Abstract The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeOxthat improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeOxinterfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeOxnanosheets. This interface structure facilitates substantial electron transfer from Pt to CeOx, resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeOxinterfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.
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Ferroelectric Modulation of Surface Electronic States in BaTiO 3 for Enhanced Hydrogen Evolution Activity
Ferroelectric nanomaterials offer the promise of switchable electronic properties at the surface, with implications for photo- and electrocatalysis. Studies to date on the effect of ferroelectric surfaces in electrocatalysis have been primarily limited to nanoparticle systems where complex interfaces arise. Here, we use MBE-grown epitaxial BaTiO3 thin films with atomically sharp interfaces as model surfaces to demonstrate the effect of ferroelectric polarization on the electronic structure, intermediate binding energy, and electrochemical activity toward the hydrogen evolution reaction (HER). Surface spectroscopy and ab initio DFT +U calculations of the well-defined (001) surfaces indicate that an upward polarized surface reduces the work function relative to downward polarization and leads to a smaller HER barrier, in agreement with the higher activity observed experimentally. Employing ferroelectric polarization to create multiple adsorbate interactions over a single electrocatalytic surface, as demonstrated in this work, may offer new opportunities for nanoscale catalysis design beyond traditional descriptors.
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- PAR ID:
- 10324936
- Date Published:
- Journal Name:
- Nano Letters
- ISSN:
- 1530-6984
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Electrocatalytic water splitting presents an exciting opportunity to produce environmentally benign hydrogen fuel to power human activities. Earth abundant Ni5P4 has emerged as an efficient catalyst for the hydrogen evolution reaction (HER) and its activity can be enhanced by admixing synergistic metals to modify the surface affinity and consequently kinetics of HER. Computational studies suggest that the HER activity of Ni5P4 can be improved by Zn doping, causing a chemical pressure-like effect on Ni3 hollow sites. Herein, we report a facile colloidal route to produce Ni5-xZnxP4 nanocrystals (NCs) with control over structure, morphology, and composition and investigate their composition-dependent HER activity in alkaline solutions. Ni5-xZnxP4 NCs retain the hexagonal structure and solid spherical morphology of binary Ni5P4 NCs with a notable size increase from 9.2-28.5 nm for x = 0.00-1.27 compositions. Elemental maps affirm the homogeneous ternary alloy formation with no evidence of Zn segregation. Surface analysis of Ni5-xZnxP4 NCs indicates significant modulation of the surface polarization upon Zn incorporation resulting in a decrease in Niδ+ and an increase in Pδ- charge. Although all compositions followed a Volmer-Heyrovsky HER mechanism, the modulated surface polarization enhances the reaction kinetics producing lower Tafel slopes for Ni5-xZnxP4 NCs (82.5-101.9 mV/dec for x = 0.10-0.84) compared to binary Ni5P4 NCs (109.9 mV/dec). Ni5-xZnxP4 NCs showed higher HER activity with overpotentials of 131.6-193.8 mV for x = 0.02-0.84 in comparison to Ni5P4 NCs (218.1 mV) at a current density of -10 mA/cm2. Alloying with Zn increases the material’s stability with only a ~10% increase in overpotential for Ni4.49Zn0.51P4 NCs at -50 mA/cm2, whereas a ~33% increase was observed for Ni5P4 NCs. At current densities above -40 mA/cm2, bimetallic NCs with x = 0.10, 0.29, and 0.51 compositions outperformed the benchmark Pt/C catalyst, suggesting that hexagonal alloyed Ni5-xZnxP4 NCs are excellent candidates for practical applications that necessitate lower HER overpotentials at higher current densities.more » « less
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