TY - JOUR
T1 - Influences of Deprotonation and Modulation on Nucleation and Growth of UiO-66
T2 - Intergrowth and Orientation
AU - Shan, Bohan
AU - James, Joshua B.
AU - Armstrong, Mitchell R.
AU - Close, Emily C.
AU - Letham, Portia A.
AU - Nikkhah, Kassandra
AU - Lin, Jerry
AU - Mu, Bin
N1 - Funding Information:
This research work was financially supported by Arizona State University and the National Science Foundation (Grant
Funding Information:
This research work was financially supported by Arizona State University and the National Science Foundation (Grant Number CBET-1748641 and CBET-1511005). We gratefully acknowledge the use of facilities within the Leroy Eyring Center for Solid State Science at Arizona State University and ASU SEMTE lab manager Fred Pena for continued support.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/2/1
Y1 - 2018/2/1
N2 - The most common products obtained in the synthesis of zirconium-based metal-organic frameworks (ZrMOFs) are fine powders. The particle size of a typical ZrMOF UiO-66 was first reported to be around 200 nm, so the original crystal structure was only solved by powder XRD coupled with Rietveld refinement due to the incapability of single crystal XRD to solve such small crystals with poor crystallinity. One may ask the reason why the particle size of UiO-66 is so small compared to that of other common MOFs and what the key factor terminating the growth of UiO-66 is. In this work, we try to answer this question by proposing a hypothesis that the partially deprotonated ligand caused by the accumulated protons in the reaction solution is the key factor preventing the continuous growth of the UiO-66 crystal. The hypothesis is verified by growth reactivation with the addition of a deprotonating agent in an in situ biphase solvothermal reaction. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium and nucleation so that an oriented attachment growth of UiO-66 film was achieved in membrane structures.
AB - The most common products obtained in the synthesis of zirconium-based metal-organic frameworks (ZrMOFs) are fine powders. The particle size of a typical ZrMOF UiO-66 was first reported to be around 200 nm, so the original crystal structure was only solved by powder XRD coupled with Rietveld refinement due to the incapability of single crystal XRD to solve such small crystals with poor crystallinity. One may ask the reason why the particle size of UiO-66 is so small compared to that of other common MOFs and what the key factor terminating the growth of UiO-66 is. In this work, we try to answer this question by proposing a hypothesis that the partially deprotonated ligand caused by the accumulated protons in the reaction solution is the key factor preventing the continuous growth of the UiO-66 crystal. The hypothesis is verified by growth reactivation with the addition of a deprotonating agent in an in situ biphase solvothermal reaction. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium and nucleation so that an oriented attachment growth of UiO-66 film was achieved in membrane structures.
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U2 - 10.1021/acs.jpcc.7b11012
DO - 10.1021/acs.jpcc.7b11012
M3 - Article
AN - SCOPUS:85041451806
SN - 1932-7447
VL - 122
SP - 2200
EP - 2206
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 4
ER -