Catalytic Synergy between Pd Nanoclusters and Ligand-Functionalized Layered Silicates for Improved Formic Acid
Esmail Doustkhah1, Muhammed Yusufoğlu2,3,4, Hamza El-Hosainy4,5
1Chemistry Department, Faculty of Engineering and Natural Sciences, Istinye University, Sariyer, Istanbul 34396, Türkiye.
ACS Applied Materials & Interfaces
|November 19, 2024
Summary
Choosing the right ligand for palladium (Pd) nanocluster synthesis is key for catalysis. Aminopropyl ligands boost formic acid dehydrogenation activity 27-fold compared to thiopropyl ligands on silicate supports.
Area of Science:
- Materials Science
- Catalysis
- Nanotechnology
Background:
- Synthesizing and stabilizing palladium (Pd) nanoclusters with optimal catalytic activity on supports is challenging.
- Surface functionalization with ligands offers solutions but involves trade-offs between reaction yield and catalyst stability.
Purpose of the Study:
- To investigate the effect of different ligands on Pd nanocluster synthesis, stabilization, and catalytic activity.
- To compare the performance of aminopropyl and thiopropyl functionalized silicate supports for Pd nanocluster catalysis.
Main Methods:
- Functionalization of layered silicate interlayers with propylamine and propylthiol.
- Synthesis and characterization of Pd nanoclusters on functionalized supports.
- Catalytic testing for formic acid dehydrogenation.
- Density functional theory (DFT) calculations to analyze Pd-ligand interactions.
Main Results:
- Pd nanoclusters on aminopropyl groups exhibited a ~27-fold higher catalytic activity for formic acid dehydrogenation at 70 °C compared to those on thiopropyl groups.
- DFT calculations indicated weaker, less covalent Pd-N bonds versus stronger, more covalent Pd-S bonds.
- Thiol-functionalized surfaces led to severe structural deformation of Pd13 clusters, reducing surface area and catalytic stability.
Conclusions:
- Aminopropyl functionalization of silicate supports enhances Pd nanocluster catalytic activity for formic acid dehydrogenation.
- While thiopropyl ligands offer better Pd-S bond stability, they induce detrimental structural changes in Pd nanoclusters, compromising overall catalytic performance.
Keywords:
H2 generationPd nanoclustersdehydrocouplingdensity functional calculationsformic acid dehydrogenationsingle-atom catalystMore Related Videos
Related Concept Videos
02:50Catalysis
26.7K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
26.7K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.2K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.2K