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.
ASJC Scopus subject areas
- Chemical Engineering(all)
- Fuel Technology
- Energy Engineering and Power Technology