In situ/operando plug-flow fixed-bed cell for synchrotron PXRD and XAFS investigations at high temperature, pressure, controlled gas atmosphere and ultra-fast heating.

A plug-flow fixed-bed cell for synchrotron powder X-ray diffraction (PXRD) and X-ray absorption fine structure (XAFS) idoneous for the study of heterogeneous catalysts at high temperature, pressure and under gas flow is designed, constructed and demonstrated. The operating conditions up to 1000°C and 50 bar are ensured by a set of mass flow controllers, pressure regulators and two infra-red lamps that constitute a robust and ultra-fast heating and cooling method. The performance of the system and cell for carbon dioxide hydrogenation reactions under specified temperatures, gas flows and pressures is demonstrated both for PXRD and XAFS at the P02.1 (PXRD) and the P64 (XAFS) beamlines of the Deutsches Elektronen-Synchrotron (DESY).

Solvent Cavitation during Ambient Pressure Drying of Silica Aerogels.

Ambient-pressure drying of silica gels stands out as an economical and accessible process for producing monolithic silica aerogels. Gels experience significant deformations during drying due to the capillary pressure generated at the liquid-vapor interface in submicron pores. Proper control of the gel properties and the drying rate is essential to enable reversible drying shrinkage without mechanical failure. Recent in operando microcomputed X-ray tomography (µCT) imaging revealed the kinetics of the phase composition during drying and spring-back. However, to fully explain the underlying mechanisms, spatial resolution is required. Here we show evidence of evaporation by hexane cavitation during the ambient-pressure drying of silylated silica gels by spatially resolved quantitative analysis of µCT data supported by wide-angle X-ray scattering measurements. Cavitation consists of the rupture of the pore liquid put under tension by capillary pressure, creating vapor bubbles within the gels. We found the presence of a homogeneously distributed vapor-air phase in the gels well ahead of the maximum shrinkage. The onset of this vapor/air phase corresponded to a pore volume shrinkage of ca. 50 vol % that was attributed to a critical stiffening of the silica skeleton enabling cavitation. Our results provide new aspects of the relation between the shape changes of silica gels during drying and the evaporation mechanisms. We conclude that stress release by cavitation may be at the origin of the resistance of the silica skeleton to drying stresses. This opens the path toward producing larger monolithic silica aerogels by fine-tuning the drying conditions to exploit cavitation.

Influence of Si3N4 fillers and pyrolysis profile on the microstructure of additively manufactured silicon carbonitride ceramics derived from polyvinylsilazane.

In this work, various methods were used to improve the printability of a photocurable polyvinylsilazane resin filled with silicon nitride particles for digital light processing. The developed resin was used as a preceramic polymer for polymer-to-ceramic conversion. The pyrolysis-induced structural changes of the additively manufactured objects were evaluated by comparing samples with different thicknesses, filler amounts and heating profiles. The printed green body retained its original geometry better and showed fewer cracks due to the addition of silicon nitride particles to the resin. Based on the thermally induced changes in a polyvinylsilazane resin system, a customized heating profile for the pyrolysis process was developed, which contributed to the reduction of pores and cracks while the average pyrolysis heating rate remained relatively high. This work provides insight into the pyrolysis of additively manufactured preceramic polymer green bodies and highlights various strategies for additive manufacturing of polymer-derived ceramics.

The presented work systematically demonstrates the microstructural optimization of additively manufactured polymer-derived ceramics through combination of high refractive index filler inclusion and pyrolysis procedure customization.

Revealing the Chemical State of Palladium in Operating In2 O3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic Inx Pdy 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-In2 O3 consisting of PdO nanoparticles loaded onto rhombohedral In2 O3 was studied as a gas sensor for H2 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-In2 O3 undergoes a series of structural and chemical transformations during operation: from PdO to Pd/PdHx and finally to the intermetallic Inx Pdy phase. The maximal sensing response (RN2 /RH2 ) of ∼5 ⋅ 107 towards 40000 ppm (4 vol %) H2 at 70 °C is correlated with the formation of PdH0.706 /Pd. The Inx Pdy intermetallic compounds formed around 250 °C significantly decrease the sensing response.

Zirconium Carbide Mediates Coke-Resistant Methane Dry Reforming on Nickel-Zirconium Catalysts.

Graphitic deposits anti-segregate into Ni0 nanoparticles to provide restored CH4 adsorption sites and near-surface/dissolved C atoms, which migrate to the Ni0 /ZrO2 interface and induce local Zrx Cy formation. The resulting oxygen-deficient carbidic phase boundary sites assist in the kinetically enhanced CO2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni-CeZrx Oy catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.

Zirconium Oxycarbide: A Highly Stable Catalyst Material for Electrochemical Energy Conversion.

Metal carbides and oxycarbides have recently gained considerable interest due to their (electro)catalytic properties that differ from those of transition metals and that have potential to outperform them as well. The stability of zirconium oxycarbide nanopowders (ZrO0.31 C0.69 ), synthesized via a hybrid solid-liquid route, is investigated in different gas atmospheres from room temperature to 800 °C by using in-situ X-ray diffraction and in-situ electrical impedance spectroscopy. To feature the properties of a structurally stable Zr oxycarbide with high oxygen content, a stoichiometry of ZrO0.31 C0.69 has been selected. ZrO0.31 C0.69 is stable in reducing gases with only minor amounts of tetragonal ZrO2 being formed at high temperatures, whereas it decomposes in CO2 and O2 gas atmosphere. From online differential electrochemical mass spectrometry measurements, the hydrogen evolution reaction (HER) onset potential is determined at -0.4 VRHE . CO2 formation is detected at potentials as positive as 1.9 VRHE as ZrO0.31 C0.69 decomposition product, and oxygen is anodically formed at 2.5 VRHE , which shows the high electrochemical stability of this material in acidic electrolyte. This peopwery makes the material suited for electrocatalytic reactions at anodic potentials, such as CO and alcohol oxidation reactions, in general.

Crystallographic and electronic evolution of lanthanum strontium ferrite (La0.6Sr0.4FeO3-δ) thin film and bulk model systems during iron exsolution.

We study the changes in the crystallographic phases and in the chemical states during the iron exsolution process of lanthanum strontium ferrite (LSF, La0.6Sr0.4FeO3-δ). By using thin films of orthorhombic LSF, grown epitaxially on NaCl(001) and rhombohedral LSF powder, the materials gap is bridged. The orthorhombic material transforms into a fluorite structure after the exsolution has begun, which further hinders this process. For the powder material, by a combination of in situ core level spectroscopy and ex situ neutron diffraction, we could directly highlight differences in the Fe chemical nature between surface and bulk: whereas the bulk contains Fe(iv) in the fully oxidized state, the surface spectra can be described perfectly by the sole presence of Fe(iii). We also present corresponding magnetic and oxygen vacancy concentration data of reduced rhombohedral LSF that did not undergo a phase transformation to the cubic perovskite system based on neutron diffraction data.

On the structural stability of crystalline ceria phases in undoped and acceptor-doped ceria materials under in situ reduction conditions.

The reduction of pure and Sm-doped ceria in hydrogen has been studied by synchrotron-based in situ X-ray diffraction to eventually prove or disprove the presence of crystalline cerium hydride (CeH x ) phases and the succession of potential structural phase (trans)formations of reduced cerium oxide phases during heating-cooling cycles up to 1273 K. Despite a recent report on the existence of bulk and surface CeH x phases during reductive treatment of pure CeO2 in H2, structural analysis by Rietveld refinement as well as additional 1H-NMR spectroscopy did not reveal the presence of any crystalline CeH x phase. Rather, a sequence of phase transformations during the re-cooling process in H2 has been observed. In both samples, the reduced/defective fluorite lattice undergoes at first a transformation into a bixbyite-type lattice with a formal stoichiometry Ce0.58 3+Ce0.42 4+O1.71 and Sm0.15 3+Ce0.39 3+Ce0.46 4+O1.73, before a transformation into rhombohedral Ce7O12 takes place in pure CeO2. This phase is clearly absent for the Sm-doped material. Finally, a triclinic Ce11O20 phase appears for both materials, which can be recovered to room temperature, and on which a phase mixture of bixbyite Ce0.66 3+Ce0.34 4+O1.67, rh-Ce0.60 3+Ce0.40 4+O1.70 and tri-Ce0.48 3+Ce0.52 4+O1.76 (for pure CeO2) or bixbyite Sm0.15 3+Ce0.47 3+Ce0.38 4+O1.69 and tri-Sm0.15 3+Ce0.31 3+Ce0.54 4+O1.77 (for Sm-doped CeO2) prevails. The absence of the rhombohedral phase indicates that Sm doping leads to the stabilization of the bixbyite phase over the rhombohedral one at this particular oxygen vacancy concentration. It is worth noting that recent work proves that hydrogen is indeed incorporated within the structures during the heat treatments, but under the chosen experimental conditions it has apparently no effect on the salient structural principles during reduction.

Reactive metal-support interaction in the Cu-In2O3 system: intermetallic compound formation and its consequences for CO2-selective methanol steam reforming.

The reactive metal-support interaction in the Cu-In2O3 system and its implications on the CO2 selectivity in methanol steam reforming (MSR) have been assessed using nanosized Cu particles on a powdered cubic In2O3 support. Reduction in hydrogen at 300 °C resulted in the formation of metallic Cu particles on In2O3. This system already represents a highly CO2-selective MSR catalyst with ~93% selectivity, but only 56% methanol conversion and a maximum H2 formation rate of 1.3 µmol gCu -1 s-1. After reduction at 400 °C, the system enters an In2O3-supported intermetallic compound state with Cu2In as the majority phase. Cu2In exhibits markedly different self-activating properties at equally pronounced CO2 selectivities between 92% and 94%. A methanol conversion improvement from roughly 64% to 84% accompanied by an increase in the maximum hydrogen formation rate from 1.8 to 3.8 µmol gCu -1 s-1 has been observed from the first to the fourth consecutive runs. The presented results directly show the prospective properties of a new class of Cu-based intermetallic materials, beneficially combining the MSR properties of the catalyst's constituents Cu and In2O3. In essence, the results also open up the pathway to in-depth development of potentially CO2-selective bulk intermetallic Cu-In compounds with well-defined stoichiometry in MSR.

H2 reduction of Gd- and Sm-doped ceria compared to pure CeO2 at high temperatures: effect on structure, oxygen nonstoichiometry, hydrogen solubility and hydroxyl chemistry.

The effect of Gd- and Sm-doping on pure CeO2 with respect to crystal structure, oxygen nonstoichiometry, hydrogen solubility and hydroxyl chemistry in a hydrogen atmosphere at elevated temperatures was studied using a combination of powder X-ray diffraction (XRD), temperature-programmed methods (such as reduction, desorption and oxidation), and Fourier-Transform Infrared Spectroscopy (FT-IR). In particular, Gd0.1Ce0.9O2-δ (GDC10) and Sm0.15Ce0.85O2-δ (SDC15) were compared to pure CeO2. After H2 reduction of GDC10/SDC15/CeO2 at 900 °C, two distinct phases form, which differ from each other in terms of oxygen nonstoichiometry. One phase is only slightly reduced and maintains a cubic fluorite unit cell. The other phase is strongly oxygen depleted and changes its lattice to triclinic. Enrichment or depletion of the dopants in the two phases upon reduction was not observed. No evidence for a long-range ordered cerium hydride could be found, despite the fact that all samples clearly incorporate hydrogen during the reduction procedure. Generally, the treatment of all three samples with flowing H2 at 700 °C, 800 °C and 900 °C causes the oxygen deficiency and the amount of bound hydrogen to increase with reduction temperature. Acceptor doping, thus, promotes hydrogen incorporation, but it at the same time decreases the amount of reactive oxygen. In conclusion, the study of hydroxyl chemistry shows that doping CeO2 with Gd or Sm creates binding sites for reactive hydroxyl groups that are not observed for pure CeO2. The distinct infrared absorption peak at ca. 2127 cm-1 - which originates from an electronic transition of Ce3+ (2F5/2 → 2F7/2) - is a viable indicator for the reduction degree of all three specimens.

Zirconium-Assisted Activation of Palladium To Boost Syngas Production by Methane Dry Reforming.

C-saturated Pd0 nanoparticles with an extended phase boundary to ZrO2 evolve from a Pd0 Zr0 precatalyst under CH4 dry reforming conditions. This highly active catalyst state fosters bifunctional action: CO2 is efficiently activated at oxidic phase boundary sites and Pdx C provides fast supply of C-atoms toward the latter.

Surface chemistry and stability of metastable corundum-type In2O3.

To account for the explanation of an eventual sensing and catalytic behavior of rhombohedral In2O3 (rh-In2O3) and the dependence of the metastability of the latter on gas atmospheres, in situ electrochemical impedance spectroscopic (EIS), Fourier-transform infrared spectroscopic (FT-IR), in situ X-ray diffraction and in situ thermogravimetric analyses in inert (helium) and reactive gases (hydrogen, carbon monoxide and carbon dioxide) have been conducted to link the gas-dependent electrical conductivity features and the surface chemical properties to its metastability towards cubic In2O3. In particular, for highly reducible oxides such as In2O3, for which not only the formation of oxygen vacancies, but deep reduction to the metallic state (i.e. metallic indium) also has to be taken into account, this approach is imperative. Temperature-dependent impedance features are strongly dependent on the respective gas composition and are assigned to distinct changes in either surface adsorbates or free charge carrier absorbance, allowing for differentiating and distinguishing between bulk reduction-related features from those directly arising from surface chemical alterations. For the measurements in an inert gas atmosphere, this analysis specifically also included monitoring the fate of differently bonded, and hence, differently reactive, hydroxyl groups. Reduction of rh-In2O3 proceeds to a large extent indirectly via rh-In2O3 → c-In2O3 → In metal. As deduced from the CO and CO2 adsorption experiments, rhombohedral In2O3 exhibits predominantly Lewis acidic surface sites. The basic character is less pronounced, directly explaining the previously observed high (inverse) water-gas shift activity and the low CO2 selectivity in methanol steam reforming.

Elucidating the impact of A-site cation change on photocatalytic H2 and O2 evolution activities of perovskite-type LnTaON2 (Ln = La and Pr).

Transition metal (oxy)nitrides with perovskite-type structures have been regarded as one of the promising classes of inorganic semiconductor materials that can be used in solar water splitting systems for the production of hydrogen as a renewable and storable energy carrier. The performance of transition metal (oxy)nitrides in solar water splitting is strongly influenced by the crystal structure-related dynamics of photogenerated charge carriers. Here, we have systematically assessed the influence of A-site cation exchange on the visible-light-induced photocatalytic H2 and O2 evolution activities, photoanodic response, and dynamics of photogenerated charge carriers of perovskite-type LnTaON2 (Ln = La and Pr). The structural refinement results reveal the orthorhombic Imma and Pnma structures for LaTaON2 and PrTaON2, respectively; the latter has a more distorted crystal structure from the ideal cubic perovskite due to the smaller size of Pr3+ cations. Compared with LaTaON2, PrTaON2 exhibits lower photocatalytic H2 and O2 gas evolution activities and photoanodic response owing to an excessive amount of intrinsic defects associated with anionic vacancies and reduced tantalum species stemming from a long high-temperature nitridation process under reductive NH3 atmosphere. Transient absorption signals evidence the faster decay of photogenerated electrons (holes) in Pt (CoOx)-loaded LaTaON2 than that in Pt (CoOx)-loaded PrTaON2, consistent with the photocatalytic and photoelectrochemical performance of the two photocatalysts. This study suggests that in addition to selecting a suitable A-site cation, it is prerequisite to synthesize LnTaON2 (Ln = La and Pr) crystals with a low defect density to improve their photo-conversion efficiency for solar water splitting.

Visible light photocatalysis with c-WO(3-x)/WO3×H2O nanoheterostructures in situ formed in mesoporous polycarbosilane-siloxane polymer.

In recent years, there have been significant efforts to find novel photocatalytic materials with improved properties. Thus, there is an active ongoing search for new materials that can operate at a broad range of wavelengths for photocatalytic reactions. Among photocatalytically active semiconductors, considerable attention has been given to tungsten oxide with a band gap of E(g) ≈ 2.6 eV, which provides the opportunity to harvest visible light. In the present work, we report on a one-step synthesis of c-WO(3-x)/WO3×H2O nanowhiskers dispersed in a hydrolytically stable mesoporous polycarbosilane-siloxane ([-Si(O)CH2-]n) matrix. The as-synthesized nanocomposites possess high photocatalytic activity for the degradation of methylene blue (MB) under visible light irradiation. The enhanced photocatalytic activity is due to (i) the reduction in the electron-hole recombination rate because of the reduced dimensions of nanowhiskers, (ii) more efficient consumption of photogenerated electrons and holes as a result of the high surface-to-bulk-ratio of the nanowhiskers, and (iii) better electron-hole pair separation due to the formation of c-WO(3-x)/WO3×H2O nanoheterostructures.

Additive manufacturing and performance of bioceramic scaffolds with different hollow strut geometries.

Additively manufactured hollow-strut bioceramic scaffolds present a promising strategy towards enhanced performance in patient-tailored bone tissue engineering. The channels in such scaffolds offer pathways for nutrient and cell transport and facilitate effective osseointegration and vascularization. In this study, we report an approach for the slurry based additive manufacturing of modified diopside bioceramics that enables the production of hollow-strut scaffolds with diverse cross-sectional forms, distinguished by different configurations of channel and strut geometries. The prepared scaffolds exhibit levels of porosity and mechanical strength that are well suited for osteoporotic bone repair. Mechanical characterization in orthogonal orientations revealed that a square outer cross-section for hollow struts in woodpile scaffolds gives rise to levels of compressive strength that are higher than those of conventional solid cylindrical strut scaffolds despite a significantly lower density. Finite element analysis confirms that this improved strength arises from lower stress concentration in such geometries. It was shown that hollow struts in bioceramic scaffolds dramatically increase cell attachment and proliferation, potentially promoting new bone tissue formation within the scaffold channel. This work provides an easily controlled method for the extrusion-based 3D printing of hollow strut scaffolds. We show here how the production of hollow struts with controllable geometry can serve to enhance both the functional and mechanical performance of porous structures, with particular relevance for bone tissue engineering scaffolds.

Origin of the Springback Effect in Ambient-Pressure-Dried Silica Aerogels: The Effect of Surface Silylation.

Ambient pressure drying (APD) can prospectively reduce the costs of aerogel fabrication and processing. APD relies solely on preventing shrinkage or making it reversible. The latter, i.e., the aerogel re-expansion after drying (so-called springback effect-SBE), needs to be controlled for reproducible aerogel fabrication by APD. This can be achieved by an appropriate surface functionalization of aerogel materials (e.g., SiO2). This work addresses the fabrication of monolithic SiO2 aerogels and xerogels by APD. The effect of several silylation agents, i.e., trimethylchlorosilane, triethylchlorosilane, and hexamethyldisilazane on the SBE is studied in detail, applying several complementary experimental techniques, allowing the evaluation of the macroscopic and microscopic morphology as well as the composition of SiO2 aerogels. Here, we show that some physical properties, e.g., the bulk density, the macroscopic structure, and pore sizes/volumes, were significantly affected by the re-expansion. However, silylation did not necessarily lead to full re-expansion. Therefore, similarities in the molecular composition could not be equated to similarities in the SBE. The influences of steric hindrance and reactivity are discussed. The impact of silylation is crucial in tailoring the SBE and, as a result, the APD of monolithic aerogels.

Hydrogenation of Carbon Dioxide to Dimethyl Ether on CuO-ZnO/ZSM-5 Catalysts: Comparison of Powder and Electrospun Structures.

The promising direct dimethyl ether (DME) production through CO2 hydrogenation was systematically analyzed in this research by synthesizing, characterizing, and testing several catalytic structures. In doing so, various combinations of precipitation and impregnation of copper- and zinc-oxides (CuO-ZnO) over a ZSM-5 zeolite structure were applied to synthesize the hybrid catalysts capable of hydrogenating carbon dioxide to methanol and dehydrating it to DME. The resulting catalytic structures, including the co-precipitated, sequentially precipitated, and sequentially impregnated CuO-ZnO/ZSM-5 catalysts, were prepared in the form of particle and electrospun fibers with distinguished chemical and structural features. They were then characterized using XRD, BET, XPS, ICP, TGA, SEM, and FIB-SEM/EDS analyses. Their catalytic performances were also tested and analyzed in light of their observed characteristics. It was observed that it is crucial to establish relatively small-size and well-distributed zeolite crystals across a hybrid catalytic structure to secure a distinguished DME selectivity and yield. This approach, along with other observed behaviors and the involved phenomena like catalyst particles and fibers, clusters of catalyst particles, or the whole catalytic bed, were analyzed and explained. In particular, the desired characteristics of a CuO-ZnO/ZSM-5 hybrid catalyst, synthesized in a single-pot processing of the precursors of all involved catalytically active elements, were found to be promising in guiding the future efforts in tailoring an efficient catalyst for this system.

Springback effect of ambient-pressure-dried silica aerogels: nanoscopic effects of silylation revealed by in situ synchrotron X-ray scattering.

Ambient pressure drying (APD) allows for synthesizing aerogels without expensive and sophisticated equipment for achieving supercritical conditions. Since APD does not eliminate the capillary stress that is induced by the liquid/vapour phase boundary, the shrinkage during drying needs to be prevented or reversed. The re-expansion of the silylated silica gels during drying is commonly referred to as the springback effect (SBE). The SBE is not only important for producing aerogels via APD, but is also a fascinating phenomenon, since it is accompanied by a significant volume change unusual for rigid ceramics. Synchrotron X-ray scattering has proven to be especially effective for the investigation of the volume change of these fractal silica structures on different length scales. In this work, we follow the drying, shrinkage, and (partial) re-expansion of various monolithic samples in situ to explore the occurrence of the SBE. For this purpose, various silylation agents, i.e., hexamethyldisilazane, trimethylchlorosilane, and triethylchlorosilane were used to investigate different shrinkage and re-expansion behavior. A scattering model was used to extract additional information of the evolving primary particle size, correlation length, fractal dimension, and other intensity contributions of the silica network and the hexane. While the primary particles pointed towards a relaxation at near molecular size, they were likely not involved in the SBE. However, structures near the size of the correlation length could be essential for the occurrence of this phenomenon. These findings may lead to the origin of this interesting phenomenon, as well as a better understanding of the production of APD aerogels.

Core-Sheath Pt-CeO2/Mesoporous SiO2 Electrospun Nanofibers as Catalysts for the Reverse Water Gas Shift Reaction.

One-dimensional (1D) core-sheath nanofibers, platinum (Pt)-loaded ceria (CeO2) sheath on mesoporous silica (SiO2) core were fabricated, characterized, and used as catalysts for the reverse water gas shift reaction (RWGS). CeO2 nanofibers (NFs) were first prepared by electrospinning (ES), and then Pt nanoparticles were loaded on the CeO2 NFs using two different deposition methods: wet impregnation and solvothermal. A mesoporous SiO2 sheath layer was then deposited by sol-gel process. The phase composition, structural, and morphological properties of synthesized materials were investigated by scanning electron microscope (SEM), scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), nitrogen adsorption/desorption method, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis, and CO2 temperature programmed desorption (CO2-TPD). The results of these characterization techniques revealed that the core-sheath NFs with a core diameter between 100 and 300 nm and a sheath thickness of about 40-100 nm with a Pt loading of around 0.5 wt.% were successfully obtained. The impregnated catalyst, Pt-CeO2 NF@mesoporous SiO2, showed the best catalytic performance with a CO2 conversion of 8.9% at 350 °C, as compared to the sample prepared by the Solvothermal method. More than 99% selectivity of CO was achieved for all core-sheath NF-catalysts.