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논문 기본 정보
- 자료유형
- 학위논문
- 저자정보
- 지도교수
- 손호진
- 발행연도
- 2021
- 저작권
- 고려대학교 논문은 저작권에 의해 보호받습니다.
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We report a collisional electron-injection process in the semi-hetero hybrid photocatalytic system consisting of non-anchored porphyrins and TiO2/Re(I) nanoparticles. The net hetero-collisional electron transfer from the non-anchored fluorescent porphyrin sensitizer to the TiO2 catalytic particles was a major event during the initial stage of the catalysis. According to in situ UV?Vis absorption spectroscopy and mass analysis of dye solution filtered after photolysis, the initially added porphyrin dye is found to experience a photomodification accompanied by a breakage of π?conjugation and loss of the bulky substituents. With the structural identification of deformed porphyrin species, two acetyl- or ethyl-group modified porphyrins were prepared, respectively referred to as ZnPAcet and ZnPEt, and this modification elevated the corresponding excited-state energy levels when comparing ZnP with ZnPEt, consequently shortening the activity delay at the early stage of photolysis. Thus, chemical modification had a favorable effect on the photosensitizing and electron transportation abilities of the dye. The high activation barrier (Ea = 57.97 kJ/mol, solvated dye → TiO2 particles) for the collisional electron transfer process, as estimated from the Arrhenius plot of the temperature-dependent quenching rate, supports that the net efficiency of electron transport to TiO2 is sensitively affected by the small difference in the reduction potential (E1/2red) of porphyrin dye. This quenching kinetic data provides the first quantitative results showing how the solution-phase dye radical anions transport their excited-state electrons to the heterogeneous semiconductor side.
목차
1. Introduction 62. Results and discussion 113. Conclusion 414. Experimental section 435. Reference 486. Table of contents 537. Supporting Information 54
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