A Tunable Multivariate Metal–Organic Framework as a Platform for Designing Photocatalysts

Abstract

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO2. Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB2OX3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100­(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 molH2 gcat. –1 min–1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10–5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

Recent advances in bimetallic metal–organic frameworks (BMOFs): synthesis, applications and challenges

“…It is worth mentioning that the M/Fe-MOF material also has a low band gap of 2.3–2.42 eV, which is conducive to sunlight absorption and can further improve the photocatalytic activity. Wang and co-workers 87 reported a series of new multi-metal–organic frameworks named MTV-MIL-100. This team studied the catalytic activity and reaction kinetics of MTV-MIL-100 (Ti, Co) at different temperatures (Fig.…”

Rationalising the multivariate modulation of MUV-10 for the defect-introduction of multiple functionalised modulators

“…Introducing multiple functional units into the same framework is known to enhance applicability in different areas such as catalysis, photocatalysis and gas uptake, among others. 3,6,8,37 Thus, as a proof-of-concept we have studied the potential of these multi-functionalised MOFs for the straightforward synthesis of b-amino alcohols through regioselective ringopening of oxiranes (epoxides) with amines, shown in Fig. 5, at room temperature in EtOH (see S.5 in the ESI † for detailed conditions).…”

Controlled Sequential Assembly of Metal–Organic Polyhedra into Colloidal Gels with High Chemical Complexity

“…[1][2][3] Such complex systems have attracted great interest, particularly for crystalline and ordered porous solids such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), in which more than two functional moieties (e.g., ligands with different functional groups or various metal clusters) can be integrated within the same structure. [4][5][6] The chemical complexity, together with the decorated pore surface of these multivariate porous frameworks, showed significant benefits in developing functional materials for catalysis, [7][8][9][10] sensing [11] and separation applications. [12,13] Yet, the lack of controllable arrangement of mixed compositions in the structure makes it difficult to position the specific molecular components in the framework scaffold.…”