期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 11, 期 3, 页码 702-709出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.9b03285
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资金
- National Science Foundation [1551964]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1551964] Funding Source: National Science Foundation
In redox-active metal-organic frameworks (MOFs), charge transfer can occur by a redox hopping mechanism, i.e., electron hopping coupled with ion diffusion to balance electroneutrality. To elucidate the correlation between MOF structure and electron and ion diffusion, we prepared three ferrocene-doped MOF (Fc-MOF) films with different pore sizes (15-47 angstrom) immobilized on conductive substrates. By applying a theoretical model to the chronoamperometric responses of three Fc-MOFs, the electron and ion diffusion coefficients (D-e approximate to 10(-12)-10(-2) cm(2) s(-1); D-i approximate to 10(-16)-10(-12) cm(2) s(-1)) and electron- and ion-transfer rate constants (k(e-hop) approximate to 10(3)-10(7) s(-1); k(i-hop) approximate to 10(-3)-10(1) s(-1)) were quantified independently Increasing MOF pore size led to an increase in k(i-hop) and a decrease in k(e-hop). The overall charge-transfer rate constant, k(hop), increased when MOF pore size increased, confirming the ability to enhance charge-transfer rates through control of MOF pores size.
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