Coordination-Chemistry-Control of Cu(II) Reduction in HKUST-1 Leads to the Enhancement of Water Stability and the Formation of Ship-in-a-Bottle Complex
Title
Coordination-Chemistry-Control of Cu(II) Reduction in HKUST-1 Leads to the Enhancement of Water Stability and the Formation of Ship-in-a-Bottle Complex
Ⅰ. INTRODUCTION . 1 IⅠ. EXPERIMENTAL METHODS & MATERIALS 3 2.1. Materials 3 2.2. Sample Preparation 3 2.2.1. Synthesis of HKUST-1. . 3 2.2.2. Synthesis of HKUST-1 Single Crystal. 4 2.2.3. Thermal Activation (TA) of HKUST-1. . 4 2.2.4. Preparation of H2Q-coordinated HKUST-1. 4 2.2.5 Sample Preparation for the Measurement of Raman and UV-vis Absorption Spectra 4 2.2.6 Sample Preparation for the 1H-NMR Measurements 5 2.2.7 Instrumentation. 5 IIⅠ. RESULTS & DISCUSSION . 6 3.1 Structural View of the Arrangement of the Cages within HKUST-1 6 3.2.1 Mechanism of Redox Reaction between HKUST-1 and H2Q 8 3.2.2 Transmission microscopy (TEM) Image of LiBH4-treated HKUST-1 . 9 3.3.1 Schematic Illustration of Reduction of Cu2+ in HKUST-1 by H2Q 10 3.3.2 Schematic Illustrations of Two Routes of Cu+ Position after Reduction . 11 3.3.3 Schematic Illustrations of Formation of Ship-in-a-bottle Complex within Small Cage of HKUST-1 . 12 3.4 1H NMR spectra of H2Q, Q, and Supernatant solutions of H2Q-HK 13 3.5 XPS and XANES Study on MeCN-HK, H2Q-HK, CuO and Cu2O. . 15 3.6 PXRD Patterns, BET, Pore Fraction results and SEM Images of Pristine-HK and H2Q-HK . 18 3.7.1 Single Crystal Analysis of H2Q-HK and FT-IR Spectra of MeCN-HK and H2Q-HK . 21 3.7.2 IR Spectra of Commercial [Cu(MeCN)4]BF4 before/after Treatment of Water . 23 3.8 Illustration of Small Cage including CuI(MeCN)4 Complex 24 3.9 UV-vis Spectra of Pristine-HK, H2Q-HK, and [Cu(MeCN)4]BF4 and Optical Microscope (OM) Images of the H2Q-HK single crystal. . 25 3.10.2 PXRD Patterns of H2Q-HK before/after CO Adsorption/Desorption 28 3.10.3 Schematic Illustrations of Charge Balance 29 3.10.4 Raman Spectra of Pristine-HK, H2Q-HK and Each of Activation Samples . 30 3.11.1 PXRD Patterns, SEM Images, and BET Results for water treatment of Pristine-HK and H2Q-HK 31 3.11.2 Pore Size Distributions of H2Q-HK and Water-treated H2Q-HK samples . 33 3.11.3 PXRD Patterns of H2Q-HK as-made and H2Q-HK samples after 6 months and 2 years . 34 3.11.2 Schematic Illustrations of Three Factors to Explain the Enhancement of Water Stability . 35 IV. CONCLUSIONS 36 V. REFERENCES . 37 VI. SUMMARY (국문요약) 42