The favorable exploitation of carbon nitride (CN) materials in photocatalysis for organic synthesis requires the appropriate fine-tuning of the CN structure. Here, we present a deep investigation of the structure/activity relationship of CN in the photocatalytic perfluoroalkylation of organic compounds. Four types of CN bearing subtle structural differences were studied via conventional characterization techniques and innovative nuclear magnetic resonance (NMR) experiments, correlating the different structures with the fundamental mechanistic nexus and especially highlighting the importance of the halogen bond strength between the reagent and the catalyst surface. The optimum catalyst exhibited an excellent performance, with a very wide reaction scope, and could prominently trigger the model reaction using natural sunlight. The work lays a platform for establishing a new approach in the development of heterogeneous photocatalysts for organic synthesis related to medical, agricultural, and material chemistry.

ZSM-5 zeolite nanoboxes with accessible mesomicro-pore architecture and strong acid sites are important in relevant heterogeneous catalysis suffering from mass transfer limitations and weak acidities.R ational design of parent zeolites with concentrated and non-protective coordination of Al species can facilitate post-synthetic treatment to produce mesoporous ZSM-5 nanoboxes.I nt his work, as imple and effective method was developed to convert parent MFI zeolites with tetrahedral extra-framework Al into Al-enriched mesoporous ZSM-5 nanoboxes with low silicon-to-aluminium ratios of % 16. The parent MFI zeolite was prepared by rapid ageing of the zeolite sol gel synthesis mixture.The accessibility to the meso-micro-porous intra-crystalline network was probed systematically by comparative pulsed field gradient nuclear magnetic resonance diffusion measurements,w hich, together with the strong acidity of nanoboxes,provided superb catalytic activity and longevity in hydrocarbon cracking for propylene production.

Immobilisation of organocatalysts onto solid supports represents a very promising solution to tackle their low productivity by enabling their reuse. Herein, the use of NMR relaxation measurements, coupled with reaction...

The aim of this work is to develop and quantify the tuning of transport properties in porous catalytic materials by tailoring their textural properties.

ZSM-5 zeolite nanoboxes with accessible mesomicro-pore architecture and strong acid sites are important in relevant heterogeneous catalysis suffering from mass transfer limitations and weak acidities.R ational design of parent zeolites with concentrated and non-protective coordination of Al species can facilitate post-synthetic treatment to produce mesoporous ZSM-5 nanoboxes.I nt his work, as imple and effective method was developed to convert parent MFI zeolites with tetrahedral extra-framework Al into Al-enriched mesoporous ZSM-5 nanoboxes with low silicon-to-aluminium ratios of % 16. The parent MFI zeolite was prepared by rapid ageing of the zeolite sol gel synthesis mixture.The accessibility to the meso-micro-porous intra-crystalline network was probed systematically by comparative pulsed field gradient nuclear magnetic resonance diffusion measurements,w hich, together with the strong acidity of nanoboxes,provided superb catalytic activity and longevity in hydrocarbon cracking for propylene production.

The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN‐based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications. Here, the CN structure is engineered by means of a microwave treatment, and the structure of the material is shaped around its suitable functionality for Ni dual photocatalysis, with a resulting boosting of the reaction efficiency toward many CX (X = N, S, O) couplings. The combination of advanced characterization techniques and first‐principle simulations reveals that this enhanced reactivity is due to the formation of carbon vacancies that evolve into triazole and imine N species able to suitably bind Ni complexes and harness highly efficient dual catalysis. The cost‐effective microwave treatment proposed here appears as a versatile and sustainable approach to the design of CN‐based photocatalysts for a wide range of industrially relevant organic synthetic reactions.

Solvent effects in homogeneous catalysis are known to affect catalytic activity. Whilst these effects are often described using qualitative features, such as Kamlet‐Taft parameters, experimental tools able to quantify and reveal in more depth such effects have remained unexplored. In this work, PFG NMR diffusion and T1 relaxation measurements have been carried out to probe solvent effects in the homogeneous catalytic reduction of propionaldehyde to 1‐propanol in the presence of aluminium isopropoxide catalyst. Using data on diffusion coefficients it was possible to estimate trends in aggregation of different solvents. The results show that solvents with a high hydrogen‐bond accepting ability, such as ethers, tend to form larger aggregates, which slow down the molecular dynamics of aldehyde molecules, as also suggested by T1 measurements, and preventing their access to the catalytic sites, which results in the observed decrease of catalytic activity. Conversely, weakly interacting solvents, such as alkanes, do not lead to the formation of such aggregates, hence allowing easy access of the aldehyde molecules to the catalytic sites, resulting in higher catalytic activity. The work reported here is a clear example on how combining traditional catalyst screening in homogeneous catalysis with NMR diffusion and relaxation time measurements can lead to new physico‐chemical insights into such systems by providing data able to quantify aggregation phenomena and molecular dynamics.

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