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@ARTICLE{Dovgaliuk:642746,
author = {Dovgaliuk, Iurii and Chen, Bingbing and Melillo, Arianna
and Wahiduzzaman, Mohammad and Khadiev, Azat and Novikov,
Dmitri and Achenbach, Bastian and Ruser, Niklas and Gosch,
Jonas and Stock, Norbert and Maurin, Guillaume and
Mouchaham, Georges and Serre, Christian},
title = {{I}n-situ {D}iffraction {C}rystallization {S}tudy of a
porous {T}i({IV}) oxo-cluster carboxylate {MOF} and its
{W}ater-{I}nduced {T}i({III}) {F}ormate},
reportid = {PUBDB-2025-05595},
year = {2025},
abstract = {The in-situ crystallization kinetics of the highly porous
Ti(IV)12 oxo-cluster based metal-organic framework (MOF)
MIP-177(Ti)-LT (MIP: Materials from Institute of porous
solids of Paris, LT: Low Temperature) were studied by
synchrotron time-resolved powder X-ray diffraction. When dry
formic acid (FA) was used as solvent the crystallization
does follow the Johnson-Mehl-Avrami-Kolmogorov kinetics with
an energy barrier of 74 kJ·mol-1 without any observed
intermediate crystalline phases. However, when small
quantities of water (≥ 2.5 $vol\%)$ were introduced in the
reaction solution, it led to the formation of the novel
clathrate Ti(HCOO)3·¾CO2·¼H2O, a microporous MOF
belonging to the ReO3 net-like CO2 clathrates in analogy to
the previously described M(III)-formates (M = Al, Mn, Fe,
Ga, In). Although the formation mechanism in the presence of
water remains unclear, one possible explanation is that
MIP-177(Ti⁴⁺)-LT decomposes formic acid under
solvothermal conditions, resulting in the production of
CO₂ and H₂, which may promote the crystallization of
Ti³⁺-formate clathrate.},
cin = {DOOR ; HAS-User / FS-PETRA-D},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PETRA-D-20210408},
pnm = {FS-Proposal: I-20210337 EC (I-20210337-EC) / FS-Proposal:
I-20220255 EC (I-20220255-EC) / 632 - Materials – Quantum,
Complex and Functional Materials (POF4-632) / 6G3 - PETRA
III (DESY) (POF4-6G3)},
pid = {G:(DE-H253)I-20210337-EC / G:(DE-H253)I-20220255-EC /
G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P23-20150101},
typ = {PUB:(DE-HGF)25},
doi = {10.26434/chemrxiv-2025-dl8vn-v2},
url = {https://bib-pubdb1.desy.de/record/642746},
}