Pt Electrodes Enable the Formation of μ4-O Centers in MOF-5 from Multiple Oxygen Sources.
The μ4-O2-ions in the Zn4O(O2C-)6secondary building units of Zn4O(1,4-benzenedicarboxylate)3(MOF-5) electrodeposited under cathodic bias can be sourced from nitrate, water, and molecular oxygen when using platinum gauze as working electrodes. The use of Zn(ClO4)2·6H2O, anhydrous Zn(NO3)2, or anhydrous Zn(CF3SO3)2as Zn2+sources under rigorous control of other sources of oxygen, including water and O2, confirm that the source of the μ4-O2-ions can be promiscuous. Although this finding reveals a relatively complicated manifold of electrochemical processes responsible for the crystallization of MOF-5 under cathodic bias, it further highlights the importance of hydroxide intermediates in the formation of the Zn4O(O2C-R) secondary building units in this iconic material and is illustrative of the complicated crystallization mechanisms of metal-organic frameworks in general.
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Minyuan M
http://orcid.org/0000-0002-4078-9435
MM
Li
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Mircea
http://orcid.org/0000-0002-1262-1264
M
Dincă
crystals; electrochemistry; electrodeposition; mechanism of reactions; metal−organic frameworks