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Graphene oxide has been prepared from an industrial coke-like waste. The morphology of this material (GO-CW) is similar to that of standard graphene oxide (GO-G), although its surface has more defects. Both materials were used to prepare hybrid NHC-Ir(I)/graphene materials, consisting of molecular Ir(NHC) complexes covalently anchored to the graphene surface through the NHC moiety, following two different synthetic routes: (a) direct graphene electrografting of the previously synthesized aniline-functionalized imidazole-2-ylidene-Ir(I) complex, and (b) a two-step sequence comprising initial electrografting of aniline-imidazolium salts and subsequent chemical reaction with Ir(I) precursor anchoring imidazole-2-ylidene-Ir(I) molecular complexes. The synthesized NHC-Ir/graphene hybrid catalysts are active in the oxygen evolution reaction (OER) resulting in current densities in a similar range to those of other NHC-iridium(I) catalysts supported on GO. The highest activity corresponds to hybrid catalysts prepared by the two-step route, with even higher activity and stability when graphene oxide from industrial waste is used. EXAFS spectra of the materials prepared from both synthesis routes before oxidation catalysis reveal the local Ir coordination shell and a structural interaction between Ir and graphene. Both XANES and EXAFS spectra after electrocatalysis point to more oxidized species in which the molecular nature of the iridium catalysts is preserved.

Iridium(I) compounds featuring bridge-functionalized bis-NHC ligands (NHC = N-heterocyclic carbene), [Ir(cod)(bis-NHC)] and [Ir(CO)2(bis-NHC)], have been prepared from the appropriate carboxylate- or hydroxy-functionalized bis-imidazolium salts. The related complexes [Ir(cod)(NHC)2]+ and [IrCl(cod)(NHC)(cod)] have been synthesized from a 3-hydroxypropyl functionalized imidazolium salt. These complexes have been shown to be robust catalysts in the oxidative dehydrogenation of glycerol to lactate (LA) with dihydrogen release. High activity and selectivity to LA were achieved in an open system under low catalyst loadings using KOH as a base. The hydroxy-functionalized bis-NHC catalysts are much more active than both the carboxylate-functionalized ones and the unbridged bis-NHC iridium(I) catalyst with hydroxyalkyl-functionalized NHC ligands. In general, carbonyl complexes are more active than the related 1,5-cyclooctadiene ones. The catalyst [Ir(CO)2{(MeImCH2)2CHOH}]Br exhibits the highest productivity affording TONs to LA up to 15,000 at very low catalyst loadings.

The magnetron sputtering technique has been successfully employed for the preparation of porous TiO2 thin films on soda-lime glasses by means of an oblique angle deposition strategy. The morphology of the thin layers is affected by the deposition parameters, such as, the angle with respect to the target, applied power, total pressure, oxygen pressure and deposition time. It has been shown that 60–65° angles, lead to a compromise between the porosity, the level of oxidation and the thickness of the film. High total pressures of the deposition process result in less dense coatings of greater porosity. Moreover, the oxygen flow during the deposition process must be carefully adjusted for each set of deposition conditions, in order to achieve an optimum degree of oxidation. The evaluation of coated-glasses in the in-flow photocatalytic oxidation of nitrogen oxide has shown that the presence of a porous film is essential to achieve photocatalytic activity. The best performing coated-glass was able to reduce the NO concentration ca. 20% for 5 h. SEM and TEM images of this film show a microstructure composed of nanometric grains and a tilted columnar structure. Nanocrystal electron diffraction, XRD and Raman spectroscopy have confirmed the deposition of TiO2 anatase.

A combined ALD/MLD (where ALD and MLD stand for atomic and molecular layer deposition, respectively) deposition strategy using TiCl4, H2O and HQ (hydroquinone) as precursors has been applied for the preparation of inorganic–organic thin films on soda-lime glasses. The alternate deposition of TiO2 layers, by pulsing TiCl4/H2O (ALD), and hybrid layers, using TiCl4/HQ (MLD), results in the formation of thin films that are precursors for porous TiO2-coatings after removal of the HQ template by annealing. The coated-glassed show good photocatalytic activity in the degradation of NO with up to 15% reduction of NO concentration in three successive photocatalytic cycles of 5 h each. Surface Scanning Electron Microscopy (SEM) images show that the TiO2-coating is composed of large grains that are made up of finer subgrains resulting in a porous structure with an average pore size of 3–4 nm. Transmission Electron Microscopy (TEM) images show two regions, a porous columnar structure on top and a denser region over the glass substrate. Energy Dispersive X-Ray (EDX) analysis, nanocrystal electron diffraction and Raman spectroscopy confirm the presence of the anatase phase, which, together with the porosity of the material, accounts for the observed photocatalytic activity.

The transition from traditional carbon-based energy systems into more sustainable and renewable ones is a crucial subject matter nowadays. In this regard, molecular hydrogen arises as one of the main and most efficient energy vectors as its reaction with oxygen provides energy and only generates water as a by-product. The difficulties in its storage and transport can be overcome with Liquid Organic Hydrogen Carriers (LOHC), organic substances that store hydrogen through catalytic hydrogenation and dehydrogenation processes over multiple cycles and may support a future hydrogen economy. In this sense formic acid is considered as one of the most promising LOHC. Dehydrogenation reactions play also a key role in the valorization of readily available and inexpensive bulk chemicals such as glycerol, or in the production of fine chemicals like carbonyl and carboxylic compounds from primary and secondary alcohols. Interestingly, under acceptorless conditions dehydrogenation reactions generate valuable molecular hydrogen as by-product, making the processes more competitive from an economic point of view. Within this context, Ir-NHC compounds have been stablished as leading catalysts in the dehydrogenation processes of a wide range of substrates. In the present work, we depict the synthesis of different Ir(I) and Ir(III) complexes bearing asymmetric NHC ligands with a pyridyl fragment and a rigid oxygen-donor moiety in its structure. These compounds have shown to be efficient catalysts for the dehydrogenation of several substrates such as glycerol, benzyl alcohol derivatives and formic acid [Scheme 1: acceptorless dehydrogenation reactions catalyzed by Ir-NHC complexes]. The coordination mode of the ligands plays an essential role in the dehydrogenation processes, resulting in marked differences in catalytic activity.

Nowadays, large-scale production of clean energy from renewable sources is needed to satisfy the growing global energy demand and replace CO2-polluting fossil fuels. In this scenario, solar energy is one of the most promising sources of energy, as it is an ideal C-neutral energy which can promote the electrolysis of water into oxygen and hydrogen. The hydrogen fuel generated in this way is named as ‘‘solar fuel’’. The hardest step in the water splitting process is the oxidation of water into protons and oxygen. Therefore, the development of catalysts that improve the results in the water oxidation catalysis (WOC) is essential. Research on water splitting catalysis has been conducted under two major perspectives: molecular and heterogeneous catalysis. A large part of the most active homogeneous catalysts in WOC are based on ruthenium and iridium complexes containing N-heterocyclic carbene ligands. It is well known that one of the main difficulties with homogeneous catalysts is their stability and recyclability. To solve it, new strategies consistent on the covalent attachment of the molecular organometallic complexes to solid surfaces, such as graphene oxides or carbon nanotubes, are being studied. Our group has previously synthesized several organometallic complexes containing NHC ligands that have shown good water splitting activity. In this work, we are looking to build water soluble iridium-NHC complexes in order to increase their solubility in water and so, improve their catalytic activity. On the other hand, the support of the complexes on thermally reduced graphene (TRGO) is reported. Finally, the catalytic activity for water splitting of all the synthesized complexes has been tested using CAN as sacrificial oxidant.

The hybrid materials resulting from the covalent attachment of iridium NHC complexes, bearing 3-methyl-imidazol-2-ylidene and 3-(propyl-3-sulfonate)-imidazol-2-ylidene ligands to carbon nanotubes through ester functions, efficiently catalyzed water oxidation under chemical and electrochemical conditions. The hybrid catalyst featuring an NHC ligand with a propyl-sulfonate wingtip has shown an improved catalytic performance compared to that of the unfunctionalized material with TOF50 numbers up to 1140 h–1 using ammonium cerium(IV) nitrate (CAN) as electron acceptor at [CAN]/[Ir] ratios higher than 2000. The positive effect of the presence of a polar sulfonate group in water oxidation has been also observed in related molecular catalysts with compound [Ir(cod){MeIm(CH2)3SO3}] being more active than [IrCl(cod){MeIm(CH2)3OH}]. The hybrid catalysts were less active than the molecular catalysts although their productivity has been improved by allowing successive additions of CAN or at least three recycling experiments. The electrochemical water oxidation by CNT-based hybrid materials resulted much more efficient. The positive influence of a water-soluble sulfonate wingtip in the hybrid catalysts has been also identified allowing with TOF values close to 22 000 h–1 at 1.4 V. The local structure around iridium atoms in the heterogeneous catalysts has been determined by means of EXAFS applied before and after water oxidation reactions. The first coordination shell is similar in both fresh and postcatalytic catalysts but a slightly increase in the oxidation state of iridium atoms is observed what can be correlated to the peaks shifts in the XPS spectra for the oxidized materials.

Zwitterionic water-soluble [Cp*IrIIICl{(MeIm)2CHCOO}] and [IrI(cod){(MeIm)2CHCOO}] complexes featuring a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand efficiently catalyzed water oxidation using ammonium cerium(IV) nitrate (CAN) or sodium periodate as sacrificial oxidants. Excellent yields with TOF50 numbers up to 1000 h−1 have been achieved using CAN as electron acceptor at [CAN]/[Ir] ratios higher than 700. The investigation of the reaction mechanism by UV-vis seems to evidence that both catalyst precursors are transformed into the same active molecular species resulting from the degradation of the hydrocarbon ligands which is partially supported by the similarity of the oxygen evolution profiles at moderate oxidant/catalyst ratios for both catalyst precursors and the same chemical oxidant. In addition, DLS studies provide evidence for the participation of homogeneous iridium molecular species as intermediates likely stabilized by the carboxylate-functionalized bis-NHC ligand.

The effect of the structural properties of graphene materials on the local structure of –OH anchored Ir(I)–NHC complexes is herein investigated. For that, two partially reduced graphene oxides exhibiting different sheet properties due to an adequate selection of the crystalline characteristics of their parent graphite were used. The main differences among them were the size of Csp2 domains within their graphenic layers and the distribution of functional groups at the basal planes and edges. Anchoring of N-methylimidazolium moieties through the graphene –OH functional groups and subsequent formation of the Ir(I)–NHC complexes resulted in graphene-based hybrid materials. The structural differences of the support have an influence in the interaction of the supported iridium compounds with the graphene sheet. The oxygenated functional groups in the material with a smaller graphene sheet are closer leaving larger Csp2 domains in the graphene layer, favoring their interaction with the supported iridium atoms therefore displacing the chlorido ligand from the first coordination shell. In contrast, the hybrid material in which the distribution of the oxygenated functional groups within the basal planes of the graphenic layer is more homogeneous shows partial chlorido displacement. This fact has an influence on the electrocatalytic performance of the iridium-based hybrid materials as water oxidation catalysts (WOCs), exhibiting improved catalytic activity the catalyst having coordinated chlorido ligands.