Physics

Organic chemistry

Deuterium

Crystallography

Crystal structure

Optics

Reaction intermediate

Adsorption

Catalysis

Physical chemistry

Inorganic chemistry

Chemistry

In situ

Raman spectroscopy

Quantum mechanics

Platinum

Kinetic isotope effect

Single crystal

Journal of the American Chemical Society

The study of the oxygen reduction reaction (ORR) at high-index Pt(hkl) single crystal surfaces has received considerable interest due to their well-ordered, typical atomic structures and superior catalytic activities. However, it is difficult to obtain direct spectral evidence of ORR intermediates during reaction processes, especially at high-index Pt(hkl) surfaces. Herein, in situ Raman spectroscopy has been employed to investigate ORR processes at high-index Pt(hkl) surfaces containing the [011̅] crystal zone—i.e., Pt(211) and Pt(311). Through control and isotope substitution experiments, in situ spectroscopic evidence of OH and OOH intermediates at Pt(211) and Pt(311) surfaces was successfully obtained. After detailed analysis based on the Raman spectra and theoretical simulation, it was deduced that the difference in adsorption of OOH at high-index surfaces has a significant effect on the ORR activity. This research illuminates and deepens the understanding of the ORR mechanism on high-index Pt(hkl) surfaces and provides theoretical guidance for the rational design of high activity ORR catalysts.

Direct <i>In Situ</i> Raman Spectroscopic Evidence of Oxygen Reduction Reaction Intermediates at High-Index Pt(<i>hkl</i>) Surfaces

Direct In Situ Raman Spectroscopic Evidence of Oxygen Reduction Reaction Intermediates at High-Index Pt(hkl) Surfaces