Toward a Rational Design of Titanium Metal-Organic Frameworks

Wang, Sujing; Reinsch, Helge; Heymans, Nicolas; Wahiduzzaman, Mohammad; Martineau‐Corcos, Charlotte; Weireld, Guy De; Serre, Christian

doi:10.1016/j.matt.2019.11.002

Cited by 68 publications

(61 citation statements)

References 48 publications

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“…Ti–oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments. [ 48 ] The number of Ti atoms in Ti–oxo clusters ranges from 3 to 32, including Ti 3 , [ 49–52 ] Ti 4 , [ 50,52–57 ] Ti 5 , [ 57 ] Ti 6 , [ 51,52,54,55,57–64 ] Ti 7 , [ 57 ] Ti 8 , [ 54,64,65 ] Ti 9 , [ 51,55,63 ] Ti 10 , [ 66 ] Ti 11 , [ 54–56,63 ] Ti 12 , [ 57,62,66,67 ] Ti 14 , [ 50,56 ] Ti 16 , [ 54,55,61,66 ] Ti 18 , [ 51,57 ] Ti 19 , [ 63 ] Ti 20 , [ 66,68 ] and Ti 32 clusters. [ 69 ] In general, during the assembly of Ti–oxo clusters, it is vital to control the competition between acids and coordinating ligands.…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

“…reported a controlled preparation of a microporous Ti‐MOF, MIP‐207. [ 65 ] The Ti 8 O 8 cluster in MIP‐207 was connected by tritopic BTC linker through ligand exchange. Eight carboxylate groups on the cluster come from the BTC linker, while the other eight coordination sites are occupied by formates and acetates due to the steric hindrance repulsion effect.…”

Section: Mofs Based On Ti (Group 4 Metal)mentioning

confidence: 99%

“…[ 144 ] Furthermore, Ti 8 ‐cluster based MIP‐207 shows good working capacity and interesting selectivity of CO 2 over N 2 . [ 65 ]…”

Section: Mofs Based On Ti (Group 4 Metal)mentioning

confidence: 99%

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Metal–Organic Frameworks Based on Group 3 and 4 Metals

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

Section: Mofs Based On Ti (Group 4 Metal)mentioning

confidence: 99%

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Metal–Organic Frameworks Based on Group 3 and 4 Metals

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“…The forming 2D layers stacked orderly along c ‐axis with numerous carboxylate groups facing the voids, giving channels of 6 Å. [ 63 ] Another three tricarboxylate ligands, H 3 TCA, H 3 BTB, and H 3 BTCA, were adopted to synthesize a series of isoreticular titanium‐based MOFs as ZSTU‐1, ZSTU‐2, and ZSTU‐3, respectively ( Figure ). [ 60 ] In the structure of ZSTU‐1, condensed Ti 6 (μ 3 ‐O) 6 (COO) 6 clusters are interlinked to each other via μ 2 ‐OH, constituting a 1D infinite TiO rod [Ti 6 (μ 3 ‐O) 6 (μ 3 ‐OH) 6 (COO) 6 ] n .…”

Section: The Structures Of Titanium‐based Mofsmentioning

confidence: 99%

Titanium‐Based MOF Materials: From Crystal Engineering to Photocatalysis

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Titanium (Ti)‐based metal–organic frameworks (MOFs) have attracted intensive attention due to the low toxicity, high earth's crust abundance, and unique photocatalytic properties of Ti elements. Great efforts have been devoted to the synthesis of novel architectures and their potential applications involving photocatalysis. However, Ti‐MOFs are still very scarce owing to their challenges in controlling the Ti chemistry in the reaction system. Until now, some significant results have been achieved, which may shed new insight into the future investigation of Ti‐MOFs. Herein, some representative researches in Ti‐MOFs are summarized and reviewed from the following four aspects: first, various synthetic strategies for preparing Ti‐MOFs are introduced; second, diverse structures containing multi‐connected ligands are presented in detail; third, the potential photocatalytic applications of Ti‐based MOFs involving H2 production, CO2 reduction, H2O2 production, N2 fixation, remediation of organic and inorganic pollutants, as well as organic transformation reaction and photocatalytic sensors are discussed; finally, perspectives on current challenges and emerging opportunities in this research field are discussed. Through summarizing this specific type of MOF, this review is expected to stimulate researchers’ interest for in‐depth investigation of novel structures synthesis, as well as new applications and concepts in these intriguing fields.

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“…Similarly, the adsorption step and capacity of MIP-206s in alcohol adsorption isotherms could be adjusted as well ( Figure S5), which is of interest for a wide range of applications including heat reallocation, separation and drug delivery 20; 21 . [22][23][24] . A mixture of the dominant compatible IPA linker with the minor, less compatible IPA-type compound functioned similarly with the major linker alone appearing in the MOF structure ( Figure 2D).…”

Section: Introductionmentioning

confidence: 99%

A Mesoporous Zirconium-Isophthalate Multifunctional Platform

et al. 2020

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Mesoporous materials suffer from limitations including poor crystallinity and hydrolytic stability, lack of chemical diversity, insufficient pore accessibility, complex synthesis and toxicity issues. Here the association of non-toxic Zr-oxo clusters and feedstock isophthalic acid (IPA) via a Homometallic-Multicluster-Dot strategy results in a robust crystalline mesoporous MOF, denoted as MIP-206, that overcomes the aforementioned limitations. MIP-206, built up from an unprecedented combination of Zr6 and Zr12 oxo-cluster inorganic building units into a single structure, exhibits accessible meso-channels of ca. 2.6 nm and displays excellent chemical stability under different hydrolytic and harsh conditions. Owing to the abundant variety of functionalized IPA linkers, the chemical environment of MIP-206 can be easily tuned without hampering pore accessibility due to its large pore windows. As a result, MIP-206 loaded with palladium nanoparticles acts as an efficient and durable catalyst for the dehydrogenation of formic acid under mild conditions, outperforming benchmark mesoporous materials. This paves the way towards the utilization of MIP-206 as a robust mesoporous platform for a wide range of potential applications. Mesoporous solids, a category of materials possessing structural voids of 2-50 nm in which large guest molecules can be accommodated, are of interest to sustainable development with potentially broad applications in fields related to energy, environment and health. Owing to their high availability and tunable pore size, traditional mesoporous materials, such as silica, metal oxides and activated carbons, are prevalent in current usage, particularly in heterogeneous catalysis 1 , energy conversion/storage 2 , analytical science 3 and medical areas 4 , although they suffer from well-recognized limitations such as lack of crystallinity, chemical diversity, structural uniformity, stability and/or reproducibility. These limitations have inhibited pursuits to improve their performance, extend their use to other applicable fields and accumulate fundamental understanding 5 of these materials. Considerable efforts have been devoted in the past two decades to develop substitutes, promote new strategies and develop alternative candidates 6. Among them, mesoporous metal-organic frameworks (MOFs) are a promising family of materials that exhibits an ordered porosity and successfully addresses some limitations of conventional benchmarks. MOFs can be composed of an almost unlimited selection of inorganic building blocks (metal ions or clusters) and organic linkers in periodic structures which are merged efficiently, exhibiting high crystallinity with atomic precision, good reproducibility of preparation over control, and, most importantly, remarkable structural and chemical tunability 7; 8. Two strategies for preparing mesoporous MOFs are well-documented. Extending the organic linker to construct mesoporous MOFs following the isoreticular chemistry strategy is the most straightforward route and illustrates well the...

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Toward a Rational Design of Titanium Metal-Organic Frameworks

Cited by 68 publications

References 48 publications

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Titanium‐Based MOF Materials: From Crystal Engineering to Photocatalysis

A Mesoporous Zirconium-Isophthalate Multifunctional Platform

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