Doping gold nanoclusters with palladium has been reported to increase their catalytic activity and stability. PdAu 24 nanoclusters, with the Pd dopant atom located at the center of the Au cluster core, were supported on titania and applied in catalytic CO oxidation, showing significantly higher activity than supported monometallic Au 25 nanoclusters. After pretreatment, operando DRIFTS spectroscopy detected CO adsorbed on Pd during CO oxidation, indicating migration of the Pd dopant atom from the Au cluster core to the cluster surface. Increasing the number of Pd dopant atoms in the Au structure led to incorporation of Pd mostly in the S–(M–S) n protecting staples, as evidenced by in situ XAFS. A combination of oxidative and reductive thermal pretreatment resulted in the formation of isolated Pd surface sites within the Au surface. The combined analysis of in situ XAFS, operando DRIFTS, and ex situ XPS thus revealed the structural evolution of bimetallic PdAu nanoclusters, yielding a Pd single-site catalyst of 2.7 nm average particle size with improved CO oxidation activity.
Pd nanoparticles (1 wt %; mean size ∼4 nm) were supported on ∼2 μm sized, but few nanometers thick, graphene nanoplatelets (GNPs) and compared to 1 wt % Pd on activated carbon or γ-alumina. Catalyst morphology, specific surface area, and Pd particle size were characterized by SEM, BET, and TEM, respectively. H 2 -TPD indicated that GNPs intercalated hydrogen, which may provide additional H 2 supply to the Pd nanoparticles during C 2 H 4 hydrogenation. Whereas the two types of Pd/GNPs (NaOH vs calcinated) catalysts were less active than Pd/C and Pd/Al 2 O 3 below 40 °C, at 55 °C they were about 3–4 times more active. As for example Pd/GNPs (NaOH) and Pd/Al 2 O 3 exhibited not too different mean Pd particle size (3.7 vs 2.5 nm, respectively), the higher activity is attributed to the additional hydrogen supply likely by the metal/support interface, as suggested by the varying C 2 H 4 and H 2 orders on the different supports. Operando XANES measurements during C 2 H 4 hydrogenation revealed the presence of Pd hydride. The Pd hydride was more stable for Pd/GNPs (NaOH) than for Pd/C, once more pointing to a better hydrogen supply by graphene nanoplatelets.
Fused Layer Modelling (FLM) is one out of several material extrusion (ME) additive manufacturing (AM) methods. FLM usually deals with processing of polymeric materials but can also be used to process metal-filled polymeric systems to produce metallic parts. Using FLM for this purpose helps to save costs since the FLM hardware is cheap compared to e.g. direct metal laser processing hardware, and FLM offers an alternative route to the production of metallic components.To produce metallic parts by FLM, the methodology is different from direct metal processing technologies, and several processing steps are required: First, filaments consisting of a special polymer-metal composition are produced. The filament is then transformed into shaped parts by using FLM process technology. Subsequently the polymeric binder is removed (”debinding”) and finally the metallic powder body is sintered. Depending on the metal powder used, the binder composition, the FLM production parameters and also the debinding and sintering processes must be carefully adapted and optimized.The focal points of this study are as following:1. To confirm that metallic parts can be produced by using FLM plus debinding and sintering as an alternative route to direct metal additive manufacturing.2. Determination of process parameters, depending on the used metal powders (steel and copper) and optimization of each process step.3. Comparison of the production paths for the different metal powders and their debinding and sintering behavior as well as the final properties of the produced parts.The results showed that both materials were printable after adjusting the FLM parameters, metallic parts being produced for both metal powder systems. The production method and the sintering process worked out well for both powders. However there are specific challenges in the sintering process that have to be overcome to produce high quality metal parts. This study serves as a fundamental basis for understanding when it comes to the processing of steel and copper powder into metallic parts using FLM processing technology.
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