Outer-Sphere Electron-Transfer Process of Molecular Donor-Acceptor Organic Dye in the Dye-Sensitized Photocatalytic System for CO2 Reduction
DC Field | Value | Language |
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dc.contributor.author | Choi, Sunghan | - |
dc.contributor.author | Kim, Yun-Jae | - |
dc.contributor.author | Kim, Soohwan | - |
dc.contributor.author | Lee, Hyun Seok | - |
dc.contributor.author | Shin, Jae Yoon | - |
dc.contributor.author | Kim, Chul Hoon | - |
dc.contributor.author | Son, Ho-Jin | - |
dc.contributor.author | Kang, Sang Ook | - |
dc.date.accessioned | 2022-11-18T07:40:47Z | - |
dc.date.available | 2022-11-18T07:40:47Z | - |
dc.date.created | 2022-11-17 | - |
dc.date.issued | 2022-09-26 | - |
dc.identifier.issn | 2574-0962 | - |
dc.identifier.uri | https://scholar.korea.ac.kr/handle/2021.sw.korea/145732 | - |
dc.description.abstract | In dye-sensitized photocatalytic (DSPC) systems, the introduction and effective operation of the precious-metal free photosensitizing components are the critical issues which affect their practical applications. In this study, it was first found that the photosensitization process of a donor-pi-acceptor (D-pi-A)-type dye, which was designed to be immobilized onto a TiO2 surface for efficient photoelectron collection, is also feasible at the outer-sphere of the TiO2 surface despite the absence of chemical anchoring of the acceptor part (in the D-pi-A dye) onto the TiO2 surface. Two ethyl-protected D-pi-A dyes, namely, (E)-2-cyano-3-(5-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)thiophen-2-yl)acrylate (1-Et) and ((E)-ethyl-3-(4-(7-(5 '-(4-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)phenyl)-[2,2 '-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylate) (2-Et), were prepared and investigated to elucidate the photoinduced electron transfer (PET) mechanism of the non-anchored D-pi-A dye in solution. From serial fluorescence and anion absorption quenching experiments, we found that the reductively quenched [D-pi-A dye](center dot-) in solution efficiently can transfer the photoexcited electrons toward solid TiO2/Re(I) catalytic particles (dye(center dot-) -> |TiO2/Re(I) catalyst) through the outer-sphere electron transfer (OSET) process. The success of the collisional OSET process is attributed to the long lifetime of the solution-phase [D-pi-A dye](center dot-) species, which sufficiently can overcome the intrinsically inefficient heterogeneous electron transfer (ET) kinetics at the interface between the dye(center dot-) in solution and the dispersed TiO2 particles and can decrease the dependency on the charge-transfer reorganization energy. The effectiveness of the OSET process was verified by the efficient photocatalytic CO2-to-CO conversion activities of binary [a turnover number (TON) of 330-470 for similar to 8 h] by the photosensitization of the free [D-pi-A dye](center dot-), which are comparable to those of the dye-anchored ternary analogues (D-pi-A dye/TiO2/Re(I) catalyst, a TON of 194-391 for 8 h) based on the conventional inner-sphere ET (ISET) process at the early stage of the photoreaction. The two-way photosensitization processing (which considers both OSET and ISET) of organic dyes can be a major strategic advantage in conventional dye-sensitized solar cells and DSPC systems for H-2 production and CO2 reduction. | - |
dc.language | English | - |
dc.language.iso | en | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | D-PI-A | - |
dc.subject | TIO2 NANOPARTICLES | - |
dc.subject | SOLAR-CELLS | - |
dc.subject | EFFICIENT | - |
dc.subject | COMPLEXES | - |
dc.subject | DESIGN | - |
dc.subject | PHOTOSENSITIZATION | - |
dc.subject | CATALYST | - |
dc.subject | PROTON | - |
dc.subject | WATER | - |
dc.title | Outer-Sphere Electron-Transfer Process of Molecular Donor-Acceptor Organic Dye in the Dye-Sensitized Photocatalytic System for CO2 Reduction | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Shin, Jae Yoon | - |
dc.contributor.affiliatedAuthor | Kim, Chul Hoon | - |
dc.contributor.affiliatedAuthor | Son, Ho-Jin | - |
dc.identifier.doi | 10.1021/acsaem.2c01229 | - |
dc.identifier.scopusid | 2-s2.0-85137294020 | - |
dc.identifier.wosid | 000848437800001 | - |
dc.identifier.bibliographicCitation | ACS APPLIED ENERGY MATERIALS, v.5, no.9, pp.10526 - 10541 | - |
dc.relation.isPartOf | ACS APPLIED ENERGY MATERIALS | - |
dc.citation.title | ACS APPLIED ENERGY MATERIALS | - |
dc.citation.volume | 5 | - |
dc.citation.number | 9 | - |
dc.citation.startPage | 10526 | - |
dc.citation.endPage | 10541 | - |
dc.type.rims | ART | - |
dc.type.docType | Article | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalResearchArea | Energy & Fuels | - |
dc.relation.journalResearchArea | Materials Science | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical | - |
dc.relation.journalWebOfScienceCategory | Energy & Fuels | - |
dc.relation.journalWebOfScienceCategory | Materials Science, Multidisciplinary | - |
dc.subject.keywordPlus | D-PI-A | - |
dc.subject.keywordPlus | TIO2 NANOPARTICLES | - |
dc.subject.keywordPlus | SOLAR-CELLS | - |
dc.subject.keywordPlus | EFFICIENT | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | DESIGN | - |
dc.subject.keywordPlus | PHOTOSENSITIZATION | - |
dc.subject.keywordPlus | CATALYST | - |
dc.subject.keywordPlus | PROTON | - |
dc.subject.keywordPlus | WATER | - |
dc.subject.keywordAuthor | donor-acceptor organic photosensitizer | - |
dc.subject.keywordAuthor | outer-/inner-sphere electron transfer | - |
dc.subject.keywordAuthor | intramolecular charge transfer | - |
dc.subject.keywordAuthor | photochemical CO(2 )reduction | - |
dc.subject.keywordAuthor | supported catalysis | - |
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