Mapping the Pore Architecture of Structured Catalyst Monoliths from Nanometer to Centimeter Scale with Electron and X-ray Tomographies

The hierarchical pore systems of Pt/Al₂O₃ exhaust gas aftertreatment catalysts were analyzed with a collection of correlative imaging techniques to monitor changes induced by hydrothermal aging. Synergistic imaging with laboratory X-ray microtomography, synchrotron radiation ptychographic X-ray computed nanotomography, and electron tomography allowed quantitative observation of the catalyst pore architecture from centimeter to nanometer scale. Thermal aging at 750 °C in air and hydrothermal aging at 1050 °C in 10% H₂O/air caused increasing structural degradation, which manifested as widespread sintering of Pt particles, increased volume and quantity of macropores (>20 nm), and reduction in effective surface area coupled with decreasing volume and frequency of mesopores (2-20 nm) and micropores (<2 nm). Electron tomography unraveled the three-dimensional (3D) structure with high resolution allowing visualization of meso- and macropores but with samples of maximum 300 nm thickness. To complement this, hard X-ray ptychographic tomography produced quantitative 3D electron density maps of 5 μm diameter samples with spatial resolution <50 nm, effectively filling the resolution gap between electron tomography and hard X-ray microtomography. The obtained 3D volumes are an essential input for future computational modeling of fluid dynamics, mass transport, or diffusion properties and may readily complement bulk one-dimensional porosimetry measurements or simulated porosity.