Amino-Polyalcohol-Solvothermal Synthesis of Titanium-Oxo Clusters: From Ti<sub>6</sub> to Ti<sub>19</sub> with Structural Diversity

Liu, Xiaoxue; Chen, Shumei; Fang, Wei‐Hui; Zhang, Lei; Zhang, Jian

doi:10.1021/acs.inorgchem.9b00293

Cited by 16 publications

(11 citation statements)

References 40 publications

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“…On the other side, alkanolamines can be directly applied as reaction media, which will enhance their hydrolysis delayed effect like the above-discussed phenol and pyrazole. Under this new synthetic method, a series of TOCs were prepared, including strawberry-like Ti 11 (μ 3 -O) 10 (μ 4 -O)(O i Pr) 14 (dea) 4 (Ti 11 , deaH 2 = diethanolamine) and unprecedented wheel-like Ti 19 (μ 2 -O) 6 (μ 3 -O) 12 (dea) 18 (NO 3 ) 4 ·(H 2 O) 6 . This work not only extends the application of amino-polyalcohol ligands in the synthesis of TOCs but also provides meaningful perspective for understanding the intrinsic coordination features of amino-polyalcohol toward titanium oxide materials during photocatalytic reactions.…”

Section: Mixed O/n-donor Hydrolysis Delayed Ligands For Toc Synthesismentioning

confidence: 89%

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Zhang

Fan

et al. 2022

Acc. Chem. Res.

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Conspectus Atomically precise titanium-oxo clusters (TOCs) are the structure and reactivity model compounds of technically important TiO2 materials, which could help build structure–property relationships and achieve property modulation at the molecular level. However, the traditional formation of TOCs has relied on the poorly controllable hydrolysis of titanium alkoxide in the solvent for a long time, limiting the development of TOC structural chemistry to a great extent. In addition, easily hydrolyzable alkoxy groups would be still coordinated on the surface of the TOCs generated by this method, making the clusters sensitive and unstable to the moisture. To achieve controllable preparation of TOCs, we believe it is crucial to attenuate the hydrolysis of titanium ions in the formation process of a cluster. To this end, we have recently applied an effective coordination-delayed-hydrolysis (CDH) strategy for TOC synthesis, which provides powerful tools for tuning their structures. In this Account, at the beginning, a brief introduction to the coordination-delayed-hydrolysis strategy is supplied, and its predominant features for constructing novel TOCs are highlighted. In subsequent sections, we discuss how the applied chelating organic/inorganic ligands (named hydrolysis delayed ligands) influence the hydrolysis process of Ti4+ ions to form a large family of TOCs with various nuclearities and core structures. Various hydrolysis delayed ligands have been explored, ranging from common O-donor ligands (carboxylate, phenol, or sulfate) to rarely used N-donor ligands (pyrazole) or bifunctional O/N-donor ones (quinoline, oxime, or alkanolamine). Breakthroughs in the symmetry, configuration, and cluster nuclei of TOCs have been accordingly achieved. Then, we show that this CDH method can be used to tune the surface structure of TOCs by modifying functional organic ligands. As a result, the physicochemical properties of TOCs, especially optical band gaps, can be optimized, and their stability under ambient conditions is significantly improved. In addition, we illustrate that the reversible bonds between hydrolysis delayed ligands and Ti ions further allows us to introduce active heterometal ions or clusters upon or inside the Ti–O cores to prepare heterometallic TOCs with unprecedented structures and properties. In particular, noble metal (Ag ions or clusters) has been incorporated into Ti–O clusters for the first time. As a summary, the coordination-delayed-hydrolysis strategy has realized the controllable hydrolysis of Ti4+ ions to some extent, breaking through the limitations of traditional synthesis methods and producing fruitful results in the field of titanium-oxo clusters. It is believed that this CDH method would also be effective for synthesizing oxo clusters of other easily hydrolyzed metal ions (Al3+, Sn4+, In3+, etc.) to afford significant contribution for the cluster community.

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Section: Mixed O/n-donor Hydrolysis Delayed Ligands For Toc Synthesismentioning

confidence: 89%

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Zhang

Fan

et al. 2022

Acc. Chem. Res.

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“…An artificial photosynthesis utilizing cost-efficient photocatalysts is one of the most-suited solutions to address these problems. − Titanium-oxo clusters (TOCs) are well-defined molecular units of nano-TiO 2 materials, and they are some of the most promising photocatalysts, due to both their well-defined structure and excellent photocatalytic performances. − However, the synthesis of structurally defined and highly stable TOCs remains a considerable challenge owing to the fact that this type of cluster is readily hydrolyzed . Recently, a number of TOCs have been isolated by introducing carboxylate and phosphonate ligands to protect the cluster core. − Nevertheless, some TOCs are not sufficiently stable because of the imperfect passivation of the TiO core surface. Additionally, the absorption of some relatively stable TOCs is limited to the ultraviolet region, leading to low solar energy utilization across the entire solar spectrum .…”

Section: Introductionmentioning

confidence: 99%

Calixarene-Protected Titanium-Oxo Clusters and Their Photocurrent Responses and Photocatalytic Performances

Wang

Kong

2021

Inorg. Chem.

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Three photosensitive tert-butylcalix[n]arene (TBC-[n], n = 4, 6, 8)-protected titanium-oxo clusters (TOCs), formulated as [Ti 4), were successfully synthesized and characterized. Because of the generation of charge transfer from TBC[n] to the TiO core, the three TBC[n]-decorated TOCs show a broadened visible-light absorption and narrowed optical band gap based on the UV−visible spectra and density functional theory calculations. The corresponding photosensitive electrodes prepared using these three TOCs exhibit stable photocurrent responses. Furthermore, their photocatalytic performances for hydrogen evolution and methylene blue degradation were evaluated, and all of the materials display excellent photocatalytic activity and stability. The calixarene-Ti coordination is therefore an effective strategy to enlarge the visible-light absorption band of Ti−O materials and improve their photoelectric/photocatalytic performances.

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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%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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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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Amino-Polyalcohol-Solvothermal Synthesis of Titanium-Oxo Clusters: From Ti₆ to Ti₁₉ with Structural Diversity

Cited by 16 publications

References 40 publications

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Calixarene-Protected Titanium-Oxo Clusters and Their Photocurrent Responses and Photocatalytic Performances

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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Amino-Polyalcohol-Solvothermal Synthesis of Titanium-Oxo Clusters: From Ti6 to Ti19 with Structural Diversity

Cited by 16 publications

References 40 publications

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Calixarene-Protected Titanium-Oxo Clusters and Their Photocurrent Responses and Photocatalytic Performances

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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Product

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Amino-Polyalcohol-Solvothermal Synthesis of Titanium-Oxo Clusters: From Ti₆ to Ti₁₉ with Structural Diversity