Enhanced Electrocatalytic Oxidation of Small Organic Molecules on Platinum-Gold Nanowires: Influence of the Surface Structure and Pt-Pt/Pt-Au Pair Site Density.
Nicole SminaAdam RosenLukasz SztaberekWilliam BeatrezKathryn KingsburyRosario TroiaYongchen WangJing ZhaoJoshua SchrierChristopher KoenigsmannPublished in: ACS applied materials & interfaces (2021)
The electrochemical oxidation of small organic molecules (SOMs) such as methanol and glucose is a critical process and has relevant applications in fuel cells and sensors. A key challenge in SOM oxidation is the poisoning of the surface by carbon monoxide (CO) and other partially oxidized intermediates, which is attributed to the presence of Pt-Pt pair sites. A promising pathway for overcoming this challenge is to develop catalysts that selectively oxidize SOMs via "direct" pathways that do not form CO as a primary intermediate. In this report, we utilize an ambient, template-based approach to prepare PtAu alloy nanowires with tunable compositions. X-ray photoelectron spectroscopy measurements reveal that the surface composition matches that of the bulk composition after synthesis. Monte Carlo method simulations of the surface structure of PtAu alloys with varying coverage of oxygen adsorbates and varying degrees of oxygen adsorption strength reveal that oxygen adsorption under electrochemical conditions enriches the surface with Pt and a large fraction of Pt-Pt sites remain on the surface even with the Au content of up to 50%. Electrochemical properties and the catalytic performance measurements of the PtAu nanowires for the oxidation of methanol and glucose reveal that the mechanistic pathways that produce CO are suppressed by the addition of relatively small quantities of Au (∼10%), and CO formation can be completely suppressed by 50% Au. The suppression of CO formation with small quantities of Au suggests that the presence of Pt-Au pair sites may be more important in determining the mechanism of SOM oxidation rather than Pt-Pt pair site density.
Keyphrases
- reduced graphene oxide
- gold nanoparticles
- sensitive detection
- hydrogen peroxide
- visible light
- healthcare
- monte carlo
- ionic liquid
- gene expression
- molecularly imprinted
- nitric oxide
- skeletal muscle
- blood pressure
- blood glucose
- induced apoptosis
- particulate matter
- insulin resistance
- cell death
- dna methylation
- adipose tissue
- computed tomography
- water soluble
- metal organic framework
- simultaneous determination
- tandem mass spectrometry