Metal–organic nanosheets formed via defect–mediated transformation of a hafnium metal–organic framework

DOI: 10.1021/jacs.7b00106

Authors: Matthew J. Cliffe (University of Cambridge) , Elizabeth Castillo-Martinez (University of Cambridge) , Yue Wu (University of Cambridge) , Jeongjae Lee (University of Cambridge) , Alexander C. Forse (University of Cambridge) , Francesca C. N. Firth (University of Cambridge) , Peyman Z. Moghadam (University of Cambridge) , David Fairen-Jimenez (University of Cambridge) , Michael W. Gaultois (University of Cambridge) , Joshua A. Hill (University of Oxford) , Oxana V. Magdysyuk (Diamond Light Source) , Ben Slater (University College London) , Andrew L. Goodwin (University of Oxford) , Clare P. Grey (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: March 2017
Diamond Proposal Number(s): 9940 , 15118 , 12554 , 13681 , 13843

Abstract: We report a hafnium containing MOF, hcp UiO-67(Hf), which is a defective layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its low- ered ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed ‘double cluster’, analogous to the condensation of coor- dination polyhedra in oxide frameworks. In oxide frameworks variable stoichiometry can lead to more complex defect structures, e.g. crystallographic shear planes or mod- ules with differing compositions, which can be the source of further chemical reactivity; likewise the layered hcp UiO-67 can react further to form two-dimensional nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions suggesting that defect ordered MOFs could be a productive route to porous two-dimensional materials.

Subject Areas: Materials, Chemistry


Instruments: I11-High Resolution Powder Diffraction , I12-JEEP: Joint Engineering, Environmental and Processing , I15-Extreme Conditions

Added On: 03/04/2017 09:59

Documents:
jacs.pdf

Discipline Tags:

Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction