Opportunities for ceria-based mixed oxides versus commercial platinum-based catalysts in the soot combustion reaction. Mechanistic implications

The aim of this paper is to study the activities of ceria–zirconia and copper/ceria–zirconia catalysts, comparing with a commercial platinum/alumina catalyst, for soot combustion reaction under different gas atmospheres and loose contact mode (simulating diesel exhaust conditions), in order to analyse the kinetics and to deduce mechanistic implications. Activity tests were performed under isothermal and TPR conditions. The NO oxidation to NO2 was studied as well. It was checked that mass transfer limitations were not influencing the rate measurements. Global activation energies for the catalysed and non-catalysed soot combustion were calculated and properly discussed. The results reveal that ceria-based catalysts greatly enhance their activities under NOx/O2 between 425 °C and 450 °C, due to the “active oxygen”-assisted soot combustion. Remarkably, copper/ceria–zirconia shows a slightly higher soot combustion rate than the Pt-based catalyst (under NOx/O2, at 450 °C).The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEOII/2014/010 project) and the Spanish Ministry of Economy and Competitiveness (CTQ2012-30703 project, UE-FEDER funding)

Influence of peroxometallic intermediaries present on polyoxometalates nanoparticles surface on the adipic acid synthesis

The cyclohexene oxidation by hydrogen peroxide catalysed by polyoxometalates (POM) has been shown as an adequate green route for the adipic acid synthesis. In this study, it has been demonstrated that POM's salts are effective catalysts for this reaction and how peroxopolyoxometalates intermediaries are the truly responsible species of the POM's salts catalytic activity and solubility. However, the latter can be reduced by calcining the catalyst previously. Polyoxomolybdates salts generally present a higher activity than polyoxotungstenates salts. Finally, it must be remarked the positive effect exerted by the acetic acid stabilising the peroxide of hydrogen against its decomposition.The authors thank the Generalitat Valenciana and FEDER (PROMETEO/2009/047), and MICINN and Plan E (CTQ2012-31762) for the financial support

Active oxygen by Ce–Pr mixed oxide nanoparticles outperform diesel soot combustion Pt catalysts

A Ce0.5Pr0.5O2 mixed oxide has been prepared with the highest surface area and smallest particle size ever reported (125 m2/g and 7 nm, respectively), also being the most active diesel soot combustion catalyst ever tested under realistic conditions if catalysts forming highly volatile species are ruled out. This Ce–Pr mixed oxide is even more active than a reference platinum-based commercial catalyst. This study provides an example of the efficient participation of oxygen species released by a ceria catalyst in a heterogeneous catalysis reaction where both the catalyst and one of the reactants (soot) are solids. It has been concluded that both the ceria-based catalyst composition (nature and amount of dopant) and the particle size play key roles in the combustion of soot through the active oxygen-based mechanism. The composition determines the production of active oxygen and the particle size the transfer of such active oxygen species from catalyst to soot.The authors thank the financial support of Generalitat Valenciana (Project PROMETEOII/2014/010), the Spanish Ministry of Economy and Competitiveness (Project CTQ2012-30703), and the UE (FEDER funding)

Nanostructured Pr-Rich CexPr1-xO2-δ Mixed Oxides for Diesel Soot Combustion: Importance of Oxygen Lability

Soot combustion experiments with 5%O2/He were conducted using model soot, and four distinct compositions of CexPr1-xO2-δ oxides of varying nominal cerium compositions (x = 0, 0.2, 0.3, and 1) were prepared. The catalyst samples were comprehensively characterized using techniques such as XRD, Raman spectroscopy, HR-TEM, N2 adsorption at −196 °C, XPS, O2-TPD, H2-TPR, and work function measurements. The Pr-rich compositions, ranging from Ce0.3Pr0.7O2-δ to PrO2-δ, resulted in a significant increase in the total evolved O2 amounts and enhanced catalyst reducibility. However, a decrease in the textural properties of the catalysts was noted, which was particularly important for the pure praseodymia under the synthesis route conducted. The catalytic activity was investigated under the two following contact modes of mixing between soot and catalyst: loose and tight. The results revealed that the catalytic performance is associated with the surface contact in tight contact mode and with the combination of surface/subsurface/bulk oxygen mobility and the BET surface area in loose contact mode. Notably, the temperatures estimated at 10% and 50% of the conversion (T10 and T50) parameters were achieved at much lower temperatures than the uncatalyzed soot combustion, even under loose contact conditions. Specifically, the 50% conversion was achieved at 511 °C and 538 °C for Ce0.3Pr0.7O2 and Ce0.2Pr0.8O2, respectively. While no direct correlation between catalytic activity and work function was observed, a significant relationship emerges between work function values and the formation of oxygen vacancies, whatever the conditions used for these measurements. On the other hand, the ability to generate a high population of oxygen vacancies at low temperatures, rather than the direct activation of gas-phase O2, influences the catalytic performance of Pr-doped ceria catalysts, highlighting the importance of surface/subsurface oxygen vacancy generation, which was the parameter that showed a better correlation with the catalytic activity, whatever the soot conversion value or the mode of contact considered.This research was funded by the financial support of the Spanish Ministry of Science and Innovation/Research Spanish Agency (PID2019-105542RB-I00/AEI/10.13039/501100011033 project), UE-FEDER funding, and Generalitat Valenciana (CIPROM/2021/070 project). I.M. also acknowledges the Algerian Ministry of Higher Education and Scientific Research for the financial support provided through the national grant

Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot

This work presents a comparative study between the catalytic performance of the 2% CuO/ceria-zirconia powder catalyst and the same catalyst supported on silicon carbide DPF (Diesel Particulate Filter) towards NO oxidation reaction and soot combustion reaction. The ceria-zirconia catalyst was prepared by the co-precipitation method and 2 wt% copper was incorporated by the incipient wetness impregnation method. The catalyst was incorporated onto the ceramic support using a simple and organic solvent-free procedure by a simply dipping the DPF into an aqueous solution of the catalyst. The powder catalyst has been characterized using N2 adsorption at −196 °C, XRD and Raman Spectroscopy; whereas the catalytic coating morphology has been evaluated by SEM and the mechanical stability by an adherence test. Both catalyst configurations were tested for NO oxidation to NO2 and for soot combustion under NOx/O2. The results revealed that incorporation of the very active copper/ceria-zirconia catalyst onto SiC-DPF has been successfully achieved by a simple coating procedure. Furthermore, the catalytic coating has shown suitable mechanical, chemical and thermal stability. A satisfactory catalytic performance of the catalytic-coated filter was reached towards the NO oxidation reaction. Moreover, it was proved that the catalytic coating is stable and the corresponding coated DPF can be reused for several cycles of NO oxidation without a significant decrease in its activity. Finally, it was verified that the loose-contact mode is a good choice to simulate the catalytic performance of this active phase in a real diesel particulate filter.The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEOII/2014/010 project), the Spanish Ministry of Economy and Competitiveness (CTQ2012-30703 project, UE-FEDER funding). S.Q.D. wishes to thank VIDI-University of Alicante her Master Thesis Grant

Behavior of different soot combustion catalysts under NOx/O2. Importance of the catalyst–soot contact

Four different catalysts (Pt/Al2O3, Ce0.8Zr0.2O2, PrO2−x and SrTiCuO3) have been investigated on a laboratory scale to evaluate their potential as diesel soot combustion catalysts under different experimental conditions, which simulate the situation found in a continuous regeneration technology trap (dual-bed configuration of catalyst and soot) or a catalyst-coated filter system (single-bed configuration, both catalyst and soot particles mixed under loose-contact mode). Under dual-bed configuration, the behavior of the catalysts towards soot combustion are very similar, despite the differences observed in the NO2 production profiles. However, under single-bed configuration, there are important differences in the soot combustion activities and in the NO2 slip profiles. The configurations chosen have an enormous impact on CO/(CO + CO2) ratios of combustion products as well. The most active catalyst under NOx + O2 is PrO2−x combining a high contribution of active oxygen-assisted soot combustion as well as high NO2 production activity along the catalytic bed.Financial support of Generalitat Valenciana (Prometeo/2009/047 project) and the Spanish Ministry of Science and Innovation (project CTQ2012-30703, which is co-funded by FEDER resources). N. G. H. wishes to thank Generalitat Valenciana her Ph.D. grant within VAL i+d Program

Ceria-based catalysts for NOx removal in NSR processes: A fundamental study of the catalyst modifications explored by in situ techniques

In this work, a fundamental and systematic study was conducted, leading to a better understanding of the phenomena occurring on the catalyst’s surface during the NOx reduction process in NSR systems. For this purpose, ceria-based catalysts, with Cu in substitution of noble metal, have been synthesized and deeply characterized by means of XRF, XPS, in situ (XRD, Raman spectroscopy and DRIFTS), temperature-programmed reduction under H2 (H2-TPR) and under NO reaction (NO isothermal reaction + NO-TPR). The whole results show the key role of copper to promote the reducibility and the creation of oxygen vacancies, allowing a high NO consumption and fast kinetics of N2O and N2 formation, until the oxygen vacancies consumption takes place. The study of the surface reactions taking place in the formation of adsorbed NOx species and the oxygen vacancies consumption with NO uptake is complex; however, a hydroxyl consumption route is found to be involved. The reduction of NO provided higher levels of N2 at higher temperatures; also, a very high efficiency of the previously created oxygen vacancies was found for this process.The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEO/2018/076 project) and the Spanish Ministry of Science and Innovation (PID2019-105542RB-I00 project) and the UE-FEDER funding. Martínez-Munuera also acknowledges Spanish Ministry of Science, Innovation and Universities for the financial support through a FPU grant (FPU17/00603)

Study of Ce/Pr ratio in ceria-praseodymia catalysts for soot combustion under different atmospheres

The effect of Ce/Pr ratio on ceria-praseodymia on structural and surface properties is studied. The catalytic activity towards soot combustion under NOx/O2 and O2/N2 atmospheres is also evaluated, together with the NO oxidation activity to NO2. CexPr1-xO2-δ compositions (x = 0.8, 0.5 and 0.2) have been prepared along with ceria and praseodymia. Catalysts were prepared by co-precipitation. The Ce0.5Pr0.5O2-δ composition, was also prepared by nitrate calcination. Ceria-praseodymia mixed oxides yield reduction profiles shifted to lower temperatures, higher NO oxidation activities to NO2 and improved catalytic activities for soot combustion with respect to pure ceria. Ce0.5Pr0.5O2-δ was the most active one. Under NOx/O2, it has greater soot combustion activity if it is prepared by nitrate calcination. However, under O2/N2, the co-precipitation method is more favorable because of the better dopant insertion achieved in the ceria lattice, which seems to lead better oxygen mobility on the surface and in the bulk oxide.The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEO/2018/076 project) and the Spanish Ministry of Economy and Competitiveness (CTQ2015-64801-R project) and the UE-FEDER funding. J.C.M.M. also acknowledges Spanish Ministry of Science, Innovation and Universities for the financial support through a FPU grant (FPU17/00603)

Ceria-Praseodymia Mixed Oxides: Relationships Between Redox Properties and Catalytic Activities Towards NO Oxidation to NO2 and CO-PROX Reactions

A series of CexPr1−xO2−δ catalysts was prepared by co-precipitation method in alkali media. These catalysts were characterized by N2 adsorption–desorption isotherms at −196 °C, X-ray diffraction, thermogravimetry combined with mass spectrometry (TG-MS), and temperature-programmed reduction with H2 and CO (H2-TPR and CO-TPR, respectively). Catalytic tests were performed for temperature programmed NO oxidation to NO2 (from 25 to 750 °C) and for the preferential oxidation of CO in H2 rich stream (CO-PROX reaction) in the range of 150–500 °C. The trends in the order of catalytic activities towards NO oxidation and CO-PROX are correlated with the redox properties of the catalysts and their composition. CexPr1−xO2−δ mixed oxides present very different catalytic behaviours towards NO oxidation and CO-PROX reactions. These experimental trends might be explained by the balance of several factors: the acid character of the NO and CO molecules, the different lattice oxygen mobility of the catalysts, the presence of surface carbonates species in the samples, and the catalysts’ reducibility under H2 and CO. The understanding of the features that govern the activity towards these environmentally relevant oxidation reactions is important in the designing of effective catalysts.The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEOII/2014/010), MINECO (CTQ2015-64801-R, MAT2013-40823-R, CSD2009-00013) and the UE (FEDER funding). X. Chen thanks the program of “Ramón y Cajal” from Ministry of Science and Innovation of Spain

Isotopic study of the influence of oxygen interaction and surface species over different catalysts on the soot removal mechanism

In order to improve the catalytic formulations for soot removal in after-treatment emission control technologies for gasoline and diesel engine vehicle, an isotopic study was approached using transitory labeled oxygen response method over model catalysts that allows the unraveling of soot oxidation mechanism. Ce-based materials promote oxygen exchange associated with the high population of lattice oxygen species (O2-) denoted as OI type. The incorporation of praseodymium produces a Pr3+ enrichment that decrease the energy for oxygen release and increase oxygen mobility through surface and subsurface oxygen centers (OII type) depending on the synthesis procedure. For PtBaK catalyst, OIII species are responsible for oxygen exchange. Gas-solid reaction between soot and gas phase molecular oxygen is responsible for direct uncatalyzed soot oxidation. For ceria containing catalysts, low-temperature soot removal takes place through the intervention of lattice atomic species and superoxide species. For DPNR model catalyst, PtBaK/Al2O3, the soot elimination occurs with the intervention OIII type centers. In the presence NO, the assisted and cooperative mechanism due to NO2 and the intervention of the adsorbed nitrate species on the trimetallic catalyst enhances soot removal capacity.MCR acknowledges the postdoctoral fellowship obtained from the University of Malaga. MCR, CH, MAL and LJA want to thank the financial support of CTQ 2017-87909R project. MCR also want to thank the University of Alicante for the financial support for the internship (INV19-07). JCMM and AGG gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEO/2018/076 project) and the Spanish Ministry of Science, Innovation and Universities (PID2019-105542RB-I00 project) and the UE-FEDER funding. JCMM also acknowledges Spanish Ministry of Science, Innovation and Universities for the financial support through a FPU grant (FPU17/00603)