This perspective illustrates the electromagnetic induction heating technology for a rational heat control in catalytic heterogeneous processes. It mainly focuses on the remarkable advantages of this approach in terms of process intensification, energy efficiency, reactor setup simplification, and safety issues coming from the use of radio frequency heated susceptors/catalysts in fixed-bed reactors under flow operational conditions. It is a real enabling technology that allows a catalytic process to go beyond reactor bounds, reducing inefficient energy transfer issues and heat dissipation phenomena while improving reactor hydrodynamics. Hence, it allows pushing catalytic processes to the limits of their kinetics. Undoubtedly, inductive heating represents a twist in performing catalysis. Indeed, it offers unique solutions to overcome heat transfer limitations (i.e. slow heating/cooling rates, nonuniform heating environments, low energy efficiency) to those endo- and exothermic catalytic transformations that make use of conventional heating methodologies.

We report on the N-decoration of multiwalled carbon nanotubes (MWCNTs) via chemical functionalization under mild reaction conditions. The introduction of tailored pyridinic functionalities as N-containing edge-type group mimics generates effective catalysts for the oxygen reduction reaction (ORR) in an alkaline environment. The adopted methodology lists a number of remarkable technical advantages, among which is an easy tuning of the electronic properties of N-containing groups. The latter aspect further increases the level of complexity for the rationalization of the role of the N-functionalities on the ultimate electrochemical performance of the as-prepared metal-free catalysts. Electrochemical outcomes crossed with the computed electronic charge density distributions on each scrutinized pyridine group have evidenced the central role played by the N-chemical environment on the final catalyst performance. Notably, small variations of the atomic charges on the N-proximal carbon atoms of the chemically grafted heterocycles change the overpotential values at which the oxygen reduction reaction starts. The protocol described hereafter offers an excellent basis for the development of more active metal-free electrocatalysts for the ORR. Finally, the asprepared catalytically active materials represent a unique model for the in-depth understanding of the underlying ORR mechanism.

A straightforward, energy- and atom-saving process to the production of tailored N-doped and catalytically active metal-free carbon nanostructures, has been set up. Our ex situ approach to the N-decoration of the carbon nanotube sidewalls contributes to elucidate the complex structure–reactivity relationship of N-doped carbon nanomaterials in oxygen reduction reactions, providing fundamental insights on the nature of the N-active sites as well as on the role of neighboring carbons.

This paper describes the exohedral N-decoration of multi-walled carbon nanotubes (MWCNTs) with NH-aziridine groups via [2+1] cycloaddition of a tert-butyl-oxycarbonyl nitrene followed by controlled thermal decomposition of the cyclization product. The chemical grafting with Ncontaining groups deeply modifies the properties of the starting MWCNTs, generating new surface microenvironments with specific base (Brønsted) and electronic properties. Both these features translate into a highly versatile single-phase heterogeneous catalyst (MW@N Az ) with remarkable chemical and electrochemical performance. Its surface base character promotes the Knoevenagel condensation with superior activity to that of related N-doped and N-decorated carbon nanomaterials of the state-of-the-art; the N-induced electronic surface redistribution drives the generation of high energy surface "C" sites suitable for O2 activation and its subsequent electrochemical reduction (ORR).

A challenging task of modern and sustainable catalysis is to rethink key processes at the heart of renewable energy technology in light of metal-free catalytic architectures designed and fabricated from cheap and easily accessible building blocks. This contribution describes the synthesis of highly N doped, carbon nanotube (CNT)-netting composites from cheap raw materials. With physical mixtures of CNTs and food-grade components as the starting materials, their thermal treatment generates foamy, N-doped carbon-based architectures. The mesoporous nature of the N-doped carbon phase grown around intertwined carbon nanotube networks and the easy control of the final material 3D shape make the protocol highly versatile for its full exploitation in the production of materials for catalysis. In addition to offering unique advantages with respect to the classical N-doped CNT powders, the 3D metal-free composites are highly versatile systems for a number of liquid-phase and gas-phase catalytic processes, under a wide operative temperature range. In this paper we demonstrate their excellent and to some extent unique catalytic performance in two fundamental and catalyst-demanding processes: (i) the electrochemical oxygen reduction reaction (ORR) and (ii) the direct, steam-free dehydrogenation of ethylbenzene (EB) to styrene (ST).

The amino-tagged bis(pyrazolate) MOF Zn(BPZNH2) is an excellent CO2 adsorbent and CO2 epoxidation catalyst under green conditions.

Ammonia–borane (NH3·BH3, AB), hydrazine (NH2NH2), lithium borohydride (Li­(BH4)), and sodium alanate (Na­(AlH4)) are popular chemical hydrogen storage inorganic solid materials featuring high gravimetric hydrogen contents (H wt %) and remarkable stability under ambient conditions. Ultrapure H2 is formed from these compounds either via pyrolysis (i.e., a simple material heating) or via hydrolysis (chemical reaction with water). In both cases, a series of homogeneous and heterogeneous catalysts have been designed to assist the process. Among the latter, metal–organic frameworks (MOFs, crystalline 3D porous lattices made of metallic nodes and organic polytopic linkers) have rapidly emerged as versatile candidates for this role. The nanoconfinement of lightweight hydrides in MOFs produces a “hydride@MOF” composite material. Hydride coordination to MOF exposed metal sites or its reaction with functional groups on the organic linkers facilitates the thermal decomposition, lowering the hydrogen release temperature and increasing the hydrogen production rate. For hydrolysis, MOFs are used as templates for the preparation of metal(0) nanoparticles (NPs) uniformly distributed in their inner cavities through a preliminary impregnation with a solution containing a metal salt followed by reduction. The “NPs@MOF” are the real active species that catalyze the reaction between the hydride and water, with concomitant H2 evolution. This perspective highlights the most representative literature examples of MOFs as heterogeneous catalysts (or catalyst supports) for H2 production from inorganic lightweight hydrides. Future trends in the field will also be discussed.

The interest for transition metal dichalcogenides (TMDs) as two-dimensional (2D) analogues of graphene is steadily growing along with the need of efficient and easy tunable protocols for their surface functionalization. This latter aspect holds a key role in the widespread application of TMDs in various technological fields and it represents the missing step to bridge the gap between the more popular C sp2-based networks and their inorganic counterparts. Although significant steps forward have already been made in the field of TMDs functionalization (particularly for MoS2), a rational approach to their surface engineering for the generation of 2D organic–inorganic hybrids capable to accommodate various molecules featured by orthogonal groups has not been reported yet. The paper paves the way toward a new frontier for “click” chemistry in material science. It describes the post-synthetic modification (PSM) of covalently decorated MoS2 nanosheets with phenylazido pendant arms and the successful application of CuAAC chemistry (copper-mediated azide–alkyne cycloaddition) towards the generation of highly homo- and hetero-decorated MoS2 platforms. This contribution goes beyond the proof of evidence of the chemical grafting of organic groups to the surface of exfoliated MoS2 flakes through covalent C–S bonds. It also demonstrates the versatility of the hybrid samples to undergo post-synthetic modifications thus imparting multimodality to these 2D materials. Several physico-chemical [SEM microscopy, fluorescence lifetime imaging (FLIM)], spectroscopic (IR, Raman, XPS, UV–vis), and analytical tools have been combined together for the hybrids’ characterization as well as for the estimation of their functionalization loading.