Processing and Thermal Conductivity of Bulk Nanocrystalline Aluminum Nitride

Producing bulk AlN with grain sizes in the nano regime and measuring its thermal conductivity is an important milestone in the development of materials for high energy optical applications. We present the synthesis and subsequent densification of nano-AlN powder to produce bulk nanocrystalline AlN. The nanopowder is synthesized by converting transition alumina (δ-Al2O3) with <40 nm grain size to AlN using a carbon free reduction/nitridation process. We consolidated the nano-AlN powder using current activated pressure assisted densification (CAPAD) and achieved a relative density of 98% at 1300 °C with average grain size, d¯~125 nm. By contrast, high quality commercially available AlN powder yields densities ~75% under the same CAPAD conditions. We used the 3-ω method to measure the thermal conductivity, κ of two nanocrystalline samples, 91% dense, d¯ = 110 nm and 99% dense, d¯ = 220 nm, respectively. The dense sample with 220 nm grains has a measured κ = 43 W/(m·K) at room temperature, which is relatively high for a nanocrystalline ceramic, but still low compared to single crystal and large grain sized polycrystalline AlN which can exceed 300 W/(m·K). The reduction in κ in both samples is understood as a combination of grain boundary scattering and porosity effects. We believe that these are finest d¯ reported in bulk dense AlN and is the first report of thermal conductivity for AlN with ≤220 nm grain size. The obtained κ values are higher than the vast majority of conventional optical materials, demonstrating the advantage of AlN for high-energy optical applications.

Phase and facet-engineering of transition alumina leads to (hydro)thermally stable alumina-supported metal catalysts

Inherent thermal instability of gamma-alumina above 800-900 ⁰C leads to deactivation of noble metal-supported alumina catalysts used in automotive applications. This is typically solved by adding toxic (barium) and/or rare-earth (lanthanum, cerium) elements. We show that facet-dependent engineering of transition-alumina leads to (hydro)thermally stable supported metal catalysts in the absence of toxic and rare-earth additives. Since pure high-surface area theta-alumina can be prepared at 1,050-1,100 ⁰C directly from gamma-alumina (or boehmite), and because of its stable major (100) facet with very low surface energy of 597 mJ/m2, we succeeded in preparing ~0.07 wt% Rh and ~3 wt% Pd catalysts active in NO reduction and hydrocarbon oxidation that survive hydrothermal aging up to 1,100 ⁰C with little-to-no deactivation.

CH4-to-CH3OH on Mononuclear Cu(II) Sites Supported on Al2O3: Structure of Active Sites from Electron Paramagnetic Resonance

The selective conversion of methane to methanol remains one of the holy grails of chemistry, where Cu-exchanged zeolites have been shown to selectively convert methane to methanol under stepwise conditions. Over the years, several active sites have been proposed, ranging from mono-, di- to trimeric Cu(II). Herein, we report the formation of well-dispersed monomeric Cu(II) species supported on alumina using surface organometallic chemistry and their reactivity towards the selective and stepwise conversion of methane to methanol. Extensive studies using various transition alumina supports combined with spectroscopic characterization, in particular electron paramagnetic resonance (EPR), show that the active sites are associated with specific facets, which are typically found in gamma- and eta-alumina phase, and that their EPR signature can be attributed to species having a tri-coordinated [(Al₂O)Cu^IIO(OH)]^-,T-shape geometry. Overall, the selective conversion of methane to methanol, a two-electron process, involve two of these isolated monomeric Cu(II) sites that play in concert.

Synthesis of submicronic α-alumina from local aluminum slags

In this study, a high valued product submicronic ?-alumina is successfully extracted from aluminum slags generated by the local aluminum industry. The extraction technique is based on the leaching of slags by H2SO4 followed by precipitation. The coarser aluminum-rich fractions of the slags are used in this study instead of the finer oxide-rich fractions that were commonly used in previous studies. The precipitation of the leached slags by NH4OH is controlled by zetameter in order to determine the optimal precipitation pH. Then, the obtained gel showing the higher precipitation rate and the finer particle size is calcined at 1200 ?C and characterized by XRF, XRD, FTIR, SEM, EDS and laser granulometry. Even without any pretreatment of slags, the XRF analysis reveals that a high purity and high extraction efficiency of 99.2% and 93.75% respectively can be achieved just at a leaching acid concentration of 15%. XRD spectrum shows that the produced alumina is a pure a-corundum, which is confirmed by FTIR spectrum showing only the Al-O bonds. The laser granulometry shows that the recovered powder exhibit a wide particle size distribution. It is between 50 nm and 20 ?m while the average particle size (d50) is about 400 nm. SEM observations reveal that the grains are in the form of submicronic whiskers. The above characteristics allow the obtained alumina powder in this study to be used in the usual applications of alumina such as refractory, ceramic fibers, abrasive, etc. The obtained powders may assume also applications as a thermally stable substitute for the commonly used transition alumina powders, which need further investigations in future studies.

Porosity and Structure of Hierarchically Porous Ni/Al2O3 Catalysts for CO2 Methanation

CO2 methanation is often performed on Ni/Al2O3 catalysts, which can suffer from mass transport limitations and, therefore, decreased efficiency. Here we show the application of a hierarchically porous Ni/Al2O3 catalyst for methanation of CO2. The material has a well-defined and connected meso- and macropore structure with a total porosity of 78%. The pore structure was thoroughly studied with conventional methods, i.e., N2 sorption, Hg porosimetry, and He pycnometry, and advanced imaging techniques, i.e., electron tomography and ptychographic X-ray computed tomography. Tomography can quantify the pore system in a manner that is not possible using conventional porosimetry. Macrokinetic simulations were performed based on the measures obtained by porosity analysis. These show the potential benefit of enhanced mass-transfer properties of the hierarchical pore system compared to a pure mesoporous catalyst at industrially relevant conditions. Besides the investigation of the pore system, the catalyst was studied by Rietveld refinement, diffuse reflectance ultraviolet-visible (DRUV/vis) spectroscopy, and H2-temperature programmed reduction (TPR), showing a high reduction temperature required for activation due to structural incorporation of Ni into the transition alumina. The reduced hierarchically porous Ni/Al2O3 catalyst is highly active in CO2 methanation, showing comparable conversion and selectivity for CH4 to an industrial reference catalyst.

CH4-to-CH3OH on Mononuclear Cu(II) Sites Supported on Al2O3: Structure of Active Sites from Electron Paramagnetic Resonance

The selective conversion of methane to methanol remains one of the holy grails of chemistry, where Cu-exchanged zeolites have been shown to selectively convert methane to methanol under stepwise conditions. Over the years, several active sites have been proposed, ranging from mono-, di- to trimeric Cu(II). Herein, we report the formation of well-dispersed monomeric Cu(II) species supported on alumina using surface organometallic chemistry and their reactivity towards the selective and stepwise conversion of methane to methanol. Extensive studies using various transition alumina supports combined with spectroscopic characterization, in particular electron paramagnetic resonance (EPR), show that the active sites are associated with specific facets, which are typically found in gamma- and eta-alumina phase, and that their EPR signature can be attributed to species having a tri-coordinated [(Al₂O)Cu^IIO(OH)]^-,T-shape geometry. Overall, the selective conversion of methane to methanol, a two-electron process, involve two of these isolated monomeric Cu(II) sites that play in concert.

CH4-to-CH3OH on Mononuclear Cu(II) Sites Supported on Al2O3: Structure of Active Sites from Electron Paramagnetic Resonance

The selective conversion of methane to methanol remains one of the holy grails of chemistry, where Cu-exchanged zeolites have been shown to selectively convert methane to methanol under stepwise conditions. Over the years, several active sites have been proposed, ranging from mono-, di- to trimeric Cu(II). Herein, we report the formation of well-dispersed monomeric Cu(II) species supported on alumina using surface organometallic chemistry and their reactivity towards the selective and stepwise conversion of methane to methanol. Extensive studies using various transition alumina supports combined with spectroscopic characterization, in particular electron paramagnetic resonance (EPR), show that the active sites are associated with specific facets, which are typically found in gamma- and eta-alumina phase, and that their EPR signature can be attributed to species having a tri-coordinated [(Al₂O)Cu^IIO(OH)]^-,T-shape geometry. Overall, the selective conversion of methane to methanol, a two-electron process, involve two of these isolated monomeric Cu(II) sites that play in concert.

Quantification of High Temperature Transition Al2O3 and Their Phase Transformations

<p>High temperature exposure of gamma-Al₂O₃ can lead to a series of polymorphic transformations, including the formation of delta-Al₂O₃ and theta-Al₂O₃. Quantification of the microstructure in the delta/theta-Al₂O₃ formation range represents a formidable challenge as both phases accommodate a high degree of structural disorder. In this work, we explore the use of XRD recursive stacking formalism for quantification of high temperature transition aluminas. We formulate the recursive stacking methodology for modelling of disorder in delta-Al₂O₃and twinning in theta-Al₂O₃ and show that explicitly accounting for the disorder is necessary to reliably model the XRD patterns of high temperature transition alumina. In the second part, we use the recursive stacking approach to study phase transformation during high temperature (1050 ºC) treatment. We show that the two different intergrowth modes of delta-Al₂O₃ have different transformation characteristics, and that a significant portion of delta-Al₂O₃ is stabilized with theta-Al₂O₃even after prolonged high-temperature exposures. In discussions, we outline the limitation of the current XRD approach and discuss a possible multimodal XRD and NMR approach which can improve analysis of complex transition aluminas.</p>