A photoactive process cascaded electrocatalysis for enhanced methanol oxidation over Pt-MXene-TiO 2 composite

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A photoactive process cascaded electrocatalysis for enhanced methanol oxidation over Pt-MXene-TiO2 composite Yue Sun§, Yunjie Zhou§, Yan Liu, Qingyao Wu, Mengmeng Zhu, Hui Huang, Yang Liu (), Mingwang Shao (), and Zhenhui Kang () Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China § Yue Sun and Yunjie Zhou contributed equally to this work. © Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 Received: 11 April 2020 / Revised: 16 May 2020 / Accepted: 30 May 2020

ABSTRACT Highly efficient photo-assisted electrocatalysis for methanol oxidation reaction (MOR) realizes the conversion of solar and chemical energy into electric energy simultaneously. Here we report a Pt-MXene-TiO2 composite for highly efficient MOR via a photoactive cascaded electro-catalytic process. With light (UV and visible light) irradiation, MXene-TiO2 serves as the photo active centre (photoinduced hole) to activate the methanol molecules, while Pt particles are the active centre for the following electro-catalytic oxidation of those activated methanol molecules. Pt-MXene-TiO2 catalyst exhibits a lower onset potential (0.33 V) and an impressive mass activity of 2,750.42 mA·mg−1Pt under light illumination. It represents the highest MOR activity ever reported for photo-assisted electrocatalysts. Pt-MXene-TiO2 also shows excellent CO tolerance ability and stability, in which, after long-term (5,000 s) reaction, still keeps a high mass activity of 1,269.81 mA·mg−1Pt (62.66% of its initial activity). The photo-electro-catalytic system proposed in this work offers novel opportunities for exploiting photo-assisted enhancement of highly efficient and stable catalysts for MOR.

KEYWORDS photoactive process, electrocatalysis, cascade, photoelectrochemistry, methanol oxidation reaction

1

Introduction

Photo-electrocatalysts play a key role in clean energy conversion technologies. As a promising technology to convert chemical energy to electrical energy, with high utilization efficiency and environmental benignity, direct methanol fuel cells (DMFCs) have attracted substantial attentions [1–6]. Notably, high efficient photo-assisted electrocatalysis for methanol oxidation reaction (MOR) can realize the conversion of solar and chemical energy into electric energy simultaneously. To date, Pt-based materials were considered as the work-of-art MOR electrocatalysts in DMFCs, though they still suffer from several problems, such as high cost and easy CO poisoning [7–10]. Few pioneer work suggested the enhanced performance of methanol oxidation by introducing semiconductors into Pt-based catalyst with the assistance of light illumination [11–16]. For those twocomponent semiconductor/Pt catalysts, the slightly enhanced current density of methanol oxidation may be attributed to the photo-oxidation of small organic molecules including adsorbed methanol and intermediates generated during MOR [17, 18].