Lanthanum nickel titanate perovskites as model systems for Ni-perovskite interfacial engineering in methane dry reforming
Not Available
Winterstein, Thomas F. (ORCID:0009000036206033)↗
Engineering topics
Bekheet, Maged F.
Publications and source records attributed to Bekheet, Maged F..
Molybdate-based double perovskite materials in methane dry reforming
Not Available
Winterstein, Thomas F. (ORCID:0009000036206033)↗
Synthesis of high-entropy carbides from multi-metal polymer precursors
Three compositions of high-entropy carbides, (TiHfVNbTa)C, (TiZrHfNbTa)C and (TiZrNbTaW)C were synthesized via a modified Pechini process, in which citric acid served as both a cation chelating agent and a carbon source. Through pyrolysis and spark plasma sintering, single phase high-entropy carbides were formed from the homogeneous precursors at a relatively low temperature of 1800 °C. The dispersion of cations in the polymer precursor facilitated shorter diffusion distances in polymer-derived materials, and thus compositional homogeneity was significantly improved relative to materials produced by a solid-state method, as quantified by a defined coefficient of variation applied to energy-dispersive X-ray spectroscopy. Finally, a finer microstructure in polymer-derived materials results in improved fracture toughness with a K IC value of 4.29 MPa·m 1/2 achieved for (TiHfVNbTa)C.
36 MATERIALS SCIENCE↗
Revealing the Chemical State of Palladium in Operating In 2 O 3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic In x Pd y Compound Blocks It
The sensing response of metal oxides activated with noble metal nanoparticles is significantly influenced by changes to the chemical state of corresponding elements under operating conditions. Here, a PdO/rh-In 2 O3 consisting of PdO nanoparticles loaded onto rhombohedral In 2 O 3 was studied as a gas sensor for H 2 gas (100–40000 ppm in an oxygen-free atmosphere) in the temperature range of 25–450 °C. The phase composition and chemical state of elements were examined by resistance measurements combined with synchrotron-based in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy. As found, PdO/rh-In 2 O 3 undergoes a series of structural and chemical transformations during operation: from PdO to Pd/PdH x and finally to the intermetallic In x Pd y phase. The maximal sensing response (R N2 /R H2 ) of ~5 · 10 7 towards 40000 ppm (4 vol %) H 2 at 70 °C is correlated with the formation of PdH 0.706 /Pd. The In x Pd y intermetallic compounds formed around 250 °C significantly decrease the sensing response.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Zirkonkarbid ermöglicht verkokungsresistente Methan‐Trockenreformierung auf Nickel‐Zirkon‐Katalysatoren
Abstract Graphitische Ablagerungen lösen sich in Ni 0 ‐Nanopartikeln auf, um rezyklierte CH 4 ‐Adsorptionsstellen und oberflächennahe/gelöste C‐Atome bereitzustellen, die zur Ni 0 /ZrO 2 ‐Grenzfläche wandern und eine lokale Zr x C y ‐Bildung induzieren. Die daraus resultierenden sauerstoffarmen karbidischen Phasengrenzflächen unterstützen die Kinetik der CO 2 ‐Aktivierung zu CO(g). Dieser Grenzflächen‐Karbid‐Mechanismus ermöglicht einen verstärkten Übertritt von Kohlenstoff auf den ZrO 2 ‐Träger und stellt einen alternativen Weg der Katalysatorregeneration im Vergleich zum umgekehrten Sauerstoffübertritt auf Ni/CeZr x O y ‐Katalysatoren dar. Er ist daher eher auf Trägern mit begrenzter Sauerstoffspeicher‐ bzw. Austausch‐Kinetik, aber signifikanter karbothermischer Reduzierbarkeit, wahrscheinlich.
Haug, Leander↗
Zirconium Carbide Mediates Coke‐Resistant Methane Dry Reforming on Nickel‐Zirconium Catalysts
Abstract Graphitic deposits anti‐segregate into Ni 0 nanoparticles to provide restored CH 4 adsorption sites and near‐surface/dissolved C atoms, which migrate to the Ni 0 /ZrO 2 interface and induce local Zr x C y formation. The resulting oxygen‐deficient carbidic phase boundary sites assist in the kinetically enhanced CO 2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO 2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni‐CeZr x O y catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts
To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm 1.5 Sr 0.5 NiO 4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm 2 O 3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm 2 O 3 or Ni/Sm 2 O 3 /SrCO 3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm 1.5 Sr 0.5 NiO 4 , and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO 3 in the case of Sm 1.5 Sr 0.5 NiO 4 , which is dominant at high temperatures. For Sm 1.5 Sr 0.5 NiO 4 , the CO : H 2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO 3 without catalytic DRM reactivity. As no Sm 2 O 2 CO 3 surface or bulk phase as a result of carbon dioxide activation was observed for any material – in contrast to La 2 O 2 CO 3 – we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm 1.5 Sr 0.5 NiO 4 and NiO/monoclinic Sm 2 O 3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm 2 O 3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm 2 O 3 interface by favoring Ni particle sintering.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomic-Scale Insights into Nickel Exsolution on LaNiO 3 Catalysts via In Situ Electron Microscopy
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Steering the methanol steam reforming performance of Cu/ZrO2 catalysts by modification of the Cu-ZrO2 interface dimensions resulting from Cu loading variation
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mechanistic in situ insights into the formation, structural and catalytic aspects of the La 2 NiO 4 intermediate phase in the dry reforming of methane over Ni-based perovskite catalysts
In this work, we focus on the stability and bulk/surface structural properties of the Ruddlesden-Popper phase La 2 NiO 4 and their consequences for dry reforming of methane (DRM) activity. Fuelled by the appearance as a crucial intermediate during in situ decomposition of highly DRM-active LaNiO3 perovskite structures, we show that La 2 NiO 4 can be equally in situ decomposed into a Ni/La 2 O 3 phase offering CO 2 capture and release necessary for DRM activity, albeit at much higher temperatures compared to LaNiO 3 . Decomposition in hydrogen also leads to an active Ni/La 2 O 3 phase. In situ X-ray diffraction during DRM operation reveals considerable coking and encapsulation of exsolved Ni, yielding much smaller Ni crystallites compared to on LaNiO 3 , where coking is virtually absent. Additionally, generalizing the importance of intermediate Ruddlesden-Popper phases, the in situ decomposition of La-based perovskite structures yields several obstacles due to the high stability of both the parent perovskite and the Ruddlesden-Popper structures and the occurrence of parasitic structures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Steering the Methane Dry Reforming Reactivity of Ni/La 2 O 3 Catalysts by Controlled In Situ Decomposition of Doped La 2 NiO 4 Precursor Structures
The influence of A- and/or B-site doping of Ruddlesden-Popper perovskite materials on the crystal structure, stability, and dry reforming of methane (DRM) reactivity of specific A 2 BO 4 phases (A = La, Ba; B = Cu, Ni) has been evaluated by a combination of catalytic experiments, in situ X-ray diffraction, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and aberration-corrected electron microscopy. At room temperature, B-site doping of La 2 NiO 4 with Cu stabilizes the orthorhombic structure ( Fmmm ) of the perovskite, while A-site doping with Ba yields a tetragonal space group ( I 4/ mmm ). We observed the orthorhombic-to-tetragonal transformation above 170 °C for La 2 Ni 0.9 Cu 0.1 O 4 and La 2 Ni 0.8 Cu 0.2 O 4 , slightly higher than for undoped La 2 NiO 4 . Loss of oxygen in interstitial sites of the tetragonal structure causes further structure transformations for all samples before decomposition in the temperature range of 400 °C-600 °C. Controlled in situ decomposition of the parent or A/B-site doped perovskite structures in a DRM mixture (CH 4 :CO 2 = 1:1) in all cases yields an active phase consisting of exsolved nanocrystalline metallic Ni particles in contact with hexagonal La 2 O 3 and a mixture of (oxy)carbonate phases (hexagonal and monoclinic La 2 O 2 CO 3 , BaCO 3 ). Differences in the catalytic activity evolve because of (i) the in situ formation of Ni-Cu alloy phases (in a composition of >7:1 = Ni:Cu) for La 2 Ni 0.9 Cu 0.1 O 4 , La 2 Ni 0.8 Cu 0.2 O 4 , and La 1.8 Ba 0.2 Ni 0.9 Cu 0.1 O 4 , (ii) the resulting Ni particle size and amount of exsolved Ni, and (iii) the inherently different reactivity of the present (oxy)carbonate species. Based on the onset temperature of catalytic DRM activity, the latter decreases in the order of La 2 Ni 0.9 Cu 0.1 O 4 ~ La 2 Ni 0.8 Cu 0.2 O 4 ≥ La 1.8 Ba 0.2 Ni 0.9 Cu 0.1 O 4 > La 2 NiO 4 > La 1.8 Ba 0.2 NiO 4 . Simple A-site doped La 1.8 Ba 0.2 NiO 4 is essentially DRM inactive. The Ni particle size can be efficiently influenced by introducing Ba into the A site of the respective Ruddlesden-Popper structures, allowing us to control the Ni particle size between 10 nm and 30 nm both for simple B-site and A-site doped structures. Hence, it is possible to steer both the extent of the metal-oxide-(oxy)carbonate interface and its chemical composition and reactivity. Counteracting the limitation of the larger Ni particle size, the activity can, however, be improved by additional Cu-doping on the B-site, enhancing the carbon reactivity. Exemplified for the La 2 NiO 4 based systems, we show how the delicate antagonistic balance of doping with Cu (rendering the La 2 NiO 4 structure less stable and suppressing coking by efficiently removing surface carbon) and Ba (rendering the La 2 NiO 4 structure more stable and forming unreactive surface or interfacial carbonates) can be used to tailor prospective DRM-active catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗