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Carbon-thin-layer protected WP with no passivation supported on acid-treated expanded graphite as efficient Pt Co-catalysts for methanol oxidation and oxygen reduction reactions

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Abstract

Application of direct methanol fuel cells (DMFCs) is hampered by the low activity, poor stability, and low CO/methanol tolerance of Pt-based catalysts used for methanol oxidation reaction (MOR)/oxygen reduction reaction (ORR). In this study, tungsten phosphide-embedded carbon-thin-layer/acid-treated expanded graphite (WP-CL/AEG) composites are synthesized as Pt-supports/co-catalysts for MOR/ORR via a one-step synthesis route. For MOR, Pt-WP-CL/AEG-3 (molar ratio of P to AEG is 3.6 in precursor) shows the highest electrochemical surface area (123.05 m2 gPt−1) and mass activity (2217.6 mA mgPt−1), which are respectively 1.92 and 4.44 times higher than those of commercial Pt/C (64.16 m2 gPt−1 and 499.2 mA mgPt−1). Pt-WP-CL/AEG catalysts also exhibit higher CO tolerance and stability than Pt/C. Moreover, Pt-WP-CL/AEG-3 also exhibits a higher ORR activity than Pt/C in acidic media, mainly via a 4e transfer pathway (OH as the main product) for ORR. As expected, AEG greatly enhances the charge transfer capacity of Pt-WP-CL/AEG catalysts; the exposed P active sites induced by W atoms on WP facilitate methanol/O2 adsorption and activation during MOR/ORR; the CL originated from citric acid can protect WP from being oxidized in air, which contributes to high activity and stability of P active sites; and charges are transferred from AEG (positively charged) to WP via the linked-CL and then from WP to Pt, which contributes to the high MOR/ORR activity of Pt-WP-CL/AEG. It indicates that WP-CL/AEGs can be considered as promising supports/co-catalysts for Pt in MOR/ORR.

Graphical abstract: Carbon-thin-layer protected WP with no passivation supported on acid-treated expanded graphite as efficient Pt Co-catalysts for methanol oxidation and oxygen reduction reactions

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Publication details

The article was received on 26 Aug 2018, accepted on 17 Oct 2018 and first published on 17 Oct 2018


Article type: Paper
DOI: 10.1039/C8TA08285E
Citation: J. Mater. Chem. A, 2018, Advance Article
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    Carbon-thin-layer protected WP with no passivation supported on acid-treated expanded graphite as efficient Pt Co-catalysts for methanol oxidation and oxygen reduction reactions

    C. Zhang, Y. Dai, H. Chen, Y. Ma, B. Jing, Z. Cai, Y. Duan, B. Tang and J. Zou, J. Mater. Chem. A, 2018, Advance Article , DOI: 10.1039/C8TA08285E

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