DLP 3D-Printed Mullite Ceramics for the Preparation of MOFs Functionalized Monoliths for CO2 Capture

The aim of this work is to compare the traditional uniaxial pressing with an innovative shaping technique, Digital Light Processing (DLP), in the preparation of porous mullite (3Al2O3·2SiO2) supports to be functionalized with an active coating for CO2 capture. Indeed, the fabrication of complex geometries with 3D-printing technologies allows the production of application-targeted solid sorbents with increased potentialities. Therefore, this research focused on the effect of the purity of the selected raw materials and of the microstructural porosity of 3D-printed ceramic substrates on the Metal Organic Frameworks (MOFs) coating efficiency. Two commercial mullite powders (Mc and Mf) differing in particle size distribution (D50 of 9.19 µm and 4.38 µm, respectively) and iron oxide content (0.67% and 0.38%) were characterized and used to produce the substrates, after ball-milling and calcination. Mc and Mf slurries were prepared with 69 wt% of solid loading and 5 wt% of dispersant: both show rheological behavior suitable for DLP and good printability. DLP 3D-printed and pressed pellets were sintered at three different temperatures: 1350 °C, 1400 °C and 1450 °C. Mf 3D-printed samples show slightly lower geometrical and Archimedes densities, compared to Mc pellets, probably due to the presence of lower Fe2O3 amounts and its effect as sintering aid. Mullite substrates were then successfully functionalized with HKUST-1 crystals by a two-step solvothermal synthesis process. Ceramic substrate porosity, depending on the shaping technique and opportunely tuned controlling the sintering temperature, was correlated with the functionalization efficiency in terms of MOFs deposition. Three-dimensional-printed substrates exhibit a higher and more homogeneous HKUST-1 uptake compared to the pressed pellets as DLP introduces desirable porosities able to enhance the functionalization. Therefore, this work provides preliminary guidelines to improve MOFs coating on mullite surfaces for CO2 capture applications, by opportunely tuning the substrate porosity.