Eduardo J. Garcia-Suarez’s research while affiliated with Ikerbasque - Basque Foundation for Science and other places

Hydroformylation of olefins forms aldehydes which are valuable final products as well as intermediates in synthesizing bulk chemicals like alcohols, amines, and esters with a yearly world production of about 12 Mt. Industrial hydroformylation processes are essentially homogeneously catalyzed systems with an economic incitement for improvement by easy separation of products and reuse of catalysts, high reactivity and selectivity by using new catalysts, novel processes and alternative methodologies. One such potential candidate for an alternative catalyst is a Supported Ionic Liquid- Phase (SILP) catalyst comprising “heterogenized” homogeneous ionic liquid (IL) catalyst systems on a porous support. Such catalysts make it possible to apply the much preferred fixed bed continuous flow process design which overcomes the troublesome and energy demanding separation of the products from the reaction mixture obtained in the traditional homogenous batch process.In our previous and very recent studies [1-2], we have prepared SILP catalysts containing immobilized Rh-complexes of TPPTS-Cs 3 in 1-butyl-3-methylimidazolium octylsulfate ([BMIM][n-C 8 H 17 OSO 3 ]) on SiO 2 support and investigated the influence of IL loading on the catalytic activity. The influence of other supports : SBA-15, MCM-41, Al2O3, ZrO2 and TiO2 has also been studied and the catalytic activity compared to the SiO2 SILP catalyst. Finaly we will report on a comparison on the catalytic activity of the SiO2 SILP catalyst by use of the ligand precurser TPPTS-Cs 3 and the much cheaper TPPTS-Na 3 salt. References. H. N. T. Ha, D. T. Duc, T. V. Dao, M. T. Le, A. Riisager, R. Fehrmann. Catal. Commun. 25 , 136-141 (2012) Nguyen, V. C., Do, V. H., Truong, D. D., Pham, T. T., Dinh, P. K., Vu, T. L., Garcia-Suarez, E. J., Riisager, A., Fehrmann, R., Le, M. T. Res. Chem. Int.. 49 , 6, 2383-2398 (2023).

The development of the most promising next-generation Lisingle bondS batteries with an improved cyclability is one of the greatest challenges nowadays. In this sense, here, a novel imidazolium-based polymeric ionic liquid (PVI10Cl) was successfully synthesized and integrated into a high-performing sulfur cathode. The lithium polysulfide trapping ability of PVI10Cl was confirmed, which helps to accelerate conversion kinetics. This synergetic effect leads to enhanced C-rate response, improving the discharge capacities and reducing the overpotentials even at 1C in comparison with conventional PVdF binder. These features also allow cells to be operated for 100 cycles with excellent capacity retention. All in one, while conventional binders are viewed only as a “glue” to hold the active material together, it has been shown that PVI10Cl binder has additional functions and plays an active role during Lisingle bondS battery operation.

The widespread deployment of renewable energies such as solar and wind implies the parallel development of energy storage systems to deal with their intermittency. Storing renewable energy as thermal energy is one of the alternatives under constant research. In this regard, phase change materials (PCMs) are able to store large amounts of energy at a nearly constant temperature in the form of latent heat. Nevertheless, most of these PCMs undergo solid-liquid transitions, which hamper their implementation due to leaking issues, forcing the need for containment and increasing the final cost of the TES system. Therefore, a class of PCMs possessing solid-solid transitions has emerged to avoid these problems, the so-called organic ionic plastic crystals (OIPCs). Currently, the scientific literature and the number of OIPCs available for TES are rather scarce. Herein, we present the synthesis, the structural, and the thermo-physical characterization of nine OIPCs based on the dioctylammonium cation combined with different organic and inorganic acids as the anions. Particular attention has been paid to the most characteristic thermal properties of PCMs (latent heat, transition temperature, subcooling, thermal conductivity, and energy storage density), evaluating their thermal stability and the reliability of the most promising materials over thermal cycling as well. Among the prepared OIPCs, 3 of them, [DOA][NO 3 ], [DOA][Cl], and [DOA][FOR], exhibited promising properties with remarkable solid-solid transition enthalpies of 156.6 J/g (at 41.4 • C), 101.2 J/g (at 20.0 • C) and 58.4 J/g (at 29.7 • C), respectively. These 3 OIPCs showed high potential to be used and integrated as PCMs in TES systems at temperatures below 45 • C.

Triphenylphosphine trisulfonate (TPPTS) is a common used ligand for homogeneous hydroformylation of olefins with Rh complexes. The synthesis of the TPPTS ligand is a rather complex procedure and it is influenced by several factors. In this work, the influence of pH on the synthesis of the TPPTS ligand was thoroughly studied and a neutralization pH of 5.5–6.5 was optimized for a successful synthesis of TPPTS-Cs3 and TPPTS-Na3 ligands. The catalytic activity of the corresponding Rh-TPPTS supported ionic liquid-phase (SILP) catalysts with SiO2 and TiO2 supports were studied for the continuous, fixed-bed gas-phase hydroformylation of ethylene to propanal. The SILP catalyst with TPPTS-Cs3 on SiO2 support exhibited superior catalytic activity compared to a corresponding catalyst with TPPTS-Na3, while the activity of the latter catalyst was found to be much higher than an analogous catalyst based on TiO2 support. Combined this clearly emphasizing the importance of both ligand and support characteristics in the SILP hydroformylation system.