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Design and Synthesis of Novel Perylenemonoimide Dyes for Solar Energy Conversion

Curtze, Allison Elizabeth
http://rave.ohiolink.edu/etdc/view?acc_num=osu1577731054149225

Abstract Details

2020, Doctor of Philosophy, Ohio State University, Chemistry.
Dye-sensitized solar cells (DSSC) and dye-sensitized photoelectrochemical cells (DSPEC) are of particular interest nowadays due to their promising potential for solar energy conversion and solar fuel production. Compared to conventional Si-based photovoltaics, dye-sensitized systems offer a greater degree of tunability by separating the roles of light absorption and charge carrier transport. The sensitizer, or dye, is crucial to these systems, as its ability to efficiently harvest light and split electron/hole pairs is central to device operation. Recently, a series of organic donor-acceptor dyes, the BH dye series, was introduced, which exhibited high molar extinction coefficients, which give rise to large photocurrents, as well as excellent photocathode stability in harsh (pH 0) aqueous conditions due to the creation of a hydrophobic “canopy” protection layer over the anchoring group and semiconductor by the dyes’ 3-hexyloligothiophene π-linker. While the highly hydrophobic nature of the BH dyes offer superior protection, it is hypothesized that, especially in aqueous electrolytes, it does not allow complete wetting of the highly porous sensitized NiO semiconductor film, which in turn, decreases the surface area of the dye-electrolyte interface, and ultimately leads to reduced photocurrents. This dissertation describes two new dyes that were designed to address the challenges in wettability and dye-electrocatalyst coupling. In an effort to enhance the contact between the dye and aqueous electrolytes, a new dye, AC2, was designed and synthesized, incorporating hydrogen-bond accepting aryl methyl ether moieties onto the BH dye scaffold. However, while AC2 exhibits a high molar extinction coefficient (9.4  104 M1 cm1) and thermodynamically favorable HOMO and LUMO potentials (1.03 V and 0.78 V vs NHE, respectively), the aryl methyl ether moieties made no significant change in sensitized NiO film wettability, and p-DSSC devices sensitized with AC2 did not show any improvement in performance as compared to the analogous BH2. While the protection offered by BH dyes affords photocathodes with long-term stability and high photocurrents in low pH aqueous conditions, p-DSPEC devices sensitized with BH4 have achieved less than ideal faradaic efficiencies attributed to catalyst decomposition. Thus, another new dye, cat-i, was designed and synthesized, featuring a pyridine moiety, which gives rise to the formation of a stable dye-catalyst supramolecule via axial coordination of the dye to the Co center of a well-known water reduction catalyst, Co(dmgBF2)2. Further, this dye-catalyst complexation could facilitate electron transfer from the photoexcited dye to the cobaloxime catalyst. When used as a sensitizer in a p-DSPEC device, the cat-i-cobaloxime complex exhibits significantly higher photocurrents than cat-i alone and produces H2 with 87% Faradaic efficiency.
Yiying Wu (Advisor)
94 p.
Chemistry

Recommended Citations

Citations

  • Curtze, A. E. (2020). Design and Synthesis of Novel Perylenemonoimide Dyes for Solar Energy Conversion [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1577731054149225

    APA Style (7th edition)

  • Curtze, Allison. Design and Synthesis of Novel Perylenemonoimide Dyes for Solar Energy Conversion. 2020. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1577731054149225.

    MLA Style (8th edition)

  • Curtze, Allison. "Design and Synthesis of Novel Perylenemonoimide Dyes for Solar Energy Conversion." Doctoral dissertation, Ohio State University, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=osu1577731054149225

    Chicago Manual of Style (17th edition)

osu1577731054149225
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