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제127회 대한화학회 학술발표회 및 총회 An Investigation of Collisional Electron-Injection Process in Semi-Heterogeneous Photocatalytic System (Porphyrin Dye + TiO2/Re(I)) for CO2 Reduction.

등록일
2021년 2월 15일 13시 50분 08초
접수번호
0179
발표코드
INOR.P-106 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
4월 23일(금) 15:00~16:00
발표형식
포스터
발표분야
Inorganic Chemistry
저자 및
공동저자
Yunjeong Seo, Daehan Lee, Sanghun Lee1, Chul Hoon Kim, Sang Ook Kang, Ho-Jin Son*
Department of Advanced Materials Chemistry, Korea University, Korea
1Department of Advanced Materials Chemistry, Korea University Sejong Campus, Korea
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 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 (Ered) of porphyrin dye.

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