3D-Printed Fe/γ-Al2O3 Monoliths from MOF-Based Boehmite Inks for the Catalytic Hydroxylation of Phenol.

The synthesis of dihydroxybenzenes (DHBZ), essential chemical reagents in numerous industrial processes, with a high degree of selectivity and yield from the hydroxylation of phenol is progressively attracting great interest in the catalysis field. Furthermore, the additive manufacturing of catalysts to produce 3D printed monoliths would provide additional benefits to enhance the DHBZ synthesis performance. Herein, 3D cellular Fe/γ-Al2O3 monoliths with a total porosity of 88% and low density (0.43 g·cm-3) are printed by Robocasting from pseudoplastic Fe-metal-organic frameworks (Fe-MOF)-based aqueous boehmite inks to develop catalytic monoliths containing a Fe network of dispersed clusters (≤5 µm), nanoclusters (<50 nm), and nanoparticles (∼20 nm) into the porous ceramic skeleton. The hydroxylation of phenol in the presence of hydrogen peroxide is carried out at different reaction temperatures (65-85 °C) in a flow reactor filled with eight stacked 3D Fe/γ-Al2O3 monoliths and with the following operating conditions: Cphenol,0 = 0.33 M, Cphenol,0/CH2O2,0 = 1:1 molar, WR = 2.2 g, and space time (τ = W·QL-1) = 0-147 gcat·h·L-1. The scaffolds present a good mechanical resistance (∼1 MPa) to be employed in a catalytic reactor and do not show any cracks or damage after the chemical reaction. DHBZ selectivity (SDHBZ) of 100% with a yield (YDHBZ) of 32% due to the presence of the Fe network in the monoliths is reported at 85 °C, which represents an improved synthesis performance as compared to that obtained by using the conventional Enichem process and the well-known titanium silicalite-1 catalysts (SDHBZ = 99.1% and YDHBZ = 29.6% at 80 °C). This printing strategy allows manufacturing novel 3D structured catalysts for the synthesis of critical chemical compounds with higher reaction efficiencies.

Thermal Transport and Thermoelectric Effect in Composites of Alumina and Graphene-Augmented Alumina Nanofibers.

The remarkable tunability of 2D carbon structures combined with their non-toxicity renders them interesting candidates for thermoelectric applications. Despite some limitations related to their high thermal conductivity and low Seebeck coefficients, several other unique properties of the graphene-like structures could out-weight these weaknesses in some applications. In this study, hybrid structures of alumina ceramics and graphene encapsulated alumina nanofibers are processed by spark plasma sintering to exploit advantages of thermoelectric properties of graphene and high stiffness of alumina. The paper focuses on thermal and electronic transport properties of the systems with varying content of nanofillers (1-25 wt.%) and demonstrates an increase of the Seebeck coefficient and a reduction of the thermal conductivity with an increase in filler content. As a result, the highest thermoelectric figure of merit is achieved in a sample with 25 wt.% of the fillers corresponding to ~3 wt.% of graphene content. The graphene encapsulated nanofibrous fillers, thus, show promising potential for thermoelectric material designs by tuning their properties via carrier density modification and Fermi engineering through doping.

Reinforced 3D Composite Structures of γ-, α-Al2O3 with Carbon Nanotubes and Reduced GO Ribbons Printed from Boehmite Gels.

The ability of boehmite to form printable inks has sparked interest in the manufacturing of 3D alumina (Al2O3) and composite structures by enabling direct ink writing methods while avoiding the use of printing additives. These materials may exhibit high porosity due to the printing and sintering procedures, depending on the intended application. The 3D-printed porous composite structures of γ-Al2O3 and α-Al2O3 containing 2 wt.% of carbon nanotubes or reduced graphene oxide ribbons were fabricated from boehmite gels, followed by different heat treatments. The reinforcing effect of these carbon nanostructures was evidenced by compression tests carried out on the different alumina structures. A maximum relative increase of 50% in compressive strength was achieved for the γ-Al2O3 composite structure reinforced with reduced graphene oxide ribbons, which was also accompanied by an increase in the specific surface area.

Applications of Ceramic/Graphene Composites and Hybrids.

Research activity on ceramic/graphene composites and hybrids has increased dramatically in the last decade. In this review, we provide an overview of recent contributions involving ceramics, graphene, and graphene-related materials (GRM, i.e., graphene oxide, reduced graphene oxide, and graphene nanoplatelets) with a primary focus on applications. We have adopted a broad scope of the term ceramics, therefore including some applications of GRM with certain metal oxides and cement-based matrices in the review. Applications of ceramic/graphene hybrids and composites cover many different areas, in particular, energy production and storage (batteries, supercapacitors, solar and fuel cells), energy harvesting, sensors and biosensors, electromagnetic interference shielding, biomaterials, thermal management (heat dissipation and heat conduction functions), engineering components, catalysts, etc. A section on ceramic/GRM composites processed by additive manufacturing methods is included due to their industrial potential and waste reduction capability. All these applications of ceramic/graphene composites and hybrids are listed and mentioned in the present review, ending with the authors' outlook of those that seem most promising, based on the research efforts carried out in this field.

Protein adsorption and in vitro behavior of additively manufactured 3D-silicon nitride scaffolds intended for bone tissue engineering.

Highly porous scaffolds of Si3N4 are fabricated by direct ink writing method (Robocasting) with a pattern of macroporous cavities of 650-700µm. Two different Si3N4 ink compositions regarding the oxide sintering aids (namely, Y2O3, Al2O3, and SiO2) are tried. Both inks reach solid volume fractions of ~0.40 with about 10-12wt% of polymeric additive content that imparts the necessary pseudoplastic characteristics. The printed structures are sintered under controlled N2 atmosphere either in a conventional graphite furnace or by the spark plasma sintering technique. Skeleton of the scaffolds reaches densities above 95% of the theoretical value with ≈18-24% of linear shrinkage. Analysis of the crystalline phases, microstructure and mechanical properties are comparatively done for both compositions. The bioactivity of these structures is addressed by evaluating the ion release rate in simulated body fluid. In parallel, atomic force microscopy is used to determine the effect of the filaments surface roughness on protein adsorption (Bovine Serum Albumin) for assessing the potential application of 3D-Si3N4 scaffolds in bone regeneration.

Remarkable Effects of an Electrodeposited Copper Skin on the Strength and the Electrical and Thermal Conductivities of Reduced Graphene Oxide-Printed Scaffolds.

Architected Cu/reduced graphene oxide (rGO) heterostructures are achieved by electrodepositing copper on filament-printed rGO scaffolds. The Cu coating perfectly contours the printed rGO structure, but isolated Cu particles also permeate inside the filaments. Although the Cu deposition conveys a certain mass augment, the three-dimensional (3D) structures remain reasonably light (bulk density ≅ 0.42 g·cm-3). The electrical conductivity (σe) of the Cu/rGO structure (∼8 × 104 S·m-1) shows a notable increment compared to σe of the rGO structure (∼2 × 102 S·m-1). The effect on the scaffold robustness is also notable with an increase of the compressive strength by nearly 10 times (from 20 kPa of the rGO scaffold to 150 kPa of the Cu/rGO structure) and cyclability as well. The improved thermal conductivity of the Cu-coated scaffolds (∼4 times higher), in addition to the σe and strength improvements, suggests that 3D Cu/rGO structures could be suitable assemblies for integration into thermal dissipation systems, particularly as thermal interface materials, for compact electronic devices.

Ultrasonic bandgaps in 3D-printed periodic ceramic microlattices.

The transmission of longitudinal ultrasonic waves through periodic ceramic microlattices fabricated by Robocasting was measured in the 2-12MHz frequency range. It was observed that these structures (scaffolds of tetragonal and hexagonal spatial arrangements with periodicity at length-scales of ∼100µm) exhibit well-detectable acoustic band structures with bandgaps. The locations of these gaps at relatively high frequencies were shown to be in close agreement with the predictions of numerical models, especially for tetragonal scaffolds. For hexagonal scaffolds, a mixing between longitudinal and shear polarizations of the propagation modes was observed in the model, which blurred the matching of the calculated band structures with the experimentally measured bandgaps.