Fundamentals and applications of photo-thermal catalysis.

Correction for 'Fundamentals and applications of photo-thermal catalysis' by Diego Mateo et al., Chem. Soc. Rev., 2021, 50, 2173-2210, DOI: 10.1039/D0CS00357C.

Fundamentals and applications of photo-thermal catalysis.

Photo-thermal catalysis has recently emerged as an alternative route to drive chemical reactions using light as an energy source. Through the synergistic combination of photo- and thermo-chemical contributions of sunlight, photo-thermal catalysis has the potential to enhance reaction rates and to change selectivity patterns, even under moderate operation conditions. This review provides the fundamentals of localized surface plasmon resonance (LSPR) that explain the photo-thermal effect in plasmonic structures, describes the different mechanistic pathways underlying photo-thermal catalysis, suggests methodologies to disentangle the reaction mechanisms and proposes material design strategies to improve photo-thermal performance. Ultimately, the goal is to pave the way for the wide implementation of this promising technology in the production of synthetic fuels and chemicals.

Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids.

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

Methanol Sensing by a Luminescent Zinc(II)-Based Metal-Organic Framework.

A luminescent zinc-based metal-organic framework (MOF; 1) was synthesized from a highly conjugated tridentate ligand, 1,3,5-tris[(1E)-2'-(4''-benzoic acid)vinyl]benzene. X-ray single crystal analysis reveals the organization of 1 in a three-dimensional porous framework. Thermogravimetric analysis shows that 1 has a good thermal stability, and resists decomposition up to 420 °C. The removal of the solvent molecules from the cavities leads to a temporary loss of crystallinity, which can be regained by heating the MOF in diethylformamide, the solvent used for the synthesis, as shown by powder X-ray diffraction. In addition, 1 shows luminescent features influenced by the chemical environment, making it suitable as optical sensor. Detection of methanol with a turn-on effect was possible in low concentration in mixtures with water (50 µL/3 mL and 10 µL/3 mL) and as vapor.

The Goldilocks principle in action: synthesis and structural characterization of a novel {Cu4(µ3-OH)4} cubane stabilized by monodentate ligands.

A {Cu4(µ3-OH)4} compound, where four copper(II) and four µ3-bridging oxygen atoms occupy alternate corners of a slightly distorted cube, has been prepared and structurally characterized. This species, formulated as [Cu4(µ3-OH)4(Htmpz)8](ClO4)4·1.5Et2O (Htmpz = 3,4,5-1H-trimethyl pyrazole), can be classified as belonging to type I Cu4O4 cubane complexes, and is better described as two Cu(II)-(µ-OH)2-Cu(II) units held together by four long Cu-O bonds. The central distorted cubane core is stabilized by neutral monodentate ligands (Htmpz) and perchlorate anions, as demonstrated by single-crystal X-ray structure analysis. The title compound was obtained by hydrolysis of a dinuclear methoxo-bridged species, [Cu(µ-OCH3)(Htmpz)2]2(ClO4)2, which was prepared by reaction of [Cu(Htmpz)4(ClO4)2] with methanol. All these reactions represent a nice example of the Goldilocks principle in action in coordination chemistry, since each single actor (solvent, counteranion, and ligand) has the "just right" electronic, steric or coordinative properties which determine the fate of the final products.