دورية أكاديمية
Effect of a redox-mediating ligand shell on photocatalysis by CdS quantum dots.
| العنوان: | Effect of a redox-mediating ligand shell on photocatalysis by CdS quantum dots. |
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| المؤلفون: | Dou FY; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Harvey SM; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Mason KG; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Homer MK; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Gamelin DR; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA., Cossairt BM; Department of Chemistry, University of Washington, Seattle, Washington 98195, USA. |
| المصدر: | The Journal of chemical physics [J Chem Phys] 2023 May 14; Vol. 158 (18). |
| نوع المنشور: | Journal Article |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Institute of Physics Country of Publication: United States NLM ID: 0375360 Publication Model: Print Cited Medium: Internet ISSN: 1089-7690 (Electronic) Linking ISSN: 00219606 NLM ISO Abbreviation: J Chem Phys Subsets: PubMed not MEDLINE; MEDLINE |
| أسماء مطبوعة: | Publication: New York, NY : American Institute of Physics Original Publication: Lancaster, Pa., American Institute of Physics. |
| مستخلص: | Semiconductor quantum dots (QDs) are efficient organic photoredox catalysts due to their high extinction coefficients and easily tunable band edge potentials. Despite the majority of the surface being covered by ligands, our understanding of the effect of the ligand shell on organic photocatalysis is limited to steric effects. We hypothesize that we can increase the activity of QD photocatalysts by designing a ligand shell with targeted electronic properties, namely, redox-mediating ligands. Herein, we functionalize our QDs with hole-mediating ferrocene (Fc) derivative ligands and perform a reaction where the slow step is hole transfer from QD to substrate. Surprisingly, we find that a hole-shuttling Fc inhibits catalysis, but confers much greater stability to the catalyst by preventing a build-up of destructive holes. We also find that dynamically bound Fc ligands can promote catalysis by surface exchange and creation of a more permeable ligand shell. Finally, we find that trapping the electron on a ligand dramatically increases the rate of reaction. These results have major implications for understanding the rate-limiting processes for charge transfer from QDs and the role of the ligand shell in modulating it. (© 2023 Author(s). Published under an exclusive license by AIP Publishing.) |
| تواريخ الأحداث: | Date Created: 20230509 Date Completed: 20230509 Latest Revision: 20230509 |
| رمز التحديث: | 20240628 |
| DOI: | 10.1063/5.0144896 |
| PMID: | 37158330 |
| قاعدة البيانات: | MEDLINE |
Find this article in full text from Scitation. | تدمد: | 1089-7690 |
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| DOI: | 10.1063/5.0144896 |