Screening Ba0.9A0.1MnO3 and Ba0.9A0.1Mn0.7Cu0.3O3 (A = Mg, Ca, Sr, Ce, La) Sol-Gel Synthesised Perovskites as GPF Catalysts

Ba0.9A0.1MnO3 (BM-A) and Ba0.9A0.1Mn0.7Cu0.3O3 (BMC-A) (A = Mg, Ca, Sr, Ce, La) perovskite-type mixed oxides were synthesised, characterised, and used for soot oxidation in simulated Gasoline Direct Injection (GDI) engine exhaust conditions. The samples have been obtained by the sol-gel method in an aqueous medium and deeply characterised. The characterization results indicate that the partial substitution of Ba by A metal in BaMnO3 (BM) and BaMn0.7Cu0.3O3 (BMC) perovskites: (i) favours the hexagonal structure of perovskite; (ii) improves the reducibility and the oxygen desorption during Temperature-Programmed Desorption (O2-TPD) tests and, consequently, the oxygen mobility; (iii) mantains the amount of oxygen vacancies and of Mn(IV) and Mn(III) oxidation states, being Mn(IV) the main one; and (iv) for Ba0.9A0.1Mn0.7Cu0.3O3 (BMC-A) series, copper is partially incorporated into the structure. The soot conversion data reveal that Ba0.9La0.1Mn0.7Cu0.3O3 (BMC-La) is the most active catalyst in an inert (100% He) reaction atmosphere, as it presents the highest amount of copper on the surface, and that Ba0.9Ce0.1Mn0.7Cu0.3O3 (BM-Ce) is the best one if a low amount of O2 (1% O2 in He) is present, as it combines the highest emission of oxygen with the good redox properties of Ce(IV)/Ce(III) and Mn(IV)/Mn(III) pairs.This research was funded by the Spanish Government (MINCINN: PID2019-105542RB-I00/AEI/10.13039/501100011033 Project), the European Union (FEDER Funds), and Generalitat Valenciana (CIPROM/2021-070 Project). N. Ghezali thanks Argelian Government for her thesis grant and Á. Díaz-Verde of the University of Alicante for his predoctoral contract

Exploring the effect of using carbon black in the sol-gel synthesis of BaMnO3 and BaMn0.7Cu0.3O3 perovskite catalysts for CO oxidation

BaMnO3 and copper-doped BaMnO3 perovskites seem to be a feasible alternative to current catalysts for the exhaust treatment. In this work, these formulations have been synthesized by a modified sol-gel method in which carbon black has been added to the conventional sol-gel process in order to improve the physical and chemical properties that modulate the catalytic performance. The samples have been deeply characterized by ICP-OES, XRD, XPS, H2-TPR and O2-TPD. The characterization results point out that the use of carbon black allows decreasing the calcination temperature which minimizes the sintering effects and improves the textural properties, the reducibility, and the oxygen mobility. The study of CO oxidation, using different simulated atmospheres, reveals that all the catalysts were active for CO to CO2 oxidation, but only when oxygen is supplied in excess, an effect of the synthesis method is observed. Additionally, as expected, the presence of copper (inserted or not into the perovskite lattice) benefits the catalytic performance. Otherwise, it seems that the catalytic performance for CO oxidation of BaMnO3-based samples is less affected by the fluctuations of CO and O2 concentrations than the platinum-based catalyst used as reference

Improving the Catalytic Performance of BaMn0.7Cu0.3O3 Perovskite for CO Oxidation in Simulated Cars Exhaust Conditions by Partial Substitution of Ba

The sol–gel method, adapted to aqueous media, was used for the synthesis of BaMn0.7Cu0.3O3 (BMC) and Ba0.9A0.1Mn0.7Cu0.3O3 (BMC-A, A = Ce, La or Mg) perovskite-type mixed oxides. These samples were fully characterized by ICP-OES, XRD, XPS, H2-TPR, BET, and O2–TPD and, subsequently, they were evaluated as catalysts for CO oxidation under different conditions simulating that found in cars exhaust. The characterization results show that after the partial replacement of Ba by A metal in BMC perovskite: (i) a fraction of the polytype structure was converted to the hexagonal BaMnO3 perovskite structure, (ii) A metal used as dopant was incorporated into the lattice of the perovskite, (iii) oxygen vacancies existed on the surface of samples, and iv) Mn(IV) and Mn(III) coexisted on the surface and in the bulk, with Mn(IV) being the main oxidation state on the surface. In the three reactant atmospheres used, all samples catalysed the CO to CO2 oxidation reaction, showing better performances after the addition of A metal and for reactant mixtures with low CO/O2 ratios. BMC-Ce was the most active catalyst because it combined the highest reducibility and oxygen mobility, the presence of copper and of oxygen vacancies on the surface, the contribution of the Ce(IV)/Ce(III) redox pair, and a high proportion of surface and bulk Mn(IV). At 200 °C and in the 0.1% CO + 10% O2 reactant gas mixture, the CO conversion using BMC-Ce was very similar to the achieved with a 1% Pt/Al2O3 (Pt-Al) reference catalyst.This research was funded by the Spanish Government (MINCINN: PID2019-105542RB-I00/AEI/10.13039/501100011033 Project), the European Union (FEDER Funds), and Generalitat Valenciana (CIPROM/2021-070 Project). N. Ghezali thanks Argelian Government for her thesis grant and Á. Díaz-Verde thanks the University of Alicante for his predoctoral contract

Analyzing the role of copper in the soot oxidation performance of BaMnO3-perovskite-based catalyst obtained by modified sol-gel synthesis

A series of BaMn0.7Cu0.3O3 solids were prepared by a modified sol-gel method in which carbon black (VULCAN XC-72R), and different calcination temperatures (BMC3-CX, where X indicates the calcination temperature) have been used. The fresh and used catalysts were characterized by ICP-OES, XRD, XPS, FESEM, TEM, O2-TPD and H2-TPR. The presence of a carbon black during sol-gel synthesis of BMC3 mixed oxide allows diminishing the calcination temperature needed to achieve the perovskite structure, but it hinders the formation of the BaMnO3 polytype. The use of low calcination temperatures during synthesis reduces the sintering effects, and the mixed oxides present lower particle size, slightly higher BET surface areas and macropores with lower diameter than BMC3. The distribution of copper in BMC3-CX catalysts depends on the calcination temperature and copper insertion into the perovskite structure is promoted as the calcination temperature increases. All BMC3-CX catalysts are active for NO to NO2 and NOx-assisted soot oxidation processes, but only BMC3-C600 and BMC3-C700 show higher catalytic activity than BMC3 reference catalyst. BMC3-C600 presents the best performance as it features a high amount of surface copper and oxygen vacancies that increase during reaction. The comparison between the performance of the two best catalysts of the BM-CX series (BM-C700) and the BMC3-CX series (BMC3-C600) suggests that the unique advantage of using copper in the modified sol-gel synthesis is an additional decrease of 100 °C in the calcination temperature used for the synthesis of the best catalyst, which is 700 °C for BM-CX and 600 °C for BMC3-CX.This research was funded by Spanish Government (PID2019-105542RB-I00) and EU (FEDER Founding)

Modified BaMnO3-Based Catalysts for Gasoline Particle Filters (GPF): A Preliminary Study

Gasoline engines, mainly gasoline direct injection engines (GDI) require, in addition to three-way catalysts (TWC), a new catalytic system to remove the formed soot. Gasoline Particle Filters (GPF) are, among others, a possible solution. BaMnO3 and copper-doped BaMnO3 perovskites seem to be a feasible alternative to current catalysts for GPF. The physical and chemical properties of these two perovskites determining the catalytic performance have been modified using different synthesis routes: (i) sol-gel, (ii) modified sol-gel and iii) hydrothermal. The deep characterization allows concluding that: (i) all samples present a perovskite-like structure (hexagonal), except BMC3 which shows a polytype one (due to the distortion caused by copper insertion in the lattice), and ii) when a low calcination temperature is used during synthesis, the sintering effect decreases and the textural properties, the reducibility and the oxygen mobility are improved. The study of soot oxidation simulating the hardest GDI scenarios reveals that, as for diesel soot removal, the best catalytic performance involves the presence of oxygen vacancies to adsorb and activate oxygen and a labile Mn (IV)/Mn (III) redox pair to dissociate the adsorbed oxygen. The combination of both properties allows the transport of the dissociated oxygen towards the soot.This research was funded by Generalitat Valenciana (CIPROM/2021/70), Spanish Government (PID2019-105542RB-I00) and EU (FEDER Founding)

Copper Catalysts Supported on Barium Deficient Perovskites for CO Oxidation Reaction

Mixed oxides with perovskite-type structure (ABO3) present interesting physico-chemical properties to be used as catalyst for atmospheric pollution control. In this work, a series of CuX/Ba0.7MnO3 catalysts (being x: 0, 4, 8 and 12 wt%) has been synthesized, characterized and tested for CO oxidation reaction. All the catalysts were active for CO oxidation in the two reactant mixtures tested: low CO mixture (0.1% CO and 1% O2 in He) and near stoichiometric mixture (1% CO and 1% O2 in He). Copper-free perovskite is the most active catalyst in the less demanding conditions (0.1% CO and 1% O2), as it presents the highest amount of oxygen vacancies working as active sites. However, at higher CO concentrations (1% CO in near stoichiometric mixture), copper-containing catalysts were more active than the perovskite support because, due to the saturation of the oxygen vacancies of perovskites, CuO seems to participate as active site for CO and O2 activation. Cu4/Ba0.7MnO3 and Cu12/Ba0.7MnO3 are more active than Cu8/Ba0.7MnO3 catalyst, since they present a larger amount of active sites on surface. These two copper-containing catalysts present a high stability and recyclability during the reaction at 300 °C in an ideal near stoichiometric mixture (1% CO and 1% O2).Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work was supported by Ministerio de Ciencia,Innovación y Universidades, (Grant No. PID2019-105542RB-I00), María José Illán Gómez, European Regional Development Fund, Generalitat Valenciana, (Grant No. CIPROM/2021-070 project), María José Illán Gómez, Universidad de Alicante

NOx Storage on BaTi0.8Cu0.2O3 Perovskite Catalysts: Addressing a Feasible Mechanism

The NOx storage mechanism on BaTi0.8Cu0.2O3 catalyst were studied using different techniques. The results obtained by XRD, ATR, TGA and XPS under NOx storage-regeneration conditions revealed that BaO generated on the catalyst by decomposition of Ba2TiO4 plays a key role in the NOx storage process. In situ DRIFTS experiments under NO/O2 and NO/N2 show that nitrites and nitrates are formed on the perovskite during the NOx storage process. Thus, it seems that, as for model NSR catalysts, the NOx storage on BaTi0.8Cu0.2O3 catalyst takes place by both "nitrite" and "nitrate" routes, with the main pathway being highly dependent on the temperature and the time on stream: (i) at T 350 °C, the catalyst activity for NO oxidation promotes NO2 generation and the nitrate formation

BaTi1−xCuxO3 perovskites: The effect of copper content in the properties and in the NOx storage capacity

BaTi1−xCuxO3 perovskites have been prepared by the Pechini's sol-gel method and the effect of copper in the structural and physico-chemical properties of the perovskites and in the performance of the catalysts for NOx storage has been studied. XRD and Raman spectroscopy results indicate that all the copper containing catalysts present a distortion of the original tetragonal structure due to the incorporation of copper into the lattice. The XPS and H2-TPR results reveal that the copper catalysts, except for BaTiCu0,5 catalyst, present two copper species (with different electronic interaction with the perovskite) and active surface oxygen species. Additionally, it seems that the fraction of copper with a strong electronic interaction with the perovskite or incorporated into the perovskite structure increases with the copper content. The active sites created on the BaTi1−xCuxO3 perovskite surface bring to the catalysts activity for the NO to NO2 oxidation and for the NOx adsorption. The NOx storage capacity increases with the copper content and reaches a limit for the BaTiCu2 catalyst (300 μmol/g, at 420 °C) which is within the range of the values reported for the noble metal-based catalysts.The authors thank to Spanish Government (MINECO projectCTQ2012-030703) and to Generalitat Valenciana (project PROM-ETEOII/2014/010) for the financial support

The selective reduction of NOx with propene on Pt-beta catalyst: a transient study

The mechanism of the NO/C3H6/O2 reaction has been studied on a Pt-beta catalyst using transient analysis techniques. This work has been designed to provide answers to the volcano-type activity behaviour of the catalytic system, for that reason, steady state transient switch (C3H6/NO/O2 → C3H6/Ar/O2, C3H6/Ar/O2 → C3H6/NO/O2, C3H6/NO/O2 → Ar/NO/O2, Ar/NO/O2 → C3H6/NO/O2, C3H6/NO/O2 → C3H6/NO/Ar and C3H6/NO/Ar → C3H6/NO/O2) and thermal programmed desorption (TPD) experiments were conducted below and above the temperature of the maximum activity (Tmax). Below Tmax, at 200 °C, a high proportion of adsorbed hydrocarbon exists on the catalyst surface. There exists a direct competition between NO and O2 for Pt free sites which is very much in favour of NO, and therefore, NO reduction selectively takes place over hydrocarbon combustion. NO and C3H6 are involved in the generation of partially oxidised hydrocarbon species. O2 is essential for the oxidation of these intermediates closing the catalytic cycle. NO2 is not observed in the gas phase. Above Tmax, at 230 °C, C3H6 ads coverage is negligible and the surface is mainly covered by Oads produced by the dissociative adsorption of O2. NO2 is observed in gas phase and carbon deposits are formed at the catalyst surface. From these results, the state of Pt-beta catalyst at Tmax is inferred. The reaction proceeds through the formation of partially oxidised active intermediates (CxHyOzNw) from C3H6 ads and NOads. The combustion of the intermediates with O2(g) frees the Pt active sites so the reaction can continue. Temperature has a positive effect on the surface reaction producing active intermediates. On the contrary, formation of NOads and C3H6 ads are not favoured by an increase in temperature. Temperature has also a positive effect on the dissociation of O2 to form Oads, consequently, the formation of NO2 is favoured by temperature through the oxygen dissociation. NO2 is very reactive and produces the propene combustion without NO reduction. These facts will determine the maximum concentration of active intermediates and consequently the maximum of activity.The authors thank the Spanish Ministry of Education and Science (project CTQ2005-01358) for the financial support

BaFe1−xNixO3 Catalysts for NOx-Assisted Diesel Soot Oxidation

In this work, it is analyzed the effect of the partial substitution of Fe by Ni in a BaFeO3 perovskite to be used as the catalyst for NOx-assisted diesel soot oxidation. A series of BaFe1−xNixO3 (x = 0, 0.2, 0.4 and 0.8) catalysts have been synthesized by using the sol–gel method. The catalysts have been characterized by ICP-OES, XRD, XPS, O2-TPD, H2-TPR- and TEM. The catalytic activity for NO to NO2 oxidation and NOx-assisted diesel soot oxidation have been determined by Temperature Programmed Reaction experiments (NOx -TPR and Soot-NOx-TPR, respectively) and by isothermal reaction at 450 °C. Ni seems not to be inserted in the BaFeO3 perovskite and, instead of that, BaNiO3 perovskite and NiO are detected on the surface of the perovskite BaFeO3. XPS data reveal the coexistence of Fe(III) and Fe(IV) on the catalyst’s surface (being Fe(III) the main oxidation state) and the presence of oxygen vacancies. All catalysts are active for NO oxidation to NO2, showing BaFeO3 and BaFe0.6Ni0.4O3 the best catalytic performance. BaFe0.6Ni0.4O3 shows the highest proportion of nickel on surface and it combines the highest activity and stability for NOx-assisted diesel soot oxidation. Also, this catalyst presents the highest initial soot oxidation rate which minimizes the accumulation of unreacted soot during reaction.Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This study was funded by the Spanish Government (MINCINN: PID2019-105542RB-I00/AEI/10.13039/501100011033 Project), by the European Union (FEDER Funds), by the Regional Government (Generalitat Valenciana CIPROM/2021-070 project) and by the University of Alicante (Final Master’s Project grant of S. Montilla-Verdú)