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synthesis

The document discusses the synthesis and functionalization of UiO metal-organic frameworks (MOFs), highlighting in-situ and post-synthesis methods for modifying their properties. It details the effects of various functional groups on the physical and chemical characteristics of UiO-66, including stability and specific surface areas. Additionally, it covers doping techniques with noble metal nanoparticles and the versatility of post-synthesis modifications to enhance the performance of UiO-MOFs in various applications.

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7 views

synthesis

The document discusses the synthesis and functionalization of UiO metal-organic frameworks (MOFs), highlighting in-situ and post-synthesis methods for modifying their properties. It details the effects of various functional groups on the physical and chemical characteristics of UiO-66, including stability and specific surface areas. Additionally, it covers doping techniques with noble metal nanoparticles and the versatility of post-synthesis modifications to enhance the performance of UiO-MOFs in various applications.

Uploaded by

coalluna0
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Synthesis of COMPOSITES

Composites of UiO can be synthesized either during in-situ process or the prepared UiO can be
modified post synthesis.

In-situ functionalization of UiO-66

In comparison with traditional porous materials, one of the most unique properties of MOFs is
the accessibility of the chemical functionalization of the structure. Through selecting ligands
with functional groups to carry out in-situ synthesis or postsynthetic exchange (PSE), groups or
metal ions with certain functions can be attached to the MOF structure, thus obtaining MOFs
with desired functions. Recently, novel methods such as single-crystal-to-singlecrystal
postsynthetic modification of UiO-66 via ozonolysis have also been investigated [147]. In-situ
synthesized functionalized UiO-66 possesses H2BDC-X with certain purposes to replace
H2BDC as the ligand, such as H2BDC-NH2, H2BDC-Br, H2BDC-NO2, H2BDC-(CH3)2, and
so on [50,106,108,148,149]. The introduction of these functional groups can alter the physical or
chemical properties of UiO-66. The functionalized UiO-66-X maintains the same crystal
structure and topology of UiO-66 but holds surface areas ranging from 600 m2 /g to 1,500 m2 /g
because of different functional ligands. The introduction of functional groups with relatively
higher volume and mass. The SEM images of UiO-66 synthesized with varied additive amounts
and different concentrations of reactants as well as hydrofluoric acid [141]. Copyright 2015, The
Royal Society of Chemistry. HF, hollow fiber. 144 D. Zou, D. Liu / Materials Today Chemistry
12 (2019) 139e165 as -Br and dNO2, would reduce the free space inside the cages of UiO-66
framework, leading to lower specific surface areas of UiO66-Br and UiO-66-NO2 when
compared with that of UiO-66. While the cavities of UiO-66-NH2 are slightly affected by -NH2,
specific surface areas analogous to that of UiO-66 can be preserved [50,148,150]. In terms of
stability, UiO-66-Br and UiO-66 can both remain stable under 450C, while UiO-66-NH2 and
UiO-66-NO2 started to decompose at 350C. However, some functional groups cannot be
attached to UiO-66 framework through in-situ synthesis, therefore the facile and efficient PSE
method can be utilized to obtain UiO-66-X [151]. Fei et al. [152] conducted ligand exchange
between UiO-66 and 2,3- dihydroxyterephthalic acid (CAT-BDC) under solvent conditions. By
courtesy of the high structural similarity between and CAT-BDC and H2BDC, CAT-BDC can
partially substitute H2BDC in UiO-66, thereby attaching dOH onto the UiO-66 network, gaining
UiO66-CAT (Fig. 6), which not only succeeds the exceptional crystallinity of UiO-66 but also
exhibits diverse specific surface areas from 968 m2 /g to 1,206 m2 /g when synthesized with
different exchange ratios, proving that the introduction of dOH is not in the form of the
encapsulation or doping of CAT-BDC in the UiO-66 cavities. The same strategy was later
applied by this research group to conduct ligand exchange between 2,3-dimercaptoterephthalic
acid (TCATBDC) and UiO-66, linking -HS group to the UiO-66 framework to eventually obtain
UiO-66-TCAT [153]. What is more, the -HS of UiO66-TCAT is adsorptive toward Pd, resulting
in UiO-66-PdTCAT with catalytic metal sites.

Doping

Doping MOFs with one or few functional materials (including other MOFs) can lead to
composites with combined advantages of their composition, such as high porosity, optical
properties, magnetism, and catalytic properties, thus granting them new physical and chemical
features, which further facilitates the applications of MOFs [168]. Noble-metal nanoparticles
(NPs) such as platinum (Pt) and palladium (Pd) have been widely utilized as heterogeneous
catalysts when carried by supporters with high surface areas [98]. Owing to the high thermal
stability (ca. 500C) and structural intensity under multiple organic solvents, UiO-66 and UiO-66-
NH2 are perfect candidates as catalyst supporters for Fig. 7. Schematic illustration of the
templating process of hexagonal microhierarchical and mesohierarchical UiO-66-NH2 [158].
Copyright 1999e2018, John Wiley & Sons, Inc. MOF, metal-organic framework. Fig. 8. The
conversion of microporous UiO-66-NH2 into ultrasmall hierarchical UiO-66-NH2 via controlled
linker thermolysis [160]. Copyright 2018, American Chemical Society. MOF, metal-organic
framework. 146 D. Zou, D. Liu / Materials Today Chemistry 12 (2019) 139e165 loading the
catalytic nanosized metal particles [169,170]. Take the doping of Au NPs for example, UiO-66
powder was first added in oil ammonia, stirred in N2 atmosphere, and heated up to 60 C, then
quickly added in HAuCl4 solvent and stirred at 90C for 0.5 h. At this point, Au3þ is reduced to
Au NPs. Au@UiO-66 composite can be obtained after the reaction system was cooled down to
room temperature and product washed with methanol [171]. Apart from noble metal NPs,
common MOF-participated composites include semiconductors (such as SiO2 [172]), organic
polymers (like urethane foam [173]), oxidized graphene [174], and so on. The uniform spatial
distribution of the functional materials inside MOF structures is the aporia and key point of
doping. Noteworthily, Kuntal et al. [175] managed to dope single-unit active metal sites in the
Zr-O clusters of UiO-68. Via the reaction between deprotonated Zr3(m3-OH) and CoCl2 or
FeBr2, the resulting UiO-CoCl or UiO-FeBr has active metal sites not only closely integrated
with the MOF framework, but also avoided aggregation, exhibiting highly efficient catalytic and
selective ability. This strategy also applies to the syntheses of UiO-66-CoCl and UiO-66-FeBr,
proving its universality.

Functionalization of UiO-MOFs by post-synthesis methods (PSMs)


In the process of functionalized MOFs synthesis, the pore size and function can be adjusted by
changing the ligand length and functionalizing the ligand or the secondary building unit (SBUs
refers to the single metal ion or metal-oxygen cluster) without change of topological structure. In
addition, the chemical properties of UiO-MOFs have gotten more and more attention, especially
in the fields of post-synthesis modification, crystal size tuning, and functionalization of pores
and the outer surface for increasing the efficiency and selectivity of adsorption (Yu et al.,
2019, Mukhopadhyay et al., 2019, Donnadio et al., 2017, Lv et al., 2016). PSMs include covalent
post-synthesis method (covalent PSMs), dative post-synthesis method (dative PSMs), and post-
synthesis deprotection (PSD) (Fig. 3) (Cohen, 2012). At present, covalent PSMs have proven to
be a powerful and versatile method for introducing a variety of chemical groups into MOFs. For
example, amino, bromo, nitro, carboxylic-acid, and polyethyleneimine-functionalized UiO-66
have been synthesized through reticular chemistry to generate novel, functionalized frameworks
by PSMs (Sarker et al., 2018, Zhu et al., 2019, Garibay and Cohen, 2010). Therefore, the
introduction of these ligands can change the physical or chemical properties of UiO-MOFs,
which maintains the same crystal structure and topology of UiO-MOFs and exhibits diverse
specific surface areas. However, when the functional ligands with larger volume and mass are
introduced, the free space in the UiO-MOFs frame cage will be reduced, such as the introduction
of –Br and –NO2, resulting in lower specific surface areas of UiO-MOFs-Br and UiO-MOFs-
NO2 than UiO-MOFs. Although the cavity of UiO-MOFs-NH2 is slightly affected by –NH2, the
specific surface areas can be preserved similar to that of UiO- MOFs. In terms of stability, for
example, both UiO-66-Br and UiO-66 can remain stable at 450 ℃, while UiO-66-NH 2 and UiO-
66-NO2 begin to decompose under 350 ℃. (Zou and Liu, 2019).

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