PhD. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Water is the essence of life, yet it is progressively polluted by dyes, heavy metal ions, food additives, medicines, detergents, agrochemicals, and other toxins from industrial, municipal, and agricultural sources. Among the different wastewater treatment technologies, adsorption is a technique that, when used in conjunction with a welldesigned system, produces high-quality treated water at a reasonable cost. For water treatment, activated carbon is the most often employed adsorbent. Its manufacture, on the other hand, is energy demanding, costly, and creates greenhouse emissions. As a result, finding low-cost alternative adsorbents from industrial and agricultural waste and biomass has attracted a lot of interest. In this context, developing sustainable platforms for wastewater treatment using sustainable nanomaterials such as cellulose nanocrystals (CNCs) is a unique technique with a low carbon footprint. CNCs, which are made by hydrolyzing pulp fibers in sulfuric acid, are rod-like nanomaterials with a lot of remarkable qualities including high specific surface area, high specific strength, hydrophilicity, biodegradability, and surface functionalization. These characteristics, as well as their accessibility, make them suitable candidates for water treatment applications. However, because of their great colloidal stability and nano-dimensions, extracting these CNCs after usage in water treatment is difficult. To overcome this problem, including these CNCs into nanocomposite systems that can be readily separated after usage in batch and continuous water treatment processes is a great concept. Furthermore, pure CNCs have low selectivity towards a wide range of water pollutants, necessitating surface functionalization to provide this selectivity. As a result, this thesis investigates the extraction of CNCs from millet husk waste and waste papers, the development of CNC-incorporated nanocomposites and evaluation of their adsorption characteristics using batch and fixed bed column adsorption studies, and (ii) the evaluation of the selective adsorption characteristics of surface functionalized CNCs and their ability to tailor the nanocomposites' characteristics for use in water treatment applications. The response surface methodology, artificial neural network, and adaptive neuro-fuzzy inference systems were also applied to model the removal of heavy metal ions. The first part of the research ( cellulose nanocrystals extraction and optimization) The cellulose nanocrystals were extracted from millet husk residue waste using a homogenized acid hydrolysis method. The effects of the process variables homogenization speed (A), acid concentration (B), and acid to cellulose ratio (C) on the yield and swelling capacity were investigated and optimized using the Box Behnken design (BBD) method in response surface methodology. The numerical optimization analysis results showed that the maximum yield of CNCs and swelling capacity from cellulose was 93.12 % and 2.81 % obtained at homogenization speed, acid concentration, and acid to cellulose ratio of 7464.0 rpm, 63.40 wt %, and 18.83 wt %, respectively. ANOVA revealed that the most influential parameter in the model was homogenization speed for Yield and acid concentration for swelling capacity. The TGA revealed that cellulose had greater heat stability than CNCs. The functional groups of CNCs and cellulose were identical according to the FTIR data. When compared to cellulose, the SEM picture of CNCs is porous and shows narrow particle size with needle-like shape. The XRD pattern revealed an increase in CNC intensity. The second part of the research ( CNCs modification for selective removal) A novel type of recyclable adsorbents with outstanding adsorption capability was produced using CNCs with succinic anhydride and EDTA. and their adsorption properties were studied in detail utilizing batch adsorption experiments of Chromium (VI) in aqueous solution. The effects of several factors on Cr (VI) adsorption were examined, including contact duration, adsorbent dose, starting concentration, pH, and temperature. The cellulose nanocrystals treated with succinic anhydride and EDTA possessed a needle-like form, high porosity, and a narrow particle size distribution. The carboxylate transition of the carboxyl group of cellulose was verified by FTIR. XRD analysis of particles after modification revealed the presence of additional phases, which were attributed to succinic anhydride and EDTA modification. A spontaneous exothermic adsorption process was validated by the observed thermodynamic characteristics. The best model for describing adsorption kinetics and mechanism was a pseudo-second order kinetic and intra-particle diffusion model. The Langmuir adsorption isotherm was seen in equilibrium adsorption data, with a maximum adsorption capacity (qmax) of 387.25± 0.88 mgL-1. We showed that the removal effectiveness of Cr (VI) maintained at 220± 0.78 mg.g-1after 6 adsorption-desorption cycles, and that the CNC-ALG hydrogel beads are excellent adsorbents for the selective removal of Cr (VI) from wastewaters. The third part of the research ( modeling of removal of heavy metal ions using RSM, ANN and quantum mechanism studies ) The effects of contact time , pH, nanoparticle dose, and beginning Cd2+ concentration on Cd2+ removal were examined using the central composite design (CCD) technique. The performance and prediction capabilities of Response Surface Methodology (RSM) and Artificial Neural Network (ANN) modelling methodologies were explored, as well as their performance and prediction capacities of the response (adsorption capacity). The process was also described using the adsorption isotherm and kinetic models. Statistical data, on the other hand, revealed that the RSM-CCD model beat the ANN model technique. The optimum conditions were determined to be a pH of 5.73, a contact time of 310 minutes, an initial Cd2+ concentration of 323.04 mg/L, a sorbent dosage of 16.36 mg, and an adsorption capacity of 440.01 mg/g. The spontaneous adsorption process was well characterized by the Langmuir model, and chemisorption was the dominant regulator. The binding energy gaps HOMO-LUMO were used to find the preferred adsorption sites. The fourth part of research ( optimization of removal using ANN and ANFIS) An artificial neural network and an adaptive neuro-fuzzy inference system were utilized to predict the adsorption capability of mix hydrogels in the removal of nickel (II) from aqueous solution. Four operational variables were evaluated in the ANFIS model to determine their influence on the adsorption study, including starting Ni (II) concentration (mg/L), pH, contact time (min), and adsorbent dosage (mg/L) as inputs and removal percentage (percent) as the single output. In contrast, 70% of the data was employed to develop the ANN model, while 15% of the data was used in testing and validation. To train the network, feedforward propagation with the Levenberg-Marquardt algorithm was used. To optimise, design, and develop prediction models for Ni (II) adsorption using blend hydrogels, (ANN) and (ANFIS) models were employed for trials. The results demonstrate that the ANN and ANFIS models are viable prediction techniques for metal ion adsorption. The fourth part of research ( mechanistic modeling and optimization of removal using ANN, RSM and ANFIS) An artificial neural network, response surface methodology and an adaptive neuro-fuzzy inference system were utilized to predict the adsorption capability of modified cellulose nanocrystals and sodium alginate for the removal of Cr (VI) from aqueous solution. Four variables such as time, pH, concentration, and adsorbent dose were evaluated to determine their influence on the adsorption study. To examine the viability of the models, five statistical functions ( RMSE, ARE, SSE, MSE, and MPSD) were applied. absorption mechanism was described via four mechanistic models (Film diffusion, Weber and Morris, Bangham, and Dummwald-Wagner models. Further statistical indices supported ANFIS as the best prediction model for adsorption compared to ANN and RSM. Film diffusion was identified as the rate-limiting process via mechanistic modelling. The sixth part of research (continuous fixed-bed column study) The hydrogel's technical feasibility for adsorption of Cu2+, Ni2+, +Cd2+, and Zn2+ ions from the packed bed column's produced AMD was assessed. The hydrogel was considered to have a high potential for significant interactions with dangerous metal ions. This characteristic, together with the adsorbent's availability, low cost, and efficient regeneration of the spent adsorbent, distinguishes it from the many other adsorbents described in the literature by other researchers. With a bed height of 25 cm, an influent metal ion concentration of 10 mg/l, and a flow velocity of 10 ml/min, the bed performed better. As a consequence, the breakthrough curve for the packed bed experiment shows that the breakthrough points were approached sooner by increasing the flow rate and influent concentration, and later by increasing the bed height. The experimental results were satisfactorily described by the BDST, Yoon–Nelson, and Thomas models. The hydrogels had a net-work structure and more homogeneous porosity, according to the SEM, TGA, XRD, and FTIR results for CNCs. The hydrogels revealed varied degrees of opacity and heavy metal ions absorption capacity depending on the temperature of the analysis. Diffraction confirmed the existence of crystalline structures and the presence of carboxyl and amide groups.

PhD (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / High levels of pollutants in water are found to have poisonous effects on human health. Due to increasing awareness about the environment and strict environmental regulations, wastewater treatment has become a very important aspect of research. Thus, this makes the adsorption of pollutants an urgent matter. The aim of this research was to investigate the adsorption capacity of black cumin seeds in the removal of cobalt-Co(II), nickel-Ni(II), copper-(II), chromium-Cr(VI), lead-Pb(II), and methylene blue (MB) dye from aqueous solution. In this research work the black cumin seeds were reacted with sodium hydroxide (NaOH), hydrochloric acid (HCl), phosphoric acid (H3PO4), potassium permanganate (KMnO4) and sulfuric acid (H2SO4). Thereafter it was carbonized at 200 and 300 °C and functionalized with magnetite-sucrose nanoparticles and further carbonized at 600 °C to improve the adsorption capacity of the materials towards different pollutants. The seeds were characterized by scanning electron microscopy (SEM), thermogravimetric analyser (TGA), X-ray diffractometer (XRD), Brunauer, Emmett and Teller (BET) and Fourier transformed infrared (FTIR) spectroscopy. The SEM images showed that the surface morphology of the treated adsorbents was more porous and had cavities more than the starting material. The TGA profile showed a major weight loss between 198-487 °C which was due to disintegration of cellulose, lignin and hemicellulose. The XRD spectra of adsorbents showed broad peaks at 2θ value of 21° associated crystalline lignocellulose content. FTIR results showed that the adsorbents had functional groups such as hydroxyl (-OH), carboxyl (-COOH), amide (-NH) and carbonyl (-C=O). The BET surface area of pristine black cumin seeds was 2.7 m2/g and increased after treatment with KMnO4 and H3PO4 to 10.1 and 9.3 m2/g respectively. The surface area of the carbon black cumin seeds was 11.67 m2/g whilst the activation of carbon from black cumin seeds with 10 and 20% H2SO4 gave the surface area of 20.14 and 21.54 m2/g respectively. The seeds activated with 20% H2SO4 showed larger pore width of 7.13 nm compared to 6.81 and 3.78 nm after treatment with 10% H2SO4 and carbon black cumin seeds respectively. The results show that there is an increase in surface area and pore size for both 10 and 20% H2SO4 in comparison with carbon black cumin seeds. The adsorption of Co(II), Ni(II), Cu(II), Cr(VI) and Pb(II) and MB in the solution was investigated by studying the effect of initial concentration, contact time, temperature and pH. The batch adsorption experiments were conducted using different ion solution concentrations of 20, 40, 60, 80 and 100 mg/L, contact time was determined at intervals of 1, 5, 10, 15, 20, 30, 60, 90 and 120 min, while temperature was studied at 298, 303, 313, 333 and 353 K. On the other hand, the effect of pH on all solutions was studied at pH 1, 3,5,7 and 9. The results showed that the acid treated black cumin seeds (AT-BCS) and base treated black cumin seeds (BT-BCS) were successfully used for quaternary adsorption study of Cu(II), Co(II), Pb(II) and Ni(II) ions from aqueous solution. The results for the adsorbents indicated that the BT-BCS adsorbed more metals than AT-BCS and the UT-BCS. The maximum capacity for BT-BCS was 190.7 mg/g for Cu(II) whilst AT-BCS and UT-BCS showed capacities of 180.1 and 135 mg/g respectively for Pb(II). The uptake of Cr(VI) and Cd(II) ions onto pristine black seeds (PBS), KMnO4 black seeds (KMBS) and H3PO4 black seeds (H3BS) treated adsorbents showed that the trend for Cr(VI) ions was KMBS>H3BS>PBS with capacities of 16.12, 15.98 and 10.15 mg/g respectively. Meanwhile the adsorption of Cd(II) ions showed maximum capacities of 19.15, 19.09 and 16.80 mg/g for KMBS, H3BS and PBS respectively. Carbon from black cumin (CBC) seeds was modified with 10 % and 20 % sulfuric acid (H2SO4) then carbonized at 200 °C to obtain the activated adsorbents of ACBC-10 and ACBC-20. The new adsorbents were used for the adsorption of Cd(II) and methylene blue (MB). The adsorbents maximum trend for Cd(II) was ACBC-10>ACBC-20>CBC meanwhile the trend for methylene blue (MB) dye was ACBC-20>ACBC-10>CBC. The overall capacities showed that the prepared materials adsorbed more MB dye (16.42 mg/g) than Cd(II) ions (13.65 mg/g). The preparation of carbon from black cumin seeds (BCC) and activation with 10 and 20 % sulfuric acid (H2SO4) at 300 °C to obtain new adsorbents namely (BCAC-10) and (BCAC-20) respectively was used for the adsorption of Pb(II) ions and MB dye from aqueous solution. The maximum adsorption of Pb(II) ions was 17.19, 17.71 and 17.98 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. Whilst for MB dye it was 11.63, 12.71 and 16.85 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. The utilization of pristine Nigella Sativa (PNS) and magnetite-sucrose functionalized Nigella Sativa (FNS) seeds as the adsorbents for the uptake of Cr(VI) and Pb(II) ions from synthetic wastewater revealed that the maximum adsorption capacities for Cr(VI) were 15.6 and 13.0 mg/g onto PNS and FNS composites respectively at pH 1. On the hand, the maximum sorption capacities for Pb(II) ions were 39.7 and 37.9 mg/g onto PNS and FNS respectively at pH 5. The sorption study of Cr(VI), Cd(II) ions and MB dye by pristine Nigella Sativa (PNS) seeds, defatted and carbonized Nigella Sativa seeds from aqueous solution was investigated. The PNS seeds were treated using acetone (then named ANS) and N,N dimethylformamide (named DNS). The defatted ANS and DNS adsorbents were carbonized at 600 °C and named CANS and CDNS. The results of pristine, defatted and carbonized seeds maximum capacities were compared with each other and found that CANS had highest adsorption capacity of 99.82 mg/g for MB, 96.89 mg/g for Cd(II) and 87.44 mg/g for Cr(VI) followed by CDNS with 93.90, 73.91 and 65.38 mg/g for MB, Cd(II) and Cr(VI) respectively. ANS capacities were 58.44, 45.28 and 48.96 mg/g whilst DNS capacities were 48.19, 32.69 and 34.65 mg/g for MB, Cd and Cr(VI) respectively. PNS had the lowest sorption capacities at 43.88, 36.01 and 19.84 mg/g for MB, Cd and Cr(VI) respectively. Therefore, this makes black cumin seeds a promising material for use in wastewater treatment to mitigate metal ions and dye pollution.

No description available.

No description available.

Metallosupramolecular chemistry involves the construction of nanoscale molecular assemblies by reacting metal atoms with bridging organic ligands. The metal atoms act as a type of molecular ‘glue’ binding together the organic ligands in specific orientations. Thus, appropriate combinations of metal ions and ligands lead to the controlled self-assembly of interesting one-, two- and three-dimensional molecular aggregates. This thesis details the preparation of a range of novel flexible bridging heterocyclic ligands using conventional organic synthesis, and then explores their reactions with a variety of transition metal precursors. By varying the nature of the organic ligand and the transition metal precursor, new and exciting supramolecular topologies and architectures can be formed. A total of forty-eight ligands were synthesised in this work, forty-seven of which are new compounds. The majority of the ligands synthesised were based around commercially available bisphenol cores. All forty-eight of the ligands had nitrogen heterocyclic groups as coordinating units. The ligands discussed in this thesis can be divided into three main sections. The first involves the synthesis and coordination chemistry of two-armed ligands based around the Bisphenol A, Bisphenol Z and Bisphenol AP cores. The second section describes the synthesis and coordination chemistry of the larger Bisphenol P and Bisphenol M based two-armed bridging ligands. The third section describes the synthesis and coordination chemistry of various multi-substituted ligands, including tripodal ligands based around a trisphenol core, four-armed ligands and six-armed ligands. The two-armed bisphenol based ligands proved very successful as synthons in metallosupramolecular chemistry and produced many products with a variety of different metal atoms. The complexes characterised included discrete dimeric products, coordination polymers and a number of helicates, including a dinuclear quadruply-stranded helicate. Multi-armed ligands are topical, because they have multiple coordination sites that are capable of binding and bridging multiple metal atoms. Such coordination can lead to the construction of cage-like species and complicated networks. A series of three-armed ligands based around a trisphenol core were synthesised with the intention to use these to form such species on coordination with appropriate metal salts. Indeed, one of the products of self-assembly was an interesting M₃L₂ cage. Various other multi-armed ligands were also investigated. The ligands and complexes in this thesis were characterised by a variety of structural techniques, such as ¹H NMR, ¹³C NMR, mass spectrometry, elemental analysis and X-ray crystallography when crystals were obtained. The crystal structures of twenty-seven ligands and forty-three complexes are described.

La dégénérescence articulaire sévère de la hanche est une pathologie fréquente et son traitement ultime est le remplacement prothétique. L’arthroplastie la plus répandue au monde est la prothèse totale de hanche (PTH) avec un couple de frottement métal-sur-polyéthylène (MPE). Cependant ce type d’intervention présente une longévité limitée à cause de l’usure de PE et ne convient pas aux patients actifs souffrant de coxarthrose sévère tôt dans leur vie. Afin de palier à ce problème, une nouvelle génération de surfaces de frottement métal-sur-métal (MM) est actuellement employée. Ces surfaces de frottement sont utilisées en PTH avec tête de 28 mm, en resurfaçage (RH) et avec la PTH à tête de grand diamètre. Alors qu’il y a beaucoup d’évidence à l’égard du bon fonctionnement des implants PTH 28 mm et du RH, les données quant aux performances in vivo des PTH MM à grand diamètre manquent. Malgré cela, ces implants sont utilisés à grande échelle. Dans un premier temps, l’objectif de ce travail de recherche était d’évaluer l’effet et de comparer les taux d’ions chrome (Cr) et cobalt (Co) chez des sujets porteurs de PTH MM à grand diamètre à ceux de 64 porteurs de RH, tous deux possédant des surfaces de frottement aux propriétés tribologiques identiques. Dans un deuxième temps, nous avons comparé les taux ioniques (Cr, Co et titane (Ti)) entre quatre PTH MM à grand diamètre provenant de fabricants différents (Zimmer, DePuy, Smith & Nephew et Biomet). Les mesures d’ions étaient effectuées dans le sang entier dans un laboratoire indépendant par la technique de spectrophotométrie de masse à haute résolution HR-ICP-MS, pour l’ensemble de ce travail de recherche. Les deux comparaisons ont démontré le rôle crucial joué par la modularité au niveau de la jonction tête-col des PTH MM à grand diamètre. En effet, des écarts considérables dans les concentrations ioniques de Co ont été retrouvés entre les RH et PTH Durom ayant un couple de frottement identique, ainsi qu’entre les 4 différents designs de PTH MM à grand diamètre comparés entre eux. La PTH MM à grand diamètre Durom était la moins favorable alors que celle de Biomet était la plus performante. Nos observations démontrent que des sources inattendues comme la jonction tête-col de certains implants PTH MM à grand diamètre peuvent contribuer au relargage ionique systémique. Une meilleure compréhension de ce phénomène est indispensable avant l’utilisation clinque de nouveaux implants de ce type. / The treatment for advanced degenerative hip disease consists in replacing the native joint with artificial implants. This is a very common procedure and the type of arthroplasty most practiced worldwide is metal-on-polyethylene (MOPE) total hip replacement (THR). However, this type of bearing has limited lifespan and is not adapted for active patients struggling with hip osteoarthritis early in their lives. In order to increase implant longevity, new generation, metal-on–metal (MOM) bearing surfaces is used nowadays in this particular population. These MOM bearings are used in 28 mm THR, in resurfacing hip arthroplasty (RH) and in large diameter head THR. Although consistent results have been obtained with the 28 mm THR and RH, large diameter head THR are increasingly used despite lack of scientific data about their performances. The main purpose of our first paper was to compare chromium (Cr) and cobalt (Co) concentrations among patients implanted with large diameter head THR and with RH. In this case, both bearing surfaces presented identical tribological properties. In the second paper, we compared performances in terms of ion release (Cr, Co and titanium (Ti)) from four different manufacturers of large diameter head THR systems (Zimmer, DePuy, Smith & Nephew and Biomet). Whole blood was used for all samples and ion measurements were conducted by an independent laboratory in a blinded fashion, using high-resolution inductive coupled plasma mass spectrophotometry (HR-ICP-MS). Both papers have emphasized the crucial role played by modularity at the head-neck junction in metal ion release from large diameter THR MOM bearings. In fact, significant differences were found in Co ion concentration between large head THR and HRA as well as among the different designs of large head THRs. Briefly, the Durom large head THR system was the least favorable implant while the Biomet large head THR system showed the best results. Our results prove that systemic ion release might origin from surprising sources such as modularity at the head-neck junction in patients implanted with certain large head MOM THR systems. A better comprehension of head-neck junction biomechanics is necessary before clinical use of such new devices.

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and the pyrimidine is reported here. The effect of substituents on substituted-benzene cations on their solvation by an HCN solvent was also investigated using ion mobility mass spectrometry and DFT computations were also investigated. We looked at the effect of the presence of electron-withdrawing substituents in fluorobenzene, 1,4 di- fluorobenzene, and benzonitrile on their solvation by up to four HCN ligands, and compared it to previous work done to determine the solvation chemistry of benzene and phenylacetylene by HCN. We report here the observed increase in the binding of the HCN molecule to the aromatic ring as the electronegativity of the substituent increased. We also show in this dissertation, DFT calculations that reveal the formation of both hydrogen-bonded and electrostatic isomers, of similar energies for each addition to the ions respectively. The catalytic activity of the 1st and 2nd row TM ions towards the polymerization of acetylene done using the reflectron time of flight mass spectrometry and DFT calculations is also reported in this dissertation. We explain the variation in the observed trend in C-H/C-C activity of these ions. We also report the formation of carbide complexes by Zr+, Nb+, and Mo+, with the acetylene ligands, and show the thermodynamic considerations that influence the formation of these dehydrogenated ion-ligand complexes. Finally, we show in this dissertation, a novel ionization technique that we employed to generate ions that could be relevant to the interstellar and circumstellar media using the reflectron time of flight mass spectrometry.

Dans cette thèse, nous avons synthétisé de nouveaux matériaux moléculaires hétérométalliques pontés par des groupements cyanures en utilisant la chimie de coordination donneur-accepteur. Les précurseurs moléculaires basés sur un ion métallique 3d (MnII/III, FeII, NiII, CuII) agissent en tant qu’unités acceptrices, alors que les précurseurs 4d (RuIII) et 5d (ReIV) de type trans-cyanido ont été utilisés comme groupements donneurs. Le chapitre I présente une approche théorique avec quelques exemples des matériaux magnétiques de basse dimensionnalité : molécule et chaîne aimant qui illustrent le rôle du ligand cyanido pour concevoir les matériaux magnétiques. En outre, nous avons sélectionné des précurseurs cyanido à base de métaux 4d/5d pour leur anisotropie magnétique plus élevée par rapport aux ions de métaux 3d. Le choix des précurseurs moléculaires, leur synthèse et leur caractérisation ont été largement décrits dans le chapitre II. Au cours de ce travail de recherche, nous avons obtenu de nombreux systèmes moléculaires hétérométalliques mais également des systèmes unidimensionnels. Les chapitres III, IV et V décrivent la synthèse, la structure cristallographique et la caractérisation magnétique de tous les complexes synthétisés. L’empilement cristallin compact des molécules conduit à un état fondamental antiferromagnétique pour la plupart des complexes ce qui perturbe souvent les phénomènes de relaxation magnétique. Nous avons donc établi les diagrammes de phases magnétiques pour la plupart de ces systèmes. De plus, certaines des chaînes ReIV/MnIII et une chaîne ReIV/FeII présentent des comportements magnétiques de type "chaîne aimant" et donc une bistabilité magnétique. / In this thesis, we have synthesised new cyanido bridged heterometallic molecule-based magnetic materials with the tool of simple donor-acceptor coordination chemistry. The 3d metal ion (MnII/III,FeII, NiII, CuII) based molecular precursors acted as acceptor building blocks, whereas the 4d (RuIII)and 5d (ReIV) trans-cyanido type molecular precursors were used as donor moieties.Chapter I contains a theoretical approach with examples of low dimensional magnetic materials:Single Molecule and Single Chain Magnets that illustrate the role of the cyanido ligand to design such magnetic materials. Furthermore, we emphasized the 4d/5d metal based cyanido precursors for their higher magnetic anisotropy over the 3d metal ions. The choice of molecular precursors, their synthesis and characterization were extensively described in chapter II. In this research work, we have obtained many heterometallic molecular complexes and also one dimensional systems. Chapter III, IV and V contain the synthesis, X-ray crystallographic and magnetic characterization of all the newly synthesized complexes. The close crystal packing of the molecules lead to an antiferromagnetic ground state for most of the complexes and this often perturbed the magnetic relaxation phenomena. As expected, we have found metamagnetic phase diagrams for most of these systems. Some of the ReIV/MnIII and a ReIV/FeII one dimensional compounds exhibited Single-Chain magnet like properties and thus magnetic bistability.

by Tsui Wai-chu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves 161-171). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Abbreviations --- p.vii / Contents --- p.ix / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Literature review --- p.1 / Chapter 1.1.1 --- Metal pollution in Hong Kong --- p.1 / Chapter 1.1.2 --- Methods for removal of metal ions from industrial effluent --- p.4 / Chapter A. --- Physico-chemical methods --- p.4 / Chapter B. --- Biosorption --- p.7 / Chapter 1.1.3 --- Chitin and chitosan --- p.11 / Chapter A. --- History of chitin and chitosan --- p.11 / Chapter B. --- Structures and sources of chitin and chitosan --- p.12 / Chapter C. --- Characterization of chitin and chitosan --- p.17 / Chapter D. --- Applications of chitin and chitosan --- p.19 / Chapter 1.1.4 --- Factors affecting biosorption --- p.22 / Chapter A. --- Solution pH --- p.22 / Chapter B. --- Concentration of biosorbent --- p.24 / Chapter C. --- Retention time --- p.25 / Chapter D. --- Initial metal ion concentration --- p.26 / Chapter E. --- Presence of other cations --- p.26 / Chapter F. --- Presence of anions --- p.28 / Chapter 1.1.5 --- Regeneration of metal ion-laden biosorbent --- p.28 / Chapter 1.1.6 --- Modeling of biosorption --- p.29 / Chapter A. --- Adsorption equilibria and adsorption isotherm --- p.29 / Chapter B. --- Langmuir isotherm --- p.33 / Chapter C. --- Freundlich isotherm --- p.34 / Chapter 1.2 --- Objectives of the present study --- p.36 / Chapter 2. --- Materials and methods --- p.37 / Chapter 2.1 --- Biosorbents --- p.37 / Chapter 2.1.1 --- Production of biosorbents --- p.37 / Chapter 2.1.2 --- Pretreatment of biosorbents --- p.39 / Chapter 2.2 --- Characterization of biosorbents --- p.39 / Chapter 2.2.1 --- Chitin assay --- p.39 / Chapter 2.2.2 --- Protein assay --- p.40 / Chapter 2.2.3 --- Metal analysis --- p.41 / Chapter 2.2.4 --- Degree of N-deacetylation analysis --- p.43 / Chapter A. --- Diffuse reflectance Fourier transform infra-red spectroscopy --- p.43 / Chapter B. --- Elemental analysis --- p.43 / Chapter 2.3 --- Batch biosorption experiment --- p.44 / Chapter 2.4 --- Selection of biosorbent for metal ion removal --- p.45 / Chapter 2.4.1 --- Effects of pretreatments of biosorbents on adsorption of Cu --- p.45 / Chapter A. --- Washing --- p.45 / Chapter B. --- Pre-swelling --- p.46 / Chapter 2.4.2 --- "Comparison of Cu2+, Ni2+ and Zn2+ removal capacities among three biosorbents" --- p.46 / Chapter 2.4.3 --- Comparison of Cu2+ removal capacity of chitins with various degrees of N-deacetylation --- p.46 / Chapter 2.5 --- "Effects of physico-chemical conditions on Cu2+, Ni2+ and Zn2+ adsorption by chitin A" --- p.48 / Chapter 2.5.1 --- Solution pH and concentration of biosorbent --- p.48 / Chapter 2.5.2 --- Retention time --- p.48 / Chapter 2.5.3 --- Initial metal ion concentration --- p.49 / Chapter 2.5.4 --- Presence of other cations --- p.49 / Chapter 2.5.5 --- Presence of anions --- p.51 / Chapter 2.6 --- Optimization of Cu2+，Ni2+ and Zn2+ removal efficiencies --- p.53 / Chapter 2.7 --- "Recovery of Cu2+, Ni2+ and Zn2+ from metal ion-laden chitin A" --- p.53 / Chapter 2.7.1 --- Performances of various eluents on metal ion recovery --- p.53 / Chapter 2.7.2 --- Multiple adsorption and desorption cycle of metal ions --- p.54 / Chapter 2.8 --- Treatment of electroplating effluent by chitin A --- p.54 / Chapter 2.8.1 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from rinsing baths" --- p.54 / Chapter 2.8.2 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from final collecting tank" --- p.55 / Chapter 2.9 --- Data analysis --- p.56 / Chapter 3. --- Results --- p.58 / Chapter 3.1 --- Characterization of biosorbents --- p.58 / Chapter 3.1.1 --- Chitin assay --- p.58 / Chapter 3.1.2 --- Protein assay --- p.58 / Chapter 3.1.3 --- Metal analysis --- p.58 / Chapter 3.1.4 --- Degree of N-deacetylation analysis --- p.62 / Chapter A. --- Diffuse reflectance Fourier transform infra-red spectroscopy --- p.62 / Chapter B. --- Elemental analysis --- p.62 / Chapter 3.2 --- Selection of biosorbent for metal ion removal --- p.67 / Chapter 3.2.1 --- Effects of pretreatments of biosorbents on adsorption of Cu2+ --- p.67 / Chapter A. --- Washing --- p.67 / Chapter B. --- Pre-swelling --- p.67 / Chapter 3.2.2 --- "Comparison of Cu2+, Ni2+ and Zn2+ removal capacities among three biosorbents" --- p.67 / Chapter 3.2.3 --- Comparison of Cu2+ removal capacity of chitins with various degrees of N-deacetylation --- p.70 / Chapter 3.3 --- "Effects of physico-chemical conditions on Cu2+, Ni2+ and Zn2+ adsorption by chitin A" --- p.70 / Chapter 3.3.1 --- Solution pH and concentration of biosorbent --- p.70 / Chapter 3.3.2 --- Retention time --- p.78 / Chapter 3.3.3 --- Initial metal ion concentration --- p.80 / Chapter 3.3.4 --- Presence of other cations --- p.93 / Chapter 3.3.5 --- Presence of anions --- p.93 / Chapter 3.4 --- "Optimization of Cu2+, Ni2+ and Zn2+ removal efficiencies" --- p.104 / Chapter 3.5 --- "Recovery of Cu2+, Ni2+ and Zn2+ from metal ion-laden chitin A" --- p.104 / Chapter 3.5.1 --- Performances of various eluents on metal ion recovery --- p.104 / Chapter 3.5.2 --- Multiple adsorption and desorption cycle of metal ions --- p.109 / Chapter 3.6 --- Treatment of electroplating effluent by chitin A --- p.117 / Chapter 3.6.1 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from rinsing baths" --- p.117 / Chapter 3.6.2 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from final collecting tank" --- p.121 / Chapter 4. --- Discussion --- p.128 / Chapter 4.1 --- Characterization of biosorbents --- p.128 / Chapter 4.1.1 --- Chitin assay --- p.128 / Chapter 4.1.2 --- Protein assay --- p.129 / Chapter 4.1.3 --- Metal analysis --- p.129 / Chapter 4.1.4 --- Degree of N-deacetylation analysis --- p.130 / Chapter A. --- Diffuse reflectance Fourier transform infra-red spectroscopy --- p.130 / Chapter B. --- Elemental analysis --- p.132 / Chapter 4.2 --- Selection of biosorbent for metal ion removal --- p.133 / Chapter 4.2.1 --- Effects of pretreatments of biosorbents on adsorption of Cu2+ --- p.133 / Chapter A. --- Washing --- p.133 / Chapter B. --- Pre-swelling --- p.133 / Chapter 4.2.2 --- "Comparison of Cu2+, Ni2+ and Zn2+ removal capacities among three biosorbents" --- p.134 / Chapter 4.2.3 --- Comparison of Cu2+ removal capacity of chitins with various degrees of N-deacetylation --- p.136 / Chapter 4.3 --- "Effects of physico-chemical conditions on Cu2+, Ni2+ and Zn2+ adsorption by chitin A" --- p.137 / Chapter 4.3.1 --- Solution pH and concentration of biosorbent --- p.137 / Chapter 4.3.2 --- Retention time --- p.138 / Chapter 4.3.3 --- Initial metal ion concentration --- p.139 / Chapter 4.3.4 --- Presence of other cations --- p.141 / Chapter 4.3.5 --- Presence of anions --- p.143 / Chapter 4.4 --- "Optimization of Cu2+, Ni2+ and Zn2+ removal efficiencies" --- p.147 / Chapter 4.5 --- "Recovery of Cu2+, Ni2+and Zn2+ from metal ion-laden chitin A" --- p.148 / Chapter 4.5.1 --- Performances of various eluents on metal ion recovery --- p.148 / Chapter 4.5.2 --- Multiple adsorption and desorption cycle of metal ions --- p.149 / Chapter 4.6 --- Treatment of electroplating effluent by chitin A --- p.150 / Chapter 4.6.1 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from rinsing baths" --- p.150 / Chapter 4.6.2 --- "Removal and recovery of Cu2+, Ni2+ and Zn2+ from electroplating effluent collected from final collecting tank" --- p.152 / Chapter 5. --- Conclusion --- p.154 / Chapter 6. --- Further studies --- p.156 / Chapter 7. --- Summary --- p.158 / Chapter 8. --- References --- p.161

Among the various heterogeneous catalytic reactions three way catalysis (TWC), catalytic combustion of hydrogen, water gas shift reaction (WGS) and preferential oxidation of CO (PROX) in the hydrogen rich stream are some of the important reactions receiving the attention presently. Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) from the automobile exhaust. Catalytic combustion of hydrogen by oxygen or hydrogen-oxygen recombination reaction is an industrially important reaction. It has variety of application such as in sealed lead acid batteries and nuclear reactors. Water gas shift (WGS) reaction is of specific importance to produce hydrogen from carbonaceous material. PROX is an important step to further purify hydrogen produced form WGS. Hydrogen purified using PROX can be directly fed to polymer electrolyte membrane fuel cells. By and large, noble metals Pt, Pd, Rh, Ru and some of their alloys are dispersed on oxide or high surface area carbon are the active catalysts. An alternative approach can be to make Pt2+, Pd2+, Rh3+, Ru4+ ions substituted in reducible support such as CeO2, Ce1-xTixO2-δ and TiO2 to increase the dispersion and bring down the cost. In this thesis we have followed this new approach and show that noble metal ionic catalysts are superior to noble metal nano particles. In the 1st chapter we present an overview of heterogeneous catalysis and important heterogeneous catalytic reactions. Monolithic catalyst and various ways to coat catalysts for application have been reviewed. Metal-support interaction till date is also reviewed. In the 2nd chapter, synthesis of noble metal ionic catalysts by solution combustion method is described. Coating of washcoat and active catalyst phase over ceramic honeycomb by a new combustion method is described. Solution combustion reaction and characterization of the catalyst by x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction and reaction is given. We have fabricated experimental systems to carryout catalytic reaction and in this chapter they have been presented. In the 3rd chapter, we report a new process of coating of active exhaust catalyst over -Al2O3 coated cordierite honeycomb. The process consists of (a) growing  -Al2O3 on cordierite by solution combustion of Al(NO3)3 and oxylyldihydrazide (ODH) at 600 0C. Active catalyst phase, Ce0.98Pd0.02O2- is coated on - Al2O3 coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2  10-3 M PdCl2 solution at 500 0C. In this way a coat layer over cordierite ceramic has been achieved and catalyst has the active sites in the form of Pd2+ ions rather than Pd metal. Weight of the active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion [1]. Adhesion of catalyst to cordierite surface is via oxide growth on oxide ceramic which is very strong. 100 % conversion of CO is achieved below 80 oC at a space velocity of 880 h-1. At much higher space velocity of 21000h-1, 100 % conversion is obtained below 245 oC. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h-1 100% NO conversion is attained below 185 oC and 100 % conversion of ‘HC’(C2H2) below 220 oC. At the same space velocity 3-way catalytic performance over Ce0.98Pd0.02O2- coated monolith shows 100% conversion of all the pollutants below 220 o C with 15% excess oxygen. Catalytic activity of cordierite honeycomb coated by this new coating method for the oxidation of major hydrocarbons in exhaust gas is discussed further in this chapter. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. 3-way catalytic test is done by putting hydrocarbon mixture along with CO (10000ppm), NO (2000ppm) and O2 (15000ppm). Below 350 oC full conversion is achieved [2]. A comparison of the results shows that Ce1-xPdxO2-δ far superior to other catalysts. In this method, handling of nano material powder is avoided. In the 4th chapter we present a detailed study on the catalytic combustion of hydrogen by oxygen (hydrogen oxygen recombination reaction). Ever since Michel Faraday showed H2 + O2 recombination reaction over platinum metal plates, Pt metal has remained the only room temperature recombination catalyst. In search of an alternative catalyst, we discovered a new Pt free Ti0.99Pd0.01O2- compound which shows high rates of this reaction above 45 oC compared to Ce0.98Pt0.02O2-, Pt/Al2O3 and Pd/Al2O3. High rates of H2+O2 recombination over Pt and Pd ion respectively in CeO2 and TiO2 is due to the protonic type H2+ adsorption on Pt2+ or Pd2+ and dissociative chemisorption of O2 on the electron rich oxide ion vacancies [3]. In the case of Ce0.98Pt0.02O2-, H2/Pt ratio in a TPR experiment is ~2.3 at 0 oC. In the case of Ti0.99Pd0.01O2- also, H2 adsorption occurs below 0 oC and H2 / Pd ratio is ~2.2. Thus, more than 4-5 H atoms are adsorbed per metal ion. This is attributed to hydrogen spillover. H2 is known to be adsorbed as hydride ion (H-) over Pt, Pd, Rh, Ru, Os and Ir metals. Proton NMR studies of H2 adsorbed on Pd metal have shown upfield i.e. negative shift of 12 ppm with respect to TMS. We have studied proton NMR of Ti0.99Pd0.01O2- + H2 which show a downfield shift of 11.35 ppm confirming H+ or H2+ kind of species over Pd2+ ion in Ti0.99Pd0.01O2-. In Ce0.98Pt0.02O2- also H2 adsorption led to H2+ like species observed at 8 ppm and DFT calculations indeed showed H2+ kind species. H2+ is a precursor for dissociation and can readily induce O2 dissociation leading to high rates of recombination. In the 5th chapter we report water gas shift reaction (WGS) and preferential oxidation of CO (PROX) over Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ. The water gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nano crystalline catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2 and Ce1-xTixO2-δ. The catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS) and it has been shown that Pt2+ ions in these reducible oxides of the form Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ are highly active. These catalysts were tested for the water gas shift reaction both in presence and absence of hydrogen. It is shown that Ti0.99Pt0.01O2- exhibits higher catalytic activity than Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ [4]. Further, experiments were conducted to determine the deactivation of these catalysts by performing the daily startup and shutdown of the reactor for over 24 hours. There was no sintering of Pt and no carbonate formation and, therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ce4+, Ti4+ ions in the catalysts. Further, PROX activity of these catalysts has been studied. Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ showed high activity, large operating temperature window and low working temperature proving them to be highly effective PROX catalysts. In the 6th chapter we study the electrocatalysis of formic acid electro-oxidation and simultaneously mapping the electronic states of the electrodes by X-ray photoelectron spectroscopy (XPS). Ionically dispersed platinum in Ce1-xPtxO2-δ and Ce1-x-yTiyPtxO2-δ is very active towards oxygen evolution and formic acid oxidation. Higher electro-catalytic activity of Pt2+ ions in CeO2 and Ce1-xTixO2 compared to Pt0 in Pt/C is due to Pt2+ ion interaction with the supports, CeO2 and Ce1-xTixO2 respectively [5]. Further, ionic platinum does not suffer from CO poisoning effect unlike Pt0 in Pt/C. Utilization of lattice oxygen from the electrodes during the reaction has been demonstrated. This lattice oxygen exchange is responsible to convert CO to CO2 in the lower potential region to remove CO poisoning effect. In 7th chapter we repeat our study on the noble metal ion reducible oxide interaction in Ce1-xPtxO2- and Ce1-xPdxO2- (x= 0.02) system by a novel electrochemical method combined with XPS. Working electrodes made of CeO2 and Ce0.98Pt0.02O2- mixed with 30% carbon are cycled between 0.0-1.2 V in potentio-static (chronoamperometry) and potentio-dynamic (cyclic voltametry) mode with reference to saturated calomel electrode (SCE). Reversible oxidation of Pt0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y= 0.35) after applying +1.2 V which is not reversible. But Ce0.98Pt0.02O2- reaches a steady state with Pt2+: Pt4+ in the ratio of 0.60: 0.40 and Ce4+: Ce3+ in the ratio of 0.55: 0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V which is reversible [6]. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2- forms a stable electrode for oxidation of H2O to O2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction of Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple. Similar studies have been performed with Ce0.98Pd0.02O2- catalyst to show the redox coupling between Pd2+/Pd0 and Ce4+/Ce3+ redox couples. We expect similar redox coupling for Pd, Pt ions substituted TiO2, and Ce1-xTixO2. In the final chapter 8, a critical review and conclusion on the results presented in the thesis is presented. The combustion synthesized catalysts reported in this thesis stabilizes the Pt and Pd metals in their ionic state rather than zero valent metallic state. Thus, the catalysts are uniform solid catalysts. High activity and stability of these catalysts are shown to be due to the electronic interaction between noble metal ions and the reducible oxide. Redox couples Pt0/Pt2+, Pt2+/Pt4+ and Pd0/Pd2+ interact with Ce4+/Ce3+, Ti4+/Ti3+ couples such that metal is oxidized and the support is reduced. This has been established in the thesis by a combined use of electrochemistry and XPS thus solving a long standing problem of metal support interaction in catalysis. We hope that the results presented in the thesis is a worthwhile contribution to catalysis. (For mathematical equations pl refer pdf file.)