RESUMEN
Palladium nanostructures are interesting heterogeneous catalysts because of their high catalytic activity in a vast range of highly relevant reactions such as cross couplings, dehalogenations, and nitro-to-amine reductions. In the latter case, the catalyst Pd@GW (palladium on glass wool) shows exceptional performance and durability in reducing nitrobenzene to aniline under ambient conditions in aqueous solutions. To enhance our understanding, we use a combination of optical and electron microscopy, in-flow single molecule fluorescence, and bench chemistry combined with a fluorogenic system to develop an intimate understanding of Pd@GW in nitro-to-amine reductions. We fully characterize our catalyst in situ using advanced microscopy techniques, providing deep insights into its catalytic performance. We also explore Pd cluster migration on the surface of the support under flow conditions, providing insights into the mechanism of catalysis. We show that even under flow, Pd migration from anchoring sites seems to be minimal over 4â¯h, with the catalyst stability assisted by APTES anchoring.
RESUMEN
This contribution addresses a frequent problem in flow photochemistry, where methodologies to determine the quantum efficiency of photoreactions are totally lacking. In spite of numerous studies being available in the literature, product reaction yields are never accompanied by measurements to determine their quantum yields. Basically, the key reagent in the reaction, light, is not measured under the experimental conditions of exposure. We report here a flow actinometer based on the photochemistry of valerophenone that can be readily implemented in the organic laboratory for irradiations in the UV region. For example for UVB lamps used in our work, the irradiance was measured as 1.1 × 10-4 einstein l-1 s-1. Our photoreactor design involves wrapping low-pressure lamps with Teflon tubbing, where the photochemistry takes place. Similar strategies could be implemented with other geometries or with lamps (e.g. LED) and actinometers with sensitivity in other spectral regions.
RESUMEN
Silver nanoparticles have become one of the most commercially and industrially relevant nanomaterials of the 21st century, owing to their potent antibacterial properties, as well as their useful catalytic and optical properties. Although many methods have been explored to produce AgNPs, we favor the photochemical approach using photoinitiators to produce AgNPs, owing to the high degree of control over reaction conditions, and the generation of so-called AgNP 'seeds' that can be used as-is, or as precursors for other silver nanostructures. In this work, we explore the scale-up of AgNP synthesis using flow chemistry and assess the usefulness of a range of industrial Norrish Type 1 photoinitiators in terms of flow compatibility and reaction time, as well as the resulting plasmonic absorption and morphologies. We establish that while all the photoinitiators used were able to generate AgNPs in a mixed aqueous/alcohol system, photoinitiators that generate ketyl radicals showed the greatest promise in terms of reaction times, while also showing greater flow compatibility compared to photoinitiators that generate ð¼-aminoalkyl and α-hydroxybenzyl radicals. These findings help to establish a guideline for adapting photochemical AgNP syntheses to flow systems, helping to improve the scalability of the method in one of the largest industries in nanomaterial chemistry.
Asunto(s)
Nanopartículas del Metal , Nanoestructuras , Plata/química , Nanopartículas del Metal/química , Antibacterianos/químicaRESUMEN
Selective semi-oxidation of tetrahydroisoquinoline (THIQ) leads to a valuable dihydroisoquinoline (DHIQ) derivative via singlet oxygen photooxidation process. Typical photosensitisers (i.e., Ru complexes) can activate the reaction even under heterogeneous conditions that facilitate catalyst separation and reusability. In contrast to DHIQ, THIQ acts as an efficient singlet oxygen quencher driving the reaction selectivity. The reaction can also be facilitated by semiconductor catalysts such as MoCo@GW, a glass wool-based catalyst that is easy to separate and reuse and compatible with flow photochemistry. Its role is to mediate the formation of isoquinoline (IQ) and thus an in situ-generated singlet oxygen catalyst. Laser flash photolysis with NIR detection provides proof of the singlet oxygen mechanism proposed and rate constants for the key steps that mediate the oxidation.
Asunto(s)
Oxígeno Singlete , Tetrahidroisoquinolinas , Cinética , Oxidación-Reducción , Oxígeno , Fotoquímica , Oxígeno Singlete/químicaRESUMEN
A catalyst based on Pd on glass wool (Pd@GW) shows exceptional performance and durability for the reduction of nitrobenzene to aniline at room temperature and ambient pressure in aqueous solutions. The reaction is performed in a flow system and completed with 100% conversion under a variety of flow rates, 2 to 100 mLmin-1 (normal laboratory fast flow conditions). Sodium borohydride or dihydrogen perform well as reducing agents. Scale-up of the reaction to flows of 100 mLmin-1 also shows high conversions and robust catalytic performance. Catalyst deactivation can be readily corrected by flowing a NaBH4 solution. The catalytic system proves to be generally efficient, performing well with a range of nitroaromatic compounds. The shelf life of the catalyst is excellent and its reusability after 6-8 months of storage showed the same performance as for the fresh catalyst.