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Ce and Zr oxides have been tested in the oxidation of cyclohexane to KA oil because of the possibility to tune their crystal structure and redox properties by introducing defects, and of modifying their mechanical and thermal stability. The redox properties of the two oxides, prepared by the inverse microemulsion technique, have been tuned by homogeneously including Cu or Fe (10 % molar) into their structures. These modifications led to very different behaviours in terms of both KA oil productivity and K/A ratios, especially upon undergoing reduction treatment, being the reduced Cu‐modified CeO2 oxide the most active catalyst, able to produce 2.2 mmol of KA oil after 5 hours with 93.2 % selectivity (K/A 2.6). The materials obtained have been characterized by solid state analytical techniques to study their structure, morphologies as well as their bulk and surface chemistry (STEM/EDX, BET, XRD, XPS). [ABSTRACT FROM AUTHOR]

The selective hydrogenation of α,β‐unsaturated aldehydes is an ideal case for studying the structure‐activity relationships in heterogeneous catalysis. In particular, cinnamaldehyde can be used as probe molecule for revealing the competition between hydrogenation of C=C and C=O bond. Here, we investigated the effect of the modification of some Pt supported on carbon catalysts by WOx species in cinnamaldehyde hydrogenation, as WOx species are reported to increase the adsorption and activation of the C=O group of α, β‐unsaturated aldehydes. Classical techniques used for correlating the catalyst activity and the selectivity to the characteristic of the materials (XRD, HAADF‐STEM, XEDS mapping and XPS) have been coupled with NMR relaxometry, as innovative application, to disclose how the molecule approaches the catalyst surface. This indeed constitutes a crucial aspect that rule the catalytic activity. Therefore, an innovative, holistic approach has been used to consider the whole catalytic system. [ABSTRACT FROM AUTHOR]

Furan‐2,5‐dimethylcarboxylate (FDMC), along with ethylene glycol (EG), is the key monomer to produce (poly‐(ethylene‐furanoate) (PEF). Noble metal‐based catalysts can convert hydroxymethyl furfural (HMF) to FDMC in methanol through liquid phase catalytic oxidative esterification. In this work, the catalytic performance of Au, Pd and AuPd NPs supported on nanosized nickel oxide (nNiO) have been evaluated under base‐free conditions at 90 °C and 3 bar O2. Synergistic effects between Au and Pd imparted high activity and higher yield to FDMC compared to the monometallic counterparts. The role of support was also investigated by depositing AuPd NPs on TiO2 and nNiO‐TiO2. Remarkable yield to FDMC (85 % after 8 h) and high stability were observed over AuPd/ nNiO‐TiO2 catalyst. This peculiar catalytic behavior could be imputed to the formation of trimetallic AuPdNi particles offering highly active interfacial sites. [ABSTRACT FROM AUTHOR]

Wastewaters from precious metal industries contain high amounts of noble metals, but their efficient recycling is hindered by the wastewater complex composition. Here, we propose an innovative approach for the efficient recovery of noble metals contained in these metal-enriched wastewaters as precursors for the synthesis of noble metal nanoparticles (NPs) and supported metal catalysts. Silver NPs were synthesized from Ag-enriched wastewater and then deposited on TiO2 to prepare photocatalysts. Then, further promotion of the photocatalytic activity of Ag-modified TiO2 was achieved by the addition of as little as 0.5 wt.% of Au. STEM-EDS analyses proved that Au NPs were located on Ag or AgOx nanoparticles. The contact between the two metal-containing NPs results in charge transfer effects, appreciable both in terms of oxidation states determined by XPS and of optical properties. In particular, the plasmon band of Au NPs shows photochromic effects: under UV light irradiation, bimetallic samples exhibit a blue-shift of the plasmon band, which is reversible under dark storage. The activity of the materials was tested towards ethanol photodegradation under UV light. Adding 0.5 wt.% Au NPs resulted in a promoted activity compared to Ag-TiO2, thus showing synergistic effects between Au and Ag. Ethanol was completely converted already after 1 h of UV irradiation, acetaldehyde was formed as the main oxidation product and fully degraded in less than 180 min. Notably, bimetallic samples showed ethylene formation by a parallel dehydration mechanism. [ABSTRACT FROM AUTHOR]

Understanding the structure of a functional catalyst is crucial to disclosing the complexity of heterogeneous processes and improving their efficiency. Herein, coprecipitated cobalt-ceria (CoCeO x ) oxides doped with Ir (IrCoCeO x ) were synthesized and used to assess the performances of metal/oxide interfaces in the N 2 H 4 ·H 2 O decomposition performed in aqueous NaOH. Kinetic experiments in batch showed that CoO is the active phase of CoCeO x and that the copresence of Ir and Co (IrCoCeO x ) enhanced H 2 productivity. A comprehensive characterization (X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy) combined with robust computational modeling based on the density functional theory was employed to attribute the IrCoCeO x performance enhancement to the Ir/CoO metal/oxide interface, the active site of the reaction. On these sites, the improved H 2 productivity in the presence of aqueous NaOH was studied operando through modulated excitation-attenuated total reflectance infrared coupled with phase sensitive detection. The formation of surface Co-hydroxyl and -imido groups at the Ir/CoO interface induced the preferential breakage of the N-H bond of N 2 H 4 ·H 2 O, favoring the production of H 2 .

The CO 2 photoreduction is a promising way to convert one of the most abundant greenhouse gases to valuable chemicals. The photoreduction in the liquid phase is limited by the low solubility of CO 2 in water, but this point is overcome here by using an innovative photoreactor, which allows one to work up to pressures of 20 bar, improving the overall productivity. The photoreduction was performed in the presence of Na 2 SO 3 and using in primis commercial titanium dioxide (P25) and a set of titania catalysts functionalized by surface deposition of either monometallic or bimetallic cocatalysts. The gaseous products were hydrogen and traces of CO, while, in the liquid phase, formic acid/formate, formaldehyde and methanol were quantitatively detected. The pH was observed to shift the products distribution. A neutral environment led mainly to hydrogen and methanol, while, at pH 14, formate was the most abundant compound. The trend for monometallic cocatalysts showed enhanced productivity when using noble metals (i.e., gold and platinum). In order to limit the cost of the catalytic material, bimetallic cocatalysts were explored, adding titania with Au+Ag or Au+Pt. This may open to the possibility of performing the reaction with a smaller amount of the most expensive metals. In the end, we have expressed some conclusions on the cost of the photocatalysts here employed, to support the overall feasibility assessment of the process., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)