Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000
Solvothermal deposition in metal–organic frameworks (MOFs) can be used to mount single-metal-atom catalytic species at chemically reactive sites on hexa-Zr(IV)–oxy(oxo,hydroxo,aqua) nodes in nanoscale crystallites of the MOF NDC–NU-1000 in a self-limiting fashion. Upon photoexcitation of the 1,3,6...
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Veröffentlicht in: | Energy & fuels 2021-12, Vol.35 (23), p.19081-19095 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Solvothermal deposition in metal–organic frameworks (MOFs) can be used to mount single-metal-atom catalytic species at chemically reactive sites on hexa-Zr(IV)–oxy(oxo,hydroxo,aqua) nodes in nanoscale crystallites of the MOF NDC–NU-1000 in a self-limiting fashion. Upon photoexcitation of the 1,3,6,8-tetrakis(p-benzoato)pyrene chromophores of the parent framework, charge transfer may occur between the chromophores and the installed heterometal sites. Extended X-ray absorption fine structure studies revealed the single-atom nature of the installed species. A combination of steady-state and ultrafast optical spectroscopy was used to uncover evidence of a charge-separated (CS) state arising in the metalated samples. The relevant dynamics were characterized with transient photoluminescence and femtosecond transient absorption spectroscopy. We find that a titanium–oxy single-atom site gives rise to the longest lived CS species compared to cobalt and nickel in a similar arrangement. This study provides guidance in designing MOF-based catalytic systems for photocatalysis and solar fuel production. |
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ISSN: | 0887-0624 1520-5029 |
DOI: | 10.1021/acs.energyfuels.1c02623 |