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Metallic nanoparticles exsolved at the surface of perovskite oxides have been recently shown to unlock superior catalytic activity and durability towards various chemical reactions of practical importance. For example, for the CO oxidation reaction, exsolved Ni nanoparticles in oxidised form exhibit site activities approaching those of noble metals. This is of particular interest for the prospect of replacing noble metals with earth-abundant metal/metal oxide catalysts in the automotive exhaust control industry. Here we show that for the CO oxidation reaction, the functionality of exsolved Ni nanoparticles can be further improved when Fe is co-exsolved with Ni, as Fe–Ni alloy nanoparticles, eventually forming mixed oxide nanoparticles. As compared to the Ni nanoparticles, the alloy nanoparticles exhibit higher site activities, greatly improved durability over 170 h of continuous testing and increased tolerance towards sulphur-based atmospheres. Similarly to the single metal nanoparticles, the alloys demonstrate outstanding microstructural stability and high tolerance towards coking. These results open additional directions for tailoring the activity and durability of exsolved materials for the CO oxidation reaction and beyond. [ABSTRACT FROM AUTHOR]

Abstract: Calibration of kinetic models of wet air oxidation (WAO) is usually performed through minimisation algorithms with respect to total organic carbon (TOC) experimental data. However, the reliability of the estimated value of the kinetic parameters is frequently not reported. Moreover, the influence of data quantity/quality in the kinetic parameters identifiability is not properly assessed. The objective of this study is to compare the calibration goodness of a proposed kinetic model when using one set of data (total effluent TOC [TOCeff]) or two sets of independent experimental measurements (total effluent TOC [TOCeff] and residual TOC of target pollutant [TOC[A]]). The systematic comparison was made using identifiability analysis with contour plots of both objective functions and the confidence intervals were calculated through the Fisher information matrix (FIM). The experimental data used in this study comes from a previous one, where WAO was investigated as a suitable precursor for the biological treatment of industrial wastewater containing high concentrations of o-cresol or 2-chlorophenol [M.E. Suárez-Ojeda, J. Carrera, I.S. Metcalfe, J. Font, Wet air oxidation (WAO) as a precursor to biological treatment of substituted phenols: refractory nature of the WAO intermediates, Chem. Eng. J. 144 (2008) 205–212.]. The results show that the model correctly fitted the experimental [TOCeff] in all cases with less than 6% as averaged relative deviation, either using one set of data ([TOCeff]) or two sets of independent experimental measures ([TOCeff] and [TOC[A]]) in the objective function. However, when using only [TOCeff], the model was not capable of fitting the proportion between [TOC[A]] and intermediates TOC. The obtained E ACT for the calibration made with [TOCeff] and [TOC[A]] were 71±20kJmol−1 (R 2 =0.92) and 47±9kJmol−1 (R 2 =0.96) for o-cresol and 2-chlorophenol, respectively. However, when using just [TOCeff], the obtained E ACT values were not in the range of the values reported in the literature and had smaller regression coefficients. Moreover, the calibration with just [TOCeff] presented a high correlation between the obtained rate constants, whereas the calibration with [TOCeff] and [TOC[A]] was statistically more reliable. As example, the D-criterion values are three to six times larger for the calibration made with ([TOCeff] and [TOC[A]] than for the calibration made only with [TOCeff], in the framework of OED/PE criteria, this is related to minimisation of the geometric mean of the identification errors. [Copyright &y& Elsevier]

Abstract: Wet air oxidation (WAO) was investigated as a suitable precursor for the biological treatment of industrial wastewaters that contained high concentrations of phenol, o-cresol or 2-chlorophenol. Two hours WAO semi-batch experiments were conducted at 2 and 9bar of oxygen partial pressure () and at 215, 240 and 265°C with total organic carbon (TOC) abatement up to 86%. The influence of hydroxyl-, methyl- and chloride ring substitution on the oxidation mechanism of aromatic compounds was established. Also, the readily biodegradable COD fraction (%CODRB) of the WAO effluents was found by respirometric techniques. The maximum %CODRB was 24% for phenol WAO at 265°C and 9bar of , 10% for o-cresol WAO at 265°C and 9bar of and 19% for 2-chlorophenol WAO at 215°C and 2bar of . These results allow comparison of whether or not the WAO effluents were suitable for a conventional activated sludge plant with non-acclimated biomass. Also, the results were compared to those obtained from a previous study for the same model compounds but using catalytic WAO (CWAO) with activated carbon (AC) as a catalyst [1]. This comparison allows us to establish whether or not the WAO effluents were less biodegradable or had more refractory intermediates than CWAO effluents. [Copyright &y& Elsevier]

Abstract: The decomposition of sodium dodecylbenzene sulfonate (SDBS) in water by means of ultrasound irradiation at 20kHz was investigated. Experiments were conducted at surfactant concentrations of 175, 260 and 350mgl−1, liquid volumes of 120, 170 and 220ml, temperatures of 20, 30 and 45°C and applied power of 40, 80 and 125W. The extent of degradation was followed monitoring substrate and organic carbon concentrations, while hydrogen peroxide concentration was also measured; the latter is a product of water sonolysis due to hydroxyl radical recombination. 80% SDBS conversion was achieved after 120min of sonication at 125W and 30°C; nonetheless, SDBS and its degradation intermediates proved difficult to oxidise as only about 20–25% of the initial carbon content was transformed to carbon dioxide. At the initial stages of the reaction, degradation rate appears to be only weakly dependent on the substrate concentration with the rate increasing from 3.1 to 4mgl−1 min−1 with increasing concentration from 175 to 350mgl−1. Degradation appears to occur at the bubble-liquid interface through hydroxyl radical-mediated reactions whose role was established by performing experiments in the presence of radical scavengers, namely potassium bromide and sodium benzoate. Degradation rates increased with increasing power and decreasing temperature and volume. [Copyright &y& Elsevier]

Graphical abstract Ni x Cu 1- x Al 2 O 4 spinel solution suppresses carbon deposition during the chemical looping oxidation of CH 4 by Ni-Cu-Al 2 O 3 oxygen carriers. The Ni-Cu-Al 2 O 3 oxygen carriers also contain highly active redox-active lattice oxygen compared to a single metal oxide (CuO or NiO) supported on Al 2 O 3. Highlights • Ni-Cu-Al 2 O 3 oxygen carriers with stable performance over 100 redox cycles. • Fully characterized phase interactions in Ni-Cu-Al 2 O 3 oxygen carriers. • CuO-NiO interaction promotes lattice oxygen activity. • Ni 1- x Cu x Al 2 O 4 spinel solid solution is resistant against carbon deposition. Abstract Chemical looping processes present great potentials to achieve carbon capture and fuel conversion with high thermodynamic efficiencies. Well-known applications of chemical looping include combustion and methane reforming, where phase interactions in oxygen carriers play important roles in determining the process performance. In this study, we systematically investigate the interactions between various phases in Ni-Cu-Al 2 O 3 mixed oxides oxygen carriers, which were prepared from layered double hydroxides precursors, synthesized hydrothermally using urea and metal nitrates. It appears that the addition of 32–45 wt% Al 2 O 3 was sufficient to prevent sintering effects over 100 redox cycles at 800 °C, 1 atm, using methane as the fuel. The oxide phases and their compositions were determined using a set of complementary analytical techniques, allowing us to establish relationships between (i) the compositions of the mixed oxides, (ii) the chemical activity of the various types of lattice oxygen present and (iii) the distributions of gaseous products of chemical looping methane oxidation. We found that the mutual doping between NiO and CuO leads to enhanced lattice oxygen activities, whilst the solid solution of NiAl 2 O 4 and CuAl 2 O 4 leads to reduced lattice oxygen activity in the spinel phase, which also turns out to be particularly resistant to carbon deposition. The generality of the composition – activity - performance relationship is demonstrated by the successful prediction of the product distributions of methane oxidation based on solely the elemental compositions of the oxygen carriers. These findings enable the rational formulation of Ni-Cu-Al 2 O 3 oxygen carriers for methane conversion with precise control of product selectivity. [ABSTRACT FROM AUTHOR]

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure () and at 180, 200 and 220°C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and were 140–160°C and 2–9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160°C and 2 bar of , which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (CODRB) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. [Copyright &y& Elsevier]