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Fermi level in vii) are shown in purple in ii)-vi) with an iso-value of ±0.003 a.u. Reprinted with permission from ref 57 . Copyright 2014 from the Royal Society of Chemistry; b) Molecular model of a corannulene-like element functionalized with three carboxylic groups from two different perspectives in the cpk representation (on the left). The final structure (190 elements in a cubic cell of 60 Å in size) obtained from random packing of the individual elements (on the right). Cyan: carbon, red: oxygen, white: hydrogen. Reprinted with permission from ref 59 Copyright 2017 from Elsevier; c) Side-views of Ru13 adsorbed on Gr-DV-2COOH site before (on left panel) and after a proton jump (right panel). C atoms are in black, O in red, H in with white and Ru in mocha. Reprinted with permission from ref 60 Copyright 2014 from Elsevier; and d) Spin-density projection in µB/a.u. 2 on the graphene plane around i) the hydrogen chemisorption defect (∆) and ii) the vacancy defect in the a sublattice. Carbon atoms corresponding to the a sublattice (o) and to the b sublattice (•) are distinguished. Simulated STM images of the defects are shown in iii) and iv), respectively. Reprinted with permission from ref 61 .

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Catalysis is currently recognized as a potential field of application for carbon nanotubes, and throughout the past decade the number of publications and patents on this subject has been increasing exponentially. In most of these cases, the use of these nanomaterials as support structures facilitates better performances than conventional supports. To date, most of the research has focused on supported metal catalysts, in which the active phase is located on the external surface of the carbon nanotubes. The selective deposition of metallic nanoparticles in the inner cavity of nanotubes, which could allow the exploitation of advantageous confinement effects, has received much less attention. In this Minireview, the different strategies for the preparation of such nanocatalysts, as well as the benefits that could be expected from the resultant confinement effects are presented, with the aim of highlighting their potential use in catalysis.

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