was then evaluated in the RZAB cell. The shallow galvanostatic charge-discharge cycle stability at 2 mA/cm2 was able to maintain 150 h in a RZAB at a voltage gap of 0.76 V to 0.80 V. The results demonstrated that enhanced rechargeability is possible with ZnO@PDA-DC for RZAB.
Synthesis of platinum-based electrocatalysts using nitrogen doped onion-like carbon and WS2 composites as the support for electrooxidation of ethanol in direct alcohol fuel cells
(University of the Witwatersrand, Johannesburg, 2024-10) Bila, Laercia Rose; Gqoba, Siziwe; Maubane-Nkadimeng, Manoko S.
The study reports on the synthesis of onion-like carbons (OLCs)/tungsten disulfide (WS2) composites as catalyst support for direct alcohol fuel cells (DAFC). OLCs were synthesized using waste engine oil over a flame pyrolysis (FP) method. The pristine OLCs (p-OLCs) were functionalized and purified using nitric acid (HNO3). The functionalized OLCs (F-OLCs) were further doped with nitrogen using melamine to increase the electronic properties of the OLCs. WS2 was synthesized using the colloidal method and oleylamine was used as the capping agent. Pt/p-OLCs, Pt/F-OLCs, and Pt/N-OLCs were synthesized using a reflux method where ethylene glycol was the reducing agent. Finally, WS2/N-OLCs were synthesized using the colloidal method and then Pt was dispersed on WS2/N-OLCs to form Pt/WS2/N-OLCs. High-resolution transmission electron microscopy showed the presence of onion-like rings in the OLCs and the quasi-spherical morphology, while a flower-like morphology was observed for WS2. Powder X-ray diffraction revealed that the synthesized WS2 had traces of WO3 due to the oxidation of WS2 which introduces WO3 impurities. Energy Dispersive X-ray Spectroscopy revealed that the OLCs derived from waste engine oil present some impurities that were attributed to the motor wear as well as the fuel. When Pt was loaded onto the WS2/N OLCs composite, the WS2 lost its original nanoflower morphology, which was attributed to the presence ethylene glycol used as a reducing agent. X-ray photon spectroscopy confirmed the successful synthesis of the Pt electrocatalysts. Cyclic voltammetry was used to determine the oxidation of ethanol and the current density of the synthesized electrocatalysts. Interestingly, the Pt/p-OLCs electrocatalyst had a higher current density compared to Pt/F-OLCs and Pt/N-OLCs. This was attributed to metal impurities found in p-OLCs, which were reduced during the purification process. The Pt/WS2/N-OLCs electrocatalyst showed higher current density compared to Pt/WS2 but this was low compared to Pt/N-OLCs. The data reveals that the addition WS2 shows a co-catalyst behaviour, rather than a support.

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