Recently, during the past10 years, with the intensified attention paid to the environment and industrial development, there has been growing interest in organocatalysis. One important area of the organocatalysis is the development of new designs of chiral catalysts for the synthesis of optically pure products. Another important area is to develop methods to simplify the purification of multi-component reactions. A chiral spirobiindane-based bisphosphine oxide catalyst was synthesized and employed in various reactions including Abramov-type phosphonylation reactions, reductive aldol reactions, direct aldol reactions, allylations, reductive cyclizations and C=N reduction reactions. The rigid and axially chiral spirobiindane skeleton of the bisphosphine oxide introduces steric hindrance and results in moderate to good enantioselectivity in Abramov phosphonylation and reductive cyclization reactions. However, the great steric hindrance of the catalyst also imposes negative effects on catalyst activity and yields of reactions. The observed slow reaction rates may possibly have led to the undesired, non-selective background reactions and therefore a lowered enantioselectivity. Secondly, the success of polymer-supported reagents in facilitating product purification prompted our attempt to prepare and examine two different types of polymer-supported benzothiazolines for hydrogen transfer reduction. An in situ generated self-supported polybenzothiazoline proved to be a rapidly formed polymer under mild conditions and could be applied to hydrogenation transfer reduction reactions with active alkenes. A rasta resin-supported benzothiazoline was also synthesized and examined in similar transformations. Both of the two polymer reagents afforded the desired reduction products, but further optimizations may be required to suppress the formation of byproducts and to improve their reactivity. / published_or_final_version / Chemistry / Master / Master of Philosophy

Both products, n-butyraldehyde and iso-butyraldehyde from propene hydroformylation are key building blocks for the synthesis of many chemical intermediates, and although high linear selectivity has been achieved, any form of branched selectivity remains very difficult to attain. This project aims to deliver a catalyst that can selectively produce branched iso-butyraldehyde as the major product from propene hydroformylation. One approach discussed is to study terphenyl phosphines as ligands. The synthesis of substituted terphenyls through Suzuki-Miyaura coupling reactions between aryl boronic acids and 2,6-dichloroanisole was studied. Novel phosphine-phosphanamine ligands with bulky terphenyl substituents were synthesised and tested in propene hydroformylation, and also asymmetric hydroformylation of other alkenes. The synthesis of several ferrocene-based phosphine-phosphoramidite ligands is also discussed. These ligands were then tested in rhodium-catalysed propene hydroformylation and their reactivities and selectivities are reported. These ligands/Rh catalysts showed a moderate reactivity for propene hydroformylation and up to 56% branched selectivity, which is close to the best selectivity known under industrially relevant conditions. The introduction of bulky substituents on the phosphoramidite part of the ligand did not deliver any huge increases in regioselectivity, but a large improvement in catalyst thermal stability was observed in experiments conducted using in situ high pressure infrared spectroscopy. The reaction conditions for rhodium-catalysed propene hydroformylation using the BOBPHOS ligand were investigated, with unprecedented branched selectivity of up to 82% achieved. A variety of aspects was examined, including the solvent, reaction temperature, reaction pressure with varying partial pressure of CO and H₂, and rhodium to ligand ratio. BOBPHOS derivatives which are more synthetically accessible and economically attractive were synthesised and tested in rhodium-catalysed propene hydroformylation. Comparable results with their parent ligand/Rh catalyst were obtained and improved thermal stabilities were observed in selected catalysts. Different directions for potential future works are suggested, which hopefully, along with the findings in this thesis, can be a major contribution to the development of an efficient, branched selective catalytic system for industrial propene hydroformylation.

Catalysis allows for the controlled formation of new bonds, whilst reducing both time and energy expenditure in the process. Catalysis has traditionally been the realm of precious metals, which have been used to carry out a bewildering array of reactions. However, there is an ever-increasing drive for the development of catalytic methodology employing sustainable and environmentally benign catalysts. Two such candidates are organocatalysis, omitting the need for metals where possible, or the use of iron catalysis. Two key areas to the advancement of the of field catalysis are the identification and development of new catalysts as well as an understanding of the mechanisms of established catalytic processes. Novel catalysts can provide many benefits such as enhanced or even novel reactivity, access to new classes of substrates or simply be more readily accessible compared with previously developed catalysts. To this end, the first example of Lewis-base-catalysis using the recently developed cyclopropenimine motif is reported. This was exploited in the trifluoromethylation of aldehydes and ketones using the Rupert-Prakash reagent (Scheme A-1). Scheme A-1 Cyclopropenimine-catalysed trifluoromethylation of aldehydes and ketones Developing an understanding of catalytic methodologies in the terms of their mechanism and active species is also a key area in catalysis. Insight into these can direct the expansion of these systems in terms of both more effective catalysts and tailoring reaction conditions as examples. The iron-catalysed hydromagnesiation of styrene derivatives was studied in detail. This culminated in a proposed mechanism, involving a novel hydride transfer process (Scheme A-2). Studies were carried out using a combination of kinetic analysis and in situ Mössbauer spectroscopy, as well as successfully isolating and studying the reactivity of a catalytically-relevant, formal iron(0)-species.

Biodiesel is a promising renewable alternative fuel to fossil energy. For the biodiesel production from low-cost feedstock, a pretreatment step is essential, which is the esterification of free fatty acids (e.g. oleic acid) in the feedstock in order to avoid soap formation and minimize catalyst deactivation. Sulfuric acid modified zirconia (H2SO4-ZrO2) is known as an effective heterogeneous catalyst for esterification. However, due to rapid 〖SO〗_4^(2-) leaching, its reusability is low and its practical use is thus largely hindered. Zirconia supported on silica (ZrO2-SiO2) serves as a kind of non-sulfated zirconia catalyst against the leaching of the active species. Moreover, the silica support offers a large surface area and excellent thermal stability, which can accommodate a number of active zirconia species. Furthermore, there are Zr-O-Si bondings at the contact area between ZrO2 and SiO2, which might result in the formation of a new strong acid species and induce an increase of the zirconia acidity accordingly. Herein, two types of ZrO2-SiO2 catalysts were prepared, by using the reverse microemulsion method and sol-gel-hydrothermal method, denoted as ZrO2-SiO2-ME and ZrO2-SiO2-SG, respectively. The as synthesized ZrO2-SiO2 were characterized by TEM, SEM, EDX, XRD, BET and IR. ZrO2-SiO2-ME demonstrated a good dispersion of ZrO2 nanoparticles, encapsulating in the monodispersed SiO2 host matrix, while ZrO2-SiO2-SG possessed the SiO2 support with a mesoporous structure, with an average pore size of ~7 nm and a surface area of 418 m2/g. The catalysts both exhibited excellent catalytic activity and stable performance in the esterification of oleic acid. Besides non-sulfated zirconia, sulfated zirconia catalysts other than traditional H2SO4-ZrO2 were also developed as solid acid catalysts for biodiesel production. Two sulfur-containing strong acids, chlorosulfonic acid (HClSO3) and (NH4)2SO4, were employed to acidify ZrO2, and two sulfated zirconia catalysts were prepared accordingly, namely HClSO3-ZrO2 and S-ZrO2. They were characterized by SEM, EDX, XRD, BET, IR, TGA and NH3-TPD. Comparing with H2SO4-ZrO2, HClSO3-ZrO2 and S-ZrO2 contained higher sulfur content and more acid sites. More importantly, both HClSO3-ZrO2 and S-ZrO2 demonstrated high catalytic activity and excellent durability in the esterification of oleic acid. It is known that consecutive esterification and transesterification reactions are suitable for direct biodiesel production and acetylation of glycerol enables the conversion of this biodiesel byproduct to a biofuel additive. Therefore, all the above mentioned catalysts were examined to compare their catalytic abilities in these reactions. Among the four catalysts, HClSO3-ZrO2 exhibited the highest catalytic activity in both reactions under optimal conditions. The thesis work here described the preparation and characterization of four types of ZrO2-based solid acid catalysts. Their catalytic activities were thoroughly investigated upon the several essential steps in biodiesel production. In addition, the synthesis condition-activity relation was studied and the synthesis and reaction conditions were delicately tuned. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

New cis-dichloro ruthenium-based pre-catalysts for olefin metathesis reaction were synthesised. This work was inspired by the report of complex cis-Caz-1 in 2010, a 2nd generation-type pre-catalyst displaying latent character and acknowledged as state-of-the-art for challenging transformation in olefin metathesis. The stability and the reactivity of such species led us to investigate the possibility to perform the catalysis in air with reagent-grade solvents, so that olefin metathesis reaction can be easily carried out in synthetic laboratories avoiding restricting inert conditions (Chapter 2). Next, further modifications of the original scaffold were attempted. Pre-catalyst cis-Caz-1 was reacted with different silver salts leading to new cis-complexes. The first examples of Ru-F species for olefin metathesis reaction are reported in Chapter 3. The phosphite ligand plays a very important role in the cis-Caz-1 scaffold and allowed the formation of the mono and the difluoro complexes selectively. Other silver salts were then employed such as trifluoroacetate, acetate, benzoate and pivalate. In all the studies involving silver salts, the anionic exchange reactions occurring among cis-Ruspecies in solution was observed. Electronic properties rather than sterics were responsible for the selective formation of the mixed complex trifluoroacetate/acetate 55 (Chapter 4). The results obtained with 2nd generation systems prompted us to evaluate triisopropyl phosphite as ligand in 1st generation-type complexes. Similar synergistic effects to complex cis-Caz-1 were observed. The mixed PCy3/P(OiPr)3 complex 56 displayed cis-geometry, high thermal stability and latent character compared to the bis-phosphine analogue Ind-I (Chapter 5). Last, a catalytic and structural study of commercially available pre-catalysts M51TM and M52TM in collaboration with Umicore was carried out together with the Grela group (Chapter 6). These Hoveyda-Grubbs type pre-catalysts showed an interesting activity in ring closing metathesis, allowing the isolation of di- and tri- substituted ring-products at room temperature, as well as in cross metathesis, where some examples of biologically active compounds were obtained.

The preparation of visible light driven photocatalysts for photocatalytic water splitting has been achieved by a CO₂ free, low cost and simple novel method. Combination of peroxide based route with organic free solvent and titanium nitride, carbon free precursor and air and moisture stable, would be useful. Clear red-brown solution of titanium peroxo species was obtained by dissolution of TiN in H₂O₂ and HNO₃ acid at room temperature without stirring. The resultant red brown solution is then used as a titanium solution precursor for yellow amorphous and yellow crystalline TiO₂ synthesis. Visible light photoactivity of the samples was evaluated by photooxidation of methylene blue and photoreduction producing hydrogen from water splitting. The high surface area of yellow amorphous TiO₂ exhibits an interesting property of being both surface adsorbent and photoactive under visible light for photodecolourisation of aqueous solution of methylene blue. However, it might not appropriate for hydrogen production. Nanoparticulate yellow crystalline TiO₂ with defect disorder of Ti³⁺ and oxygen vacancies depending upon synthesis conditions has been characterised by ESR, XPS, CHN analysis and SQUID. Single phase rutile can be produced at low temperature. It is stable at high temperature and the red shift of absorption edge increases with the treatment temperature. Yellow crystalline TiO₂ exhibits an interesting property of being photoactive under visible light. The best photocatalytic performance was observed for 600°C calcination, probably reflecting a compromise between red shift and surface area with changing temperature. Moreover, overall water splitting into hydrogen and oxygen might be obtained by using this material even in air atmosphere. Photoactivity can be improved by testing under anaerobic atmosphere and/or adding sacrificial agent. Quantum efficiency under visible light is still low but comparable to other reports. The maximum efficiency varies from 0.03 % to 0.37 % for hydrogen production and from 0.03 % to 0.12 % for oxygen production, depending on photon energy and sacrificial agents.

Submitted in fulfillment of the academic requirements for the award of the degree of Master of Engineering, Durban University of Technology, Durban, South Africa, 2018. / Overdependence on fossil-based fuels and their effect on environment is a global concern by energy stake holders. Bulk of present day hydrogen comes from gasification of coal, steam reforming and partial oxidation of hydrocarbons. Steam reforming accounts for over 50% of world hydrogen production despite producing carbonaceous gases which are harmful to the environment and poisonous to both; proton exchange fuel cells and alkaline fuel cells. Natural gas is a preferred feed for hydrogen production, because it is abundantly available on earth. Catalytic decomposition of ammonia can produce clean hydrogen but ammonia itself is an air pollutant. Catalytic decomposition of methane into carbon and hydrogen is an attractive option to producing clean hydrogen because its products are carbon and hydrogen. In this work, five different catalysts comprising of varying quantities of nickel and lithium, supported on calcium oxide were synthesized by incipient wetness impregnation method and designated according to weight % as; 30%Ni/CaO, 37.5%Ni-12.5%Li/CaO, 25.0%Ni- 25.0%Li/CaO, 12.5%Ni-37.5%Li/CaO and 50%Li/CaO. The synthesized catalysts were characterized by (XRD, SEM, BET and TEM) and tested for methane decomposition. From the XRD patterns of the synthesized catalysts, distinct crystalline phases of CaO and NiO were positively identified in 50%Ni/CaO according to their reference JCPDS files. Introduction of Lithium hydroxides improved the crystalline structure of the Ni/CaO catalyst. SEM analyses of the catalyst material using Image-J software confirmed that all catalyst materials were nanoparticles ranging from 3.09-6.56nm. BET results confirmed that, all the catalysts are mesoporous with pore sizes ranging from 20.1nm to 45.3nm. Introduction of LiOH to Ni/CaO generates mesoporous structures by destructing the lattices of the CaO structure during the formation of Ni-Li/CaO species. Particle size distribution in TEM analyses revealed that, a higher nickel loading in the catalyst favours the formation of carbon nanotubes while higher lithium hydroxide loading favours the formation of carbon fibres (CF). Low yield of carbon fibres from methane decomposition on unsupported Ni catalyst in 50%Ni/CaO was attributed to the presence of large Ni particles with low index planes which were incapable of dissociating the unreactive methane molecule. The aim of this work was to synthesize a catalyst for use in decomposition of methane into carbon and hydrogen, that addresses drawbacks of traditional solid metal catalysts such as sintering and coking. From the experimental results, 37.5%Ni-12.5%Li/CaO catalyst recorded 65.7% methane conversion and 38.3%hydrogen yield while 50%Ni/CaO recorded the lowest methane conversion of 60.2% and a hydrogen yield of 35.7% at 650℃. Outstanding performance of the 37.5%Ni-12.5%Li/CaO catalyst is attributed to the incorporation of lithium hydroxide which provided more catalyst active sites and a molten environment for proper dispersion of the nickel metal. The solid 50%Ni/CaO catalyst readily deactivated due to coking unlike the supported molten 37.5%Ni-12.5%Li/CaO catalyst in which methane decomposition reaction took place by both surface reaction and chemisorption. / M

Mankind makes extensive use of crude oil to fuel its insatiable demands for energy and hydrocarbon derivatives. The refining of crude oil is based on a process known as cracking, where long-chain hydrocarbons are systematically broken into smaller chain hydrocarbons known as fractions with each fraction allowing for the production of a specific material. The maximum efficiency of cracking can be achieved in the petroleum refining processes by controlling the operating parameters of the units, and over the years many studies have attempted to optimize the cracking conditions such as temperatures, pressures and the use of a variety of catalysts to reach maximum productivity. Catalysts such as the Y-type zeolite catalysts are often used because their acidity and thermal stability makes them an ideal cracking catalyst; however the developments of enhanced catalytic properties for zeolite-Y catalysts are essential to increase the production yields. Optimization of the Y-type zeolite catalyst is the focus of this research and accordingly the synthesis, characterization, modifications and catalysis have been studied in depth. A review of the literature has shown that there are three main techniques used to improve the zeolite properties following the synthesis process; (Cation exchange, Dealumination and Desilication), since the crystalline structure of a Y-type zeolite is prepared from an alkaline aluminosilicates gel. However, the literature focuses mainly on the reaction variables used in the modifications. As such this study focuses on the effects of treatment processes on the composition, behaviour and catalytic properties of the synthesized Y-zeolite framework. Laboratory experimental data has confirmed that a synthesis process using 24 h aging for crystal nuclei at 25 °C and 18 h crystallization time for crystal growth at 100 °C produced the desired zeolite NaY morphology, and NaNH4Y zeolite forms with various cation contents (3, 1.5 and 0.5 wt% Na+) were obtained by subjecting the NaY form to a multi-stage ion exchange using 0.5 M NH4NO3 at 80 °C, while the HY form was obtained by the calcination of NH4Y form under high temperature. Calcination temperatures above 450 °C were shown to indicate a removal of the framework hydroxyl groups via dehydroxylation, which led to a collapse of zeolite-Y structure, whereas raising the level of Na+ inside the zeolite lattice throughout the calcination was led to a delay in the starting point of the dehydroxylation region as confirmed via TG and DSC-analyses. This finding was also used in the preparation of the USY form by steaming the HY form, as the former is a traditional zeolite-Y form utilized in the refining units. It was found that Na-ions hindered the extraction of Al-atoms from the Y-lattice thus reducing the rate of dehydroxylation, and minimising rapid contraction of the unit cells and Y-structure collapse, which helped make a rigid structure and a more resilient lattice for steaming at high temperature. In addition, analyses data confirmed that the extraction of EFAl-species from the USY-structures using an EDTA chemical treatment led to an increase in the acidity of treated catalyst and the introduction of mesopores. Lower lattice Si/Al ratio and larger porosity were also found using the dealuminated-desilicated rather than the desilicated-dealuminated leaching method in the treatment of both Y and USY structures via dislodgement of both Si and Al-atoms in NaOH and HCl solution. Cracking was performed on deactivated catalysts (450 °C) in a PFTR using nC7 in N2 at 325 - 425 °C and W/F = 22 - 44 g.h.mol-1, and confirmed that the tuned steaming/leaching conditions succeeded in modifying the catalytic properties of the in house made catalysts, as they possess superior performance when compared to the industrial catalysts typically used.

D.Phil. / Clean water (i.e. water that is free of toxic chemicals and pathogens) is essential to human health and in South Africa the demand is fast exceeding the supply. The prevalence of toxic contaminants in water remains a huge challenge for water supplying companies and municipalities. However, the presently used water treatment technologies either fail to remove these contaminants to acceptable levels or they transform them into more toxic substances (e.g., DBPs). Nanocatalysts, especially TiO2 (titania) have a proven potential to treat ‘difficult-to-remove’ contaminants and hence are expected to play an important role in solving many serious environmental and pollution challenges. In this study TiO2 nanocatalysts were used for the degradation of Rhodamine B dye both under UV and visible light irradiation. Two phases of titania, i.e. anatase and rutile phases, were compared for the degradation of Rhodamine B under UV light irradiation. The anatase titania was found to be more photocatalytically active for the degradation of Rhodamine B than the rutile phase. It completely degraded 100 mg ℓ–1 (100 mℓ) of Rhodamine B within 270 min and was two times more photocatalytically active than the rutile phase (Kapp of 0.017 min–1 compared to 0.0089 min–1). To extend the band edge of the titania nanocatalysts towards visible-light, TiO2 was doped with metal ions (Ag, Co, Ni and Pd). These metal-ion-doped titania nanocatalysts were photocatalytically active under visible-light illumination. The Pd-doped titania had the highest photodegradation efficiencies, followed by Ag-doped and Co-doped, while Ni-doped had the lowest. The optimum metal-ion loading percentage was found to be at 0.4%, with the exception of Co-doped titania as it had the highest efficiencies at 1% loadings. The free and metal-ion-doped titania nanocatalysts were embedded on carbon-covered alumina (CCA) supports. The CCA-supported TiO2 nanocatalysts were more photocatalytically active under visible light illumination than they were under UV-light irradiation. The CCA-supported metal-ion-doped titania nanocatalysts were more photocatalytically active under visible light than their unsupported counterparts. The CCA-supported Pd-TiO2 nanocatalysts were the most active while CCA-supported Ni-TiO2 catalysts were the least active. The improved photocatalytic activities observed were as a result of increased surface areas of the CCA-supported nanocatalysts. Also, supporting the nanocatalysts did not destroy the anatase phase of the titania while doping with metal ions and supporting on CCAs resulted in decreased band gap energies, hence the visible-light photocatalytic activities. Finally, the metal-ion-doped titania nanocatalysts were supported on glass slides using the layer-by-layer thin film self-assembly technique. This was to overcome the aggregation and post treatment problems associated with the use of TiO2 in suspension form. PAH and PSS were the polyelectrolytes used. These metal-ion-doped titania thin films were highly porous and strongly adhered by the polyelectrolytes onto the glass slides. The thin films were photocatalytically active for the degradation of Rhodamine B under visible light irradiation. The photocatalytic degradation efficiencies observed were similar for all four metal-ions (i.e. Ag, Co, Ni and Pd) with average degradation of 30%, 50%, 70% and 90% for 5 catalysts (5 glass slides) of 1, 3, 5 and 10 bi-layers, respectively, after 330 min. Although, these were less active than the suspended titania nanocatalysts, this study proved as a stepping stone towards large scale use of titania nanocatalysts using solar energy as the irradiation source. Also, catalyst reusability studies were performed and the PAH/PSS m-TiO2 thin films were found to be highly stable over the five cycles it was tested for.

Chiu, Ka Lok = 多孔生物遺態氧化銅/氧化鈰/氧化鋁之複合物料的製作及其定性分析 / 趙家樂. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstract also in Chinese. / Chiu, Ka Lok = Duo kong sheng wu yi tai yang hua tong/yang hua shi/yang hua lu zhi fu he wu liao de zhi zuo ji qi ding xing fen xi / Zhao Jiale. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgment --- p.v / Table of contents --- p.vi / List of table captions --- p.x / List of figure captions --- p.xi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Carbon monoxide (CO) --- p.1 / Chapter 1.2 --- Production of hydrogen from methanol for fuel cell --- p.2 / Chapter 1.3 --- Catalysts for CO oxidation and methanol reforming --- p.5 / Chapter 1.4 --- Copper-based catalysts --- p.6 / Chapter 1.5 --- Mechanisms in the catalytic processes --- p.7 / Chapter 1.6 --- Synthesis of Cu-based catalysts --- p.10 / Chapter 1.7 --- Potential applications of the biomorphic CuO/CeO2/Al2O3 catalyst --- p.11 / Chapter 1.8 --- Objectives and the thesis layout --- p.12 / Chapter 1.9 --- References --- p.13 / Chapter Chapter 2 --- Methods and Instrumentation --- p.16 / Chapter 2.1 --- Sample preparations --- p.16 / Chapter 2.1.1 --- Syntheses of the biomorphic samples --- p.16 / Chapter 2.1.2 --- Syntheses of the control samples (R1 and R2) --- p.17 / Chapter 2.2 --- Characterization --- p.18 / Chapter 2.2.1 --- Scanning electron microscope (SEM) --- p.18 / Chapter 2.2.2 --- Transmission electron microscopy (TEM) --- p.19 / Chapter 2.2.3 --- X-ray powder diffractometry (XRD) --- p.20 / Chapter 2.2.4 --- Fourier transform infrared (FTIR) spectroscopy --- p.21 / Chapter 2.2.5 --- Raman scattering (RS) spectroscopy --- p.22 / Chapter 2.2.6 --- Differential thermal analysis (DTA) --- p.22 / Chapter 2.2.7 --- Thermogravimetric analysis (TGA) --- p.23 / Chapter 2.2.8 --- Gas sorption surface analysis (GSSA) --- p.24 / Chapter 2.3 --- Catalytic activity --- p.25 / Chapter 2.3.1 --- CO oxidation --- p.25 / Chapter 2.3.2 --- Partial oxidation of methanol (POMe) --- p.27 / Chapter 2.3.3 --- Steam reforming of methanol (SRMe) --- p.28 / Chapter 2.4 --- References --- p.29 / Chapter Chapter 3 --- "Results, discussions and characterization" --- p.31 / Chapter 3.1 --- Biomorphic samples --- p.31 / Chapter 3.1.1 --- Macrostructures --- p.31 / Chapter 3.1.2 --- SEM and TEM results --- p.32 / Chapter 3.1.3 --- XRD analysis and chemical compositions --- p.35 / Chapter 3.1.4 --- RS results --- p.41 / Chapter 3.1.5 --- FTIR results --- p.44 / Chapter 3.1.6 --- Thermal property --- p.46 / Chapter 3.1.7 --- Porosity analysis --- p.48 / Chapter 3.2 --- Control sample R1 --- p.52 / Chapter 3.2.1 --- Microstructures --- p.52 / Chapter 3.2.2 --- Surface area and porosity --- p.55 / Chapter 3.2.3 --- Thermal property --- p.56 / Chapter 3.2.4 --- "XRD, FTIR and RS results" --- p.58 / Chapter 3.3 --- Control sample R2 --- p.60 / Chapter 3.3.1 --- Microstructures --- p.60 / Chapter 3.3.2 --- Surface area and porosity --- p.61 / Chapter 3.3.3 --- "XRD, FTIR and RS results" --- p.62 / Chapter 3.3.4 --- Thermal property --- p.63 / Chapter 3.4 --- Formation mechanisms of the biomorphic samples --- p.64 / Chapter 3.5 --- Impacts of the Cu/Ce/Al ratios on the CuO dispersion --- p.66 / Chapter 3.6 --- Cotton biotemplate --- p.66 / Chapter 3.7 --- Formation mechanisms of R1 and R2 --- p.67 / Chapter 3.8 --- References --- p.69 / Chapter Chapter 4 --- Evaluations of Catalytic Activities --- p.71 / Chapter 4.1 --- CO oxidation --- p.71 / Chapter 4.2 --- POMe --- p.79 / Chapter 4.3 --- SRMe --- p.91 / Chapter 4.4 --- Physical properties of the biomorphic samples before and after the reactions --- p.97 / Chapter 4.5 --- Structure of the sample and its catalytic performance --- p.102 / Chapter 4.6 --- CuO dispersion and the catalytic performance --- p.103 / Chapter 4.7 --- Al2O3 and CeO2 and the catalytic performance --- p.105 / Chapter 4.8 --- Catalytic performance of the biomorphic samples and R2 --- p.108 / Chapter 4.9 --- References --- p.109 / Chapter Chapter 5 --- Conclusions and suggestions for further studies --- p.110 / Chapter 5.1 --- Conclusions --- p.110 / Chapter 5.2 --- Future works --- p.112 / Chapter 5.3 --- References --- p.114