Designing the Nanoconfined Environment for Energy-Efficient Metal Nanoparticle/Ligand-Based Electrocatalysts

Journal Article · Thu Jun 12 00:00:00 EDT 2025 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5c00675· OSTI ID:2571381

Jana, Asmita; Yang, Peidong; Qian, Jin; Crumlin, Ethan J

Nanoconfined electrocatalysts demonstrate enhanced selectivity and activity owing to new phenomena emerging from chemical species confined at the interface. Creating these nanoconfined pockets at the interface is not trivial. We need highly negative potentials to create the pockets in metal/ligand catalysts like Ag-nanoparticle/ordered ligand interlayer catalysts. Lowering this activation potential can make the electrocatalysis more energy-efficient, and changes in the environment can impact this potential. We used Density Functional Theory (DFT) to evaluate the impact of ligand length and density, interfacial protons, and surface defects like Ag vacancies and Cu and Au dopants. The nanoconfined configuration is stabilized when the ligands are longer and more densely packed, leading to better agglomeration. It is also stabilized when the ligands adsorb protons and when the ligands detach from the surface easily owing to lower charge transfer. Au-doped surfaces displayed the lowest charge transfer and decreased the activation potential.

• Research Organization: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 )
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 2571381
• Journal Information: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 23 Vol. 16
• Country of Publication: United States
• Language: English