Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal?Organic Framework NDC?NU-1000 [electronic resource]
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Full Text (via OSTI) |
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| Format: | Government Document Electronic eBook |
| Language: | English |
| Published: |
Arlington, Va. : Oak Ridge, Tenn. :
United States. Office of Naval Research ; Distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2021.
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| Abstract: | Solvothermal deposition in metal?organic frameworks (MOFs) can be utilized 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(<em>p</em>-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 utilized 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. Here, 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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| Item Description: | Published through Scitech Connect. 09/21/2021. "Journal ID: ISSN 0887-0624." "Other: 170702." Kramar, Boris V. ; Phelan, Brian T. ; Sprague-Klein, Emily A. ; Diroll, Benjamin T. ; Lee, Sungsik ; Otake, Ken-ichi ; Palmer, Rebecca ; Mara, Michael W. ; Farha, Omar K. ; Hupp, Joseph T. ; et al. |
| Physical Description: | Size: p. 19081-19095 : digital, PDF file. |