Thesis (M.Sc. (Chemistry)) -- University of Limpopo, 2015 / The study has focused on the effects of different acids treatments on the nanostructure of MWCNTs; doping metal oxides (copper oxide (CuO), Iron (III) oxide (Fe2O3), nickel oxide (NiO) and cobalt oxide (Co3O4)) on MWCNTs and investigates their electrochemical hydrogen and energy storage capabilities. Fourier transform infrared (FTIR) confirmed the formation of functional groups on the surface of the acid treated MWCNTs. X-ray diffraction (XRD) showed that the graphitic structure of the MWCNTs was retained after treatment with mild acids (nitric acid (HNO3), hydrogen peroxide (H2O2), a mixture of the acids, hydrogen peroxide: nitric acid (H2O2:HNO3) and hydrogen peroxide: sulfuric acid (H2O2:H2SO4)). Transmission electron microscopy (TEM) confirms the removal of bamboo carbon structures inside the inner tubes of the MWCNTs after treatment with mild acids. Brunauer-Emmet- Teller (BET) showed an increase in the surface area of mild acids treated MWCNTs. Thermogravimetric analysis (TGA) results demonstrated that the thermal stability of MWCNTs increases after treatment with mixtures of the acids. Different metal oxides treated at different temperatures were incorporated into MWCNTs (treated by a mixture of H2O2:HNO3). X-ray diffraction (XRD), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) confirmed the presence of different metal oxides inside/on the surface of the acid treated MWCNTs. The MWCNTs treated by H2O2:HNO3 gave both the highest discharge capacity (72.63 mAh/g) and capacitance (8.61 F/g), as compared to the other electrode materials. The improved hydrogen storage capacity and specific capacitance can be attributed to high surface area, wider pore size distribution and the amount of functional groups on the surface of H2O2:HNO3-treated MWCNTs; with the functional groups acting as electron transmitters. The 5wt.% CuO@300oC-MWCNTs composite showed the highest hydrogen storage capacity of 159 mAh/g. This capacity was further improved by addition of manganese oxide resulting in the highest discharge capacity of 172 mAh/g (which is equivalent to 0.64 wt.% of hydrogen stored). The highest specific capacitance of 9.70 F/g was obtained on 5wt% Fe2O3@400oCMWCNTs composite.

<p>Predmet&nbsp; istraživanja&nbsp; ove&nbsp; doktorske&nbsp; disertacije&nbsp; je&nbsp; procena&nbsp; potencijalno&nbsp; biodostupne&nbsp; frakcije odabranih&nbsp; prioritetnih&nbsp; organskih&nbsp; polutanata&nbsp;&nbsp; (pentahlorbenzena,&nbsp; heksahlorbenzena,&nbsp; lindana, trifluralina, 4-oktilfenola i 4-nonilfenola) u sedimentu, ispitivanje biodegradacionog potencijala ovih&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; u&nbsp; različitim&nbsp; uslovima,&nbsp; kao&nbsp; i&nbsp; procena&nbsp; potencijala&nbsp; stabilizacije<br />sedimenta&nbsp; dodatkom&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa.&nbsp; U&nbsp; cilju&nbsp; razvoja&nbsp; metoda&nbsp; za&nbsp; određivanje biodostupnosti odabranih organskih polutanata ispitivane su i&nbsp; optimizovane metode vi&scaron;estepene i jednostepene parcijalne ekstrakcije primenom sledećih hemijskih agenasa:&nbsp; Tenaks&nbsp; smole, XAD-4&nbsp; smole&nbsp; i&nbsp; rastvora&nbsp; ciklodekstrina&nbsp; (2-hidroksipropil-&beta;-ciklodekstrina,&nbsp; &beta;-ciklodekstrina&nbsp; i&nbsp; metil-&beta;-ciklodekstrina).&nbsp; Optimalni&nbsp; agens&nbsp; za&nbsp; procenu&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih&nbsp; organskih zagađujućih&nbsp; materija&nbsp; sa&nbsp; sedimenta&nbsp; XAD-4&nbsp; smola,&nbsp; a&nbsp; optimalno&nbsp; vreme&nbsp; ekstrakcije&nbsp; primenom jednostepenih&nbsp; ekstrakcija&nbsp; je&nbsp; oko&nbsp; 8&nbsp; h.&nbsp; Procena&nbsp; biodegradacionog&nbsp; potencijala&nbsp; odabranih prioritetnih&nbsp; organskih&nbsp; zagađujućih&nbsp; materija&nbsp; u&nbsp; sedimentu&nbsp; ispitana&nbsp; je&nbsp; u&nbsp; različitim&nbsp; aerobnim&nbsp; i anaerobnim uslovima uz optimizaciju uslova putem biostimulacije i bioaugmentacije. Pokazano je&nbsp; da&nbsp; svih&nbsp; &scaron;est&nbsp; odabranih&nbsp; jedinjenja&nbsp; poseduju&nbsp; značajan&nbsp; potencijal&nbsp; biodegradacije&nbsp; u&nbsp; anaerobnoj sredini&nbsp; pri&nbsp; čemu&nbsp; u&nbsp; slučaju&nbsp; lindana&nbsp; i&nbsp; trifluralina&nbsp; dolazi&nbsp; do&nbsp; potpunog&nbsp; uklanjanja&nbsp; biodostupne količine&nbsp; jedinjenja&nbsp; primenom&nbsp; sva&nbsp; četiri&nbsp; ispitana&nbsp; inokuluma.&nbsp; Aerobni&nbsp; potencijal&nbsp; u&nbsp; ispitanim uslovima&nbsp; pokazali&nbsp; su&nbsp; samo&nbsp; alkil&nbsp; fenoli,&nbsp; gde&nbsp; je&nbsp; takođe&nbsp; uklonjena&nbsp; skoro&nbsp; celokupna&nbsp; količinabiodostupne&nbsp; frakcije&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; (78-85%).&nbsp; Potencijal&nbsp; remedijacije&nbsp; sedimenta dodatkom&nbsp; ugljeničnih&nbsp; materijala&nbsp; ispitan&nbsp; je&nbsp; sa&nbsp; aspekta&nbsp; odabira&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa (aktivni&nbsp; ugalj,&nbsp; biougalj&nbsp; i&nbsp; humus);&nbsp; određivanja&nbsp; optimalne&nbsp; količine&nbsp; materijala;&nbsp; isptivanja dugoročnih i kratkoročnih efekata dodatka ovih agenasa na biodostupnost organskih zagađujućih materija&nbsp; kako&nbsp; bi&nbsp; se&nbsp; ispitao&nbsp; efekat&nbsp; starenja &nbsp; i&nbsp; toksičnosti&nbsp; dobijenih&nbsp; sme&scaron;a.&nbsp; Rezultati&nbsp; stabilizacije zagađujućih&nbsp; supstanci&nbsp; u&nbsp; sedimentu&nbsp; pokazuju&nbsp; da:&nbsp; (1)&nbsp; povećanje&nbsp; doze&nbsp; sva&nbsp; tri&nbsp; sorpciona&nbsp; agensa dovodi&nbsp; do&nbsp; povećanja&nbsp; efikasnosti&nbsp; imobilizacije&nbsp; i&nbsp; smanjenja&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih organskih jedinjenja; (2) starenjem sme&scaron;a sedimenta i&nbsp; sorbenata u toku prvih 90 dana dolazi do daljeg smanjenja biodostupne frakcije svih jedinjenja, nakon čega se biodostupna koncentracija ispitivanih&nbsp; jedinjenja&nbsp; primenom&nbsp; aktivnog&nbsp; uglja&nbsp; ne&nbsp; menja,&nbsp; dok&nbsp; primenom&nbsp; biouglja&nbsp; i&nbsp; humusa&nbsp; dolazi&nbsp; do&nbsp; porasta&nbsp; biodostupne&nbsp; frakcije&nbsp; jedinjenja.&nbsp; Testovi&nbsp; fitotoksičnosti&nbsp; su&nbsp; pokazali&nbsp; da&nbsp; je&nbsp; <em>Zea mays&nbsp; </em>akumulirao&nbsp; značajno&nbsp; veće&nbsp; količine&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; iz&nbsp; netretiranog&nbsp; sedimenta&nbsp; u poređenju sa&nbsp; <em>Cucurbita pepo</em>&nbsp; i&nbsp;<em> Lactuca sativa. </em>Toksičnost sme&scaron;a sedimenta sa aktivnim ugljom i humusom&nbsp; procenjena&nbsp; na&nbsp; osnovu&nbsp; inhibicije&nbsp; luminiscencije&nbsp; na&nbsp; <em>Vibrio&nbsp; fischeri</em>&nbsp; kao&nbsp; i&nbsp; ispitivanjem <em>Zea&nbsp; mays&nbsp; </em>germinacije&nbsp; i&nbsp; produkcije&nbsp; biomase&nbsp; je&nbsp; pokazala&nbsp; značajno&nbsp; smanjenje&nbsp; u&nbsp; odnosu&nbsp; na netretirani&nbsp; sediment.&nbsp; Akumulacija&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; u&nbsp; biomasi&nbsp; <em>Zea&nbsp; mays&nbsp; </em>u&nbsp; netretiranom sedimentu je bila značajno veća u odnosu na sve sme&scaron;e sedimenta i aktivnog uglja i humusa. Sva tri&nbsp; sorbenta&nbsp; pokazala&nbsp; su&nbsp; veliki&nbsp; remedijacioni&nbsp; potencijal&nbsp; za&nbsp; sediment&nbsp; zagađen&nbsp; organskim zagađujućim supstancama, ali je aktivni ugalj pokazao najbolje performance.</p> / <p>The&nbsp; aim&nbsp; of&nbsp; the&nbsp; research&nbsp; in&nbsp; this&nbsp; PhD&nbsp; dissertation&nbsp; is&nbsp; the&nbsp; assessment&nbsp; of&nbsp; the&nbsp; potentially biodegradable&nbsp; fraction&nbsp; of&nbsp; selected&nbsp; organic&nbsp; pollutants&nbsp;&nbsp; (pentachlorbenzene,&nbsp; hexachlorobenzene, lindane,&nbsp; trifluraline,&nbsp; 4-octylphenol&nbsp; and&nbsp;&nbsp;&nbsp; 4-nonylphenol)&nbsp; in&nbsp; the&nbsp; sediment,&nbsp; estimation&nbsp; of&nbsp; the biodegradation potential of these compounds in sediment in different conditions, as well as the assessment&nbsp; of&nbsp; the&nbsp; stabilization&nbsp; potential&nbsp; sediment&nbsp; by&nbsp; the&nbsp; sediment&nbsp; amendment&nbsp; with&nbsp; of&nbsp; carbon rich sorption agents. In order to develop and optimise&nbsp; methods for the bioavailability assessment of&nbsp; the&nbsp; selected&nbsp; organic&nbsp; pollutants,&nbsp; methods&nbsp; of&nbsp; multistage&nbsp; and&nbsp; single-step&nbsp; non&nbsp; exhaustive extraction&nbsp; were&nbsp; studied&nbsp; using&nbsp; the&nbsp; following&nbsp; chemical&nbsp; agents:&nbsp; Tenax&nbsp; resin,&nbsp; XAD -4&nbsp; resin&nbsp; and&nbsp; a cyclodextrin&nbsp; solution&nbsp; (2-hydroxypropyl- &beta;-cyclodextrin,&nbsp; &beta;-cyclodextrin&nbsp; and&nbsp; methyl-&beta;-cyclodextrin).&nbsp; Results&nbsp; showed&nbsp; that&nbsp; optimal&nbsp; agent&nbsp; for&nbsp; estimating&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of selected organic pollutants from the sediment is XAD-4 resins, and that the optimum extraction time using single-step extraction is about 8 h. The assessment of the biodegradation potential of selected&nbsp; priority&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was&nbsp; examined&nbsp; in&nbsp;&nbsp; various&nbsp; aerobic&nbsp; and anaerobic&nbsp; conditions,&nbsp; with&nbsp; the&nbsp; optimization&nbsp; of&nbsp; conditions&nbsp; through&nbsp; biostimulation&nbsp; and bioaugmentation.&nbsp; It&nbsp; has&nbsp; been&nbsp; shown&nbsp; that&nbsp; all&nbsp; six&nbsp; selected&nbsp; compounds&nbsp; possess&nbsp; significant biodegradation&nbsp; potential&nbsp; in&nbsp; the&nbsp; anaerobic&nbsp; environment,&nbsp; where&nbsp; in&nbsp; the&nbsp; case&nbsp; of&nbsp; lindane&nbsp; and trifluraline there is complete removal of the bioavailable amount of the compound&nbsp;&nbsp; using all four inoculum tested. Aerobic potential under the applied conditions has been showen only for alkyl phenols,&nbsp; where&nbsp; almost&nbsp; all&nbsp; of&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of&nbsp; the&nbsp; compound&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was removed (78-85%). The potential of sediment remediation with the amendment of sediment withcarbon&nbsp; rich&nbsp; materials&nbsp; was&nbsp;&nbsp; examined&nbsp; from&nbsp; the&nbsp; aspect&nbsp; of&nbsp; selecting&nbsp; carbon&nbsp; sorption&nbsp; agents (activated carbon, biochar and humus); estimation the optimal material doses; the long -term and short-term effects of the addition&nbsp; of these agents on the bioavailability of organic pollutants&nbsp; in order to examine the effect of aging and the toxicity of the resulting mixtures. The results of the stabilization of pollutants in the sediment show that: (1)&nbsp; increasing the dose of all three&nbsp;&nbsp; sorption agents&nbsp; leads&nbsp; to&nbsp; an&nbsp; increase&nbsp; in&nbsp; the&nbsp; immobilization&nbsp; efficiency&nbsp; and&nbsp; reduction&nbsp; of&nbsp; the&nbsp; bioavailable fraction of the selected&nbsp; organic compounds; (2) aging of the amended sediment during the first 90 days results in a further reduction of the biodegradable fraction of all compounds, after which the&nbsp; biodegradable&nbsp; concentration&nbsp; of&nbsp; the&nbsp; selected&nbsp; compounds&nbsp; remain&nbsp; the&nbsp; same&nbsp; in&nbsp; the&nbsp; case&nbsp; of activated carbon amendment, while the bioavailable fraction of&nbsp; the compound increases with the use&nbsp; of&nbsp; biohar&nbsp; and&nbsp; humus.&nbsp; Phytotoxicity&nbsp; tests&nbsp; showed&nbsp; that&nbsp; <em>Zea&nbsp; mays&nbsp;</em> accumulated&nbsp; significantly higher amount of selected organic pollutants from unamended sediment, comparing to&nbsp; <em>Cucurbita pepo&nbsp;</em> and <em>Lactuca sativa</em>. Toxicity of activated carbon and humus amended sediment assessed by <em>Vibrio&nbsp; fischeri&nbsp;</em> luminescence&nbsp; inhibition&nbsp; test&nbsp; and&nbsp; by&nbsp; measuring&nbsp; <em>Zea&nbsp; mays&nbsp; </em>germination&nbsp; and biomass yield was significantly reduced in the amended sediment samples. Accumulation of the selected&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; <em>Zea&nbsp; mays</em>&nbsp; biomass&nbsp; in&nbsp; the&nbsp; unamended&nbsp; sediment&nbsp; were&nbsp; a significantly&nbsp; higher&nbsp; than&nbsp; in&nbsp; the&nbsp; humus&nbsp; and&nbsp; activated&nbsp; carbon&nbsp; amended&nbsp; sediment.&nbsp; Both&nbsp; sorbents show&nbsp; potential&nbsp; to&nbsp; be&nbsp; used&nbsp; as&nbsp; remediation&nbsp; agents&nbsp; for&nbsp; organically&nbsp; contaminated&nbsp; sediment,&nbsp; but activated carbon exhibited the better performance.</p>