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Nickel modified strontium hydroxyapatite (Ni/Sr-HAP) supported catalysts are studied in selective methanation of CO/CO₂. In this work, a new type of nano rod-shaped strontium hydroxyapatite-based catalysts with two different sizes and aspect ratios were prepared by sol–gel method and in next step, Ni precursor was wet impregnated i.e., denoted as Ni/Sr-HAP and Ni/Sr-HAP(F127). The catalytic tests were performed in CO and CO2 methanation reactions and evaluated the light-off temperatures curves (225–450 °C) under ambient pressure in a fixed-bed flow reactor. The physicochemical properties of the prepared catalysts were characterized by XRD, N2 physisorption, TEM, SEM, TPR, CO₂/H₂-TPD and H₂-chemisorption techniques. From XRD analysis, both Ni/Sr-HAP and Ni/Sr-HAP(F127) were identified as the hydroxyapatite type structure with high crystallinity and very low intensity peaks corresponds to strontium phosphates as the main phase and structure. The TEM and SEM micrographs of Ni/Sr-HAP catalysts displayed a nano- rod shaped morphology with different dimensions and exhibited average Ni particle size of ~ 9.2 nm. While Ni/Sr-HAP(F127) shown the rod size in the length in the range of 100–250 nm and width in the range of 20–40 nm with average Ni particle size 5.7 nm. The F127 mediated support Sr-HAP synthesis i.e., Ni/Sr-HAP(F127) mesoporous catalyst possessed higher metal surface with smaller Ni particles size and possessed higher CO₂ adsorption capacity. The medium strength basic sites of Ni/Sr-HAP catalyst played an important role in methanation reactions. Based on the characterization and the catalysts activity results, small sized nanorods of Ni/Sr-HAP(F127) is the most active and selective catalyst due to the higher Ni dispersion, higher amounts of medium basic sites, and reducibility character than the bigger nanorods based Ni/Sr-HAP catalyst.

Glycerol is an important by-product (biowaste) from biodiesel production. Transformation of glycerol into value-added compounds is critical in improving the overall efficiency of the biodiesel production. In this work, a sustainable and cleaner production of 1,3-propanediol (1,3-PDO) by vapor phase hydrogenolysis of glycerol was performed over titanium phosphate (TiP) supported catalysts by varying the Pt and WO₃ loadings (5–20 wt.%). The WO₃ promoted Pt modified TiP catalysts were prepared by a simple wet impregnation method and characterized by various analytical techniques in determining the key properties. Furthermore, the catalyst activity and stability were studied under different reaction conditions. The synergistic effects of Pt and WO₃ loadings on the final performance of the catalyst has been significant in improving the hydrogen transfer rate. Both Pt and WO₃ promotional effects is envisaged the enhanced catalytic properties in conjunction with TiP support acidity. WO₃ incorporation increased Brønsted acidity and formed strong interactions with Pt over TiP support. Both Lewis and Brønsted acid sites presented but BAS played a key role in enhancing the 1,3-PDO selectivity in a bifunctional dehydration-hydrogenation reaction mechanism of glycerol. The effect of reaction temperature, contact times and the weight hour space velocity were evaluated. Overall, under optimized reaction conditions, 2 wt.% Pt-10 wt.% WO₃/TiP catalyst displayed superior activity with a maximum glycerol conversion of ~ 85% and ~ 51% of 1,3-PDO selectivity achieved at time on stream of 4 h.

In this work, biomass-based platform molecule lactic acid conversion to acrylic acid has been studied. A series of lanthanum phosphate (LaP) catalysts prepared by varying the lanthanum to phosphorus (La/P) mole ratio (i.e., 0.2, 0.35, 0.5, 1.0, and 2.0) and also prepared at different calcination temperatures (i.e., 400, 500, 600, and 800 °C) were investigated. The catalysts were characterized by using different techniques and tested in the dehydration of lactic acid (LA) to acrylic acid (AA) production. All the synthesized catalysts were characterized to analyze the physicochemical properties such as degree of crystallinity, total surface acidity, specific surface area, and morphology. The La/P mole ratio was found to be significant in designing the optimized catalytic system. The NH₃-TPD results imply that all the catalysts exhibited varied amount of total acidity with phosphate loadings, which are mostly weak acid sites. The weak acid sites which are mainly Lewis acidity type played an important role in producing AA selectively and efficiently from the LA conversion. The most optimized reaction conditions were determined to obtain the highest LA conversion, selectivity, and AA yield. The catalyst with an La/P mole ratio of 0.35 and calcined at 500 °C exhibited the best performance with complete LA conversion, AA selectivity of ~ 74%, and a maximum yield of AA of ~ 74%. Furthermore, the LaP(0.35)[500] catalyst was successfully tested at three different time on streams and found to be stable.

Geopolymers have not been extensively employed as catalytic materials despite of their zeolite-resembling Si–Al structure. Geopolymerization offers a novel way for preparation of catalysts and possibility to use waste or industrial side-stream derived raw material as a resource for catalyst manufacturing. This work concentrates on metakaolin-based geopolymer materials that were prepared, characterized and tested as alternative environmentally benign catalyst supports for the oxidation of dichloromethane. The geopolymers with the Si/Al ratio of 1.5 were modified with HCl to increase their specific surface area, which is important in catalytic applications. Significant increase in specific surface areas was achieved via leaching of Na and Al from the geopolymer structure. Highest specific surface areas achieved for calcined geopolymers were over 500 m²g⁻¹. Use of acid concentrations higher than 1 M led to the dehydroxylation of the geopolymer. Dehydroxylation decreased the total acidity of geopolymer through the loss of the Brønsted acid sites, which are responsible for the adsorption of dichloromethane in the beginning of the catalytic reaction. Absence of Brønsted acid sites was observed by the formation of CH₂O as the only reaction intermediate. The best result in the dichloromethane oxidation was found with the geopolymer treated with 1 M HCl. Without using any additional active sites, the maximum dichloromethane conversion of 90% was reached at 525 °C with the maximum HCl yield of 83%. This result indicates the good potential of modified geopolymers to be used as catalyst supports in environmental applications.

Designing and developing non-noble metal-based heterogeneous catalysts have a substantial importance in biomass conversion. Meerwein-Ponndorf-Verley (MPV) reaction is a significant pathway for eco-friendly catalytic transfer hydrogenation (CTH) of biomass derived furfural into furfuryl alcohol. In this work, a series of copper-supported hydroxyapatite (HAp) catalysts with different copper loadings (2–20 wt.%) were prepared by a facile impregnation method and tested in the reduction of furfural to furfuryl alcohol using 2-propanol as a hydrogen donor. The structural and chemical properties of the synthesised catalysts were analysed by using various techniques (XRD, N₂ sorption, SEM, TEM, UV-DRS, ICP, FTIR, TPR, TPD-CO₂ and N₂O titration). The effect of copper loading was found to be significant on the total performance of the catalysts. The results demonstrate that 5CuHAp catalyst possess highly dispersed copper particles and high basicity compared to all other catalysts. Overall, 5CuHAp exhibited highest conversion (96%) and selectivity (100%) at 140 °C at 4 h time on stream. The optimised reaction conditions were also determined to gain the high activity.

The energy consumption around the globe is on the rise due to the exponential population growth and urbanization. There is a need for alternative and non-conventional energy sources, which are CO₂-neutral, and a need to produce less or no environmental pollutants and to have high energy efficiency. One of the alternative approaches is hydrogen economy with the fuel cell (FC) technology which is forecasted to lead to a sustainable society. Hydrogen (H₂) is recognized as a potential fuel and clean energy carrier being at the same time a carbon-free element. Moreover, H₂ is utilized in many processes in chemical, food, metallurgical, and pharmaceutical industry and it is also a valuable chemical in many reactions (e.g. refineries). Non-renewable resources have been the major feedstock for H₂ production for many years. At present, ~50% of H₂ is produced via catalytic steam reforming of natural gas followed by various down-stream purification steps to produce ~99.99% H₂, the process being highly energy intensive. Henceforth, bio-fuels like biomass derived alcohols (e.g. bio-ethanol and bio-glycerol), can be viable raw materials for the H₂ production. In a membrane based reactor, the reaction and selective separation of H₂ occur simultaneously in one unit, thus improving the overall reactor efficiency. The main motivation of this work is to produce H₂ more efficiently and in an environmentally friendly way from bio-alcohols with a high H₂ selectivity, purity and yield. In this thesis, the work was divided into two research areas, the first being the catalytic studies using metal decorated carbon nanotube (CNT) based catalysts in steam reforming of ethanol (SRE) at low temperatures (<450 °C). The second part was the study of steam reforming (SR) and the water-gas-shift (WGS) reactions in a membrane reactor (MR) using dense and composite Pd-based membranes to produce high purity H₂. CNTs were found to be promising support materials for the low temperature, Tiivistelmä Maailman energiankulutus on kasvussa räjähdysmäisen väestönkasvun ja voimakkaan kaupungistumisen myötä. Tällä hetkellä energian tuottamisen aiheuttamat ympäristöongelmat ja taloudellinen epävarmuus ovat seikkoja, joiden ratkaisemiseksi tarvitaan vaihtoehtoisia ja ei-perinteisiä energialähteitä, joilla on korkea energiasisältö ja jotka tuottavat vähän hiilidioksidipäästöjä. Eräs vaihtoehtoisista lähestymistavoista on vetytalous yhdistettynä polttokennotekniikkaan, minkä on esitetty helpottavan siirtymistä kestävään yhteiskuntaan. Vety on puhdas ja hiilivapaa polttoaine ja energian kantaja. Lisäksi vetyä käytetään monissa prosesseissa kemian-, elintarvike-, metalli- ja lääketeollisuudessa ja se on arvokas kemikaali monissa prosesseissa (mm. öljynjalostamoissa). Uusiutumattomat luonnonvarat ovat olleet tähän saakka merkittävin vedyn tuotannon raaka-aine. Tällä hetkellä noin 50 % vedystä tuotetaan maakaasun katalyyttisellä höyryreformoinilla. Puhtaan (yli 99,99 %) vedyn tuotanto vaatii kuitenkin useita puhdistusvaiheita, jotka ovat erittäin energiaintensiivisiä. Integroimalla reaktio- ja puhdistusvaihe samaan yksikköön (membraanireaktori) saavutetaan huomattavia kustannussäästöjä. Biopolttoaineet, kuten biomassapohjaiset alkoholit (bioetanoli ja bioglyseroli), ovat vaihtoehtoisia lähtöaineita vedyn valmistuksessa. Tämän työn tavoitteena on tuottaa vetyä bioalkoholeista tehokkaasti (korkea selektiivisyys ja saanto) ja ympäristöystävällisesti. Tutkimus on jaettu kahteen osaan, joista ensimmäisessä tutkittiin etanolin katalyyttistä höyryreformointia matalissa lämpötiloissa (<450 °C) hyödyntämällä metallipinnoitettuja hiilinanoputkia. Työn toisessa osassa höyryreformointia ja vesikaasun siirtoreaktioa tutkittiin membraanireaktorissa käyttämällä vedyn tuotantoon tiheitä palladiumpohjaisia kalvoja sekä huokoisia palladiumkomposiittikalvoja. Hiilinanoputket (CNT) havaittiin lupaaviksi katalyyttien tukimateriaaleiksi verrattuna tavanomaisesti valm