Probing Surface Transformations of Lanthanum Nickelate Electrocatalysts during Oxygen Evolution Reaction.

Monitoring the spontaneous reconstruction of the surface of metal oxides under electrocatalytic reaction conditions is critical to identifying the active sites and establishing structure-activity relationships. Here, we report on a self-terminated surface reconstruction of Ruddlesden-Popper lanthanum nickel oxide (La2NiO4+δ) that occurs spontaneously during reaction with alkaline electrolyte species. Using a combination of high-resolution scanning transmission electron microscopy (HR-STEM), surface-sensitive X-ray photoelectron spectroscopy (XPS), and soft X-ray absorption spectroscopy (sXAS), as well as electrochemical techniques, we identify the structure of the reconstructed surface layer as an amorphous (oxy)hydroxide phase that features abundant under-coordinated nickel sites. No further amorphization of the crystalline oxide lattice (beyond the ∼2 nm thick layer formed) was observed during oxygen evolution reaction (OER) cycling experiments. Notably, the formation of the reconstructed surface layer increases the material's oxygen evolution reaction (OER) activity by a factor of 45 when compared to that of the pristine crystalline surface. In contrast, a related perovskite phase, i.e., LaNiO3, did not show noticeable surface reconstruction, and also no increase in its OER activity was observed. This work provides detailed insight into a surface reconstruction behavior dictated by the crystal structure of the parent oxide and highlights the importance of surface dynamics under reaction conditions.

The Impact of Oxygen Surface Coverage and Carbidic Carbon on the Activity and Selectivity of Two-Dimensional Molybdenum Carbide (2D-Mo2C) in Fischer-Tropsch Synthesis.

Transformations of oxygenates (CO2, CO, H2O, etc.) via Mo2C-based catalysts are facilitated by the high oxophilicity of the material; however, this can lead to the formation of oxycarbides and complicate the identification of the (most) active catalyst state and active sites. In this context, the two-dimensional (2D) MXene molybdenum carbide Mo2CTx (Tx are passivating surface groups) contains only surface Mo sites and is therefore a highly suitable model catalyst for structure-activity studies. Here, we report that the catalytic activity of Mo2CTx in Fischer-Tropsch (FT) synthesis increases with a decreasing coverage of surface passivating groups (mostly O*). The in situ removal of Tx species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H2 at 400 °C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of Tx groups reaching a catalyst state that is close to 2D-Mo2C (i.e., a material containing no passivating surface groups). Under steady-state FT conditions, 2D-Mo2C yields higher hydrocarbons (C5+ alkanes) with 55% selectivity. Alkanes up to the kerosine range form, with value of α = 0.87, which is ca. twice higher than the α value reported for 3D-Mo2C catalysts. The steady-state productivity of 2D-Mo2C to C5+ hydrocarbons is ca. 2 orders of magnitude higher relative to a reference ß-Μo2C catalyst that shows no in situ activation under identical FT conditions. The passivating Tx groups of Mo2CTx can be reductively defunctionalized also by using a higher H2 pretreatment temperature of 500 °C. Yet, this approach leads to a removal of carbidic carbon (as methane), resulting in a 2D-Mo2C1-x catalyst that converts CO to CH4 with 61% selectivity in preference to C5+ hydrocarbons that are formed with only 2% selectivity. Density functional theory (DFT) results attribute the observed selectivity of 2D-Mo2C to C5+ alkanes to a higher energy barrier for the hydrogenation of surface alkyl species relative to the energy barriers for C-C coupling. The removal of O* is the rate-determining step in the FT reaction over 2D-Mo2C, and O* is favorably removed in the form of CO2 relative to H2O, consistent with the observation of a high CO2 selectivity (ca. 50%). The absence of other carbon oxygenates is explained by the energetic favoring of the direct over the hydrogen-assisted dissociative adsorption of CO.

Structure and Role of a Ga-Promoter in Ni-Based Catalysts for the Selective Hydrogenation of CO2 to Methanol.

Supported, bimetallic catalysts have shown great promise for the selective hydrogenation of CO2 to methanol. In this study, we decipher the catalytically active structure of Ni-Ga-based catalysts. To this end, model Ni-Ga-based catalysts, with varying Ni:Ga ratios, were prepared by a surface organometallic chemistry approach. In situ differential pair distribution function (d-PDF) analysis revealed that catalyst activation in H2 leads to the formation of nanoparticles based on a Ni-Ga face-centered cubic (fcc) alloy along with a small quantity of GaOx. Structure refinements of the d-PDF data enabled us to determine the amount of both alloyed Ga and GaOx species. In situ X-ray absorption spectroscopy experiments confirmed the presence of alloyed Ga and GaOx and indicated that alloying with Ga affects the electronic structure of metallic Ni (viz., Niδ-). Both the Ni:Ga ratio in the alloy and the quantity of GaOx are found to minimize methanation and to determine the methanol formation rate and the resulting methanol selectivity. The highest formation rate and methanol selectivity are found for a Ni-Ga alloy having a Ni:Ga ratio of ∼75:25 along with a small quantity of oxidized Ga species (0.14 molNi-1). Furthermore, operando infrared spectroscopy experiments indicate that GaOx species play a role in the stabilization of formate surface intermediates, which are subsequently further hydrogenated to methoxy species and ultimately to methanol. Notably, operando XAS shows that alloying between Ni and Ga is maintained under reaction conditions and is key to attaining a high methanol selectivity (by minimizing CO and CH4 formation), while oxidized Ga species enhance the methanol formation rate.

Probing the Local Structure of Na in NaNO3-Promoted, MgO-Based CO2 Sorbents via X-ray Absorption Spectroscopy.

This work provides insight into the local structure of Na in MgO-based CO2 sorbents that are promoted with NaNO3. To this end, we use X-ray absorption spectroscopy (XAS) at the Na K-edge to interrogate the local structure of Na during the CO2 capture (MgO + CO2 ↔ MgCO3). The analysis of Na K-edge XAS data shows that the local environment of Na is altered upon MgO carbonation when compared to that of NaNO3 in the as-prepared sorbent. We attribute the changes observed in the carbonated sorbent to an alteration in the local structure of Na at the NaNO3/MgCO3 interfaces and/or in the vicinity of [Mg2+···CO32-] ionic pairs that are trapped in the cooled NaNO3 melt. The changes observed are reversible, i.e., the local environment of NaNO3 was restored after a regeneration treatment to decompose MgCO3 to MgO. The ex situ Na K-edge XAS experiments were complemented by ex situ magic-angle spinning 23Na nuclear magnetic resonance (MAS 23Na NMR), Mg K-edge XAS and X-ray powder diffraction (XRD). These additional experiments support our interpretation of the Na K-edge XAS data. Furthermore, we develop in situ Na (and Mg) K-edge XAS experiments during the carbonation of the sorbent (NaNO3 is molten under the conditions of the in situ experiments). These in situ Na K-edge XANES spectra of molten NaNO3 open new opportunities to investigate the atomic scale structure of CO2 sorbents modified with Na-based molten salts by using XAS.

Of Glasses and Crystals: Mitigating the Deactivation of CaO-Based CO2 Sorbents through Calcium Aluminosilicates.

CaO-based sorbents are cost-efficient materials for high-temperature CO2 capture, yet they rapidly deactivate over carbonation-regeneration cycles due to sintering, hindering their utilization at the industrial scale. Morphological stabilizers such as Al2O3 or SiO2 (e.g., introduced via impregnation) can improve sintering resistance, but the sorbents still deactivate through the formation of mixed oxide phases and phase segregation, rendering the stabilization inefficient. Here, we introduce a strategy to mitigate these deactivation mechanisms by applying (Al,Si)Ox overcoats via atomic layer deposition onto CaCO3 nanoparticles and benchmark the CO2 uptake of the resulting sorbent after 10 carbonation-regeneration cycles against sorbents with optimized overcoats of only alumina/silica (+25%) and unstabilized CaCO3 nanoparticles (+55%). 27Al and 29Si NMR studies reveal that the improved CO2 uptake and structural stability of sorbents with (Al,Si)Ox overcoats is linked to the formation of glassy calcium aluminosilicate phases (Ca,Al,Si)Ox that prevent sintering and phase segregation, probably due to a slower self-diffusion of cations in the glassy phases, reducing in turn the formation of CO2 capture-inactive Ca-containing mixed oxides. This strategy provides a roadmap for the design of more efficient CaO-based sorbents using glassy stabilizers.

Nature of GaOx Shells Grown on Silica by Atomic Layer Deposition.

Gallia-based shells with a thickness varying from a submonolayer to ca. 2.5 nm were prepared by atomic layer deposition (ALD) using trimethylgallium, ozone, and partially dehydroxylated silica, followed by calcination at 500 °C. Insight into the atomic-scale structure of these shells was obtained by high-field 71Ga solid-state nuclear magnetic resonance (NMR) experiments and the modeling of X-ray differential pair distribution function data, complemented by Ga K-edge X-ray absorption spectroscopy and 29Si dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) studies. When applying one ALD cycle, the grown submonolayer contains mostly tetracoordinate Ga sites with Si atoms in the second coordination sphere ([4]Ga(Si)) and, according to 15N DNP SENS using pyridine as the probe molecule, both strong Lewis acid sites (LAS) and strong Brønsted acid sites (BAS), consistent with the formation of gallosilicate Ga-O-Si and Ga-µ2-OH-Si species. The shells obtained using five and ten ALD cycles display characteristics of amorphous gallia (GaOx), i.e., an increased relative fraction of pentacoordinate sites ([5]Ga(Ga)), the presence of mild LAS, and a decreased relative abundance of strong BAS. The prepared Ga1-, Ga5-, and Ga10-SiO2-500 materials catalyze the dehydrogenation of isobutane to isobutene, and their catalytic performance correlates with the relative abundance and strength of LAS and BAS, viz., Ga1-SiO2-500, a material with a higher relative fraction of strong LAS, is more active and stable compared to Ga5- and Ga10-SiO2-500. In contrast, related ALD-derived Al1-, Al5-, and Al10-SiO2-500 materials do not catalyze the dehydrogenation of isobutane and this correlates with the lack of strong LAS in these materials that instead feature abundant strong BAS formed via the atomic-scale mixing of Al sites with silica, leading to Al-µ2-OH-Si sites. Our results suggest that [4]Ga(Si) sites provide strong Lewis acidity and drive the dehydrogenation activity, while the appearance of [5]Ga(Ga) sites with mild Lewis activity is associated with catalyst deactivation through coking. Overall, the atomic-level insights into the structure of the GaOx-based materials prepared in this work provide a guide to design active Ga-based catalysts by a rational tailoring of Lewis and Brønsted acidity (nature, strength, and abundance).

Understanding the Synergy between Fe and Mo Sites in the Nitrate Reduction Reaction on a Bio-Inspired Bimetallic MXene Electrocatalyst.

Mo- and Fe-containing enzymes catalyze the reduction of nitrate and nitrite ions in nature. Inspired by this activity, we study here the nitrate reduction reaction (NO3 RR) catalyzed by an Fe-substituted two-dimensional molybdenum carbide of the MXene family, viz., Mo2 CTx : Fe (Tx are oxo, hydroxy and fluoro surface termination groups). Mo2 CTx : Fe contains isolated Fe sites in Mo positions of the host MXene (Mo2 CTx ) and features a Faradaic efficiency (FE) and an NH3 yield rate of 41 % and 3.2 µmol h-1 mg-1 , respectively, for the reduction of NO3 - to NH4 + in acidic media and 70 % and 12.9 µmol h-1 mg-1 in neutral media. Regardless of the media, Mo2 CTx : Fe outperforms monometallic Mo2 CTx owing to a more facile reductive defunctionalization of Tx groups, as evidenced by in situ X-ray absorption spectroscopy (Mo K-edge). After surface reduction, a Tx vacancy site binds a nitrate ion that subsequently fills the vacancy site with O* via oxygen transfer. Density function theory calculations provide further evidence that Fe sites promote the formation of surface O vacancies, which are identified as active sites and that function in NO3 RR in close analogy to the prevailing mechanism of the natural Mo-based nitrate reductase enzymes.

Amine-Functionalized Amyloid Aerogels for CO2 Capture.

Climate change caused by excessive CO2 emissions constitutes an increasingly dire threat to human life. Reducing CO2 emissions alone may not be sufficient to address this issue, so that the development of emerging adsorbents for the direct capture of CO2 from the air becomes essential. Here, we apply amyloid fibrils derived from different food proteins as the solid adsorbent support and develop aminosilane-modified amyloid fibril-templated aerogels for CO2 capture applications. The results indicate that the CO2 sorption properties of the aerogels depend on the mixing ratio of aminosilane featuring different amine groups and the type of amyloid fibril used. Notably, amine-functionalized ß-lactoglobulin (BLG) fibril-templated aerogels show the highest CO2 adsorption capacity of 51.52 mg (1.17 mmol) CO2 /g at 1 bar CO2 and 25.5 mg (0.58 mmol) CO2 /g at 400 ppm; similarly, the CO2 adsorption capacity of chitosan-BLG fibril hybrid aerogels is superior to that of pure chitosan. This study provides a proof-of-concept design for an amyloid fibril-templated hybrid material facilitating applications of protein-based adsorbents for CO2 capture, including direct air capture.

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu-Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol.

The direct synthesis of methanol via the hydrogenation of CO2, if performed efficiently and selectively, is potentially a powerful technology for CO2 mitigation. Here, we develop an active and selective Cu-Zn/SiO2 catalyst for the hydrogenation of CO2 by introducing copper and zinc onto dehydroxylated silica via surface organometallic chemistry and atomic layer deposition, respectively. At 230 °C and 25 bar, the optimized catalyst shows an intrinsic methanol formation rate of 4.3 g h-1 gCu-1 and selectivity to methanol of 83%, with a space-time yield of 0.073 g h-1 gcat-1 at a contact time of 0.06 s g mL-1. X-ray absorption spectroscopy at the Cu and Zn K-edges and X-ray photoelectron spectroscopy studies reveal that the CuZn alloy displays reactive metal support interactions; that is, it is stable under H2 atmosphere and unstable under conditions of CO2 hydrogenation, indicating that the dealloyed structure contains the sites promoting methanol synthesis. While solid-state nuclear magnetic resonance studies identify methoxy species as the main stable surface adsorbate, transient operando diffuse reflectance infrared Fourier transform spectroscopy indicates that µ-HCOO*(ZnOx) species that form on the Cu-Zn/SiO2 catalyst are hydrogenated to methanol faster than the µ-HCOO*(Cu) species that are found in the Zn-free Cu/SiO2 catalyst, supporting the role of Zn in providing a higher activity in the Cu-Zn system.

Renewable Energy from Livestock Waste Valorization: Amyloid-Based Feather Keratin Fuel Cells.

Increasing carbon emissions have accelerated climate change, resulting in devastating effects that are now tangible on an everyday basis. This is mirrored by a projected increase in global energy demand of approximately 50% within a single generation, urging a shift from fossil-fuel-derived materials toward greener materials and more sustainable manufacturing processes. Biobased industrial byproducts, such as side streams from the food industry, are attractive alternatives with strong potential for valorization due to their large volume, low cost, renewability, biodegradability, and intrinsic material properties. Here, we demonstrate the reutilization of industrial chicken feather waste into proton-conductive membranes for fuel cells, protonic transistors, and water-splitting devices. Keratin was isolated from chicken feathers via a fast and economical process, converted into amyloid fibrils through heat treatment, and further processed into membranes with an imparted proton conductivity of 6.3 mS cm-1 using a simple oxidative method. The functionality of the membranes is demonstrated by assembling them into a hydrogen fuel cell capable of generating 25 mW cm-2 of power density to operate various types of devices using hydrogen and air as fuel. Additionally, these membranes were used to generate hydrogen through water splitting and in protonic field-effect transistors as thin-film modulators of protonic conductivity via the electrostatic gating effect. We believe that by converting industrial waste into renewable energy materials at low cost and high scalability, our green manufacturing process can contribute to a fully circular economy with a neutral carbon footprint.

Deciphering the structural dynamics in molten salt-promoted MgO-based CO2 sorbents and their role in the CO2 uptake.

The development of effective CO2 sorbents is vital to achieving net-zero CO2 emission targets. MgO promoted with molten salts is an emerging class of CO2 sorbents. However, the structural features that govern their performance remain elusive. Using in situ time-resolved powder x-ray diffraction, we follow the structural dynamics of a model NaNO3-promoted, MgO-based CO2 sorbent. During the first few cycles of CO2 capture and release, the sorbent deactivates owing to an increase in the sizes of the MgO crystallites, reducing in turn the abundance of available nucleation points, i.e., MgO surface defects, for MgCO3 growth. After the third cycle, the sorbent shows a continuous reactivation, which is linked to the in situ formation of Na2Mg(CO3)2 crystallites that act effectively as seeds for MgCO3 nucleation and growth. Na2Mg(CO3)2 forms due to the partial decomposition of NaNO3 during regeneration at T ≥ 450°C followed by carbonation in CO2.

Activation in the rate of oxygen release of Sr0.8Ca0.2FeO3-δ through removal of secondary surface species with thermal treatment in a CO2-free atmosphere.

We elucidate the underlying cause of a commonly observed increase in the rate of oxygen release of an oxygen carrier with redox cycling (here specifically for the perovskite Sr0.8Ca0.2FeO3-δ ) in chemical looping applications. This phenomenon is often referred to as activation. To this end we probe the evolution of the structure and surface elemental composition of the oxygen carrier with redox cycling by both textural and morphological characterization techniques (N2 physisorption, microscopy, X-ray powder diffraction and X-ray absorption spectroscopy). We observe no appreciable changes in the surface area, pore volume and morphology of the sample during the activation period. X-ray powder diffraction and X-ray absorption spectroscopy analysis (at the Fe and Sr K-edges) of the material before and after redox cycles do not show significant differences, implying that the bulk (average and local) structure of the perovskite is largely unaltered upon cycling. The analysis of the surface of the perovskite via X-ray photoelectron and in situ Raman spectroscopy indicates the presence of surface carbonate species in the as-synthesized sample (due to its exposure to air). Yet, such surface carbonates are absent in the activated material, pointing to the removal of carbonates during cycling (in a CO2-free atmosphere) as the underlying cause behind activation. Importantly, after activation and a re-exposure to CO2, surface carbonates re-form and yield a deactivation of the perovskite oxygen carrier, which is often overlooked when using such materials at relatively low temperature (≤500 °C) in chemical looping.

Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System.

Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn3 O4 :M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn3 O4 :M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δf H°(MO), and the Lewis acidity of the M2+ substituent. Incorporation of elements M with low Δf H°(MO) enhances the oxygen binding strength in Mn3 O4 :M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.

Advancing MXene Electrocatalysts for Energy Conversion Reactions: Surface, Stoichiometry, and Stability.

MXenes, due to their tailorable chemistry and favourable physical properties, have great promise in electrocatalytic energy conversion reactions. To exploit fully their enormous potential, further advances specific to electrocatalysis revolving around their performance, stability, compositional discovery and synthesis are required. The most recent advances in these aspects are discussed in detail: surface functional and stoichiometric modifications which can improve performance, Pourbaix stability related to their electrocatalytic operating conditions, density functional theory and advances in machine learning for their discovery, and prospects in large scale synthesis and solution processing techniques to produce membrane electrode assemblies and integrated electrodes. This Review provides a perspective that is complemented by new density functional theory calculations which show how these recent advances in MXene material design are paving the way for effective electrocatalysts required for the transition to integrated renewable energy systems.

Onset and dynamics of avalanches in a rotating cylinder: From experimental data to a geometric model.

Particle image velocimetry has been applied to measure particle velocities on the free surface of a bed of particles within a rotating cylinder during avalanching. The particle velocities were used to examine the validity of existing avalanche models and to propose an alternative model. The movement of particles depends on their location on the surface of the bed: Particles located near the center of the bed travel the farthest, while the distance traveled decreases at an increasing rate for particles located farther from the center. The start of an avalanche can be determined to a single initiation point that can be located on the bottom half of the bed; the avalanche quickly propagates through the entire free surface with 90% of the surface in motion within 257 ms (approximately 20% of the total duration of an avalanche). The experimental insight is used to formulate a geometric model, in which three equal-sized sections flow down the bed surface during an avalanch. The predictions of the model are validated by experimental mixing measurements.

From ethene to propene (ETP) on tailored silica-alumina supports with isolated Ni(ii) sites: uncovering the importance of surface nickel aluminate sites and the carbon-pool mechanism.

Catalysts with well-defined isolated Ni(ii) surface sites have been prepared on three silica-based supports. The outer shells of the support were comprised either of an amorphous aluminosilicate or amorphous alumina (AlO x ) layer - associated with a high and low density of strong Brønsted acid sites (BAS), respectively. When tested for ethene-to-propene conversion, Ni catalysts with a higher density of strong BAS demonstrate a higher initial activity and productivity to propene. On all three catalysts, the propene productivity correlates closely with the concentration of C8 aromatics, suggesting that propene may form via a carbon-pool mechanism. While all three catalysts deactivate with time on stream, the deactivation of catalysts with Ni(ii) sites on AlO x , i.e., containing surface Ni aluminate sites, is shown to be reversible by calcination (coke removal), in contrast to the deactivation of surface Ni silicate or aluminosilicate sites, which deactivate irreversibly by forming Ni nanoparticles.

Yolk-shell-type CaO-based sorbents for CO2 capture: assessing the role of nanostructuring for the stabilization of the cyclic CO2 uptake.

Improving the cyclic CO2 uptake stability of CaO-based solid sorbents can provide a means to lower CO2 capture costs. Here, we develop nanostructured yolk(CaO)-shell(ZrO2) sorbents with a high cyclic CO2 uptake stability which outperform benchmark CaO nanoparticles after 20 cycles (0.17 gCO2 gSorbent-1) by more than 250% (0.61 gCO2 gSorbent-1), even under harsh calcination conditions (i.e. 80 vol% CO2 at 900 °C). By comparing the yolk-shell sorbents to core-shell sorbents, i.e. structures with an intimate contact between the stabilizing phase and CaO, we are able to identify the main mechanisms behind the stabilization of the CO2 uptake. While a yolk-shell architecture stabilizes the morphology of single CaO nanoparticles over repeated cycling and minimizes the contact between the yolk and shell materials, core-shell architectures lead to the formation of a thick CaZrO3-shell around CaO particles, which limits CO2 transport to unreacted CaO. Hence, yolk-shell architectures effectively delay CaZrO3 formation which in turn increases the theoretically possible CO2 uptake since CaZrO3 is CO2-capture-inert. In addition, we observe that yolk-shell architectures also improved the carbonation kinetics in both the kinetic- and diffusion-controlled regimes leading to a significantly higher cyclic CO2 uptake for yolk-shell-type sorbents.

The structural evolution of Mo2C and Mo2C/SiO2 under dry reforming of methane conditions: morphology and support effects.

The thermal carburization of MoO3 nanobelts (nb) and SiO2-supported MoO3 nanosheets under a 1 : 4 mixture of CH4 : H2 yields Mo2C-nb and Mo2C/SiO2. Following this process by in situ Mo K-edge X-ray absorption spectroscopy (XAS) reveals different carburization pathways for unsupported and supported MoO3. In particular, the carburization of α-MoO3-nb proceeds via MoO2, and that of MoO3/SiO2 via the formation of highly dispersed MoO x species. Both Mo2C-nb and Mo2C/SiO2 catalyze the dry reforming of methane (DRM, 800 °C, 8 bar) but their catalytic stability differs. Mo2C-nb shows a stable performance when using a CH4-rich feed (CH4 : CO2 = 4 : 2), however deactivation due to the formation of MoO2 occurs for higher CO2 concentrations (CH4 : CO2 = 4 : 3). In contrast, Mo2C/SiO2 is notably more stable than Mo2C-nb under the CH4 : CO2 = 4 : 3 feed. The influence of the morphology of Mo2C and its dispersion on silica on the structural evolution of the catalysts under DRM is further studied by in situ Mo K-edge XAS. It is found that Mo2C/SiO2 features a higher resistance to oxidation under DRM than the highly crystalline unsupported Mo2C-nb and this correlates with an improved catalytic stability. Lastly, the oxidation of Mo in both Mo2C-nb and Mo2C/SiO2 under DRM conditions in the in situ XAS experiments leads to an increased activity of the competing reverse water gas shift reaction.

Model structures of molten salt-promoted MgO to probe the mechanism of MgCO3 formation during CO2 capture at a solid-liquid interface.

MgO is a promising solid oxide-based sorbent to capture anthropogenic CO2 emissions due to its high theoretical gravimetric CO2 uptake and its abundance. When MgO is coated with alkali metal salts such as LiNO3, NaNO3, KNO3, or their mixtures, the kinetics of the CO2 uptake reaction is significantly faster resulting in a 15 times higher CO2 uptake compared to bare MgO. However, the underlying mechanism that leads to this dramatic increase in the carbonation rate is still unclear. This study aims to determine the most favourable location for the nucleation and growth of MgCO3 and more specifically, whether the carbonation occurs preferentially at the buried interface, the triple phase boundary (TPB), and/or inside the molten salt of the NaNO3-MgO system. For this purpose, a model system consisting of a MgO single crystal that is structured by ultra-short pulse laser ablation and coated with NaNO3 as the promoter is used. To identify the location of nucleation and growth of MgCO3, micro X-ray computed tomography, scanning electron microscopy, Raman microspectroscopy and optical profilometry were applied. We found that MgCO3 forms at the NaNO3/MgO interface and not inside the melt. Moreover, there was no preferential nucleation of MgCO3 at the TPB when compared to the buried interface. Furthermore, it is found that there is no observable CO2 diffusion limitation in the nucleation step. However, it was observed that CO2 diffusion limits MgCO3 crystal growth, i.e. the growth rate of MgCO3 is approximately an order of magnitude faster in shallow grooves compared to that in deep grooves.

Atomic-scale changes of silica-supported catalysts with nanocrystalline or amorphous gallia phases: implications of hydrogen pretreatment on their selectivity for propane dehydrogenation.

This work explores how H2 pretreatment at 550 °C induces structural transformation of two gallia-based propane dehydrogenation (PDH) catalysts, viz. nanocrystalline γ/ß-Ga2O3 and amorphous Ga2O3 (GaO x ) supported on silica (γ-Ga2O3/SiO2 and Ga/SiO2, respectively) and how it affects their activity, propene selectivity and stability with time on stream (TOS). Ga/SiO2-H2 shows poor activity and propene selectivity, no coking and no deactivation with TOS, similar to Ga/SiO2. In contrast, the high initial activity and propene selectivity of γ-Ga2O3/SiO2-H2 decline with TOS but to a lesser extent than in calcined γ-Ga2O3/SiO2. In addition, γ-Ga2O3/SiO2-H2 cokes less than γ-Ga2O3/SiO2. Ga K-edge X-ray absorption spectroscopy suggests an increased disorder of the nanocrystalline γ/ß-Ga2O3 phases in γ-Ga2O3/SiO2-H2 and the emergence of additional tetrahedral Ga sites (GaIV). Such GaIV sites are strong Lewis acid sites (LAS) according to studies using adsorbed pyridine and CO probe molecules, i.e., the abundance of strong LAS is higher in γ-Ga2O3/SiO2-H2 compared to γ-Ga2O3/SiO2 but lower than in Ga/SiO2 and Ga/SiO2-H2. Dissociation of H2 on the Ga-O linkages in γ-Ga2O3/SiO2-H2 yields high-frequency Ga-H bands that are observed in Ga/SiO2 and Ga/SiO2-H2 but not detected in γ-Ga2O3/SiO2. We attribute the increased amount of GaIV sites in γ-Ga2O3/SiO2-H2 mostly to an increased disorder in γ/ß-Ga2O3. X-ray photoelectron spectroscopy detects the formation of Ga+ and Ga0 species in both Ga/SiO2-H2 and γ-Ga2O3/SiO2-H2. Therefore, it is likely that a minor amount of GaIV sites also forms through the interaction of Ga+ (such as Ga2O) and/or Ga0 with silanol groups of SiO2.