Insights into the Dynamic Interfacial and Bulk Composition of Copper-Modified, Hydrogen-Alloyed, Palladium Nanocubes under Electrocatalytic Conditions

Metzroth, Lucy J. T.; Miller, Elisa M.; Pach, Gregory F.; Norman, Andrew G.; Carroll, Gerard Michael

doi:10.1021/acs.jpcc.1c02186

Insights into the Dynamic Interfacial and Bulk Composition of Copper-Modified, Hydrogen-Alloyed, Palladium Nanocubes under Electrocatalytic Conditions

Journal Article · Tue Jul 13 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c02186· OSTI ID:1810541

Metzroth, Lucy J. T. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)

Understanding and controlling the alloying properties of nanomaterials under electrochemical conditions are critically important for fields ranging from energy storage and catalysis to electrochromic window technology. Hydrogen-absorbing nanomaterials, like palladium, are especially interesting due to their ability to reversibly absorb and store hydrogen in their lattice at near-stoichiometric amounts. Palladium’s work function is also significantly deeper than that of most transition metals, which enables electrochemical underpotential deposition of conformal monolayer and submonolayer amounts of transition metals onto the palladium surface. The simultaneous existence of these two properties is unique and opens new and exciting avenues for electrochemical applications. However, the intersection of surface-modified, hydrogen-alloyed palladium nanomaterials is poorly understood, and specifically, how these structures evolve during electrochemical operating conditions remains an open question. Here, we synthesize {100}-terminated palladium nanocubes and deposit between 0.5 and 22 monolayers of copper at the palladium surface. We then electrochemically alloy these surface-modified structures with hydrogen. Using a combination of analytical electrochemistry, spectroscopy, and microscopy, we track the positional evolution of the Cu at the surface of Pd, its impact on palladium’s ability to absorb hydrogen, and copper’s effect on hydrogen evolution electrocatalysis. We show that Cu readily alloys into the palladium nanocube at potentials more negative than the Cu^2+/0 deposition, but a 0.5 monolayer thick copper layer remains at the Pd surface regardless of potential. Finally, we discuss the implications of these findings within the framework of CO₂ reduction catalysis for carbon–carbon bond-forming chemistry.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1810541

Report Number(s):: NREL/JA--5900-79406; MainId:33632; UUID:4f6726fc-a0fd-4210-9d23-2e67fe57ae59; MainAdminID:25840

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 28 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copper
electrocatalysis
nanomaterials
palladium

Insights into the Dynamic Interfacial and Bulk Composition of Copper-Modified, Hydrogen-Alloyed, Palladium Nanocubes under Electrocatalytic Conditions

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