Catalytic reactivity of face centered cubic PdZn_α for the steam reforming of methanol

Addition of Zn to Pd changes its catalytic behavior for steam reforming of methanol. Previous work shows that improved catalytic behavior (high selectivity to CO2) is achieved by the intermetallic, tetragonal L10 phase PdZnβ1, where the Pd:Zn ratio is near 1:1. The Pd–Zn phase diagram shows a number of other phases, but their steady-state reactivity has not been determined due to the difficulty of precisely controlling composition and phase in supported catalysts. Hence, the role of Zn on Pd has generally been studied only on model single crystals where Zn was deposited on Pd(1 1 1) with techniques such as TPD and TPR of methanol or CO. The role of small amounts of Zn on the steady-state reactivity of Pd–Zn remains unknown. Therefore, in this work, we have synthesized unsupported powders of phase pure PdZnα, a solid solution of Zn in fcc Pd, using a spray pyrolysis technique. The surface composition and chemical state were studied using Ambient Pressure-XPS (AP-XPS) and were found to match the bulk composition and remain so during methanol steam reforming (MSR) (Ptot = 0.25 mbar). Unlike the PdZnβ11 phase, we find that PdZnα is 100% selective to CO during methanol steam reforming with TOF at 250 °C of 0.12 s−1. Steady-state ambient pressure micro-reactor experiments and vacuum TPD of methanol and CO show that the α phase behaves much like Pd, but Zn addition to Pd improves TOF since it weakens the Pd–CO bond, eliminating the poisoning of Pd by CO during MSR over Pd. The measured selectivity for fcc PdZnα therefore confirms that adding small amounts of Zn to Pd is not enough to modify the selectivity during MSR and that the PdZnβ1 tetragonal structure is essential for CO2 formation during MSR

Aerosol Derived Bimetallic Alloy Powders Bridging the Gap

We present aerosol-derived alloy powders as a uniquely useful platform for studying the contribution of the metal phase to multifunctional supported catalysts. Multimetallic heterogeneous catalysts made by traditional methods are usually nonhomogenous while UHV-based methods, such as mass selected clusters or metal vapor deposited on single crystals, lead to considerably more homogeneous, well-defined samples. However, these well-defined samples have low surface areas and do not lend themselves to catalytic activity tests in flow reactors under industrially relevant conditions. Bimetallic alloy powders derived by aerosol synthesis are homogeneous and single phase and can have surface areas ranging 1-10 m2/g, making them suitable for use in conventional flow reactors. The utility of aerosol-derived alloy powders as model catalysts is illustrated through the synthesis of single phase PdZn which was used to derive the specific reactivity of the L10 tetragonal alloy phase for methanol steam reforming. Turnover frequencies on unsupported PdZn were determined from the experimentally determined metal surface area to be 0.21 molecules of methanol reacted per surface Pd at 250 °C and 0.06 molecules of CO oxidized to CO2 per surface Pd at 185 °C. The experimentally measured activation energies for MSR and CO-oxidation on PdZn are 48 and 87 kJ/mol, respectively

Catalytic reactivity of face centered cubic PdZn alpha for the steam reforming of methanol

Addition of Zn to Pd changes its catalytic behavior for steam reforming of methanol. Previous work shows that improved catalytic behavior (high selectivity to CO2) is achieved by the intermetallic, tetragonal L10 phase PdZnβ1, where the Pd:Zn ratio is near 1:1. The Pd–Zn phase diagram shows a number of other phases, but their steady-state reactivity has not been determined due to the difficulty of precisely controlling composition and phase in supported catalysts. Hence, the role of Zn on Pd has generally been studied only on model single crystals where Zn was deposited on Pd(1 1 1) with techniques such as TPD and TPR of methanol or CO. The role of small amounts of Zn on the steady-state reactivity of Pd–Zn remains unknown. Therefore, in this work, we have synthesized unsupported powders of phase pure PdZnα, a solid solution of Zn in fcc Pd, using a spray pyrolysis technique. The surface composition and chemical state were studied using Ambient Pressure-XPS (AP-XPS) and were found to match the bulk composition and remain so during methanol steam reforming (MSR) (Ptot = 0.25 mbar). Unlike the PdZnβ11 phase, we find that PdZnα is 100% selective to CO during methanol steam reforming with TOF at 250 °C of 0.12 s−1. Steady-state ambient pressure micro-reactor experiments and vacuum TPD of methanol and CO show that the α phase behaves much like Pd, but Zn addition to Pd improves TOF since it weakens the Pd–CO bond, eliminating the poisoning of Pd by CO during MSR over Pd. The measured selectivity for fcc PdZnα therefore confirms that adding small amounts of Zn to Pd is not enough to modify the selectivity during MSR and that the PdZnβ1 tetragonal structure is essential for CO2 formation during MSR

Temperature-Induced Modifications of PdZn Layers on Pd(111)

Ultrathin PdZn surface alloys on Pd(111) are model systems well-suited for obtaining a microscopic understanding of the mechanisms of Pd/Zn-based catalysis for methanol steam reforming. The temperature-induced compositional and structural changes of these alloy films are investigated in the catalytically relevant temperature range. Heating of multilayer Zn films to 500 K results in the formation of multilayer PdZn alloy films with surface and near-surface composition close to 1:1. In the temperature regime above 550 K the subsurface layers deplete quickly in Zn due to diffusion of Zn atoms into the Pd bulk. In contrast, the composition of the surface layer changes only slightly, indicating formation of a PdZn film with strong monolayer character. This change in subsurface composition triggers a change of the original Zn-out/Pd-in surface corrugation, leading ultimately to a Pcl-out/Zn-in situation for annealing temperatures beyond 700 K. The altered corrugation pattern is also obtained when submonolayer amounts of Zn are heated to similar to 500 K. The observed structural changes are in qualitative agreement with predictions by DFT calculations