PdO self-assembly on zeolite SSZ-13 with rows of O3Al(IV)OH selectively incorporated in PdO(101) facets for moisture-resistant methane oxidation

We describe an efficient way to prepare moisture-tolerant methane (hydrocarbon) combustion catalysts based on PdO nanoparticles supported on siliceous SSZ-13 zeolite. Only zeolites with high Si/Al ratios >15 are hydrophobic enough to exclude the Pd from the micropores while forming well-faceted PdO nanoparticles. Simultaneously, during self-assembly mobile Al hydroxo species get incorporated into the as-formed PdO nanoparticles. For the first time, we reveal selective incorporation of rows of O3Al(IV)-OHbridging aluminum hydroxo-species into the (101) facets of PdO nanoparticles that form during thermal self-assembly in Pd/SSZ-13 using state-of-the-art atomically-resolved HAADF-STEM imaging, solid-state NMR, DFT calculations and reactivity measurements. The Al+3-OH moieties form atom-thin rows in place of tri-coordinate Pd ions Pd+2 in Pd1O3 on (101) facets: these tri-coordinate Pd1+2O3 are responsible for C-H bond dissociation of methane and hydrocarbons during catalytic methane oxidation. However, on unmodified or non-zeolite supported PdO nanoparticles in the presence of water vapor from engine exhaust, water competes with methane by forming a deactivated Pdtetra(OH)(H2O)Pdtetra site with two water molecules on contiguous 3-coordinate Pd, which is not active for C-H bond activation. When Al-OH moieties are present in place of some tri-coordinate Pd1O3 sites, water dissociation becomes kinetically unfavorable due to disruption of Pdtetra(OH)(H2O)Pdtetra species formation. Consequently, our catalytic measurements reveal a significantly more stable performance of such catalysts in methane combustion in the presence of water vapor. Our findings provide an unprecedented atomic-level insight into structure-property relationships for supported PdO materials in catalytic methane oxidation and offer a new strategy to prepare moisture-tolerant Pd-containing methane combustion catalysts for green-house gas mitigation by selectively doping atomically thin rows of non-precious metal into specific facets of PdO.

High catalytic methane oxidation activity of monocationic μ-nitrido-bridged iron phthalocyanine dimer with sixteen methyl groups

High catalytic methane oxidation activity of a μ-nitrido-bridged iron phthalocyanine dimer was achieved by introducing 16 electron-donating methyl groups onto the phthalocyanine rings.

Size effects of Pd nanoparticles supported over CeZrPAl for methane oxidation

Pd nanoparticles accompanied with distorted morphology result in considerable active sites and enhance the intrinsic activity for catalytic methane oxidation.

Catalytic methane oxidation by a supramolecular conjugate based on a μ-nitrido-bridged iron porphyrinoid dimer

Catalytic CH4 oxidation using a μ-nitrido-bridged iron porphyrinoid dimer was successfully activated by supramolecular complexation.

Natural clay-supported palladium catalysts for methane oxidation reaction: effect of alloying

Bimetallic Pd-supported halloysite nanotubes revealed outstanding catalytic activity towards catalytic methane oxidation especially PdNi.