多階孔洞結構材料的合成及其藥物傳遞與電化學電池上的應用

Abstract

本論文利用自蝕刻、硬模板法等技術，合成具有多階孔洞結構的材料：中空結構的微孔配位聚合物，以及巨孔碳材微米球。除了材料的合成，上述材料進一步地應用於生醫領域的藥物載體，以及電化學元件如鋰離子電池、葡萄糖燃料電池等。以下簡述各章節涵括的內容。 第一章介紹奈米孔洞材料的分類與常見的製備方式，以及多階孔洞結構可提供的優勢，並在第二章回顧創造多階孔洞結構的合成方法。第三章為中空微孔配位聚合物（普魯士藍）的製備，並且作為藥物載體進行抑制癌細胞。粒子大小110 nm的普魯士藍介晶質，經過自蝕刻處理，於粒子內部創造80 nm大小的中空巨孔孔穴。此中空普魯士藍具有高生物相容性、酸鹼穩定性，並擔任藥物載體的角色。裝載的抗癌藥物順鉑大多陷入殼層的微孔縫隙，無法自載體釋出，但仍可利用粒子表面吸附的順鉑，與癌細胞的DNA進行交聯作用，有效地達成毒殺癌細胞之目的。 第四章為巨孔碳材微米球的製備，並且評估作為鋰離子電池負極的表現。於乳液系統中利用揮發誘導自組裝技術，獲得氧化矽蛋白石微米球，並擔任硬模板，獲得孔徑260 nm的巨孔碳材微米球。巨孔碳材微米球提供大量的崁鋰位置，獲得1542.2 mAh/g的首次充電電容量，為石墨理論電容量的4.1倍。此外，電容量隨循環次數而上升，於第60次循環時，可逆電容量達到1478.4 mAh/g。結合巨孔結構與石墨化的優勢，相較於0.1C速率，於20C高速率下仍可保有254.5 mAh/g的電容量。 第五章藉由低溫催化石墨化法，使巨孔碳材轉化成石墨相碳材，並將此巨孔石墨微米球作為觸媒擔體，應用於葡萄糖燃料電池。結合巨孔結構、石墨碳相等優勢，巨孔石墨微米球可作為一優秀擔體。在鈀粒子大小、含量相近的條件下，相較於商業化碳材（石墨塊材、XC72），巨孔石墨微米球擔體可獲得最高的電化學催化表面積。組裝成為葡萄糖燃料電池後，巨孔石墨微米球擔體獲得最高輸出功率是XC72的2倍、商業化石墨的11.8倍。第六章總結本論文各項實驗，並且提出建議事項。

In this dissertation, techniques such as self-etching and hard template method were employed to synthesize materials with hierarchically porous structure, including microporous coordination polymer with hollow structure and macroporous carbon microballs. These synthesized porous materials were further applied in drug carrier, lithium-ion battery and glucose fuel cell. In chapter 1, classification and common synthesis of nanoporous materials, and advantages of hierarchically porous structure are introduced. In chapter 2, facile synthesis of materials with hierarchically porous structure is reviewed. In chapter 3, microporous coordination polymer (Prussian blue, PB) with hollow structure is synthesized and employed as drug carrier to load anti-cancer drug for killing tumor. PB mesocrystal with size of 110 nm went through self-etching to create a macorporous hollow interior with diameter of 80 nm. Hollow PB showed high biocompatibility and pH stability, and these properties assumed a potential drug carrier. Anti-cancer drug (cisplatin) got stuck in micropores tightly to reduce drug leakage in advance; even so, cisplatin adsorbed on the surface of hollow PB still performed cytotoxicity through cross-linking DNA of cancer cell. In chapter 4, macroporous carbon microballs (MCM) are synthesized and work as anode of lithium ion battery. At first, silica opal microballs were prepared through evaporation-induced self-assembly in emulsion, and then served as a hard template to obtain macroporous amorphous carbon microball (A-MCM) with pore diameter of 260 nm. A-MCM provided large number of storage sites for lithium, and obtained first charge capacity of 1542.2 mAh/g, which is around 4.1 times higher than theoretical capacity of graphite. In addition, reversible capacity of A-MCM climbed to 1478.4 mAh/g after 60 cyles. By synergistic effect of macroporous structure and graphitization (G-MCM), capacity still remained 254.5 mAh/g while rate changed from 0.1C to 20C. In chapter 5, macroporous graphite microballs (G-MCM) acted as catalyst support for glucose fuel cell. Taking advantage of macoporous structure and graphite phase, Pd@G-MCM exhibited the highest electrochemical active surface area among all electrocatalysts under similar Pd size and amount. Assembling as glucose fuel cell, G-MCM performed maximum power density 2 times higher than XC72 and 11.8 times higher than conventional graphite. In chapter 6, studies and suggestions in every chapter are summarized.