Boosting the Methanol Oxidation Reaction Activity of Pt–Ru Clusters via Resonance Energy Transfer

Abstract

The sluggish kinetics of the methanol oxidation reaction (MOR) with PtRu electrocatalyst severely hinder the commercialization of direct methanol fuel cells (DMFCs). The electronic structure of Pt is of significant importance for its catalytic activity. Herein, it is reported that low‐cost fluorescent carbon dots (CDs) can regulate the behavior of the D‐band center of Pt in PtRu clusters through resonance energy transfer (RET), resulting in a significant increase in the catalytic activity of the catalyst participating in methanol electrooxidation. For the first time, the bifunction of RET is used to provide unique strategy for fabrication of PtRu electrocatalysts, not only tunes the electronic structure of metals, but also provides an important role in anchoring metal clusters. Density functional theory calculations further prove that charge transfer between CDs and Pt promotes the dehydrogenation of methanol on PtRu catalysts and reduces the free energy barrier of the reaction associated with the oxidation of CO* to CO2. This helps to improve the catalytic activity of the systems participating in MOR. The performance of the best sample is 2.76 times higher than that of commercial PtRu/C (213.0 vs 76.99 ). The fabricated system can be potentially used for the efficient fabrication of DMFCs.

Mixed‐Dimensional Partial Dealloyed PtCuBi/C as High‐Performance Electrocatalysts for Methanol Oxidation with Enhanced CO Tolerance

“…These factors collectively contribute to improvement of electron transfer ability and electronic structure tuning in the metal, weakening binding strength of intermediates in the Pt active site, leading to a significant enhancement of the electrocatalytic performance. [ 68 ] This point has been confirmed by experimental results, XPS, and XANES analysis. Last, EXAFS and WT analysis indicate that the strong interactions between the multi‐active sites of Pt‐M (Cu, Pt, and Bi) also contribute to the enhancement of the catalytic activity.…”

Cascaded p–d Orbital Hybridization Interaction in Ultrathin High‐Entropy Alloy Nanowires Boosts Complete Non‐CO Pathway of Methanol Oxidation Reaction

“…In comparison with PtRu and other state‐of‐art catalysts, HEA‐8 UNWs also exhibit an excellent performance of MOR (Figure S7 , Supporting Information). [ 24 , 25 , 26 , 27 , 28 , 29 , 30 ] To further evaluate the catalytic properties of these catalysts, the CVs was measured at different scan rates from 10 to 100 mV s −1 . Figure 2c shows the plots of the forward current density ( J m ) versus the square root of the scan rate ( v 1/2 ).…”

Enhanced Activity of Small Pt Nanoparticles Decorated with High‐Loading Single Fe─N4 for Methanol Oxidation and Oxygen Reduction via the Assistive Active Sites Strategy

“…At 0.90 V versus RHE, the excellent durability of Pt/HFe SA -HCS is demonstrated by the much lower degradation of MA (3.0%) and SA (2.2%) after 20 000 ADT cycles compared to that of Pt/HCS (50.1% for MA and 32.1% for SA) and Pt/C (62.5% for MA and 40.0% for SA). Moreover, both Pt/LFe SA -HCS (22.7% for MA and 20.9% for SA) and Pt/LFe SA -NC (29.4% for MA and 21.1% for SA) also exhibit higher electrochemical stability than that of Pt/HCS and Pt/C, this may be due to the fact that the strong interaction between atomic dispersed Fe─N 4 sites and [29][30][31][32][33][34][35][36][37][38][39][40][41][42] Pt NPs enhances the ORR stability. In addition, The Pt/HFe SA -HCS also exhibited much lower degradation than both Pt/LFe SA -HCS and Pt/LFe SA -NC, which have single Fe atoms but at lower loadings.…”

“…e) CO-stripping CV curves for different catalysts in CO-saturated 0.1 m HClO 4 . f) The MA and SA activity of Pt/HFe SA -HCS at peak in comparison to those of other Pt-based MOR catalysts under acidic media [29][30][31][32][33][34][35][36][37][38][39][40][41][42].…”