Hierarchically Structured Porous Spinels via an Epoxide-Mediated Sol–Gel Process Accompanied by Polymerization-Induced Phase Separation

Enhancing the activity and stability of catalysts is a major challenge in scientific research nowadays. Previous studies showed that the generation of an additional pore system can influence the catalytic performance of porous catalysts regarding activity, selectivity, and stability. This study focuses on the epoxide-mediated sol–gel synthesis of mixed metal oxides, NiAl₂O₄ and CoAl₂O₄, with a spinel phase structure, a hierarchical pore structure, and Ni and Co contents of 3 to 33 mol % with respect to the total metal content. The sol–gel process is accompanied by a polymerization-induced phase separation to introduce an additional pore system. The obtained mixed metal oxides were characterized with regard to pore morphology, surface area, and formation of the spinel phase. The Brunauer–Emmett–Teller surface area ranges from 74 to 138 m²·g^–1 and 25 to 94 m²·g^–1 for Ni and Co, respectively. Diameters of the phase separation-based macropores were between 500 and 2000 nm, and the mesopore diameters were 10 nm for the Ni-based system and between 20 and 25 nm for the cobalt spinels. Furthermore, Ni–Al spinels with 4, 5, and 6 mol % Ni were investigated in the dry reforming of CH₄ (DRM) with CO₂ to produce H₂ and CO. CH₄ conversions near the thermodynamic equilibrium were observed depending on the Ni content and reaction temperature. The Ni catalysts were further compared to a noble metal-containing catalyst based on a spinel system showing comparable CH₄ conversion and carbon selectivity in the DRM

Morphology of Porous Hosts Directs Preferred Polymorph Formation and Influences Kinetics of Solid/Solid Transitions of Confined Pharmaceuticals

The pore morphology of a porous host may determine which polymorph a crystallizable guest preferentially forms and may influence the kinetics of solid/solid transitions. Slow cooling of the drug acetaminophen (ACE) inside the straight cylindrical pores of anodic aluminum oxide (AAO, tortuosity = 1) in contact with a bulk ACE surface film preferentially yields uniformly oriented form II and/or form III crystals. The occurring orientations of form II and form III crystals are characterized by high structural registry along the AAO pores. The uniformly oriented form III crystals inside the AAO pores were readily converted into likewise uniformly oriented form II crystals by a solid/solid transition. Thus, we obtained uniformly oriented form II crystals in AAO at high yields. We suggest that sporadic heterogeneous nucleation at bulk crystals formed in the bulk surface film on top of the AAO coupled with kinetic selection of crystal orientations results in fast growth of properly oriented crystals along the 100 μm deep AAO pores. This mechanism is suppressed in controlled porous glass (CPG) having isotropic spongelike pores (tortuosity > 1.5) with free growth paths on the order of 100 nm, where form I formed instead. Moreover, the transition from form III to form II is suppressed in CPG. Possible reasons may include impingement of the propagation front of the solid/solid transition on the CPG pore walls after short propagation paths and inevitable formation of form II grains with different orientations separated by energetically disadvantageous grain boundaries. The results reported here are relevant to mesoscopic crystal engineering aimed at controlled drug release from nanoscale delivery systems. Polymorphs not accessible otherwise in nanoscale containers may be produced at high yields. The principles reported here may be transferred to areas such as nanowire-based organic electronics

Reactive Additive Capillary Stamping with Double Network Hydrogel-Derived Aerogel Stamps under Solvothermal Conditions

Integration of solvothermal reaction products into complex thin-layer architectures is frequently achieved by combinations of layer transfer and subtractive lithography, whereas direct additive substrate patterning with solvothermal reaction products has remained challenging. We report reactive additive capillary stamping under solvothermal conditions as a parallel contact-lithographic access to patterns of solvothermal reaction products in thin-layer configurations. To this end, corresponding precursor inks are infiltrated into mechanically robust mesoporous aerogel stamps derived from double-network hydrogels. The stamp is then brought into contact with a substrate to be patterned under solvothermal reaction conditions inside an autoclave. The precursor ink forms liquid bridges between the topographic surface pattern of the stamp and the substrate. Evaporation-driven enrichment of the precursors in these liquid bridges, along with their liquid-bridge-guided conversion into the solvothermal reaction products, yields large-area submicron patterns of the solvothermal reaction products replicating the stamp topography. For example, we prepared thin hybrid films, which contained ordered monolayers of superparamagnetic submicron nickel ferrite dots prepared by solvothermal capillary stamping surrounded by nickel electrodeposited in a second orthogonal substrate functionalization step. The submicron nickel ferrite dots acted as a magnetic hardener, halving the remanence of the ferromagnetic nickel layer. In this way, thin-layer electromechanical systems, transformers, and positioning systems may be customized