Abstract
Efficiently treating methane emissions in transportation remains a challenge. Here, we investigate palladium and platinum mono- and bimetallic ceria-supported catalysts synthesized by ...mechanical milling and by traditional impregnation for methane total oxidation under dry and wet conditions, reproducing those present in the exhaust of natural gas vehicles. By applying a toolkit of in situ synchrotron techniques (X-ray diffraction, X-ray absorption and ambient pressure photoelectron spectroscopies), together with transmission electron microscopy, we show that the synthesis method greatly influences the interaction and structure at the nanoscale. Our results reveal that the components of milled catalysts have a higher ability to transform metallic Pd into Pd oxide species strongly interacting with the support, and achieve a modulated PdO/Pd ratio than traditionally-synthesized catalysts. We demonstrate that the unique structures attained by milling are key for the catalytic activity and correlate with higher methane conversion and longer stability in the wet feed.
Bimetallic Pt–Pd catalysts supported on ceria have been prepared by mechanochemical synthesis and tested for lean methane oxidation in dry and wet atmosphere. Results show that the addition of ...platinum has a negative effect on transient light-off activity, but for Pd/Pt molar ratios between 1:1 and 8:1 an improvement during time-on-stream experiments in wet conditions is observed. The bimetallic samples undergo a complex restructuring during operation, starting from the alloying of Pt and Pd and resulting in the formation of unprecedented “mushroom-like” structures consisting of PdO bases with Pt heads as revealed by high-resolution transmission electron microscopy (HRTEM) analysis. On milled samples, these structures are well-defined and observed at the interface between palladium and ceria, whereas those on the impregnated catalyst appear less ordered and are located randomly on the surface of ceria and of large PdPt clusters. The milled catalyst prepared by first milling Pd metal and ceria followed by the addition of Pt shows better performances compared to a conventional impregnated sample and also to a sample obtained by inverting the Pd–Pt milling order. This has been ascribed to the intimate contact between Pd and CeO2 generated at the nanoscale during the milling process.
Development of cost-effective oxygen evolution catalysts is of capital importance for the deployment of large-scale energy-storage systems based on metal–air batteries and reversible fuel cells. In ...this direction, a wide range of materials have been explored, especially under more favorable alkaline conditions, and several metal chalcogenides have particularly demonstrated excellent performances. However, chalcogenides are thermodynamically less stable than the corresponding oxides and hydroxides under oxidizing potentials in alkaline media. Although this instability in some cases has prevented the application of chalcogenides as oxygen evolution catalysts and it has been disregarded in some others, we propose to use it in our favor to produce high-performance oxygen evolution catalysts. We characterize here the in situ chemical, structural, and morphological transformation during the oxygen evolution reaction (OER) in alkaline media of Cu2S into CuO nanowires, mediating the intermediate formation of Cu(OH)2. We also test their OER activity and stability under OER operation in alkaline media and compare them with the OER performance of Cu(OH)2 and CuO nanostructures directly grown on the surface of a copper mesh. We demonstrate here that CuO produced from in situ electrochemical oxidation of Cu2S displays an extraordinary electrocatalytic performance toward OER, well above that of CuO and Cu(OH)2 synthesized without this transformation.
Display omitted
•Ceria 3D-printing is shown for the first time.•Ni-CeO2 3D-printed structures are tested for NH3 decomposition to obtain H2.•3D-printed Ni-CeO2 shows better performance than ...cordierite honeycombs.
Binder-free ceria pastes have been formulated and used to prepare ceria structures with a woodpile arrangement of microchannels through 3D printing. After loading them with nickel, these catalytic structures have been tested for ammonia decomposition to obtain hydrogen, and their performance has been compared with those of conventional Ni/CeO2 powder catalysts and with that of a conventional cordierite honeycomb washcoated with Ni/CeO2. Samples have been characterized by N2 physisorption, inductively coupled plasma optical emission spectrometry (ICP-OES), X-Ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy. At the same reaction temperature and flow rate to catalyst weight ratio (F/W), the 3D-printed ceria structures show a catalytic activity much higher than that of the cordierite honeycomb on a reactor volume basis. Additive manufacturing represents a valuable tool to prepare customized ceria-based catalytic structures for practical application with a variety of geometries not attainable with conventional methods.
The hydrogenation of CO2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the ...influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including the formation and stabilization of the most active sites. Here, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis. A combination of ex situ, in situ, and operando microscopy, spectroscopy, and diffraction methods revealed drastic changes in the morphology and composition of the shaped pre-catalysts under reaction conditions. In particular, the rounding of the cubes and partial loss of the (100) facets were observed, although such motifs remained in smaller domains. Nonetheless, the initial pre-catalyst structure was found to strongly affect its subsequent transformation in the course of the CO2 hydrogenation reaction and activity/selectivity trends. In particular, the cubic Cu particles displayed an increased activity for methanol production, although at the cost of a slightly reduced selectivity when compared to similarly sized spherical particles. These findings were rationalized with the help of density functional theory calculations.
Although Cu/ZnO-based catalysts have been long used for the hydrogenation of CO
to methanol, open questions still remain regarding the role and the dynamic nature of the active sites formed at the ...metal-oxide interface. Here, we apply high-pressure operando spectroscopy methods to well-defined Cu and Cu
Zn
nanoparticles supported on ZnO/Al
O
, γ-Al
O
and SiO
to correlate their structure, composition and catalytic performance. We obtain similar activity and methanol selectivity for Cu/ZnO/Al
O
and CuZn/SiO
, but the methanol yield decreases with time on stream for the latter sample. Operando X-ray absorption spectroscopy data reveal the formation of reduced Zn species coexisting with ZnO on CuZn/SiO
. Near-ambient pressure X-ray photoelectron spectroscopy shows Zn surface segregation and the formation of a ZnO-rich shell on CuZn/SiO
. In this work we demonstrate the beneficial effect of Zn, even in diluted form, and highlight the influence of the oxide support and the Cu-Zn interface in the reactivity.
Display omitted
•Nanodomains of reduced ceria in the form of Ce6O11 develop during soot oxidation reaction.•The mechanism of soot oxidation with ceria implies the extraction of oxygen from the ...fluorite lattice.•Reduction of ceria occurs mainly in the soot-CeO2 contact region.
The behavior of a series of CeO2 catalysts in soot combustion reaction was investigated by HRTEM and XPS. It is shown that nanodomains of reduced ceria in the form of Ce6O11 develop during reaction under oxygen-containing atmosphere, supporting the idea that the reaction between CeO2 and carbon particulate results in the formation of a reduced ceria phase. The fact that oxygen-deficient cerium oxide particles are not in contact with soot, whereas regular CeO2 particles are also found in contact with particulate, may suggest that reaction with soot implies the extraction of oxygen from the CeO2 fluorite lattice, confirming the importance of redox mechanism in ceria-catalyzed soot oxidation.
Catalysts used for heterogeneous processes are usually composed of metal nanoparticles dispersed over a high–surface-area support. In recent years, near-ambient pressure techniques have allowed ...catalyst characterization under operating conditions, overcoming the pressure gap effect. However, the use of model systems may not truly represent the changes that occur in real catalysts (the so-called material gap effect). Supports can play an important role in the catalytic process by providing new active sites and may strongly affect both the physical and chemical properties of metal nanoparticles. We used near-ambient pressure x-ray photoelectron spectroscopy to show that the surface rearrangement of bimetallic (rhodium-palladium) nanoparticles under working conditions for ethanol steam reforming with real catalysts is strongly influenced by the presence of a reducible ceria support.
The development of better catalysts is a passionate topic at the forefront of modern science, where operando techniques are necessary to identify the nature of the active sites. The surface of a ...solid catalyst is dynamic and dependent on the reaction environment and, therefore, the catalytic active sites may only be formed under specific reaction conditions and may not be stable either in air or under high vacuum conditions. The identification of the active sites and the understanding of their behaviour are essential information towards a rational catalyst design. One of the most powerful operando techniques for the study of active sites is near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), which is particularly sensitive to the surface and sub-surface of solids. Here we review the use of NAP-XPS for the study of ceria-based catalysts, widely used in a large number of industrial processes due to their excellent oxygen storage capacity and well-established redox properties.
PDF
