Samuel Thomas Stolz
The intermetallic compound PdGa has recently attracted considerable interest for combining high catalytic activity with high reaction selectivity in symmetric heterogeneous catalysis, in particular semi-hydrogenation of acetylene and methanol steam reforming. However, its potential for asymmetric heterogeneous catalysis, for which its chiral bulk crystal structure predestines it, remained largely unexplored. The possibility to prepare clean, atomically well-defined, and bulk-truncated low Miller-index surfaces of chiral PdGa (Pd1Ga1) under ultra-high vacuum conditions paves the way to tackle several fundamental research questions in chemistry and physics under idealized conditions. In particular, the PdGa{111} surfaces and their unique properties are ideally suited to serve as model system to study ensemble (geometry) and ligand (electronic) effects and show the enormous potential of PdGa towards asymmetric heterogeneous catalysis. In this work, the focus is on obtaining fundamental insights into chirality transfer of intrinsically chiral surfaces on the electronic structure and on each of the principal steps of a catalytic reaction pathway by experimental surface analytical tools.
With regard to the relation of the chiral crystal structure of PdGa and its electronic structure, crystals of the space group P213, such as PdGa, are predicted to exhibit peculiar symmetry-protected fermionic quasiparticles. Using ARPES, we were able to evidence such symmetry-protected fermionic quasiparticles in PdGa, to exhibit multifold band-crossings at the high-symmetry points G and R in the Brillouin zone are fermionic quasiparticles with topological charge of magnitude 4
The non-centrosymmetry of PdGa is not only manifested in the emergence of chiral Fermi-arcs, but its chirality governs also the interaction with molecules and its surfaces, which is expressed, for instance in unidirectional motion or enantioselective on-surface reactions. In particular, we have evidenced and induced directed rotation with a directionality of 98% of isolated small, achiral acetylene (C2H2) molecules on Pd3-terminated PdGa{111} surfaces by using LT-STM. The rotor of this exceptionally small motor consists of 4 atoms only and thus operates not only in the classical, electrically driven regime, but also in an unexpected quantum tunneling regime with persisting high directionality.
This strong chirality transfer from the substrate to the molecule is also encountered in enantiospecific interactions with prochiral molecules which is a prerequisite for enantioselective control in on-surface reactions, i.e., asymmetric heterogeneous catalysis. With this focus, we have studied three different reactions on the two structurally different Pd1- and Pd3-terminated PdGa{111} surfaces with regard to enantiomeric excess and the relevance of ensemble effect (geometry) over the ligand effect (electronic structure):
Enantioselective debromination of 5-Bromo-7Methylbenz(a)Anthracene (BMA)
Nearly enantiopure homocoupling of 9-Ethynylphenanthrene (9-EP)
Regio- and enantioselective azide-alkyne Huisgen cycloaddition between 3-(4-Azidophenyl)propionic azid (APA) and 9-EP
Our results highlight the outstanding potential of intermetallic PdGa in numerous fields of research, specifically as a chiral topo-logical material with non-trivial bandstructure, as stator for molecular motors, or as template for asymmetric heterogeneous catalysis.
EPFL2020
