Lithium cobalt oxide was synthesized by solid-state reactions and SPRAY-DRY method. Its investigation of the formation were perform of lithium and cobalt acetate, lithium and cobalt citrate, LiOH and Co(NO3)2· 6H2O mixtures in high-temperatures. Their formation was analyzed and with the help of the X-ray diffraction the structure of the products of the solid-state reactions was determined. The thermal processes, that take place during the synthesis, were analyzed with the help of differential-thermal analysis.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Water is a limited resource and pollution has become an increasing problem due to industrialization. Aromatic organic pollutants are resistant to biodegradation, and thus chemical methods like the Fenton reaction is required for degradation. The Fenton reaction is catalyzed by cobalt oxide. This study aims to investigate the effect of size and shape of cobalt oxide nanoparticles on the catalytic activity. Methylene blue (MB) was used as a model pollutant. The size and shape of nanoparticles are known to influence the activity of catalysts. The study used a precipitation method to prepare spherical and cubic-shaped cobalt oxide nanoparticles of different sizes using preparation parameters like cobalt precursor, amount and type of oxidant and time of reaction. The XRD patterns of all the prepared cobalt oxide nanoparticles showed a pure cubic Co3O4 phase. The shape of the nanoparticles changed from spherical to cubic when the cobalt precursor was changed from cobalt nitrate to cobalt acetate. The size of the nanoparticles increased when lower amounts of hydrogen peroxide and longer reaction times were used. Nanoparticles between 4.6 to 19.5 nm for spherical particles and between 6.6 and 43.3 nm for cubic particles were prepared. FTIR spectra analysis showed the presence of both nitrate and acetate ions on the surface of cobalt oxide nanoparticles. The TGA results indicated that the adsorption of the acetate ions is stronger than the nitrate ions on the surface of the cobalt oxide nanoparticles. The rate of degradation of methylene blue, the pseudo first order rate constant and the amount of leaching increased with a decrease in the nanoparticles size. The Turn Over Frequency (TOF), which is the moles of methylene blue converted per mole of surface cobalt atoms, decreased with a decrease in the size for both the spherical and cubic nanoparticles. The TOF for the spherical and cubic nanoparticles were similar indicating that the catalytic activity may not be dependent on the shape of the nanoparticles. FTIR analyses showed that degradation occurred, and that methylene blue was not just decolourised to leuco methylene blue.

No description available.

Nowadays, Lithium-ion batteries (LIBs) have dominated the power source market in a variety of applications. Lithium cobalt oxide (LiCoO2) is one of the most common cathode materials for LIBs in consumer electronics. The recycling of LIBs is important because cobalt is an expensive element that is dependent on foreign sources for production. Lithium-ion batteries need to be recycled and disposed properly when they reach the end of life (EOL) to avoid negative environmental impact. This project focuses on recycling cathode material (LiCoO2) by direct method. Two automation stages, tape peeling stage and unrolling stage, are designed for disassembling prismatic winding cores. Different sintering conditions (e.g., temperature, sintering atmosphere, the amount of lithium addition) are investigated to recycle EOL cathode materials. The results show that the capacity of the recycled cathode materials increases with increasing temperature. The extra Li addition leads to worse cycling performance. In addition, the sintering atmosphere has little influence on small- scale sintering. Also, most of directly recycled cathode materials have better electrochemical (EC) performance than commercial LiCoO2 (LCO) from Sigma, especially when cycling with 4.45V cutoff voltage. / Master of Science / Nowadays, Lithium-ion batteries (LIBs) have dominated the power source market in a variety of applications. A LIB contains an anode, a cathode and electrolyte. The cathode material is the most valuable component in the LIB. Lithium cobalt oxide (LiCoO2) is one of the most common cathode materials for LIBs in consumer electronics. The recycling of LIBs is important because cobalt is an expensive element that is dependent on foreign sources for production. Lithium-ion batteries need to be recycled and disposed properly when they reach end of life (EOL) to avoid negative environmental impact. The direct recycling is a cost effective and energy conservative method which can be divided into two steps: retrieving the cathode materials from EOL LIBs and regenerating the cathode materials. This project focuses on recycling LiCoO2 by direct method. Two automation modules, tape peeling stage and unrolling stage, are designed for a disassembling line which is the automation line to collect the cathodes materials. The EOL cathode materials is lithium deficient (Li1-xCoO2). To regenerate the EOL cathode materials, lithium is added into structure of cathode materials which is called the re-lithiation process. The different sintering conditions (e.g., temperature, sintering atmosphere, the amount of lithium addition) are investigated for the re-lithiation process. The results show that the capacity of the recycled cathode materials increases with increasing temperature. The extra Li addition in iv Li1-xCoO2 leads to worse cycling performance. In addition, sintering atmosphere has little influence on small- scale sintering. Most of directly recycled cathode materials have better electrochemical (EC) performance than commercial LiCoO2, especially when cycling with 4.45V cutoff voltage.

No description available.

No description available.

This project is an exploration of practices around the critical raw materialcobalt, it’s history, and current relevance in Swedish discourse. Critical raw materials are identified by the European Commission as materials of high importance to the EU’s economic system as well as the high risks related to their supply and production. As the demand for cobalt grows due to it’s usefulness in rechargeable batteries in for example smartphones, laptops and electric cars, the metal is predicted to become scarce in a near future. In Sweden there is a discourse on whether or not to mine for cobalt, among other earth elements, locally, and the industry is lookingfor ways to recycle old rechargeable batteries at larger scales to secure the resource. The criticality of cobalt does not only concern supply and economic importance however. In Congo some mines have been reported to still be dug by hand, under extremely poor conditions and risking the health and safety of the workers, as well as the surrounding societies. Through a critical research and design process these topics are explored alongside the more locally known use of cobalt oxide as a vibrant blue colour pigment for ceramics and glass. With the process I aim to create a design that engages with the criticality as well as a designerly fascinationwith the material. The end result being a speculative design fiction of the mythological creature cobelt, and how complex narratives can be unearthed in craft based practice.

Este trabalho compreende a síntese e caracterização de um novo catalisador magneticamente recuperável de CoO para oxidação alílica de alcenos. O catalisador foi preparado através da deposição de nanopartículas (de tamanho entre 2-3 nm) do metal cataliticamente ativo em nanopartículas de magnetita revestidas por sílica. A natureza magnética do suporte permitiu a fácil separação do catalisador do meio reacional após o termino das reações pela simples aproximação de um ímã na parede do reator. O catalisador pôde ser completamente separado da fase líquida, fazendo com que a utilização de outros métodos de separação como filtração e centrifugação, comumente utilizados em sistemas heterogêneos líquidos, fossem completamente dispensados. O catalisador foi inicialmente testado em reações de oxidação do substrato modelo cicloexeno e mostrou seletividade para a produção do produto alílico, cicloex-2-en-1-ona, que é reagente de partida de grande interesse para a síntese de diversos materiais na indústria química. As reações de oxidação foram realizadas utilizando-se apenas O2 como oxidante primário, dispensando o uso de oxidantes tóxicos como cromatos ou permanganatos, que não são recomendados do ponto de vista ambiental. O catalisador sintetizado mostrou ser reutilizável em sucessivos ciclos de oxidação, destacando-se o aumento da seletividade para a formação da cetona alílica conforme o catalisador perde atividade. A lixiviação da espécie ativa para o meio reacional, problema comum na catálise heterogênea, não foi observada. Um estudo cinético mostrou que mesmo no inicio da reação o catalisador tem seletividade para a ocorrência de oxidação alílica em detrimento da reação de oxidação direta que dá origem ao produto epóxido. Em todos os tempos estudados o produto principal da reação foi sempre a cicloexenona. Os estudos também revelaram que CoO é a espécie mais ativa quando comparado com Co2+, Co3O4 e Fe3O4 nas mesmas condições reacionais. O catalisador de CoO foi empregado na oxidação de monoterpenos mostrando alta seletividade para a formação dos produtos alílicos, resultando em derivados oxigenados altamente valiosos para a indústria de fragrâncias. / This master thesis describes the synthesis and characterization of a magnetically recoverable CoO catalyst for allylic oxidation of alkenes. The catalyst was prepared through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles. The magnetic nature of the support allowed the easy separation of catalyst from the reaction medium after the completion of the reaction by simply placing a magnet on the reactor wall.The magnetic separation technique used was able to completely isolate the solid from the liquid phase, making the use of other separation methods such as filtration and centrifugation, commonly used in liquid heterogeneous systems, unnecessary.The catalyst was initially tested in the oxidation of cyclohexene, as a model substrate, and showed high selectivity to the formation of the allylic product, cyclohex-2-en-1-one, an interesting starting reactant for many reactions in the chemical industry. The oxidation reactions were performed using O2 as primary oxidant, eliminating the use of toxic oxidants such as chromate or permanganate, which are not environmentally friendly. The synthesized catalyst was found to be reusable in successive runs, with the increasing selectivity to the allylic ketone as the catalyst lost its activity. The leaching of active species to the reaction medium, a common problem in heterogeneous catalysis, was not observed. A kinetic study showed that even at initial times the catalyst is selective for the allylic oxidation despite the direct oxidation, which leads to the formation of the epoxy product. For all reactions studied in different times, the product was always cyclohexenone. The studies also revealed that CoO is the most active species when compared to Co2+, Co3O4 and Fe3O4 in the catalytic conditions studied. The CoO catalyst was used in the oxidation of monoterpenes and showed high selectivity for the allylic products, giving oxygenate derivatives of highly value for flagrance industry.

Este trabalho compreende a síntese e caracterização de um novo catalisador magneticamente recuperável de CoO para oxidação alílica de alcenos. O catalisador foi preparado através da deposição de nanopartículas (de tamanho entre 2-3 nm) do metal cataliticamente ativo em nanopartículas de magnetita revestidas por sílica. A natureza magnética do suporte permitiu a fácil separação do catalisador do meio reacional após o termino das reações pela simples aproximação de um ímã na parede do reator. O catalisador pôde ser completamente separado da fase líquida, fazendo com que a utilização de outros métodos de separação como filtração e centrifugação, comumente utilizados em sistemas heterogêneos líquidos, fossem completamente dispensados. O catalisador foi inicialmente testado em reações de oxidação do substrato modelo cicloexeno e mostrou seletividade para a produção do produto alílico, cicloex-2-en-1-ona, que é reagente de partida de grande interesse para a síntese de diversos materiais na indústria química. As reações de oxidação foram realizadas utilizando-se apenas O2 como oxidante primário, dispensando o uso de oxidantes tóxicos como cromatos ou permanganatos, que não são recomendados do ponto de vista ambiental. O catalisador sintetizado mostrou ser reutilizável em sucessivos ciclos de oxidação, destacando-se o aumento da seletividade para a formação da cetona alílica conforme o catalisador perde atividade. A lixiviação da espécie ativa para o meio reacional, problema comum na catálise heterogênea, não foi observada. Um estudo cinético mostrou que mesmo no inicio da reação o catalisador tem seletividade para a ocorrência de oxidação alílica em detrimento da reação de oxidação direta que dá origem ao produto epóxido. Em todos os tempos estudados o produto principal da reação foi sempre a cicloexenona. Os estudos também revelaram que CoO é a espécie mais ativa quando comparado com Co2+, Co3O4 e Fe3O4 nas mesmas condições reacionais. O catalisador de CoO foi empregado na oxidação de monoterpenos mostrando alta seletividade para a formação dos produtos alílicos, resultando em derivados oxigenados altamente valiosos para a indústria de fragrâncias. / This master thesis describes the synthesis and characterization of a magnetically recoverable CoO catalyst for allylic oxidation of alkenes. The catalyst was prepared through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles. The magnetic nature of the support allowed the easy separation of catalyst from the reaction medium after the completion of the reaction by simply placing a magnet on the reactor wall.The magnetic separation technique used was able to completely isolate the solid from the liquid phase, making the use of other separation methods such as filtration and centrifugation, commonly used in liquid heterogeneous systems, unnecessary.The catalyst was initially tested in the oxidation of cyclohexene, as a model substrate, and showed high selectivity to the formation of the allylic product, cyclohex-2-en-1-one, an interesting starting reactant for many reactions in the chemical industry. The oxidation reactions were performed using O2 as primary oxidant, eliminating the use of toxic oxidants such as chromate or permanganate, which are not environmentally friendly. The synthesized catalyst was found to be reusable in successive runs, with the increasing selectivity to the allylic ketone as the catalyst lost its activity. The leaching of active species to the reaction medium, a common problem in heterogeneous catalysis, was not observed. A kinetic study showed that even at initial times the catalyst is selective for the allylic oxidation despite the direct oxidation, which leads to the formation of the epoxy product. For all reactions studied in different times, the product was always cyclohexenone. The studies also revealed that CoO is the most active species when compared to Co2+, Co3O4 and Fe3O4 in the catalytic conditions studied. The CoO catalyst was used in the oxidation of monoterpenes and showed high selectivity for the allylic products, giving oxygenate derivatives of highly value for flagrance industry.

The scope of this thesis was to study thermodynamics of lead oxide and cobalt oxide as the chemical looping agent for oxygen. Furthermore, the theoretical results were verified experimentally. Ellingham diagrams were constructed for the selected oxides. Then, detailed thermodynamic analysis was conducted for stability analysis at different temperatures and pressures. Equilibrium product compositions for various reactions involving these oxides were calculated via Gibbs free energy minimization analysis. Finally, it was shown that cobalt, lead and their oxide forms can be used for syngas production. In the experimental part PbOx, CoOx, Pt-doped CoOx and Pt-doped cobalt alumina, and mixed lead cobalt oxides were synthesized. In addition, technical grade cobalt oxide and lead rods were also used. XRD analysis indicated that Co3O4, Pb2O3 and &alpha / -PbO were the main crystal structures. Oxygen evolution from mixed oxides was monitored by TPD in a home built system. Re-oxidation of the reduced metals was successfully conducted using CO2 and H2O as oxidizing agents. Oxygen TPD studies indicated that oxygen evolution rates and amounts were higher and started at lower temperatures when two oxides were together. These observations were consistent with the predictions obtained from thermodynamics. In a series packed bed reactor, evolved oxygen from the mixed oxides were used to react with coal packed upstream of the oxides. It was found that coal oxidation can be achieved around 400oC and 600oC by using Pb/Co=3 (wt./wt.) looping media with almost no CO2 formation. It was also found that desired product selectivity (CO) can be increased by controlling reactive agent (O2) concentration in reaction environment.