Large Titanium-Oxo Clusters as Precursors to Synthesize the Single Crystals of Ti-MOFs

Abstract

Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years because of their numerous photocatalytic applications; however, the synthesis of new Ti-MOFs with precise crystal structures is still challenging. Herein, three new Ti-MOFs with single-crystal structures (denoted as FIR-125−FIR-127) are rationally synthesized by employing a large Ti 44 -oxo cluster as the precursor to assembly with the organic ligand. Big single-crystals can be successfully obtained and structurally determined by single-crystal X-ray diffraction. During the synthesis, the large Ti 44 -oxo cluster is transferred to small Ti 8 O 8 (CO 2 ) 16 building units in the Ti-MOF. In addition, FIR-125 exhibit high stability, permanent porosity, and photocatalytic activity. This work provides a new strategy toward the big crystal growth of Ti-MOFs through the slow transformation of large titanium-oxo clusters.

Hydrolytically Stable and Trifunctional Zirconium-Based Organic Frameworks toward Cr2O72– Detection, Capture, and Photoreduction

“…Metal–organic frameworks (MOFs) have evolved as a rising category of porous materials and exhibited promising prospects in many fields, including fluorescence sensing, physical adsorption, and photochemical removal of toxic contaminants. − Regrettably, for most MOF platforms, some deficiencies, for example, poor hydrolytic stability, low fluorescence sensitivity and selectivity, and unsatisfactory trapping and photocatalytic efficiency, still remain as barriers to be overcome for practical applications. It is extremely urgent to modulate their properties for achieving more practical applications, that is, stable metal nodes and photosensitive antennas combined with free functional groups (anchoring sites) to achieve desirable properties.…”

A Novel Cerium(IV)‐Based Metal‐Organic Framework for CO2 Chemical Fixation and Photocatalytic Overall Water Splitting

“…Over the last few decades, MOFs constructed by the coordination connection of organic ligands to the metal ions or clusters in a periodic manner have emerged as multifunctional porous materials for diverse applications on the basis of their tunable pore sizes, high specific surface areas and diverse chemical functionalities. [1][2][3][4][5][6] In recent years, tetravalent cerium [Ce IV ]based MOFs have attracted much growing research attentions due to their unique and attractive properties: (i) Lewis acidity similar to the widely studied Zr IV /Hf IV based MOFs; (ii) redox activity derived from the inherent switching tendency between the Ce 4 + /Ce 3 + redox couple; (iii) photocatalytic characteristics gifted by the ligand-to-metal charge transfer (LMCT) profiting from the low-lying empty 4f orbitals of Ce 4 + . [7,8] However, the syntheses and applications of Ce IV -MOFs are still in its infancy and challenging to be developed.…”

Installation of high-valence tungsten in MIL-125(Ti) for boosted photocatalytic hydrogen evolution

“…Metalorganic frameworks (MOFs) featuring porous structure and tunable framework, which are liable to modify precisely and explore the catalytic mechanism, have played an increasingly important role in the field of catalysis [21][22][23][24][25][26]. In recent years, increasing number of attempts have been made to apply MOFsbased materials in the photocatalytic hydrogen production [27][28][29][30][31].…”