Enzyme-mimicking single atoms enable selectivity control in visible-light-driven oxidation/ammoxidation to afford bio-based nitriles

Abstract

Nitriles are versatile nitrogen-containing scaffolds that exist widely in medicines, dyes and functional materials, and are typically synthesized over homogeneous catalysts under relatively harsh conditions. Herein, through mimicking the key...

Thermo-/photo-catalysts for aerobic oxidative cyanation of diverse oxygen-containing feedstocks

“…The Fe/CNS catalyst demonstrated good photocatalytic performance in the oxidative cyanation of a broad range of alcohols into nitriles using NH 2 OH·HCl as the nitrogen source. 51 Under light illumination, the isolated Fe–N 4 sites captured photogenerated electrons (e − ) and O 2 to generate superoxide radicals (˙O 2 − ) while the surrounding S atoms served to confine photogenerated holes (h + ). These active species (˙O 2 − and h + ) played a pivotal role in the formation of nitriles.…”

“…However, in the case of using the more readily available NH 3 as the nitrogen source, many photocatalytic systems necessitate additives such as inorganic bases or halides. 51,52 A recent study by Li et al presented a compelling O-vacancy-rich BiOBr photocatalyst for the ammoxidation of benzyl alcohol to benzonitrile without the use of any additives. The universality of this photocatalyst in facilitating the conversion of diverse feedstocks remains to be substantiated.…”

Regulating the Flexibility to Assemble Porous Single-Atom Fe-Coordinated Metallopolymers for Efficient Heterogeneous Catalytic Oxidations

“…22 On the other hand, the utilization of dynamic covalent bonding, such as imine bonds, 5 not only enhances crystallinity but also enables the design of dentate, tridentate, and tetradentate coordination structures to form single-atom metallopolymers. 23,24 The classic pincer structure, a frequently employed tridentate coordination mode, 25 exhibits strong chelating ability while maintaining a semiopen structure that promotes interactions between the active sites and reactants. Consequently, the generated pincer ligands chelating with single-metal atoms have demonstrated outstanding performance in homogeneous catalysis.…”

“…Moreover, the amphiphilic metallopolymers hybridized with the CdS quantum dots by self-assembly endow them with synergistically boosting photoreduction of CO 2 . On the other hand, the utilization of dynamic covalent bonding, such as imine bonds, not only enhances crystallinity but also enables the design of dentate, tridentate, and tetradentate coordination structures to form single-atom metallopolymers. , The classic pincer structure, a frequently employed tridentate coordination mode, exhibits strong chelating ability while maintaining a semiopen structure that promotes interactions between the active sites and reactants. Consequently, the generated pincer ligands chelating with single-metal atoms have demonstrated outstanding performance in homogeneous catalysis. − Developing the pincer catalytic sites into heterogeneous metallopolymeric catalysts is highly intriguing, but the challenges faced are the low catalytic efficiency due to the inaccessible embedded catalytic sites.…”

Thin silica shell on Ag3PO4 nanoparticles augments stability and photocatalytic reusability

“…15–17 Among them, a Ag 3 PO 4 photocatalyst attracts the attention of the scientific community with its capability to produce highly efficient holes for the oxidation of water or organic contaminants under visible light. 18–20 Thus far, the Ag 3 PO 4 photocatalyst has emerged as a versatile material for the ease of synthesis, usability and its high ability of water oxidation. Besides, capabilities, such as recyclability, photostability, and the ability to degrade all kinds of organic contaminants, are essential for an ideal photocatalyst.…”