Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66

Rebecca H. Palmer, Jian Liu, Chung Wei Kung, Idan Hod, Omar K. Farha, Joseph T. Hupp

研究成果: Article同行評審

17 引文 斯高帕斯(Scopus)


Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.

頁(從 - 到)4707-4714
出版狀態Published - 2018 4月 24

All Science Journal Classification (ASJC) codes

  • 材料科學(全部)
  • 凝聚態物理學
  • 表面和介面
  • 光譜
  • 電化學


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