Metal/oxide interface is of fundamental significance to heterogeneous catalysis because the seemingly “inert” oxide support can modulate the morphology, atomic and electronic structures of the metal catalyst through the interface. The interfacial effects are well studied over a bulk oxide support but remain elusive for nanometer-sized systems like clusters, arising from the challenges associated with chemical synthesis and structural elucidation of such hybrid clusters. We hereby demonstrate the essential catalytic roles of a nanometer metal/oxide interface constructed by a hybrid Pd/Bi2O3 cluster ensemble, which is fabricated by a facile stepwise photochemical method. The Pd/Bi2O3 cluster, of which the hybrid structure is elucidated by combined electron microscopy and microanalysis, features a small Pd-Pd coordination number and more importantly a Pd-Bi spatial correlation ascribed to the heterografting between Pd and Bi terminated Bi2O3 clusters. The intra-cluster electron transfer towards Pd across the as-formed nanometer metal/oxide interface significantly weakens the ethylene adsorption without compromising the hydrogen activation. As a result, a 91% selectivity of ethylene and 90% conversion of acetylene can be achieved in a front-end hydrogenation process with a temperature as low as 44 °C.
Ligand-stabilized
metal nanoparticles (MNPs) have attracted much
attention due to their promising catalytic applications. Fully/partially
removing these ligands is critical to realize their proper functions.
The traditional ligand-removing approaches (e.g., thermal annealing)
focus on the ligand side. Herein, we demonstrate an electrochemical
method that pays attention to the MNPs side. By rationally regulating
the potential (oxidizing Pt and hydrogen evolution) to construct robust
Pt–O or Pt–H covalent bond to displace Pt–ligand
coordination bond, the approach could effectively remove almost all
kinds of ligands from Pt NPs. For the oxidizing Pt method, up potential
> 1.3 V and cycling number (n) > 20 are preferred
to completely remove the ligands. The water-soluble ligands (such
as poly(vinylpyrrolidone), cetyltrimethylammonium bromide, sodium
acetate) can be removed by just one cycle after thoroughly being washed
by water to remove the unattached ligands. However, the oil-soluble
ligands (such as oleylamine, triphenylphosphine, dodecanethiol) need
more cycles (n > 20), which may due to the strong
coordination interaction between the ligands and Pt NPs. For the hydrogen
evolution method, the generated Pt–H bond during hydrogen evolution
reaction (HER, potential < −0.1 V) could break the interaction
between the ligands and Pt NPs, resulting in the cleaned surface of
Pt. The reverse adsorption of ligands and their further removal demonstrate
the reliability of the above two methods. In addition, these methods
can be extended to remove the ligands from other noble metals, such
as Pd and Au NPs, without altering the particle size and morphology.
This work verifies the effectiveness of using electrochemical strategies
to remove the ligands. The successful removal of ligands is useful
and important in getting the reliable data in many areas which are
not limited to electrocatalysis, electrochemical sensing, and surface-enhanced
Raman scattering.
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