Mesoporous multicomponent materials with uniform pore sizes and well-defined network geometries are viewed as highly attractive candidates in the catalysis field. However, their synthesis at a high homogeneity level is considered quite challenging. Herein, alumina based mixed oxides (Al/Ce/Cu or Fe) are produced through a facile evaporation-induced-self-assembly route and tested towards preferential oxidation of CO in H2-rich gas. The effect of several synthetic parameters is investigated, with citric acid addition identified as a key factor in view of obtaining high mesoscopic order and notable homogeneity, particularly at high dopant amounts. Following thermal aging at 900 & DEG;C, metal oxides distribution and nanoporous nature are well-preserved with a parallel nucleation of ceria nanoparticles into the semi-crystalline inorganic framework. CO-PROX assessment of the aged samples reveals a drastic enhancement in catalytic activity, especially for the ternary Cu-Ce-Al system, associated with material's structural reconstruction strongly affecting metal-support interaction.& COPY; 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Supported CuO catalysts onto a highly crystalline mesoporous TiO2 material are produced via an ammonium driven deposition precipitation method and tested for prefere degrees ntial oxidation of CO in H-2-rich gases. The effect of Cu loading on the oxidation activity is investigated by producing samples with final Cu content varying between 2.5 and 10 wt%. According to the analysis results, the chemical nature of the CuO species differs in each sample depending on the Cu loading. All materials tested are highly selective towards CO oxidation up to 160 degrees C. The 5 wt% Cu loaded material demonstrates the optimum CO-PROX performance, which is ascribed to the formation of finely dispersed and easily reducible copper oxide nanoparticles. Stability and durability of the latter sample are assessed by performing multiple testing cycles corresponding to >100hrs on stream as well as by the separate and combined addition of CO2 and H2O in the feeding stream.
Hydrothermal deoxygenation of tall oil fatty acids (TOFA) was investigated in the presence of aqueous formic acid (0.5–7.5 wt%) as a H 2 donor in the presence of subcritical H 2 O pressure (569–599 K). Pd and Ru nanoparticles supported on carbon (5% Pd/CSigma, 5% Ru/CSigma, 10% Pd/CO850_DP, and 5% Ru/COPcomm_DP) were found to be efficient catalysts for deoxygenation of TOFA. The reaction pathway was mainly influenced by the concentration of formic acid and the catalyst. In case of Pd catalysts, in the presence of 0–2.5 wt% formic acid, decarboxylation was the dominant pathway producing n-paraffinic hydrocarbons with one less carbon atom (heptadecane yield up to 94 wt%), while with 5–7.5% formic acid, a hydrodeoxygenation/hydrogenation mechanism was favored producing C18 deoxygenation products octadecanol and octadecane as the main products (yields up to 70 wt%). In contrast, Ru catalysts produced a mixture of C5-C20 (n-and iso-paraffinic) hydrocarbons via decarboxylation, cracking and isomerization (up to 58 wt% C17 yield and total hydrocarbon yield up to 95 wt%) irrespective of formic acid concentration. Kinetic studies showed that the rates of deoxygenation displayed Arrhenius type behavior with apparent activation energies of 134.44 ± 31.36 kJ/mol and 148.92 ± 3.66 kJ/mol, for the 5% Pd/CSigma and 5% Ru/CSigma catalyst, respectively. Furthermore, the experiments with glycerol tristearate, rapeseed oil, sunflower oil, rapeseed biodiesel, and hydrolyzed rapeseed oil produced identical products confirming the versatility of the aforementioned catalytic systems for deoxygenation of C18 feedstocks.