Nowadays, energy exhaust and environment pollution are two major challenges facing human health, ecological balance, sustained development of economy and society. Numerous efforts have been paid to reduce energy consumption and environmental pollution. The design of new catalysts and the development of green catalytic technologies are vital for renewable energy generation and environmental protection. Although the efficiency of heterogeneous catalysis is generally inferior to that of homogeneous systems, it usually displays the easy recovery from reaction mixtures and repetitive use of the catalysts, which could reduce the cost and even diminish the pollution from catalysts themselves. Accordingly, the goal of the current research is to develop novel heterogenerous catalysts with high efficiencies matchable with correspondinmg homogeneous catalysts for water-medium organic reactions, which could decrease the pollution from both organic solvents and heavy metallic ions. Based on the surfactant co-assembly technologie, many heterogeneous catalysts including metal catalysts, organometallic catalysts, organocatalysts, bifunctional organometallic catalysts, and even chiral bifunctional catalysts have been developed. Many organic reactions including"one-pot"cascade reactions applied in the environmental friendly field have been chosen to evaluate catalytic performance of these catalysts. These immobilized homogeneous catalysts exhibit much higher activities and selectivities than those prepared by traditional methods. Furthermore, most of them show comparable catalytic efficiencies with their corresponding homogeneous catalysts and could be used repetitively. This thesis mainly contains the following six parts:1. A facile approach was developed to prepare "ship in bottle" type of the metal supported catalysts by in situ encapsulating nano metal particles (Au) in hollow silica spheres with ordered and radially oriented amino-functionalized mesochannels (HMS). The radially oriented porous structure was beneficial for catalytic activiy. The mesoporous hollow spheres have radially oriented pore structure and high surface area which could facilitate the adsorption of organoic substrates on the catalyst. Meanwhile, the hollow spheres with ordered mesopores and large surface area could promote the dispersion of metal nanoparticles and also prevent them from agglomeration. More importantly, such "ship in bottle" type catalyst could efficiently inhibit the leaching of Au active phase through controlling pore size of supports. The Au @ HMS catalyst could be recycled many times without significant decrease in the catalytic activity.2. Phenyl-bridged periodic mesoporous organosilicas (PMO) functionalized with CH2CH2-PPh2 ligand was synthesized, which could be used as a support for post-grafting homogenerous Rh(I) or Pd(II) organometallic catalysts by coordination way. The as-prepared Rh(I)-PPh2-PMO(Ph) and Pd(II)-PPh2-PMO(Ph) catalysts exhibited high activity in water-medium Heck-type and Barbier reactions respectively, and the supported catalysts could be used repetitively. The high activity could be attributed to the high dispersion of Rh(I) or Pd(II) active sites and ordered mesopore channels which effectively diminished the steric hindrance and diffusion limit. Furthermore, the Phenyl fragments and the PPh2-CH2CH2 ligands in the support could co-enhance catalyst hydrophobicity, which promoted the adsorption for organic reactant molecules especial for the water-medium organic reactions.3. A general approach was developed to prepare a new class of organometallic catalyst, denoted as M-PPh2-Ts, where M refers to Pd2+, Rh+, or Ru2+ ions, PPh2- to PPh2CH2CH2-ligands, and Ts to triethoxysilane groups. Meanwhile, a Ru-PPh2-Ts-DPEN chiral catalyst was also synthesized by modifying the Ru-PPh2-Ts with DPEN, where DPEN refers to (1R, 2R)-1, 2-diphenylethylenediamine. All these catalysts could act as homogeneous catalysts with high efficiencies for various organic reactions and even asymmetric reactions conducted in either tetrahydrofuran (THF) or methylene dichloride (CH2Cl2) solvent as the reaction medium and could be easily separated from the reaction system by adding pentane for recycling uses.4. A general approach for preparing periodic mesoporous organometallic catalyst (M-PMO(R), M=Pd2+,Pt2+,Ru2+,Ir+,Au+,Rh+, R=Ph or Ph2) with adjustable chemical compositions and pore structure was developed. Firstly, organometal-bridged silanes were synthesized by coordinating metallic ions with PPh2-CH2CH2 ligands covalently bonded to silianes. The organometal-bridged silanes are allowed to co-assemble with organosilane-bridged and P123 surfactant. Removal of surfactant micelles via extraction in ethanol solution led to the M-PMO(R) samples. These M-PMO(R) organomental catalysts exhibited much higher activity than the grafted M-PPh2-PMO(R) in water medium organic reactions due to the high surface area, large pore size, strong surface hydrophobicity. Maenwhile, they displayed stronger durability owing to the excellent hydrothermal stability against the leaching and structural collapse5. Bifunctional catalysts containing two organometal active sites were prepared by P123 surfactant directed co-condensation of Rh(I) organometal-bridged silane, Pd(II)organometal-bridged silane and Ph-bridged silane. The as-prepared Rh/Pd-PMO(Ph) display highly ordered mesoporous structure with Rh(I) and Pd(II) active sites uniformly distributed in the silica walls. Meanwhile, a chiral bifunctional catalyst was also synthesized. The Pd/Rh-PMO(Ph) exhibits much high activity than the grafted Pd/Rh-PPh2-PMO(Ph) in"one-pot"cascade reactions comprised of the Methylenation reaction and Heck reaction sequence, which could be mainly attributed to the higher SBET and DP. Moreover, it displays both higher activity and better selectivity than the mechanically mixed Rh-PPh2-PMO(Ph) and Pd-PPh2-PMO(Ph), showing the synergic effect from Rh(I) and Pd(II) active sites. The chiral catalyst Fe/Cp*Rh-TsDPEN-PMO(Et) also showed high efficiencies in water medium"one-pot"cascade chiral reactions, a manner similar to enzyme catalysis in biological systems. Furthermore, these catalysts could be easily recycled and used repetitively.6. A Zr-MOF catalyst was successfully synthesized through the microwave technology and applied in environmently friendly organic reactions. Moreover, the hollow ZIF-8-H and Zr-MOF/CNT noval catalytic materials were also prepared. Their catalytic performances were vriefly evaluated. |