Gas-phase oxidative dehydrogenation of long chain alkenols for the production of key fragrance ingredients: from Rosalva isomers to Costenal analogues

The continuous-flow, gas-phase oxidative dehydrogenation (ODH) of an actual mixture of decen-1-ol isomers ("Isorosalva" alcohol) towards the corresponding mixture of aldehydes ("Costenal" analogues, valuable ingredients in perfumes formulation) is herein reported for the first time over noble metal-free catalysts. In particular, the optimisation of the reaction conditions over a copper ferrite (Cu/Fe/O), as well as dedicated characterizations and comparisons between the fresh, the post-reaction (reduced) and regenerated (re-oxidised) catalytic material, allowed us to underline the key role of well dispersed copper oxide over a Fe-enriched spinel in promoting the selective ODH of Isorosalva alcohol. The superior catalytic activity and selectivity of CuO/gamma-Fe2O3 synthesized ad hoc were attributed to the very high dispersion of Cu over the support as well as to a cooperative effect between Cu and Fe species in promoting the redox cycle

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity. In this framework, the electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is studied. Nanostructured Ag deposited on Cu is an active and selective electrocatalyst for the formation of BHMF in basic media. However, this catalyst deserves further research to elucidate the role of the morphology and size of the coated particles in its performance as well as the actual catalyst surface composition and its stability. Herein, Ag is coated on Cu open-cell foams by electrodeposition and galvanic displacement to generate different catalyst morphologies, deepening on the particle growth mechanism, and the samples are compared with bare Ag and Cu foams. The chemical–physical and electrochemical properties of the as-prepared and spent catalysts are correlated to the electroactivity in the HMF conversion and its selectivity toward the formation of BHMF during electroreduction. AgCu bimetallic nanoparticles or dendrites are formed on electrodeposited and displaced catalysts, respectively, whose surface is Cu-enriched along with electrochemical tests. Both types of bimetallic AgCu particles evidence a superior electroactive surface area as well as an enhanced charge and mass transfer in comparison with the bare Ag and Cu foams. These features together with a synergistic role between Ag and Cu superficial active sites could be related to the twofold enhanced selectivity of the Ag/Cu catalysts for the selective conversion of HMF to BHMF, that is, >80% selectivity and ∼ 100% conversion, and BHMF productivity values (0.206 and 0.280 mmol cm–2 h–1) ca. 1.5–3 times higher than those previously reported

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we propose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h−1 gcat-1 at 300 °C, 30 bar, 40,800 mL h−1 gcat-1) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by threefold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h−1 gIn2O3-1 of a Pd- In2O3 catalyst operating at 300 °C, 30 bar, 40,800 mL h−1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH

LA CORROSIONE ATMOSFERICA DEI MONUMENTI IN BRONZO: PROVE DI INVECCHIAMENTO ARTIFICIALE

I monumenti in bronzo esposti all’aperto risentono di diverse tipologie di degrado, in conseguenza delle diversecondizioni di esposizione all’ambiente e, in particolare, alla pioggia.Allo scopo di studiare la correlazione causa-effetto tra l’evoluzione della corrosione di un bronzo e la suadifferente esposizione alla pioggia (pioggia stagnante o pioggia lisciviante), è stato intrapreso un lavoro di ricercamultidisciplinare. Nel presente lavoro vengono quindi riportati i risultati delle prove eseguite sul bronzo quaternarioG85, largamente impiegato per fusioni artistiche. La soluzione aggressiva impiegata è stata formulata sulla base dellecaratteristiche di piogge reali raccolte nell’area urbana di Bologna. La condizione di stagnazione è stata riprodottamediante un dispositivo wet&dry specificamente progettato e realizzato, in cui il bronzo viene ciclicamente immersonella pioggia sintetica, che viene periodicamente analizzata per valutare l’evoluzione del pH e della concentrazionedi metalli dissolti. Parallelamente, anche i materiali esposti vengono caratterizzati mediante misure gravimetriche,VPSEM+EDS+micro-Raman e XRD. La condizione di pioggia battente (run-off) viene invece simulata medianteun apposito dispositivo di dropping, che intende riprodurre, in condizioni controllate, l’azione della pioggia suuna superficie inclinata a piacere. Anche in questo caso sia le superfici esposte che la soluzione lisciviante vengonoanalizzate parallelamente nel corso dell’esposizione.L’analisi dei dati ottenuti ha permesso la formulazione di modelli interpretativi per i processi di corrosione delbronzo quaternario; inoltre, il confronto con casi reali di corrosione di monumenti bronzei ha consentito di stimarel’affidabilità dei modelli proposti e la loro efficacia a fini diagnostici e conservativi

Influence of stabilisers on the catalytic activity of supported Au colloidal nanoparticles for the liquid phase oxidation of glucose to glucaric acid: understanding the catalyst performance from NMR relaxation and computational studies

Supported Au colloidal nanoparticles have been prepared in the presence of stabilising polymers, such as, PVA, PVP and PEG (polyvinylalcohol, polyvinylpyrrolidone, polyethylene glycol). The effect of the polymer to Au weight ratio was investigated, for the synthesis of Au nanoparticles with varying particle size and particle size distribution. By varying the polymer/Au wt/wt ratio, Au nanoparticles with mean diameters from 3 to 8 nm were synthesised. The synthesised Au catalysts were studied in the liquid phase oxidation of glucose to glucaric acid under alkaline conditions. We demonstrated that the choice of polymer and polymer to Au weight ratio, have an important influence in terms of catalytic activity and yield to glucaric acid. The highest yield to glucaric acid (22%) was obtained using Au–PVA catalysts. A strong deactivation was observed using Au catalysts. Further evaluation of the possible reasons for deactivation were investigated using experimental, computational and NMR relaxation studies

Understanding structure-activity relationships in highly active La promoted Ni catalysts for CO₂ methanation

Ni-based catalysts are selective in the hydrogenation of CO_{2} to CH_{4} but their activity and stability need improvement. Herein, we propose a hydrotalcite-derived high loaded Ni-Al_{2}O_{3} catalyst promoted by La. The effect of La on the catalyst properties is investigated and compared with that of Y and Ce. The NiO_{x} rystallite size and basic properties (rather than the nickel reducibility) as well as the catalytic activity depend on the rare-earth element. The La-catalyst achieves a more relevant activity enhancement at low temperature and high space velocity (480 L g^{-1} h^{-1}, CO_{2}/H_{2}/N_{2} = 1/4/1 v/v), high CH_{4} productivity (101 L_{CH4} gNi^{-1} h^{-1}) and stability, even under undiluted feeds. In situ DRIFTS and the characterization of spent catalysts confirm that this enhanced performance is related to the combination of dissociative and associative CO_{2} activation on more reduced, highly dispersed and stable Ni nanoparticles and basic sites in the La_{2}O_{3}-Al_{2}O_{3} matrix, respectively

In Situ Development of a 3D Cu-CeO2 Catalyst Selective in the Electrocatalytic Hydrogenation of Biomass Furanic Compounds

The renewable electricity-driven electrocatalytic hydrogenation of biomass-derived furanic compounds produces biopolymer (polyurethane) precursors under mild reaction conditions. The widely used Ag and Cu electrocatalysts failed in the selective conversion of the aldehyde into the alcohol in concentrated electrolytes due to the contribution of the electrodimerization. Herein, we proposed 3D CeO2-based catalysts for the electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) electrolytes (0.02, 0.05, and 0.10 M) to 2,5-bishydroxymethylfuran (BHMF). An electrodeposition approach was adopted to coat CeO2 on Cu open-cell foams. The ex-situ characterization of electrocatalysts revealed that they were made of a CeO2 layer containing Cu species. The migration of Cu from the foam to the coating started during the electrodeposition, while the electroreduction conditions provoked the formation of Cu particles. The in situ characterization by X-ray absorption spectroscopy evidenced that the Ce4+ to Ce3+ reduction occurred just after the application of the cathodic potential; moreover, copper species were reduced to Cu0 during the experiments. The combination of partially reduced CeO2 and Cu particles not only provided selective reaction sites but also increased the electrical conductivity of the electrode. Consequently, the in situ-developed Cu-CeO2 electrocatalysts promoted the selective electrocatalytic hydrogenation of the more concentrated 0.10 M HMF electrolytes, overperforming previously reported AgCu materials at -0.51 V vs RHE

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we pro -pose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h-1 gcat-1 at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1 ) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by three-fold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h-1 gIn2O3-1 of a Pd-In2O3 catalyst operating at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we propose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h−1 gcat-1 at 300 \ub0C, 30 bar, 40,800 mL h−1 gcat-1) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by threefold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h−1 gIn2O3-1 of a Pd- In2O3 catalyst operating at 300 \ub0C, 30 bar, 40,800 mL h−1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH