本研究首先利用高分子與結晶性溶劑混合物的相分離行為，成功製備奈米多孔高分子材料，依此為模板，經模板化無電電鍍法，製備具有奈米網狀結構的多孔鎳。研究發現可透過使用具結晶性溶劑之溶液中的聚苯乙烯之使用濃度及分子量的控制，達到此多孔鎳之孔隙度、孔洞大小及骨架大小等結構因子之操控。同時，藉由模板化無電電鍍法中成核成長機制對金屬離子還原的特性，透過還原時間的長短，成功製備具有微米尺度可調控的奈米多孔鎳球。相較於商用的雷尼鎳，所製備的具奈米孔洞之微米鎳球，做為氫化觸媒，由於奈米級孔洞的高比表面積，將具有較優異的催化效果，而其微米尺度則提供良好的觸媒反應與回收所需之條件。同時，為了進一步提高觸媒催化效率，本實驗亦成功利用賈凡尼置換法，將鎳以鈀和鉑進行置換反應，修飾此奈米網狀鎳球形成雙金屬系統，呈現更為優異之氫化效率。

Herein, we aim to fabricate nanonetwork-structured Ni spheres via templated electroless plating by using mesoporous polymers from spinodal decomposition of polymer/crystalline solvent mixture as templates. With the control of polymer concentration and molecular weight of the PS in the solution using crystalline solvents, the porosity, pore size, and framework size of the fabricated Ni nanonetwork from templated electroless plating could be well tuned. By taking advantage of a nucleation and growth mechanism for the reduction of metallic ions from templated electroless plating, nanoporous Ni sphere in micrometer scale with controlled particle size can be successfully fabricated at which higher reduction potential materials such as Pd can be used as an initial nucleus for the reduction of Ni ion. In contrast to the commercial Raney® Ni, the fabricated nanoporous Ni sphere gives rise to superior performance as hydrogenation catalysts due to its high specific surface area while the controlled micrometer-sized sphere gives the optimized particle size for recyclability. To further enhance the catalytic efficiency, we aim to carry out galvanic replacement reaction for the electroless plating of Pd and Pt from the replacement of Ni, giving nanonetwork Ni decorated with noble metals. With the decoration of Pd or Pt, the modified Ni sphere is expected to give bimetallic nanonetwork catalysts for outstanding hydrogenation efficiency.

Abstract........................................................I
Contents......................................................III
List of Table...................................................V
Figure Caption................................................VII
Chapter 1 Introduction..........................................1
1.1 Mesoporous polymers from polymer mixtures...................1
1.2 Nanoporous polymers from block copolymers...................8
1.3 Templated electroless plating..............................15
1.3.1 Fabrication of Nanoporous metallics......................15
1.3.2 Nanoporous nickel for catalytic hydrogenation............26
1.4 Galvanic replacement reaction..............................31
Chapter 2 Objectives...........................................37
Chapter 3 Experimental methods.................................39
3.1 Sample Preparation.........................................39
3.1.1 Mesoporous PS templates..................................39
3.1.2 Nanoporous Ni from templated electroless plating.........39
3.1.3 Removal of PS template...................................41
3.1.4 Galvanic replacement reaction............................42
3.2 Hydrogenation experiments..................................42
3.2.1 Hydrogenation of monomers................................42
3.2.2 Hydrogenation of polymers................................43
3.3 Instrumentation............................................43
Chapter 4 Results and Discussion...............................46
4.1 Fabrication of mesoporous PS...............................46
4.2 Fabrication of nanoporous Ni sphere........................53
4.3 Performance of catalytic hydrogenation for monomers........60
4.3.1 Hydrogenation for cyclohexene and toluene................60
4.3.2 Hydrogenation for p-phenylenediamine.....................66
4.4 Galvanic replacement reaction for bimetallics..............70
4.4.1 Pd-Ni bimetallic system..................................70
4.4.2 Pt-Ni bimetallic system..................................77
4.5 Performance of catalytic hydrogenation for polymers........84
Chapter 5 Conclusion and Perspectives...........................95
References.....................................................98

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