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京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20708号 / 工博第4405号 / 新制||工||1684(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study aims to investigate chemical, physical, mechanical and surface properties of Eucalyptus grandis and Eucalyptus cloeziana wood subjected to different treatments of freezing and heat. To achieve this, six trees for each specie were used to prepare sample for each mechanical test. The samples were subjected to six thermal treatments. Freezing treatment was performed in a horizontal freezer at -22 ± 2°C for 72 hours, while heat treatment was performed using an oven with force air circulation at 180 and 200 ± 1°C for 3.5 hours. Sampling to perform chemical, physical and surface tests were obtained from samples used in mechanical characterization of wood. Chemical changes were evaluated quantitatively through wet process and qualitatively through infrared spectroscopy (ATR-IR). Physical properties evaluated were: weight loss, specific gravity, equilibrium moisture content, dimensional stability and hygroscopicity of wood. Mechanical evaluation was performed through static bending, impact strength, compression parallel to fibers and Janka hardness. Color and wettability of wood were evaluated using colorimetry and contact angle techniques, respectively. The main findings showed that freezing slightly affected the chemical properties of wood, in which the main changes were found in heat treatments, mainly at 200°C. Freezing improve in weight and equilibrium moisture content of wood, while heat treatment caused weight loss and decrease of equilibrium moisture content of wood. Both heat treatments improved dimensional stability of wood, however when freezing and heat was performed in a combination, they did not showed the best results. Regarding the hygroscopicity of wood, results obtained in heat treatment at 200°C should be highlighted. On the other hand, freezing treatment increased absorption of water. In general, freezing reduced mechanical properties of wood. Heat treatments increased stiffness at static bending and strength at compression parallel to fibers of wood however was responsible for reduction in other mechanical properties. Color of wood was affected mainly for heat treatments, in which a darkening of surface was observed and quantified by decrease of parameter L*. Wettability of wood slightly decreased after heat treatments. Influence of freezing on wettability of wood was related to the natural characteristic of wood from species studied because they did not showed a defined tendency. Therefore, it is believed that treatments performed in this study changed significantly the technological properties of wood. / O presente estudo teve como objetivos investigar as propriedades químicas, físicas, mecânicas e superficiais da madeira de Eucalyptus grandis e Eucalyptus cloeziana submetida a diferentes tratamentos de congelamento e termorretificação. Para tanto, foram confeccionados, a partir de seis árvores de cada espécie, corpos de prova para cada ensaio mecânico. Os corpos de prova foram submetidos a seis tratamentos térmicos. O congelamento foi realizado em um freezer horizontal sob condições de temperatura e tempo de -22 ± 2°C durante 72 horas, enquanto que a termorretificação foi realizada em uma estufa laboratorial com circulação de ar forçada, à 180 e 200 ± 1°C durante 3,5 horas. A amostragem para realização dos ensaios químicos, físicos e superficiais foram provenientes dos corpos de prova utilizados na caracterização mecânica da madeira. As modificações químicas foram avaliadas quantitativamente em ensaios via úmida e qualitativamente por espectroscopia no infravermelho (ATR-IR). As propriedades físicas avaliadas foram a perda de massa e massa específica, teor de umidade de equilíbrio, estabilidade dimensional e higroscopicidade da madeira. Para avaliação das propriedades mecânicas foram realizados ensaios de flexão estática, flexão dinâmica, compressão paralela e dureza Janka. Também foram avaliadas a colorimetria e molhabilidade da madeira, por meio das técnicas de colorimetria e ângulo de contato. Os principais resultados encontrados mostraram que o congelamento pouco afetou as propriedades químicas da madeira, sendo as principais alterações oriundas do processo de termorretificação, principalmente a 200°C. O congelamento causou acréscimos na massa e no teor de umidade de equilíbrio da madeira, enquanto que a termorretificação ocasionou a perda de massa e redução do teor de umidade de equilíbrio. Os dois tratamentos térmicos causaram melhoria na estabilidade dimensional, entretanto, quando combinados, não apresentaram os melhores resultados. Para a higroscopicidade destacam-se os resultados obtidos na termorretificação a 200°C, por outro lado, o congelamento aumentou a absorção de água. De maneira geral, o congelamento causou redução nas propriedades mecânicas da madeira. A termorretificação causou aumento na rigidez a flexão estática e resistência a compressão paralela e redução nas demais propriedades mecânicas. A coloração da madeira foi afetada principalmente pela termorretificação, em que ocorreu um escurecimento superficial, quantificado pelo decréscimo do parâmetro de claridade L*. A molhabilidade da madeira diminuiu sensivelmente após a realização dos tratamentos de termorretificação. A influência do congelamento sobre a molhabilidade foi atribuída a características naturais da madeira das espécies estudadas, sem apresentar tendência definida. Dessa forma, verificou-se que os tratamentos realizados alteraram significativamente as propriedades tecnológicas da madeira.

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.

L'auto-assemblage des copolymères à bloc (CPBs) attire beaucoup d'intérêt grâce à leur capacité de générer spontanément des matériaux ordonnés avec des propriétés uniques. Les techniques Langmuir-Blodgett (LB) et Langmuir-Schaefer (LS) sont couramment utilisées pour produire des monocouches ou des films ultraminces à l'interface air/eau suivi de transfert aux substrats solides. Les films LB/LS de CPBs amphiphiles s'auto-assemblent dans des morphologies variables dépendamment de la composition du CPB ainsi que d'autres facteurs. Dans notre travail, nous avons étudié les films LB/LS de polystyrène-b-poly(4-vinyl pyridine) (PS-P4VP) et leurs complexes supramoléculaires avec le naphtol (NOH), l'acide naphtoïque (NCOOH) et le 3-n-pentadécylphenol (PDP). La première partie de ce mémoire est consacré à l'investigation du PS-P4VP complexé avec le NOH et le NCOOH, en comparaison avec le PS-P4VP seul. Il a été démontré qu'un plateau dans l'isotherme de Langmuir, indicatif d'une transition de premier ordre, est absent à des concentrations élevées des solutions d'étalement des complexes. Cela a été corrélé avec l'absence de morphologie en nodules avec un ordre 2D hexagonal à basse pression de surface. L'ordre au-delà de la pression de cette transition, lorsque présente, change à un ordre 2D carré pour tout les systèmes. La deuxième partie du la mémoire considère à nouveau le système PS-P4VP/ PDP, pour lequel on a démontré antérieurement que la transition dans l'isotherme correspond a une transition 2D d'un ordre hexagonal à un ordre carré. Cela est confirmé par microscopie à force atomique, et, ensuite, on a procédé à une étude par ATR-IR des films LB pour mieux comprendre les changements au niveau moléculaire qui accompagnent cette transition. Il a été constaté que, contrairement à une étude antérieure dans la littérature sur un autre système, il n'y a aucun changement dans l'orientation des chaînes alkyles. Au lieu de cela, on a découvert que, aux pressions au-delà de celle de la transition, le groupe pyridine, qui est orienté à basse pression, devient isotrope et qu'il y a une augmentation des liaisons hydrogènes phénol-pyridine. Ces observations sont rationalisées par un collapse partiel à la pression de transition de la monocouche P4VP, qui à basse pression est ordonné au niveau moléculaire. Cette étude a mené à une meilleure compréhension des mécanismes moléculaires qui se produisent à l'interface air/eau, ce qui fournit une meilleure base pour la poursuite des applications possibles des films LB/LS dans les domaines de nanotechnologie. / Self-assembly of block copolymers (BCPs) attracts much interest due to their ability to spontaneously generate ordered materials with unique properties. For many applications, such as masks in nanolithography, separation membranes in medical diagnostics, and nanotemplates for nanowire fabrication, manufacturing into thin films is required. The Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) techniques are commonly used to produce ultrathin or monolayer films at the air/water interface that are transferred to solid substrates. LB/LS films of amphiphilic BCPs self-assemble into various morphologies, depending on the BCP composition and other factors. In our work, we investigated LB/LS films of polystyrene-b-poly(4-vinyl pyridine) (PS-P4VP) and their supramolecular complexes with, naphthol (NOH), naphthoic acid (NCOOH) and 3-n-pentadecylphenol (PDP). The first part of the thesis was devoted to the investigation of PS-P4VP complexes with NOH and NCOOH, in comparison to PS-P4VP alone. It was shown that a plateau in the Langmuir isotherm, indicative of a first-order transition, is absent at high spreading solution concentrations for the complexes. This was correlated with an absence of the expected dot morphology with 2D hexagonal-like order at low surface pressure. Above the transition, when present, the morphology has 2D square order. The second part of the thesis re-examines the PS-P4VP/PDP system, which was previously shown to undergo a transition from 2D hexagonal to square order at the isotherm plateau pressure. This was confirmed here, and a detailed ATR-IR study of LB films was then undertaken to better understand molecular-level changes occurring at this transition. It was found that, contrary to another study in the literature on a different system, there is no change in alkyl chain orientation. Instead, it was found that the pyridine group loses its low-pressure orientation and there is increased phenol-pyridine hydrogen-bonding above the transition pressure, which is rationalized by a partial collapse of the low-pressure molecularly ordered P4VP monolayer at the transition pressure. This study leads to an improved understanding of the processes occurring at the air/water interface, which is a basis for the further possible applications of LB/LS films in nanotechnologies.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.:Inhaltsverzeichnis 6 Abkürzungsverzeichnis 10 Kapitel I Einleitung und Zielstellung 13 I.I Poly(dimethyl)siloxan 13 I.II Funktionalisierung von Oberflächen 15 I.III Reversible Polymere an Oberflächen 18 I.IV Photoaktive Oberflächen 20 Kapitel II Sauerstoffplasma-Modifizierung 21 II.I Vorbetrachtung 21 II.I. a) Plasmen – Definition und Charakterisierung 21 II.I. b) Technisch angewandte Plasmaprozesse 24 II.II Hintergrund und Motivation Sauerstoffplasma-modifizierter PDMS-Oberflächen 27 II.II. a) ATR-IR-spektroskopische Charakterisierung von Sauerstoffplasma-modifizierten PDMS-Oberflächen 28 II.II. b) Rasterkraftmikroskopische Charakterisierung von Sauerstoffplasma-modifizierten PDMS-Oberflächen 34 II.II. c) Untersuchungen zum Quellverhalten von PDMS 35 II.III Zusammenfassung 38 II.IV Experimenteller Teil 39 II.IV. a) Herstellung von Substraten aus Poly(dimethyl)siloxan 39 II.IV. b) Sauerstoffplasma-Modifikation von Poly(dimethyl)siloxan 39 Kapitel III Amino-funktionalisierte Oberflächen 40 III.I Hintergrund und Motivation Amino-funktionalisierter Oberflächen 40 III.I. a) Amino-Funktionalisierung mittels 3 Aminopropyltriethoxysilan (APTES) 41 III.I. b) Amino-Funktionalisierung nach Balachander & Sukenik 43 III.I. c) Amino-Funktionalisierung mittels Phenylendiisocyanat (PDI) 45 III.II Kontaktwinkelanalyse von unterschiedlichen Amino-Beschichtungen 48 III.III Zusammenfassung 49 III.IV Experimenteller Teil 50 III.IV. a) Amino-Funktionalisierung von PDMS-Substraten mittels APTES 50 III.IV. b) Amino-Funktionalisierung von PDMS-Substraten nach Balachander & Sukenik 50 III.IV. c) Amino-Funktionalisierung von PDMS-Substraten mittels PDI 51 Kapitel IV Maleimid-funktionalisierte Oberflächen 52 IV.I Hintergrund und Motivation Maleimid-funktionalisierter Oberflächen 52 IV.II Synthese Maleimid-funktionalisierter PDMS-Oberflächen 53 IV.II. a) Syntheseroute via Maleinsäureanhydrid (MSA-Route) 53 IV.II. b) Trichlorosilyl-funktionalisierte Maleimid-Derivate 56 IV.III Experimenteller Teil 59 IV.III. a) Synthese eines furangeschützten Maleimids 59 IV.III. b) Synthese eines furangeschützten Undec-10-enyl-1-maleimids (13) 59 IV.III. c) Synthese eines furangeschützten 11-Trichlorosilyl-undecyl-1-maleimids (14) 60 IV.III. d) Maleimid-Funktionalisierung von PDMS-Substraten mittels MSA 61 IV.III. e) Maleimid-Funktionalisierung von PDMS-Substraten mittels trichlorosilyl-funktionalisierter Maleimid-Derivate 62 Kapitel V Furan-funktionalisierte Oberflächen 63 V.I Hintergrund und Motivation Furan-funktionalisierter Oberflächen 63 V.II Herstellung Furan-funktionalisierter PDMS-Oberflächen 65 V.II. a) Trichlorosilyl-funktionalisierte Furan-Derivate an Hydroxyl-Oberflächen 65 V.II. b) Furfural an Amino-Oberflächen 67 V.II. c) Furfurylalkohol an Isocyanat-Oberflächen 69 V.III Zusammenfassung 71 V.IV Experimenteller Teil 72 V.IV. a) Synthese von Undec-10-enyl-furan-2-carboxylat (15) vgl. 72 V.IV. b) Synthese von 11-(Trichlorosilyl)undecyl- furan-2-carboxylat (16) vgl. 72 V.IV. c) Furan-Funktionalisierung mittels 11 (Trichlorosilyl)undecyl furan 2 carboxylat (16) 73 V.IV. d) Furan-Funktionalisierung mittels Furfural nach 74 V.IV. e) Furan-Funktionalisierung mittels Furfurylalkohol vgl. 74 Kapitel VI Reversible Polymere 75 VI.I Hintergrund und Motivation reversibler Polymere 75 VI.II Thermisch-kontrollierte reversible Polymerisation (DIELS-ALDER-Reaktion) 77 VI.II. a) Hintergrund thermisch-kontrollierter reversibler Polymerisationen 77 VI.II. b) DIELS-ALDER-AB-Monomer mit flexiblem Spacer 80 VI.II. c) Charakterisierung der thermisch-kontrollierten Polymerisation 83 VI.III Zusammenfassung 96 VI.IV Photochemisch-kontrollierte reversible Polymerisation 97 VI.IV. a) Hintergrund photochemisch-kontrollierter reversibler Polymerisationen 97 VI.IV. b) Synthese geeigneter Biscumarine 101 VI.V Experimenteller Teil 108 VI.V. a) Thermisch-kontrollierte reversible Polymerisationen 108 VI.V. b) Photochemisch-kontrollierte reversible Polymerisationen 114 Kapitel VII Reversible Polymere an Oberflächen 117 VII.I Anbinden von DIELS-ALDER-AB-Polymeren an Maleimid- und Furan-Oberflächen 117 VII.I. a) ATR-IR-spektroskopische Charakterisierung 119 VII.II Zusammenfassung 121 VII.III Anbinden von Biscumarinen an Cumarin-Oberflächen 122 VII.III. a) ATR-IR-spektroskopische Charakterisierung 123 VII.IV Zusammenfassung 125 VII.V Experimenteller Teil 126 VII.V. a) Anbinden von DIELS-ALDER-AB-Polymeren an Maleimid-Oberflächen 126 VII.V. b) Anbinden von DIELS-ALDER-AB-Polymeren an Furan-Oberflächen 126 VII.V. c) Anbinden von Biscumarin an Cumarin-Oberflächen 126 Kapitel VIII Photoaktive Oberflächen 127 VIII.I Hintergrund und Motivation Cumarin-funktionalisierter Oberflächen 127 VIII.II Synthese Cumarin-funktionalisierter PDMS-Oberflächen 129 VIII.II. a) Funktionalisierung von PDMS-Oberflächen mit Cumarin-Gruppen 129 VIII.II. b) Allgemeine Bemerkung zur Wahl des Lösungsmittels 130 VIII.II. c) Photochemie von Cumarin-funktionalisierten PDMS-Oberflächen 131 VIII.II. d) ATR-IR-spektroskopische Charakterisierung photoaktiver Cumarin-Beschichtungen 132 VIII.III UV/Vis-spektroskopische Charakterisierung photoaktiver Cumarin-Beschichtungen 137 VIII.III. a) Belichtung mit UVA-Strahlung 137 VIII.III. b) Belichtung mit UVC-Strahlung 140 VIII.IV Zusammenfassung 142 VIII.V Experimenteller Teil 144 VIII.V. a) Funktionalisierung von PDMS-Substraten mit Isocyanat 144 VIII.V. b) Funktionalisierung von PDMS-Substraten mit Cumarin 144 VIII.V. c) Photochemisch-kontrollierte Modifikation von PDMS-Substraten mit Cumarin-Beschichtung 144 Kapitel IX Zusammenfassung und Ausblick 145 Kapitel X Anhang 150 X.I Messmethoden 150 X.I. a) ATR-IR-Spektroskopie 150 X.I. b) UV/Vis-Spektroskopie 150 X.I. c) Kontaktwinkelanalyse 151 X.I. d) Rasterkraftmikroskopie (AFM) 151 X.I. e) NMR-Spektroskopie 152 X.I. f) Größenausschluss-Chromatographie (SEC) 152 X.I. g) Thermoanalyse (TA) 152 X.I. h) Thermogravimetrie (TGA) 153 X.I. i) Dynamische Differenzkalorimetrie (DSC) 153 X.II Trocknen von Lösungsmitteln , 153 Kapitel XI Literatur 154 Selbstständigkeitserklärung 161 Lebenslauf 162 Danksagung 163

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.