Controlling Catalytic Properties of Layered PtTe2 by Engineering Surface Defects

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薛景文(Jing-Wen Hsueh) 查詢紙本館藏

畢業系所

物理學系

論文名稱

(Controlling Catalytic Properties of Layered PtTe2 by Engineering Surface Defects)

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摘要(中)

缺陷工程已被證明是觸發二維材料惰性表面的有效方法，因為表面缺陷通常是活性位點。在我們的研究中，我們通過製造表面的碲缺陷（對應於未鍵結滿的鉑(Ptuc)）增強了 PtTe2 表面的反應能力，並且可以通過控制氬離子 (Ar+) 轟擊的量來調控表面的缺陷密度。通過反射高能電子衍射 (RHEED)、光電子能譜 (PES) 和近常壓 X 射線光電子能譜 (APXPS)，我們證明氬離子轟擊主要產生表面碲缺陷，並且其數量幾乎與氬離子轟擊的劑量成高度正相關。
藉由光電子能譜我們看到了甲醇有缺陷的 PtTe2 表面上分解成CHxO 和 CHx這兩種產物，並且這些產物的產量Ptuc 的數量之間存在高度正相關，這意味著對於甲醇分解來說Ptuc 是表面的活性位點。因此我們可以通過控制氬離子轟擊的時間來控制表面 Ptuc 的數量，並進一步影響 PtTe2 的表面反應能力。
使用基於同步輻射光源的近常壓 X 射線光電子能譜，我們發現了在接近常壓的環境中吸附的甲醇引發了PtTe2表面上碲缺陷的形成。由Te 4d 與 Pt 4f的光電子能譜強度的比例降低和未鍵結滿的鉑光電子訊號的增加我們進一步的證實表面碲缺陷的增加是由分解性吸附的甲醇所引起。隨著甲醇氣壓逐漸增加至0.01 mbar，進一步增強的甲醇分解反應（由原子碳和 CHx 的產生表明）和逐漸增加的碲缺陷數量意味著甲醇的分解和反應能力的增強是相輔相成的。增強的反應能力加速了甲醇的分解；而加速的甲醇分解議會促進反應能力的加強。
我們還注意到碲缺陷的數量在甲醇壓力 0.01 mbar 左右達到飽和。該結果意味著，除了傳統的缺陷工程策略（例如，退火、離子轟擊或等離子體處理）之外，我們提出了另一種在二維材料上製造表面缺陷的方法。

摘要(英)

Defect engineering has been shown as an efficient way to activate inert basal planes of 2D materials, as surface defects are typically active sites. In this study, we show that the reactivity of PtTe2 basal plane is enhanced by introducing surface Te-vacancies, corresponding to under-coordinated surface Pt (Ptuc), and the defect density can be controlled with Argon ion (Ar+) bombardment. With reflection high energy electron diffraction (RHEED), photoelectron spectroscopy (PES), and ambient pressure X-ray photoelectron spectroscopy (APXPS), we demonstrate that the Ar+ bombardment produces primarily surface Te-vacancies and the number of Ptuc grows almost in linear proportion with the Ar+ bombardment time. These spectra also indicate the decomposition of methanol adsorbed on the defective PtTe2 surface, evidenced by the formation of CHxO and CHx, and a highly positive correlation between the numbers of decomposed methanol and Ptuc, implying Ptuc as an active site toward the methanol decomposition. The surface reactivity of PtTe2 can therefore be manipulated by controlling the number of Ptuc through the Ar+ bombardment. With synchrotron-based APXPS, we show that the surface Te-vacancies on PtTe2 were enhanced by adsorbed methanol. The increased surface Te-vacancies were indicated by the decreased ratio of the Te 4d to Pt 4f core-level signals and increased Pt 4f signals at smaller binding energy, reflecting increased undercoordinated Pt (Ptuc). With increasing methanol exposure from high vacuum to near-ambient pressure (up to 0.1 mbar), both methanol decomposition, indicated by the production of atomic carbons and CHx, and the number of Te-vacancies were significantly promoted, implying that these processes could promote each other. We also noted that the number of Te-vacancies was saturated at about methanol pressure 0.01 mbar. The result implies, in addition to traditional defect engineering strategies (e.g., annealing, ion bombardment or plasma treatment), an alternative approach to engineer surface defects on layered 2D materials.

關鍵字(中)

★ 二維材料
★ 異相催化
★ 甲醇分解反應
★ 缺陷工程
★ 光電子能譜
★ 近常壓光電子能譜

關鍵字(英)

★ 2D materials
★ Heterogeneous catalysis
★ Methanol decomposition reaction
★ Defect engineering
★ XPS
★ APXPS

論文目次

Contents
摘要 i
Abstract ii
致謝 iii
Contents v
List of Figures vi
Chapter 1 Introduction 1
Chapter 2 Literature Survey 3
2.1 Activate the inert basal plane of layered PtTe2 3
2.1.1 Reactivity of pristine basal plane of PtTe2 3
2.2.2 Activate the PtTe2 basal plane with Argon-ion (Ar+) bombardment 4
2.2 The Enhanced Reactivity of MoS2 with Defect Engineering 5
2.2.1 Defect Engineering with Helium ion 6
2.2.2 Sulfur vacancy-rich MoS2 with H2-pretreated 8
2.2.3 Methoxy Formation Induced Defects on MoS2 10
2.3 Efficiency of Ar+ Bombardment in Different Energy on MoS2 12
3.1 Experimental method 14
3.1.1 Sample preparation 14
3.1.2 Ar+ bombardment treatment 16
3.2 Reflective High Energy Electron Diffraction (RHEED) 19
3.3 Photoelectron spectroscopy (PES) 21
3.4 Ambient pressure experiments 24
Chapter 4 Results and Discussion 26
4.1 Defect Engineering on layered PtTe2 with Ar+ Bombardment 26
4.1.1 Alteration of surface morphology with Ar+ bombardment 26
4.1.2 Alteration of surface chemical bonding with Ar+ bombardment 27
4.2 Reactivity of defected PtTe2 toward methanol decomposition 31
4.3 Methanol Decomposition in Near-Ambient Pressure Condition 38
4.4 Defect engineering with dissociated adsorbed methanol 43
Chapter 5 Conclusion 54
References 55

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指導教授

羅夢凡(Meng-Fan Luo)

審核日期

2022-9-12

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