In-Situ-Grown Cu Dendrites Plasmonically Enhance Electrocatalytic Hydrogen Evolution on Facet-Engineered Cu<sub>2</sub> O.
basic_science · Level V
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- Record sourced from PubMed, PMID 37667462.
- Also identified by DOI 10.1002/adma.202305742.
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Abstract
Herein, facet-engineered Cu<sub>2</sub> O nanostructures are synthesized by wet chemical methods for electrocatalytic HER, and it is found that the octahedral Cu<sub>2</sub> O nanostructures with exposed crystal planes of (111) (O-Cu<sub>2</sub> O) has the best hydrogen evolution performance. Operando Raman spectroscopy and ex-situ characterization techniques showed that Cu<sub>2</sub> O is reduced during HER, in which Cu dendrites are grown on the surface of the Cu<sub>2</sub> O nanostructures, resulting in the better HER performance of O-Cu<sub>2</sub> O after HER (O-Cu<sub>2</sub> O-A) compared with that of the as-prepared O-Cu<sub>2</sub> O. Under illumination, the onset potential of O-Cu<sub>2</sub> O-A is ca. 52 mV positive than that of O-Cu<sub>2</sub> O, which is induced by the plasmon-activated electrochemical system consisting of Cu<sub>2</sub> O and the in-situ generated Cu dendrites. Incident photon-to-current efficiency (IPCE) measurements and the simulated UV-Vis spectrum demonstrate the hot electron injection (HEI) from Cu dendrites to Cu<sub>2</sub> O. Ab initio nonadiabatic molecular dynamics (NAMD) simulations revealed the transfer of photogenerated electrons (27 fs) from Cu dendrites to Cu<sub>2</sub> O nanostructures is faster than electron relaxation (170 fs), enhancing its surface plasmons activity, and the HEI of Cu dendrites increases the charge density of Cu<sub>2</sub> O. These make the energy level of the catalyst be closer to that of H<sup>+</sup> /H<sub>2</sub> , evidenced by the plasmon-enhanced HER electrocatalytic activity.