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The imperative reduction of carbon dioxide into valuable fuels stands as a crucial step in the transition towards a more sustainable energy system. Perovskite oxides, with their high compositional and property adjustability, emerge as promising catalysts for this purpose, whether employed independently or as a supporting matrix for other active metals. In this study, an A-site-deficient La0.9FeO3 perovskite underwent surface decoration with Ni, Cu or Ni + Cu via a citric acid-templated wet impregnation method. Following extensive characterization through XRD, N2 physisorption, H2-TPR, SEM-EDX, HAADF STEM-EDX mapping, CO2-TPD and XPS, the prepared powders underwent reduction under diluted H2 to yield metallic nanoparticles (NPs). The prepared catalysts were then evaluated for CO2 reduction in a CO2/H2 = 1/4 mixture. The deposition of Ni or Cu NPs on the perovskite support significantly enhanced the conversion of CO2, achieving a 50% conversion rate at 500 °C, albeit resulting in only CO as the final product. Notably, the catalyst featuring Ni-Cu co-deposition outperformed in the intermediate temperature range, exhibiting high selectivity for CH4 production around 350 °C. For this latter catalyst, a synergistic effect of the metal–support interaction was evidenced by H2-TPR and CO2-TPD experiments as well as a better nanoparticle dispersion. A remarkable stability in a 20 h time-span was also demonstrated for all catalysts, especially the one with Ni-Cu co-deposition. [ABSTRACT FROM AUTHOR]

Ammonia exhibits interesting features as fuel to feed Solid Oxide Fuel Cell. Herein, Ni and La co-doped strontium titanate was synthetized using wet chemistry route. Ni nanoparticles emerged via exsolution in reducing environment to decorate the surface. X-Ray Diffraction measurements exhibits perovskite structure was also preserved after the exsolution, as expected. H2 – Temperature Programmed Reduction highlights the great resistance of titanates in anode operation condition. Ammonia conversion in nitrogen and hydrogen were investigated by catalytic tests. It begins to decompose at 560°C and the full yield was achieved at 720°C. Electrochemical measurements were recorded at 800°C using 10% of ammonia in Ar. They were analysed though the model of equivalent circuit and two processes were attributed. Results certify Ni exsolution strongly enhances the hydrogen oxidation and the total polarisation resistance in ammonia approaches to the one in hydrogen.

Carbon dioxide valorisation is one of the most discussed topics amongst researchers; indeed, finding a way to significantly reduce CO2 concentration in the atmosphere is crucial in order to mitigate climate change effects in the next decades. In this study, SrTiO3-supported Cu nanoparticles are exploited as Localised Surface Plasmon Resonance (LSPR)-mediated catalysts for CO2 reduction. The materials were prepared via sol–gel citrate route methodology, inserting Cu as a dopant in the perovskite structure; reducing treatments at different temperatures were performed to promote copper atom exsolution, thus forming nanostructures upon the surface. The perovskitic structure was confirmed via ex situ and operando XRD analysis, while compositional analysis was carried out through XPS and EDS; SEM and TEM images revealed morphological changes with different reducing treatments, and bulk reducibility was analysed with H2-TPR, revealing different Cu species in the material. Band gap analysis via DRS showed the successful incorporation of copper in the perovskite, affecting the light absorption properties. Finally, catalytic tests showed that copper nanoparticles play a role in CO2 activation with sunlight, proving that LSPR could be exploited for catalytic means. [ABSTRACT FROM AUTHOR]

LaMnO3-based perovskites are widely recognized as promising catalysts for several oxidation reactions, but the final physicochemical and catalytic properties can be greatly influenced by the adopted synthesis procedure. In this work, a series of A-site-deficient perovskites of composition La0.8MnO3 and La0.8Mn0.9B0.1O3 (B = Ni, Cu) were prepared through the citrate combustion route with variations in two synthesis parameters: a citric acid/metal cations molar ratio (CA/M) of either 1.1 or 1.5 and either acidic (given by HNO3 + citric acid) or neutral (after NH3 addition) pH of the precursor solution. The obtained samples were characterized by XRD, H2-TPR, O2-TPD, N2 physisorption, SEM-EDX and XPS. Acidic pH coupled with a CA/M ratio of 1.1 clearly emerged superior among all the other combinations of the two parameters, resulting in smaller crystallite size, higher surface area and porosity, enhanced Mn4+ reducibility and the ability to release oxygen species; these features were even further improved by B-site substitution with 10 mol% Ni and Cu cations. The synthesized catalysts were tested in CH4 oxidation to CO2 under stoichiometric O2, confirming the great superiority of samples prepared in acidic pH with a CA/M ratio of 1.1. Ni and Cu doping had a beneficial effect on catalytic activity, which, however, was more evident for less optimized perovskites (acidic pH and CA/M ratio of 1.5), without significance differences among the two dopants. [ABSTRACT FROM AUTHOR]

From the plethora of energy-intensive synthetic processes, ammonia production has a particularly negative impact due to the high-energy consumption caused by the Haber–Bosch process and the high greenhouse gas (GHG) emission rate. Thus, new and effective ways to activate N2 and synthesise NH3 are crucial to reduce production costs and the anthropogenic footprint derived from the current harsh reaction conditions. In this study, two-dimensional materials have been employed in the photoactivation of nitrogen in an aqueous medium; MI(II)MII(III) (with MI = Cu or CuNi, and MII = Cr or Al) layered double hydroxides have been synthesised using a simple, economical and scalable co-precipitation/filtration method. The structural and functional properties were systematically investigated by XRD, SEM, TPR and BET; the results indicate that the prepared LDHs were successfully synthesised, possess high surface areas and, in the case of CuAl LDH, the material showed a nanoplate-like structure, thus confirming the two-dimensional nature of this class of catalyst. The N2 fixation performances were evaluated using a scalable, cost-effective and low-energy-consuming setup; from the catalytic tests, a NH3 production rate of 99 μmol g−1 h−1 was observed, demonstrating LDHs' high potential and the scalability of the overall process. [ABSTRACT FROM AUTHOR]

From the plethora of energy-intensive synthetic processes, ammonia production has a particularly negative impact due to the high-energy consumption caused by the Haber-Bosch process and the high greenhouse gas (GHG) emission rate. Thus, new and effective ways to activate N 2 and synthesise NH 3 are crucial to reduce production costs and the anthropogenic footprint derived from the current harsh reaction conditions. In this study, two-dimensional materials have been employed in the photoactivation of nitrogen in an aqueous medium; M I (II)M II (III) (with M I = Cu or CuNi, and M II = Cr or Al) layered double hydroxides have been synthesised using a simple, economical and scalable co-precipitation/filtration method. The structural and functional properties were systematically investigated by XRD, SEM, TPR and BET; the results indicate that the prepared LDHs were successfully synthesised, possess high surface areas and, in the case of CuAl LDH, the material showed a nanoplate-like structure, thus confirming the two-dimensional nature of this class of catalyst. The N 2 fixation performances were evaluated using a scalable, cost-effective and low-energy-consuming setup; from the catalytic tests, a NH 3 production rate of 99 μmol g -1 h -1 was observed, demonstrating LDHs' high potential and the scalability of the overall process.

To promote the diffusion on the market of solid oxide fuel cell (SOFC) devices, the use of fuels other than the most appealing hydrogen and also decreasing the working temperature could show the way forward. In the first part, we concentrated our efforts on cathodes; hereby, we focused on anodes and concentrated our efforts to develop a sustainable multifuel anode. We decided to develop LSGF (La 0.6 Sr 0.4 Ga 0.3 Fe 0.7 O 3 )-based nanocomposites by depositing manganite oxide to enhance the performance toward propane. MnO x has been deposited by a wet impregnation method, and the powders have been largely characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction, oxygen temperature-programmed desorption, and N 2 adsorption. Cell performances were first collected in hydrogen as a function of both the temperature and hydrogen content. EIS measurements were studied using Nyquist and Bode plots, and they show two processes at high frequency, assigned to charge transfer at the electrode/electrolyte interface, and at low frequency due to the dissociative adsorption of hydrogen. The Arrhenius plot of area specific resistance suggests two different trends, and the activation energy decreases from 117 kJ/mol at 750 °C to 46 kJ/mol above that temperature. This behavior is often connected to chemical modification of the catalyst or changes in the limiting step processes. Power densities in hydrogen and propane were determined at 744 °C after 1 h of operation, achieving 70 mW/cm 2 in H 2 and 67 mW/cm 2 in C 3 H 8 . The open-circuit voltage increases from 1.10 V in hydrogen to 1.13 V in propane., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)