ja7b13211_si_001.pdf (1.49 MB)
Charge-Transfer within Zr-Based Metal–Organic Framework: The Role of Polar Node
journal contribution
posted on 2018-02-09, 00:00 authored by Andrea Van Wyk, Tanner Smith, Jaehong Park, Pravas DeriaMetal–organic
frameworks (MOFs) are emerging materials for
electro- and photo-chemical applications, where an understanding of
the underlying charge-transfer (CT) process will facilitate designing
new materials. However, the involvement of counterions in traditional
electrochemical experiments complicates the probe on the role of various
components during a CT event. A CT reaction between photoexcited MOF
linker and a node–anchored ferrocene, within mesoporous framework
NU-1000, was spectroscopically probed without the involvement of electrolyte
based counterions. Dielectric dependent CT kinetics indicate that
the process involves a high reorganization energy that is required
to polarize the node bound hydroxyl/aqua ligands. The findings have
clear implication on the design of MOF-based electrocatalysis and
photoelectrochemical devices.