| Acknowledgment | 第1-9页 |
| Abstract | 第9-10页 |
| Resume | 第10-12页 |
| 摘要 | 第12-17页 |
| Chapter 1 General introduction | 第17-24页 |
| ·History of heterogeneous catalyst | 第17-21页 |
| ·Aims and objectives of this Research | 第21-22页 |
| ·Structure of manuscript | 第22-24页 |
| Chapter 2 Literature survey | 第24-76页 |
| ·Silica-based mesoporous materials | 第24-39页 |
| ·Early steps of mesoporous materials | 第25-26页 |
| ·Synthesis of mesoporous materials | 第26-27页 |
| ·Different types of mesoporous materials | 第27-28页 |
| ·Formation mechanism | 第28-32页 |
| ·Textual properties | 第32-35页 |
| ·Morphology control | 第32-33页 |
| ·Adjustable pore size | 第33-34页 |
| ·High silanol density | 第34-35页 |
| ·Characterization | 第35-39页 |
| ·X-ray diffraction (XRD) | 第35-36页 |
| ·Fourier transform infrared spectroscopy (FT-IR) | 第36-38页 |
| ·N_2 sorption isotherm | 第38-39页 |
| ·Mesoporous materials immobilizing organic groups | 第39-44页 |
| ·Grafting method | 第40-42页 |
| ·Grafting with passive surface groups | 第40-41页 |
| ·Grafting with reactive surface groups | 第41-42页 |
| ·Co-condensation method (one-pot synthesis) | 第42-43页 |
| ·Preparation of periodic mesoporous organosilicas (PMOs) by co-condensation (one-pot synthesis) approach | 第43-44页 |
| ·Incorporation of metals in mesoporous materials | 第44-64页 |
| ·Without organic ligands | 第44-45页 |
| ·With organic ligands | 第45-53页 |
| ·Incorporation by grafting | 第46-52页 |
| ·Incorporation by one-pot synthesis | 第52-53页 |
| ·Incorporation of metal-amino complexes into silica materials | 第53-54页 |
| ·Incorporation of metal-Schiff base complexes into silica materials | 第54-58页 |
| ·Characterization | 第58-64页 |
| ·Electronic paramagnetic resonance (EPR) spectroscopy | 第59-64页 |
| ·Applications of mesoporous materials modified with metal complexes | 第64-74页 |
| ·Catalysis | 第65-71页 |
| ·Hydroxylation of phenol with supported Cu(Ⅱ) materials | 第65-68页 |
| ·Cyanosilylation of aldehyde catalyzed by supported vanadyl complexes | 第68-71页 |
| ·Enzymatic reaction | 第71-73页 |
| ·Adsorption | 第73-74页 |
| ·Strategy and choices of this work | 第74-76页 |
| Chapter 3 Experimental part | 第76-95页 |
| ·Commercial products and treatment | 第76-78页 |
| ·Solvents | 第76页 |
| ·Reagents | 第76-78页 |
| ·Gas | 第78页 |
| ·Glossary of the nomenclature | 第78-80页 |
| ·Experimental part | 第80-90页 |
| ·Synthesis of Ni(Ⅱ) complexes | 第80-81页 |
| ·Synthesis of Cu(Ⅱ)-L (L= L~2, L~3) complexes | 第81-83页 |
| ·Synthesis of L~2 | 第81-82页 |
| ·Synthesis of HL_(ref)~3 and HL~3 | 第82页 |
| ·Synthesis of [Cu(L~2)]~+ and [Cu(L~2)_2] complexes | 第82-83页 |
| ·Synthesis of [Cu(L_(ref)~3)(OAc)] and [Cu(L~3)(OAc)] | 第83页 |
| ·One-pot synthesis of mesoporous hybrid materials | 第83-84页 |
| ·Synthesis of M-OP-XNi(YL~1) and M-OP-XCu(YL~1) [Ni(YL~1)@PMOs, Cu(YL~1)@PMOs] | 第83页 |
| ·Synthesis of M-OP-XCu(YL~2) [Cu(YL~2)@PMOs] | 第83-84页 |
| ·One-pot synthesis of metal-free material (M) | 第84页 |
| ·Template (surfactant) extraction | 第84-85页 |
| ·Method TA | 第84-85页 |
| ·Method T | 第85页 |
| ·Method TO | 第85页 |
| ·Method H | 第85页 |
| ·Post-synthesis of hybrid materials ("MSP" technique) | 第85-86页 |
| ·Synthesis of M'(at high temperature, i.e.130℃) | 第85页 |
| ·Partial surfactant extraction of M' | 第85-86页 |
| ·Partial silylation of M'-EP | 第86页 |
| ·Extraction of remaining surfactant of M'-EPS | 第86页 |
| ·Grafting complex onto M'-EPS | 第86页 |
| ·Metal exchange | 第86-88页 |
| ·Metal exchange 1 | 第87页 |
| ·Metal exchange 2 | 第87页 |
| ·Metal exchange 3 | 第87-88页 |
| ·Metal exchange 4 | 第88页 |
| ·Metal displacement | 第88-89页 |
| ·Metal displacement 1 | 第88页 |
| ·Metal displacement 2 | 第88-89页 |
| ·Catalytic tests | 第89页 |
| ·Oxidation of DTBC | 第89页 |
| ·Hydroxylation of phenol | 第89页 |
| ·Preparation of phosphate buffer solution | 第89-90页 |
| ·Analytical Techniques | 第90-92页 |
| ·Original data from elemental analysis | 第92-95页 |
| Chapter 4 Incorporation of nickel ethylenediamine complexes in the wall of ananostructured porous silica:Nickel (Ⅱ) used as a probe | 第95-139页 |
| ·Introduction | 第95-97页 |
| ·Study of the nickel complex precursors in solution | 第97-107页 |
| ·Results and discussion | 第97-107页 |
| ·Structure of the Ni(Ⅱ)-Pren complexes | 第97-102页 |
| ·Comparison Ni(Ⅱ)-Pren complexes with Ni(Ⅱ)-L~1 complexes | 第102-107页 |
| ·Conclusions | 第107页 |
| ·Incorporation of the nickel precursors in the wall of nanostructuredporous silica | 第107-137页 |
| ·Results | 第107-129页 |
| ·Synthesis and characterization of PMOs materials | 第107-122页 |
| ·Nickel exchange ability and metal displacement | 第122-125页 |
| ·Coordination state of Ni(Ⅱ) in the materials | 第125-127页 |
| ·Nickel accessibility | 第127-129页 |
| ·General discussion | 第129-137页 |
| ·Conlusions | 第137-139页 |
| Chapter 5 Incorporation of copper ethylenediamine and Schiff base complexes in ananostructured porous silica | 第139-211页 |
| ·Properties of copper (Ⅱ)-ethylenediamine complex depending on its location in the nanostructured silica | 第139-156页 |
| ·Introduction | 第139-140页 |
| ·Results and discussion | 第140-155页 |
| ·Synthesis and porosity characterization | 第140-148页 |
| ·Physicochemical properties of the metal centers | 第148-152页 |
| ·Preliminary study of the electrochemical properties by cyclic voltammetry | 第152-153页 |
| ·Compared catalytic activity of copper (Ⅱ) complex in the wall and in the channel | 第153-155页 |
| ·Conclusions | 第155-156页 |
| ·Incorporation of Schiff base complex (Cu-L~2) with 2N2O coordination sphere using a one-pot synthesis | 第156-183页 |
| ·Introduction | 第157-158页 |
| ·Study of the copper-L~2 complexes in solution | 第158-166页 |
| ·Results and discussion | 第158-165页 |
| ·Conclusions | 第165-166页 |
| ·Mesoporous hybrid materials incorporation Cu(Ⅱ)-L~2 complex using one-pot synthesis | 第166-183页 |
| ·Synthesis and characterization | 第166-172页 |
| ·N_2 sorption isotherms of hybrid materials | 第172-174页 |
| ·Cu (Ⅱ) coordination state characterization | 第174-179页 |
| ·Metal displacement | 第179-180页 |
| ·Location of metal complexes on PMOs | 第180-181页 |
| ·Catalytic hydroxylation of phenol | 第181-182页 |
| ·Conclusions | 第182-183页 |
| ·Schiff base complex with 3N1O coordination sphere in the channel | 第183-211页 |
| ·Introduction | 第183-185页 |
| ·Stability study of L_(ref)~3 and 1-L_(ref)~3 in aqueous solution | 第185-192页 |
| ·Structural study of the Cu-L_(ref)~3 complex | 第186-187页 |
| ·Stability study of L_(ref)~3 and Cu(Ⅱ)-L_(ref)~3 complex | 第187-192页 |
| ·Conclusions | 第192页 |
| ·Grafting complex [Cu(L~3)]~+ onto mesoporous material | 第192-200页 |
| ·Synthesis and characterization of hybrid materials | 第192-197页 |
| ·Cu(Ⅱ) coordination state | 第197-200页 |
| ·Catalytic hydroxylation of phenol | 第200-209页 |
| ·Comparison of the heterogeneous catalyst and its homogeneous analogue | 第201-202页 |
| ·Reaction time | 第202页 |
| ·Effect of the H_2O_2 addition mode | 第202-203页 |
| ·pH effect | 第203-205页 |
| ·Substrate/oxidant effect | 第205页 |
| ·Solvent effect | 第205-206页 |
| ·Recycle tests | 第206-207页 |
| ·Characterization of the recovered catalyst | 第207-208页 |
| ·Mechanism proposed | 第208-209页 |
| ·Conclusions | 第209-211页 |
| Chapter 6 General conclusions and perspectives | 第211-216页 |
| ·General conclusions | 第211-215页 |
| ·Perspectiyes | 第215-216页 |
| Appendix A:IR quantitative treatment | 第216-218页 |
| Appendix B:EPR quantitative treatment | 第218-219页 |
| Appendix C:Conversion of reactant and yield of product determined from GC and | 第219-222页 |
| References | 第222-228页 |
