The catalytic and structural changes due to the presence of 0.25 wt% indium on a 3% Ni/CeO2-Al2O3 catalyst prepared by impregnation method were investigated. Catalyst characterizations by XRD, TPR, XPS, TEM and DRIFTS (in presence of CO/CO2/CH4 +CO2) were carried out. In the short (6 h) catalytic methane dry reforming tests at 650 °C both samples were stable, produced essentially no carbon, but indium lowered the activity. In the 4 day longevity tests at 675 °C, stable activity was achieved by the In-promoted catalyst in contrast with the continuous deactivation of the unpromoted Ni sample due to coking and sintering. Indium, partially alloyed with nickel, could better keep nickel in metallic state, and the increased CO2 activation ability, the intimate Ni(In)-CeO2 interface inside the support pores resulted in practically no coking.

Dry reforming of methane with ratio CH4/CO2 = 1 is studied using supported Ni catalysts on SBA-15 modified by CeMnOx mixed oxides with different Ce/Mn ratios (0.25, 1 and 9). The obtained samples are characterized by wide-angle XRD, SAXS, N2 sorption, TPR-H2, TEM, UV-vis and Raman spectroscopies. The SBA-15 modification with CeMnOx decreases the sizes of NiO nanoparticles and enhances the NiO-support interaction. When Ce/Mn = 9, the NiO forms small particles on the surface of large CeO2 particles and/or interacts with CeO2 , forming mixed phases. The best catalytic performance (at 650 oC, CH4 and CO2 conversions are 51 and 69%, respectively) is achieved over the Ni/CeMnOx/SBA-15 (9:1) catalyst. The peculiar CeMnOx composition (Ce/Mn = 9) also improves the catalyst stability: In a 24 h stability test, the CH4 conversion decreases by 18 rel.% as compared to a 30 rel.% decrease for unmodified catalyst. The enhanced catalytic stability of Ni/CeMnOx/SBA-15 (9:1) is attributed to the high concentration of reactive peroxo (O-) and superoxo (O2-) species that significantly lower the amount of coke in comparison with Ni-SBA-15 unmodified catalyst (weight loss of 2.7% vs. 42.2%). Ni-SBA-15 modified with equimolar Ce/Mn ratio or Mn excess is less performing. Ni/CeMnOx/SBA-15 (1:4) with the highest content of manganese shows the minimum conversions of reagents in the entire temperature range (X(CO2) = 4-36%, X(CH4) = 8-58%). This finding is possibly attributed to the presence of manganese oxide, which decorates the Ni particles due to its redistribution at the preparation stage.

This paper reports a new sustainable protocol for the microwave-assisted catalytic conversion of levulinic acid into N- substituted pyrrolidones over tailor-made mono (Pd, Au) or bimetallic (PdAu) catalysts supported on either highly mesoporous silica (HMS) or titania-doped HMS, exploiting the advantages of dielectric heating. MW-assisted reductive aminations of levulinic acid with several amines were first optimized in batch mode under hydrogen pressure (5 bar) in solvent-free conditions. Good-to-excellent yields were recorded at 150 °C in 90 min over the PdTiHMS and PdAuTiHMS, that proved recyclable and almost completely stable after six reaction cycles. Aiming to scale-up this protocol, a MW-assisted flow reactor was used in combination with different green solvents. Cyclopentyl methyl ether (CPME) provided a 99% yield of N-(4-methoxyphenyl) pyrrolidin-2-one at 150 °C over PdTiHMS. The described MW- assisted flow synthesis proves to be a safe procedure suitable for further industrial applications, while averting the use of toxic organic solvents.

In accordo a quanto riportato precedentemente che ha individuato nelle SrFeO3 materiali interessanti per l'applicazione come elettrodi per celle reversibili e in particolare per celle simmetriche, grazie alla presenza della coppia Fe4+/Fe3+, l'attività svolta al Mese 9 del progetto ha riguardato la sintesi tramite Solution Combustion Synthesis di n. 6 composizioni a base di SrFeO3 drogate, al sito A con Ce, Y, Sm ed al sito B con Ti, Al, Mo. I suddetti materiali sono stati forniti ad ICMATE-CNR per misure elettrochimiche realizzando una cella simmetrica con elettrolita in Samarium-doped Ceria (SDC) di composizione Ce0.8Sm0.2O2-?.

Soybean hulls (SBHs) are one of the main by-products of soybean crushing, usually destined for animal feeding or to become a putrescible waste. In this work, we upgraded the SBHs to materials with antimicrobial properties. After the extraction of soybean peroxidase from SBHs, an enzyme applicable in different technological sectors and naturally present in soybean hulls, the exhausted biomass was subjected to an acid-base treatment to isolate cellulose. The obtained material was, in turn, functionalized with 3-aminopropyl triethoxysilane (APTES) to achieve new hybrids with antimicrobial properties. The synthetic procedure was optimized by varying the solvent type (ethanol or toluene) and APTES amount. Overall, the amino-functionalization process was effective and the activity was outstanding against both gram-positive and gram-negative bacteria, reaching complete disinfection practically in all cases. The samples were studied by means of several characterization techniques, demonstrating that the solvent and cellulose types had a significant influence on the physical-chemical features, together with the eco-sustainability of the process. In particular, the use of greener ethanol and waste cellulose (with respect to a commercial one) resulted in a higher APTES immobilization efficiency and superior thermal stability of the final materials. Interestingly, the presence of various unremoved compounds from the lignocellulosic SBH matrix, although in small quantities, emerged as a crucial factor, also in terms of antibacterial activity, hypothesizing a role of residual phytochemicals.

Ce-doped SrFeO3 perovskite-type compounds are known as good thermocatalysts for the abatement of wastewater contaminants of emerging concern. In this work, Sr0.86Ce0.14FeO3-CeO2 perovskite-oxide systems with increasing amounts of cerium excess (0, 5, 10 and 15 mol% Ce), with respect to its maximum solubility in the perovskite, were prepared in one-pot by solution combustion synthesis and the effects of cerium excess on the chemical physical properties and thermocatalytic activity in the bisphenol A degradation were evaluated. The powders were characterized by powder X-ray diffraction combined with Rietveld refinement, X-ray photoelectron spectroscopy, thermal gravimetry, temperature programmed reduction, nitrogen adsorption, scanning electron microscopy and energy dispersive X-ray spectroscopy techniques. Results highlight that the perovskite structural, redox, surface, and morphological properties are affected by the in situ co-growth of the main perovskite phase and ceria and that a larger cerium excess has a beneficial effect on the thermocatalytic performance of the perovskite oxide-ceria biphasic system, although ceria is not active as a thermocatalyst itself. Perovskite properties and performance are enhanced by the tetragonal distortion induced by the introduction of cerium excess in the synthesis. It is supposed that a larger oxygen mobility and an easier reducibility are among the most relevant features that contribute to superior thermocatalytic properties of these perovskite oxide-based systems. These results also suggest new perspectives in the nanocomposite preparation and their catalytic applications.

Perovskite-type LaCo1-xNixO3-delta (x = 0, 0.2, 0.4, 0.6, and 0.8) powders were synthesized by solution combustion synthesis. The crystal structure, morphology, texture, and surface were characterized by X-ray powder diffraction combined with Rietveld refinement, scanning electron microscopy, N-2-adsorption, X-ray photoelectron spectroscopy, and zeta-potential analysis. The thermocatalytic properties of the perovskites were investigated by UV-Vis spectroscopy through degradation of rhodamine B in the temperature range 25-60 degrees C. For the first time, this perovskite system was proven to catalyze the degradation of a water pollutant, as the degradation of rhodamine B occurred within 60 min at 25 degrees C. It was found that undoped LaCoO3-delta is the fastest to degrade rhodamine B, despite exhibiting the largest energy band gap (1.90 eV) and very small surface area (3.31 m(2) g(-1)). Among the Ni-doped samples, the catalytic performance is balanced between two main contrasting factors, the positive effect of the increase in the surface area (maximum of 12.87 m(2) g(-1) for 80 mol% Ni) and the negative effect of the Co(III) stabilization in the structure (78% in LaCoO3 and 89-90% in the Ni-containing ones). Thus, the Co(II)/Co(III) redox couple is the key parameter in the dark ambient degradation of rhodamine B using cobaltite perovskites.

The effect of the synthesis and processing parameters on the thermocatalytic performance of Ce-doped SrFeO3 inorganic perovskites was investigated to improve the reproducibility and reliability of the synthetic methodology and of the testing procedure. A structural, surface and redox characterization was performed to check the extent of variability in the chemical-physical properties of the prepared materials, revealing that a strict control of the synthesis parameters is indeed crucial to optimize the thermocatalytic properties of Ce-doped SrFeO3 inorganic perovskites. The thermocatalytic tests, aimed to degrade organic pollutants in water, were performed using Orange II and Bisphenol A as target compounds, in view of a later technological application. The main issues in the synthesis and testing of Ce-doped SrFeO3 perovskite thermocatalysts are highlighted and described, giving specific instructions for the resolution of each of them. A limited number of prepared materials showed an efficient thermocatalytic effect, indicating that a full gelification of the sol, an overstoichiometric reducer-to-oxidizer ratio, a nominal cerium content of 15 mol%, slightly higher than its solubility limit (i.e., 14 mol%), a pH of 6 and a thermal treatment at 800 degrees C/2 h are the best synthesis conditions to obtain an effective Ce-doped SrFeO3 perovskite. Regarding the testing conditions, the best procedure is to follow the degradation reaction without any preconditioning with the pollutant at room temperature. The severe leaching of the active perovskite phase during tests conducted at acidic pH is discussed. Briefly, we suggest confining the application of these materials to a limited pH range. Variability between thermocatalysts prepared in two different laboratories was also checked. The issues discussed and the proposed solutions overcome some of the obstacles to achieving a successful scale up of the synthesis process. Our results were favorable in comparison to those in the literature, and our approach can be successfully extended to other perovskite catalysts.

Glycerol is a high-value commercial chemical whose production has increased quite a bit in recent years, as an important by-product of biodiesel. The conversion of glycerol in added value products allows not only to reintroduce a waste as secondary raw material, but also to improve sustainability of the production steps. The conversion of glycerol under microwave irradiation is still a new procedure and, for this reason, few processes are reported in the literature. Moreover, with the use of suitable catalysts, the procedure is very effective in terms of saving energy, time and economy. One of the most investigated processes to valorize glycerol using microwaves as a heating source is the production of oxygenated fuel additives as acetins, ethers and ketals. In this chapter recent studies on microwave assisted glycerol etherification and acetalisation will be addressed.

Structured hydrotalcite NiAl-HT material with Ni/Al atomic ratio of 2.5 was prepared by co-precipitation of Ni and Al nitrate precursors and then modified by the addition of 1 wt% Ce and/or 3 wt% Au species. The obtained materials, after calcination at 600 C, were characterized by XRD, XPS and TPR. Their catalytic performance was tested through dry reforming of methane (DRM) and by the temperature-programmed surface reaction of methane (TPSR-CH4). Thermal gravimetry analysis (TGA) of the spent catalysts was performed to determine the amount of carbon accumulated during the reaction. The effects of the addition of cerium as a support promoter and gold as nickel promoter and the sequential addition of cerium and gold on the structural properties and on the catalytic efficiency were investigated. Under the severe condition of high space velocity (600,000 mL g?1 h?1), all the catalysts were quite active, with values of CH4 conversion between 67% and 74% at 700 C. In particular, the combination of cerium and gold enhanced the CH4 conversion up to 74%. Both additives, individually and simultaneously, enhanced the nickel dispersion with respect to the unpromoted NiAl and favored the reducibility of the nickel. During DRM all the catalysts formed graphitic carbon, contributing to their deactivation. The lower carbon gasification temperature of the promoted catalysts confirmed a positive effect played by Ce and Au in assisting the formation of an easier-to-remove carbon. The positive effect was testified by the better stability of the Ce/NiAl with respect to the other catalysts. In the gold-containing samples, this effect was neutralized by Au diffusing towards the catalyst surface during DRM, masking the nickel active sites. TPSR-CH4 test highlighted different CH4 activation capability of the catalysts. Furthermore, the comparison of the deposited carbon features (amount and removal temperature) of the DRM and TPSR spent catalysts indicated a superior activation of CO2 by the Au/Ce/NiAl, to be related to the close interaction of gold and ceria enhancing the oxygen mobility in the catalyst lattice.

The electrochemical reduction of molecular oxygen is a fundamental process in Solid Oxide Fuel Cells and requires high efficiency cathode materials. Two La0.25Ba0.25Sr0.5Co0.8Fe0.2O3-?-based perovskite compounds were prepared by solution combustion synthesis, and characterized for their structural, microstructural, surface, redox and electrochemical properties as potential cathodes in comparison with Ba0.5Sr0.5Co0.8Fe0.2O3-? and La0.5Sr0.5Co0.8Fe0.2O3-? perovskites. Results highlighted that calcination at 900 °C led to a "bi-perovskite heterostructure", where two different perovskite structures coexist, whereas at higher calcination temperatures a single-phase perovskite was formed. The results showed the effectiveness of the preparation procedures in co-doping the A-site of perovskites with barium and lanthanum as a strategy to optimize the cathode's properties. The formation of nanometric heterostructure co-doped in the A-site evidenced an improvement in oxygen vacancies' availability and in the redox properties, which promoted both processes: oxygen adsorption and oxygen ions drift, through the cathode material, to the electrolyte. A reduction in the total resistance was observed in the case of heterostructured material.

L'attività svolta nei primi 6 mesi del progetto, [D3.2.2.2 [M6], ha riguardato anche l'individuazione dei migliori protocolli di sintesi per la preparazione di elettroliti innovativi, come ad esempio BaCeO3 e bario cerati drogati, come elettroliti protonici, oppure sistemi misti a composizione BCZYYb da impiegare nelle celle reversibili. E' ben noto che elettroliti anionici (come YSZ) sono generalmente impiegati per dispositivi SOCs (solid-oxide cells) ad alta temperatura (700-100°C), mentre elettroliti protonici (come bario cerati drogati) vengono utilizzati in celle a conduzione protonica che operano a media temperatura (500-700°C). Gli elettroliti a conduzione mista, sia anionica che protonica, sono stati invece, attualmente proposti come nuovo tipo di elettrolita per celle reversibili a temperatura ridotta, 450-650 °C con il vantaggio che il trasporto simultaneo di ioni ossigeno e idrogeno contribuisce ad aumentare la conduttività totale del sistema, riducendo la resistenza ohmica. Inoltre, l'abbassamento della temperatura di esercizio, limita notevolmente il degrado dei materiali. In accordo al M3.2.2.2 [M6] sono stati preparati i primi materiali innovativi a base di perovskiti SrFeO3 e sono state individuate le principali metodiche di sintesi di elettroliti innovativi a base di BaCeO3.

Le celle elettrochimiche ad ossido solido funzionanti in modo reversibile (rSOC) hanno la potenzialità termodinamica e cinetica per operare con elevate efficienze in un ampio range di temperature e di modalità di esercizio, che li rende adatti per l'uso tanto per applicazioni stazionarie quanto per piccoli generatori portatili. Queste celle possono funzionare sia in modalità cella a combustibile che di elettrolizzatori, a seconda della direzione della corrente. In modalità cella a combustibile, la cella produce potenza elettrica consumando un combustibile come l'idrogeno o gli idrocarburi (gas-to-power). In modalità elettrolisi, la cella consuma elettricità (di preferenza rinnovabile) per produrre un combustibile, come l'idrogeno o il gas di sintesi, scindendo le molecole di acqua o anidride carbonica (power-to-gas). Pertanto, queste tipologie di celle hanno anche il potenziale per essere utilizzate nei sistemi per la cattura e lo stoccaggio dell'anidride carbonica, che potrebbero aiutare a mitigare l'effetto serra e ridurre l'impronta di carbonio complessiva della produzione di energia. Tuttavia, le rSOC sono ancora una tecnologia emergente e sono necessarie ulteriori ricerche per ottimizzarne le prestazioni e ridurne i costi. Gli sforzi principali di questa ricerca sono perciò improntati allo sviluppo di nuovi materiali con caratteristiche elettrochimiche migliori di quelli normalmente usati per la fabbricazione di celle commerciali che allo stato attuale presentano forti limitazioni in termini di temperatura di esercizio, versatilità di impiego, tolleranza agli inquinanti ed ai cicli operativi.

Report tecnico delle attività svolte per l'individuazione e/o realizzazione di reattori e di stazioni di prova per test catalitici di reforming del biogas, lo sviluppo dei protocolli di test dei materiali e delle condizioni operative Accordo Ministero della Transizione Ecologica - ENEA PNRR Ricerca e Sviluppo sull'Idrogeno Piano di ricerca operativo 2022-2025 - M06 Obiettivo: OBIETTIVO 1 - Produzione di idrogeno verde e pulito Work package: WP 1.1 Ricerca e sviluppo di elettrolizzatori avanzati (bassa e alta temperatura), o altre tecnologie innovative, per la produzione di idrogeno verde e a basse emissioni Linea di attività: LA 1.1.25 Sviluppo di materiali e processi catalitici per il reforming di biogas in idrogeno Responsabile del Progetto: G. Monteleone Responsabile per CNR: A. Aricò/A. Sanson Responsabile Obiettivo: A. Giaconia Responsabile della WP: A. Giaconia Referente LA: C. Evangelisti (ICCOM-CNR)

Rapporto tecnico delle attività svolte per la definizione dello stato dell'arte aggiornato su catalizzatori e processi catalitici di reforming del biogas Accordo Ministero della Transizione Ecologica - ENEA PNRR Ricerca e Sviluppo sull'Idrogeno Piano di ricerca operativo 2022-2025 - M03 Obiettivo: OBIETTIVO 1 - Produzione di idrogeno verde e pulito Work package: WP 1.1 Ricerca e sviluppo di elettrolizzatori avanzati (bassa e alta temperatura), o altre tecnologie innovative, per la produzione di idrogeno verde e a basse emissioni Linea di attività: LA 1.1.25 Sviluppo di materiali e processi catalitici per il reforming di biogas in idrogeno Responsabile del Progetto: G. Monteleone Responsabile per CNR: A. Aricò/A. Sanson Responsabile Obiettivo: A. Giaconia Responsabile della WP: A. Giaconia Referente LA: C. Evangelisti (ICCOM-CNR)

L'OR2 è composto dai seguenti 3 WP: WP2.1 - Produzione di combustibili low carbon da reflui/scarti; WP2.2 - Propulsori termici dual fuel; WP2.3 - Abbattimento delle emissioni efficiente. Nel WP 2.1, il CNR-ITAE, dopo l'individuazione della tipologia e quantità di rifiuti solidi stoccati a bordo e sui possibili metodi di conversione in syngas, ha effettuato la caratterizzazione chimico-fisica di campioni di differenti materiali di scarto/rifiuti individuati ed ha allestito una stazione di prova per la gassificazione di materiali di scarto selezionati (Att 2.1.1). Per il trattamento dei rifiuti in fase supercritica sono stati individuati i sistemi catalitici solidi, attivi nella gassificazione a metano a partire da substrati organici; messo a punto il sistema di reazione e di analisi; condotto uno studio chimico-fisico di alcuni sistemi catalitici; messo a punto l'impianto sperimentale da laboratorio per le misure catalitiche (Att 2.1.2). Per i sistemi catalitici REDOX sono state prese in considerazione diverse formulazioni catalitiche, a base di ossidi metallici non preziosi; caratterizzate dal punto di vista chimico-fisico; condotti test catalitici per valutare gli effetti delle condizioni operative di processo per la sintesi di carburanti "low carbon"; verificate prestazioni e fattibilità economica dell'intero processo di conversione dei rifiuti a carburanti attraverso l'analisi sull'attività di idrogenazione catalitica di CO/CO2 a carburanti per il motore dual-fuel (Att. 2.1.3). UNIME ha condotto un'indagine conoscitiva in merito alla tipologia di modelli matematici predittivi più idonei alla simulazione del processo di gassificazione; condotto campagne di simulazione basate sui risultati delle analisi ultimali e prossimali dei campioni dei differenti materiale di scarto/rifiuti selezionati; realizzato un modello di un generico processo di gassificazione all'equilibrio termodinamico; modificato il modello per potersi discostare dall'equilibrio termodinamico come nei reali sistemi; individuato e inserito nel modello due parametri, la temperatura d'approccio e la percentuale di carbonio non convertito in gas, necessari per ottenere un modello di simulazione basato su un approccio termodinamico non all'equilibrio; effettuato l'analisi di sensitività e confrontato i risultati delle simulazioni con dati di letteratura con riferimento all'utilizzo del legno come feedstock del gassificatore (Att 2.1.1). Per la produzione di combustibili low-carbon mediante CLC e CLR è stata, dapprima, effettuata, da parte di UNIPA, un'analisi approfondita dello stato dell'arte più recente, successivamente, CNR-ISMN ha effettuato una fase ricognitiva verso i processi per CLC e CLR e la selezione e lo sviluppo di materiali, concentrandosi sui materiali OC (Oxygen Carrier) per il trasporto ciclico di ossigeno fra i due reattori coinvolti nelle reazioni di ossidazione (Air Reactor) e di riduzione (Fuel Reactor) (Att 2.1.4). Nel WP2.2, riguardante i propulsori termici dual fuel (DF), CNR-STEMS ha effettuato un'analisi della tecnologia DF con iniezione al collettore di aspirazione, a bassa pressione, in combustione omogenea innescata da un'iniezione pilota di combustibile diesel, allo scopo di individuare le diverse problematiche alla base dello sviluppo di motorizzazioni DF, di schematizzare le possibili strategie utili all'ottimizzazione dei motori DF e valutare le strategie più utili per l'applicazione sul prototipo di motore marino al banco. Infine, per analizzare il maggior numero possibile di casi, ha condotto un'analisi numerica, con modello monodimensionale del motore disponibile al banco prova, con l'ausilio di dati sperimentali (Att. 2.2.1). In una seconda fase, ha studiato l'ottimizzazione di un motore DF, con prove sperimentali condotte su un motore pluricilindro di minore cilindrata unitaria rispetto al prototipo marino, e condotto un'approfondita campagna sperimentale per studiare le prestazioni e le emissioni di un motore diesel light duty in funzionamento DF, con la legge di iniezione ottimizzata (Att. 2.2.2). IFM ha condotto l'analisi dei sistemi di iniezione del combustibile gassoso a bassa pressione nel collettore di aspirazione che ha portato alla selezione della valvola da impiegare nei test su motore mono-cilindro (Att. 2.2.3). Nel WP2.3, CNR-ISMN dopo un'indagine di letteratura, per individuare i catalizzatori più adatti all'abbattimento di NOx attraverso il processo di Selective Catalytic Reduction (SCR), ha studiato l'influenza dei diversi ossidi presenti nel catalizzatore sull'efficienza del processo chimico di abbattimento; ha effettuato la selezione e definizione dei metodi di sintesi di catalizzatori a base di Vanadio Tungsteno (V2O5-WO3) per l'abbattimento di inquinanti aerei; effettuato la sintesi, per co-precipitazione, di un campione supportato su Titania (V2O5 2%-WO3 8%/TiO2) (Att 2.3.1).UNIME, a seguito di una sistematica analisi di letteratura, sui sistemi catalitici di ossidazione per il trattamento dell'aria, ha individuato i sistemi a base di ossidi di metalli di transizione, in sostituzione dei costosi metalli nobili supportati; ha sviluppato e studiato sistemi catalitici a base di ossidi di Ce/Mn con rapporto atomico variabile da 0 a 1; ha avviato un sistematico programma di caratterizzazione (XRD, XPS, CO-TPR e H2-TPR) per determinare la funzionalità catalitica di ossidazione dei sistemi sintetizzati per l'abbattimento ossidativo di composti organici volatili (VOC's) (Att 2.3.1)

Mn-WO/TiO catalysts were investigated for Selective Catalytic Reduction (SCR) of NO with NH. The catalysts were synthesized by wetness impregnation method with different Mn loadings (1.5-3-12 wt%) on 8wt%WO/TiO. All three catalysts were compared with 8wt%WO/TiO and bare MnO oxide, used as references. The 1.5wt%Mn-8wt%WO/TiO exhibited the highest performance in NO conversion and N selectivity. A commercial catalyst, based on titania supported vanadia and tungsta, (VO-WO/TiO), widely used for its high efficiency, was also investigated in the present work. The morphological, structural, redox and electronic properties of the catalysts and their thermal stability were studied by several techniques (N adsorption/desorption, X-ray diffraction, H temperature-programmed reduction, NH temperature programmed desorption, X-ray photoelectron spectroscopy). The aim of this paper is to study the effect of different Mn loadings on 8wt%WO/TiO with the ambition to obtain highly active and selective catalysts in a large window of temperature. The replacement of toxic vanadium used in the classic VO-WO/TiO catalyst with MnO in the best performing catalyst, 1.5wt%Mn-8wt%WO/TiO represents an important achievement to improve the environmental sustainability.

We report the first example of successful heterogenization of the classical PdI carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI@MWCNT-imi-X, X = Br, I) present the PdI anion supported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reaction, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50-84%, starting from various substrates). The heterogeneous catalyst could be easily recycled and showed a good efficiency even after the fourth recycle, when deactivation began to occur owing to the formation of inactive Pd(0) species, as confirmed by XPS analysis. Hot and cold filtration tests were compatible with an essentially heterogeneous catalytic process, and limited metal contamination in the final organic compounds occurred, as assessed by ICP-MS analysis of representative carbonylation products.

Here, we report the development of a new biocide based on hybrid mesoporous silica nanoparticles (MSN). The MSN was synthesized by condensation method in emulsion followed by grafting with two different silylated ionic liquid moieties, namely butyl imidazolinium bromide and imidazolinium propansulfonate betaine. Features of nanoparticles were characterized by Thermogravimetry, Infrared and ss-NMR Spectroscopy, and Transmission Electron Microscopy. The antibacterial properties were tested against a Gram-positive bacterial strain previously isolated from artefacts of interest in the field of Cultural Heritage. Interestingly, the hybrid material presents an antibacterial activity higher than its single constituents, showing a synergic effect probably due to the high local concentration of the ionic liquid anchored to nanoparticles. The more promising material was applied to fragments of stones retrieved from the Santa Margherita cave (Italy) and affected by bio-deterioration, comparing its antibacterial action with a commercial biocide.

Sulfonic and propylsulfonic silica-based catalysts were synthesized, characterized and tested in the acetalization of glycerol (G) by a sustainable, solvent-free and fast procedure, under microwave irradiation, to produce solketal (S). The catalysts were prepared by different grafting procedures and their surface and structural properties were investigated by means of N2 adsorption isotherms, Thermogravimetric Analysis (TGA), X-ray Photoelectron Spectroscopy (XPS) and XRay Fluorescence Spectroscopy (XRF). Under the optimized reaction conditions (Temperature 40°C, microwave power ?100W, time 2 min and 1:12 glycerol/acetone molar ratio) the sulfonic materials, produced by the hydrothermal grafting, showed excellent performance in terms of activity, selectivity and stability, with no leaching of sulfonic groups after several cycles. By the correlation of the structure properties of the materials and their activity, the performance of the catalysts was shown strictly correlated both to the acidity and the surface density of the active sites.