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Synthesis of Modified Fullerenes for Oxygen Reduction Reactions Journal of Materials Chemistry A View Article Online PAPER View Journal | View Issue Synthesis of modified fullerenes for oxygen reduction reactions† Cite this: J. Mater. Chem. A,2016,4, 14284 a a bc a Rosa Mar´ıa Giron,´ Juan Marco-Mart´ınez, Sebastiano Bellani, Alberto Insuasty, Hansel Comas Rojas,bd Gabriele Tullii,b Maria Rosa Antognazza,*b a ae Salvatore Filippone* and Nazario Mart´ın* The oxygen reduction reaction (ORR) is a key process common in several energy converting systems or electro-chemical technologies such as fuel cells, metal–air batteries, oxygen sensors, etc., which is based on the use of expensive and scarcely available platinum metal. In the search for carbon-based catalysts for ORRs, two different classes of new fullerene hybrids and metal-free fullerene derivatives endowed with suitable active sites have been prepared by highly selective metal- and organo-catalyzed synthetic methodologies. Along with their classical behavior as electron acceptors in polymer-based Received 1st August 2016 photo-electrochemical cells, the new fullerene derivatives are able to efficiently catalyze ORRs by using Accepted 15th August 2016 no metals or very low amounts of metals. Remarkably, the activity of metal-free fullerenes has proved to Creative Commons Attribution-NonCommercial 3.0 Unported Licence. DOI: 10.1039/c6ta06573b be as high as that observed for metallofullerenes bearing noble metals, and up to ten-fold higher than www.rsc.org/MaterialsA that of PCBM. 1 Introduction capability led to their extended use as suitable n-type mate- rials,10 widely employed in organic electronics and photovoltaic The oxygen reduction reaction (ORR) is a key process in devices,11 including the most recent perovskite solar cells.12 different energy converting systems or electrochemical tech- Thus, bulk heterojunction (BHJ) organic photovoltaic cells nologies (fuel cells, metal air batteries, oxygen sensors, etc.).1 In (OPVs) are a notable application, which consist of p-type This article is licensed under a these elds the replacement of the traditional platinum based conjugated polymers (e.g. poly(3-hexylthiophene-2,5-diyl), 2 catalysts with non-precious metals or metal-free electro- P3HT) and n-type fullerene derivatives, [6,6]phenyl-C61-butyric catalysts is currently a hot scientic challenge.3 Particularly, the acid methyl ester (PCBM) being the most widely used. In Open Access Article. Published on 15 August 2016. Downloaded 08/03/2017 10:05:27. use of carbon nanomaterials such as nitrogen-doped carbon a typical BHJ approach, a bi-continuous network is created, nanotubes4 or graphene,5 represents an interesting and novel which allows the promotion of exciton dissociation processes approach. and the achievement of a high power conversion efficiency. The In this context, among the different allotropic forms of next frontier in the use of acceptor/donor BHJs, based on PCBM, carbon, fullerenes combine unique chemical,6 optical,7 elec- is the realization of photo-electrochemical cells, able to work in tronic8 and photophysical9 properties with a dened molecular contact with aqueous and/or non-aqueous electrolytes upon structure. Indeed, their good electron accepting and transport visible light illumination. One notable example is the realiza- tion of efficient photocathodes for hydrogen production by photo-electrochemical water splitting.13,14 Recently, some of us aDepartamento de Qu´ımica Organica´ I, Facultad de Ciencias Qu´ımicas, Universidad have reported a high sensitivity, photo-electrochemical oxygen Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain. E-mail: sensor based on an organic BHJ formed using a low band gap [email protected]; [email protected] bCenter for Nano Science and Technology@PoliMi, Istituto Italiano di Tecnologia, Via polymer (APFO-3) and PCBM, revealing photo-activity towards 15 Pascoli 70/3, 20133 Milano, Italy. E-mail: [email protected] the ORR. In the proposed scheme, polymer excitation by cIstituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, Genova 16163, Italy visible light leads to the efficient generation of bounded dHigher Institute for Applied Sciences and Technologies (INSTEC), Salvador Allende y charged species (excitons), which are promptly dissociated into Luaces, 6163, La Habana, Cuba free charges (polarons) by a highly efficient electron transfer eIMDEA-Nanociencia, Campus de la Universidad Autonoma´ de Madrid, 28049 Madrid, process to the fullerene-based acceptor domain. We have Spain recently reported that this process, typical of solid-state † Electronic supplementary information (ESI) available: Experimental details of the preparation of the fullerene derivatives, polymer blend absorption spectra, photovoltaic cells, occurs in the hybrid system with fully ffi 16 spectroscopic and chromatographic data for the characterization of comparable dynamics and e ciency. Photogenerated holes compounds, linear scan voltammetry and Cyclic Voltammetry (CV) are collected at the underlying uorine-doped tin oxide (FTO) measurements. CCDC 960717. For ESI and crystallographic data in CIF or other electrode, while electrons are efficiently transferred at the electronic format see DOI: 10.1039/c6ta06573b 14284 | J. Mater. Chem. A,2016,4,14284–14290 This journal is © The Royal Society of Chemistry 2016 View Article Online Paper Journal of Materials Chemistry A a suitable functionality on the fullerene cage to become cata- lytically active towards the ORR. 2.1.1. Pyrrolino-metallo-fullerenes. With the aim of preparing stable metallo-fullerene hybrids, we rst directed our attention onto iridium(III) complexes due to their wide use in hydrogenation processes and for their ability to form stable and easily isolable complexes. Thus, the design of the iridium– fullerene complexes was based on the preparation of pyrrolino [60]fullerene ligands endowed with a carboxylic group to bind iridium(III) as well as other active metals efficiently. To this purpose, we carried out the 1,3-dipolar cycloaddition reaction of azlactone 1 with [60]fullerene by using a racemic silver BINAP catalyst, followed by the addition of the iridium dimer [Cp*IrCl2]2 (see Scheme 1). A unique compound, 2Ir, was ob- tained in “one-pot” and in good yield (ca. 40%) as a result of two Fig. 1 Schematic sketch of an organic-based photo-electrochemical sequential processes where two chiral centers are formed: in the device for the ORR, based on P3HT:fullerene BHJ thin films. The rst step, a pyrrolino[3,4:1,2][60]fullerene carboxylic acid is working mechanism and the energy level schemes are also formed with a stereogenic center in the C-5 of the pyrroline ring. represented. In the second process, iridium(III) is covalently linked diaster- eoselectively to the [60]fullerene derivative through the forma- tion of two new bonds, one with the nitrogen of the pyrroline interface with the aqueous solution, thus giving rise to photo- ring and the other one with the oxygen of the carboxylate group. electrochemical reactions and, in particular, to the ORR (Fig. 1). Creative Commons Attribution-NonCommercial 3.0 Unported Licence. The presence of the metal is con rmed by the IR spectrum of Here, we report the synthesis of new fullerene derivatives, the isolated solid, since the n(CO) of the starting pyrroline shis À À suitably functionalized with catalytically active sites towards the from 1700 cm 1 to 1660 cm 1 in the nal product, which is in ORR. This allows us to exploit a doubled fullerene functionality, agreement with the previously observed behaviour of fullerene- by employing them both as electron acceptors in P3HT-based iminocarboxylate as (N,O)-chelating monoanionic ligands.22 It BHJ, and as redox active sites, thus avoiding the use of expen- is worth noting that, despite iridium(III), with its typical pseudo- sive noble metals. tetrahedral geometry, being able to adopt two possible cong- Two main approaches have been undertaken in parallel: (i) urations and, therefore, afford a diastereomeric mixture, the the synthesis of new fullerene hybrid derivatives endowed with overall process occurs diastereoselectively, in sharp contrast to This article is licensed under a noble metals active in redox processes, such as Ir, Rh or Pt; (ii) other related examples.23 the synthesis of metal-free fullerene catalysts, based on the Indeed, this behaviour was observed by 1H-NMR (see the – presence of active C60 H bonds. To this aim, both metal- and ESI†) and its structure could be conrmed by X-ray diffraction organo-catalytic methodologies have been employed, to obtain Open Access Article. Published on 15 August 2016. Downloaded 08/03/2017 10:05:27. analysis of a monocrystal obtained by slow evaporation of 2Ir in fullerene derivatives with tailored electronic and photocatalytic 24 CS2/hexane. properties characterized by high regio- and stereo-selectivity. As is shown in Fig. 2, the iridium atom adopts a pseudo- Photoelectrochemical devices for the ORR based on BHJ octahedral geometry where the Cp* group occupies a face of the P3HT:fullerene thin lms have been nally realized, con rming octahedron, 1.775 A˚ being the distance between the metal and an enhanced photocatalytic property of the novel compounds, the ring centroid. Two other octahedral positions involve the when compared with the extensively used PCBM, taken as the chelate pyrrolinofullerene carboxylate featuring Ir–N and Ir–O reference fullerene. bonds of 2.103(4) A˚ and 2.095(4) A˚ length, respectively. Finally, the determined Ir–Cl bond distance resulted to be 2.393(2) A,˚ 2 Results and discussion 2.1. Synthesis of metallo- and organo-fullerenes catalysts Over the last few years, fullerene chemistry has been widening its synthetic tools, in the search for more sophisticated struc- tures,17 for a better control on the stereochemistry of the fullerene derivatives18 and for a control on the regio- and site- selectivity when higher fullerenes19 or endohedral fullerenes20 are used. Following this trend, on one hand, we have directed our attention to the achievement of new selective catalytic methodologies aimed at the preparation of both metallo- fullerenes and regiopure fullerene hydrides.
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