Two examples of confined molecular catalysts are presented. PtCl42− complexes are attached to a thiol-terminated monolayer by ligand exchange of Cl− with a thiolate group and incorporated in a multilayer of viologen moieties by ion exchange. All Cl− ligands are replaced by OH− or H2O before HER takes place. Ex situ and in situ XAFS measurements confirm that the Pt complexes accelerate HER without being converted into Pt particles.
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