| 摘要: | 近年來，能源議題在全球備受關注，我國也積極朝向淨零碳排邁進，期望藉此減少化石燃料使用並降低二氧化碳排放，而在眾多再生能源中，太陽能具備取之不盡且能量充沛的優勢，成為發展重點。過渡金屬硫化物因能隙適中與能帶位置理想，常被應用於光催化產氫相關研究，但其光生電子電洞對容易再結合，進而限制了其整體光催化效率。為改善此問題，本研究選擇將不同的金屬有機骨架材料 (MOFs) 與 ZnIn₂S₄ (ZIS) 建立異質結構，藉以調控載流子遷移行為，提升產氫效率並抑制光生載流子再結合。
本研究藉由水熱法及溶劑熱法分別合成Ni-MOF-74和MIL-68-NH2，並分別和過度金屬硫化物ZnIn2S4形成異質結構，以此來提升觸媒在光催化產氫反應當中的性能，本研究主要探討Ni-MOF@ZnIn2S4的產氫效率，並比較兩種不同異質結構在光生電子電洞對遷移機制上的差異，利用原位X光光電子能譜儀的技術，來判斷材料在形成異質結構時所產生的內建電場與能帶彎曲方向，以及異質結構經過照光後，材料內部的光生電子與電洞的遷移方向，以此來確定異質結構類型。Ni-MOF-74會呈現層狀的奈米片結構，可以提供更多表面積以更好的和ZnIn2S4形成異質結構，同時也能有效提升材料整體對可見光的利用率，且為了降低光催化產氫反應的研究成本，本實驗並未添加其他種類的貴金屬作為共觸媒來提高產氫效率。
;In recent years, energy-related issues have drawn considerable global attention. Our country is also actively moving toward the goal of net-zero carbon emissions, aiming to reduce the consumption of fossil fuels and lower CO₂ emissions. Among various renewable energy sources, solar energy stands out due to its abundant and inexhaustible nature, making it a key focus for future development. Transition metal sulfides, owing to their moderate band gaps and suitable band edge positions, have been widely studied in photocatalytic hydrogen production. However, their rapid recombination of photogenerated electron–hole pairs significantly limits their overall photocatalytic efficiency. To address this issue, this study constructs heterostructures by coupling different metal-organic frameworks (MOFs) with ZnIn₂S₄ (ZIS), aiming to regulate charge carrier migration, enhance hydrogen evolution performance, and suppress carrier recombination.
In this research, Ni-MOF-74 and MIL-68-NH₂ were synthesized via hydrothermal and solvothermal methods, respectively, and were then combined with the transition metal sulfide ZnIn₂S₄ to form heterostructured photocatalysts. The primary focus was placed on evaluating the hydrogen evolution performance of Ni-MOF@ZnIn₂S₄ and comparing the charge transfer mechanisms of the two heterostructures. In-situ X-ray photoelectron spectroscopy (XPS) was employed to investigate the internal electric fields and band bending at the interface of the heterojunctions, as well as the migration behavior of photogenerated charge carriers upon illumination, which helps to determine the type of heterostructure formed. Ni-MOF-74 exhibits a layered nanosheet morphology, offering a high surface area that facilitates effective heterojunction formation with ZnIn₂S₄ and improves visible light utilization. Furthermore, to reduce the cost of the photocatalytic hydrogen production system, no additional noble-metal co-catalysts were introduced in this study. |
