本論文合成多種具備良好水穩定性的金屬有機骨架及其複合材料，並將其沉積於導電基材上，所得到的修飾電極再接著應用於水相電化學系統當中，包含超級電容器、電化學感測器及電催化反應等。
由於大多數金屬有機骨架不具備良好的導電性，限制其直接利用於電化學系統當中，因此本論文首先將錳離子修飾於三種結構不同的以鋯為基底之金屬有機骨架(Zr-MOF-808, Zr-UiO-66, Zr-CAU-24)，並探討其在電化學系統中基於氧化還原躍遷機制的電荷傳遞過程。研究成果顯示透過錳離子於三價跟四價之間的電化學反應，可以使得電荷在硫酸鈉水溶液中進行氧化還原躍遷以傳遞電荷於骨架當中。而透過調控電解液的濃度，氧化還原躍遷的速率決定步驟由離子擴散轉變為電子傳遞；此外，錳離子修飾的Zr-MOF-808結構具有較大孔徑，可以達到較高的擴散係數。本研究針對以氧化還原躍遷機制在金屬有機骨架上傳遞電荷於水相系統中，提供結構的選擇與材料設計的方向。
接續前一段落，本論文進一步探討以具氧化還原活性的鈰離子作為節點之金屬有機骨架(Ce-MOF-808)在水相電解液中的氧化還原躍遷行為，該材料亦擁有與錳修飾的Zr-MOF-808相同的拓撲結構。研究成果顯示，Ce-MOF-808在硫酸鈉水溶液的電化學系統當中亦具有電化學活性，但其氧化還原躍遷行為十分有限。為了使更多的鈰離子參與電化學反應，本論文將Ce-MOF-808晶體生長於具有羧酸基的奈米碳管表面，藉由奈米碳管本身具有的導電特性可以將電子快速地於晶體之間傳遞，其所形成的複合材料被作為超級電容器的電極材料，並可以展現出大幅提升的比電容值。
而除了作為需具備良好電荷傳遞能力的電化學活性薄膜外，本論文亦提出水穩定性金屬有機骨架的另一種應用方向：將其作為調控電極表面局部環境以改變電化學反應速率的非活性薄膜。類似概念的材料為富含負電荷磺酸基團的Nafion聚合物，其常作為修飾薄膜應用在有涉及帶電荷反應物參與的電化學系統當中。在本論文中，磺酸基團被後修飾於Zr-MOF-808孔洞當中，所得到的材料可以視為是一種具高度孔洞性的Nafion薄膜並應用在電化學系統，進而取代傳統質傳受阻礙的Nafion薄膜。透過將此磺酸基團修飾的金屬有機骨架薄膜塗佈於對多巴胺有電化學活性的電極表面上，該修飾電極憑藉磺酸基團帶負電荷的特性與金屬有機骨架的高度孔洞性，在對正電荷的多巴胺感測靈敏度以及負電荷的干擾物選擇性（如抗壞血酸與尿酸）方面皆顯著地優於常用的Nafion薄膜。
另一方面，除了將電荷於金屬有機骨架薄膜的傳遞納入考量之外，亦需要考慮到電化學過程中反應物於薄膜的擴散。儘管金屬有機骨架具備相互連通的孔洞性結構，但其大多數為微孔材料，往往會阻礙體積較大的反應物擴散於孔洞當中，並造成電化學系統的反應位點受限。在本論文中，透過軟模板劑將有規律的中孔引入以鈰為基底之金屬有機骨架(UiO-66(Ce))晶體當中，並進一步把具有硝酸根電化學催化產氨的銅活性位點安裝於骨架之中。透過中孔幫助反應物擴散於修飾薄膜當中，其所製備的電極可以比僅有微孔的材料所製備的電極展現出更高的法拉第效率與產氨速率。本研究強調在金屬有機骨架晶體開創規律的中孔結構對於反應物質傳效率的影響，並進而提升其在電化學催化的表現。

In this dissertation, various water-stable metal–organic frameworks (MOFs) and MOF-based composites were synthesized and deposited on conducting substrates. The resulting modified electrodes were applied in a range of aqueous electrochemical systems, including supercapacitors, electrochemical sensors, and electrocatalytic reactions.
Since the electrically insulating nature of most MOFs limits their direct use in electrochemical applications, a charge-transport pathway, redox-hopping process, is first investigated within three topologically distinct manganese-decorated zirconium-based MOFs (Zr-MOFs) in this dissertation. The hopping-based electrochemical reaction between the installed Mn(III) and Mn(IV) occurring within thin films of these MOFs in Na2SO4 aqueous electrolytes is studied. By adjusting the concentration of counter ions in the electrolyte, the rate-determining step of the redox-hopping process can be tuned from ionic transport to electronic transport, and the manganese-decorated zirconium-based MOF-808 (Zr-MOF-808), which possesses the largest pore size among the studied materials, exhibits the highest value of apparent diffusivity. Findings here shed light on the selection of topology of MOFs for applications relying on redox-hopping processes within MOF thin films in aqueous electrolytes.
Thereafter, the redox-hopping behavior of cerium-based MOF-808 (Ce-MOF-808), which exhibits the same topology as manganese-decorated Zr-MOF-808 but possesses redox-active hexa-cerium nodes, is investigated in aqueous electrolytes. Results here suggest that pristine Ce-MOF-808 is electrochemically active but exhibits a limited charge-transport behavior. To render more cerium sites electrochemically addressable, nanocrystals of Ce-MOF-808 are directly grown on the surface of carboxylic acid-functionalized carbon nanotubes (CNTs). As a demonstration, Ce-MOF-808, CNT, and nanocomposites are used as electrode materials for supercapacitors, where the capacitive performance of the redox-active Ce-MOF-808 can be significantly boosted with the facile electronic conduction between MOF crystals provided by CNTs.
Instead of serving as electrochemically active thin films which require efficient charge transport between active units, another concept for using such water-stable MOFs is to apply them as electrochemically “inactive” thin films for modulating the microenvironment near the underlying electrocatalyst surface and adjusting the reaction rates of complex electrochemical reactions. Nafion, a polymer containing negatively charged sulfonate groups, is commonly used as a modified thin film in electrochemical reactions involving charged reactants. Accordingly, enriched sulfonate groups are immobilized within Zr-MOF-808, and the resulting material is proposed as a “porous Nafion” ─ an appealing alternative to the conventional Nafion coating. Thereafter, such sulfonate-grafted MOF thin film is coated on the active electrode surface for electrochemical sensing of dopamine. With its negative charge and high porosity, the sulfonate-grafted MOF remarkably outperforms the commercially used Nafion thin film in both sensitivity toward positively charged dopamine and selectivity against negatively charged interferents (e.g., ascorbic acid and uric acid).
On the other hand, beyond the issue of charge transport, mass transport behavior during electrochemical processes should also be considered. Although MOFs possess interconnected porous structures, most MOFs with the inherent microporous nature may hinder the transport of reactants with large molecular sizes, leading to poor activity in electrochemical reactions. Herein, ordered pore engineering of a cerium-based MOF, UiO-66(Ce), is demonstrated by a soft-template strategy, and copper active units are further confined within the framework for electrochemical nitrate reduction to ammonia. By providing mesoporous channels with facile diffusion of reactants, the resulting material achieves a higher Faradaic efficiency and ammonia production rate than the one without mesopores. Findings here highlight the importance of pore engineering in MOF-based electrocatalysts for facilitating mass transport of reactants to enhance the electrocatalytic activity.

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