Regular ArticleEnhanced electrocatalytic activity of PtRu/nitrogen and sulphur co-doped crumbled graphene in acid and alkaline media
Graphical abstract
Introduction
Platinum on carbon (Pt/C) is a widely used electrocatalyst for hydrogen evolution reaction (HER) due to its low overpotential and enhanced durability in harsh environment [1], [2], [3]. Despite these favorable properties, the extremely high price and low natural abundance have severely constrained Pt large-scale industrial application. In order to make fuel cells commercially viable, several strategies have been attempted through the reduction of Pt amount or using non-noble metal electrocatalysts without sacrificing their performance [4], [5], [6]. The best performing non-noble metal electrocatalysts reported often contain a transition metal cation such Fe [7], [8], Co [9], [10] or Ni [11], [12]. Unfortunately, their Tafel slopes (thus kinetics) and overpotential values are higher than those of common Pt-based catalysts for HER. Additionally, to achieve low Tafel slopes and small overpotentials, high loadings of these non-precious catalysts are required [13], preventing their widespread usage in fuel cells.
Reduction of Pt amount while preserving the electrocatalytic efficiency is another viable alternative. Over the past decade, countless attempts have been devoted to research for the reduction of the amount of Pt, which in turn allows reducing the cost [14]. From the literature survey, introducing one or several different metals to contact with single-phase Pt nanomaterials has brought great hope to alleviate the above challenges, owing to their dramatic enhancement of the electrocatalytic properties and stability, as compared to single element Pt catalyst. For example, Zhang et al. demonstrated the enhanced performance of CoFePt alloys towards the HER with an overpotential of 18 mV at 10 mA cm−2 [15]. Liang et al. described an effective way to improve alkaline HER performance of Pt-Ni alloys through tuning their H and OH adsorption abilities [16]. Liu et al. prepared a Pt monolayer catalyst supported on complex 3D structures with improved HER [17], [18], [19]. In general, in most of these methods, a similar strategy was adopted, consisting of Pt loading onto large specific surface area materials and highly dispersible nanomaterials with the aim to reduce the Pt amount [20], [21], [22], [23], [24]. However, these approaches necessitate strict technical requirements and are associated with expensive production costs. Additionally, the low stability of these catalysts also restricts their performance for fuel cell applications, because this could eventually lead to a substantial catalytic activity loss, meaning that these catalysts need to be replaced soon upon their utilization. In order to increase the efficiency, the electrocatalyst should exhibit good stability, high activity, and low cost. Alternatively, coupling Pt with Ru in various configurations such as core–shell and alloys represents a viable approach to prepare electrocatalysts with improved catalytic properties and durability for the oxygen evolution reaction (OER) [25], HER [26], [27], [28], [29] and hydrazine oxidation reaction [29].
In this study, we describe the synthesis of high-performance platinum-ruthenium (Pt-Ru) nanoparticles loaded on sulphur- and nitrogen-co-doped crumbled graphene derived from polyethylenedioxythiophene with trace amount of Fe (PF) [30]. These catalysts have several merits as the amount of Pt used was reduced to a minimum, and Ru being relatively cheap (~4% of Pt) and displaying a comparable bond strength for hydrogen as Pt [31]. PF was investigated as the support, owing to its corrosion resistance and high surface area (Fig. 1). Interestingly, the PtRu2/PF catalyst, with a small amount of Pt, displayed improved performance than the catalyst with higher Pt loading (PtRu/PF) for HER in acidic media. Additionally, the catalyst also had an excellent performance for oxygen reduction reaction (ORR) and OER in alkaline media compared to many reported noble-metal catalysts.
Section snippets
Materials
Ruthenium (III) chloride (RuCl3), potassium tetrachloroplatinate (II) (K2PtCl4), iron chloride hexahydrate (FeCl3·6H2O), dimethylformamide (DMF), methanol (MeOH), cetyltrimethylammonium bromide (CTAB), ammonium persulfate [(NH4)2S2O8], ethylenedioxythiophene (EDOT), platinum on graphitized carbon (20% Pt/C), ruthenium dioxide (RuO2), potassium hydroxide (KOH), hydrochloric acid (HCl), and sulfuric acid (H2SO4, 98%) were procured from Sigma-Aldrich, France, and used as-received.
Preparation of sulphur- and nitrogen-co-doped crumbled graphene with trace amounts of iron (PF)
Sulphur- and
Synthesis and characterization of PtmRun/PF electrocatalysts
The sulphur- and nitrogen-co-doped crumbled graphene with trace amounts of iron (PF) was prepared according to a previously reported procedure [30]. Then a mixture of n mg of RuCl3 (n = 30, 20, 15, 0), m mg of K2PtCl4 (m = 0, 10, 15, 30), 60 mg of prepared PF, 36 mL of DMF, and 9 mL of methanol was heated for 15 h at 160 °C. The products (using the original mass ratio of K2PtCl4 and RuCl3 named as PtmRun/PF) were collected and dried at 60 °C. The electrocatalytic activity of the obtained
Conclusion
We have successfully assessed the ultimate limit of Pt in PtRu/PF catalysts via a facile hydrothermal approach. The high dispersibility and bimetallic synergy make the PtRu2/PF catalyst have an outstanding HER electrocatalytic activity in acid conditions, considerably better than those reported using a regular Pt-based and commercial 20% Pt/C catalysts. Furthermore, the PtRu2/PF displayed excellent ORR performance (onset potential of 0.96 V vs. RHE and a limit current density of 6.5 mA·cm−2),
CRediT authorship contribution statement
Liuqing Pang: Methodology, Validation, Investigation, Writing - original draft. Yuanyuan Miao: Investigation. Siddheshwar N. Bhange: Investigation. Alexandre Barras: Investigation. Ahmed Addad: Investigation. Pascal Roussel: Investigation. Mohammed A. Amin: Methodology, Validation, Investigation. Sreekumar Kurungot: Investigation. Sabine Szunerits: Validation, Investigation. Rabah Boukherroub: Conceptualization, Validation, Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgement
The authors thank the Centre National de la Recherche Scientifique (CNRS), the University of Lille, and the Hauts-de-France region for financial support. L.P. and Y.M. thank the Chinese government for the China Scholarship Council (CSC) fellowship. The authors are also thankful to the Taif University Researchers Supporting Project number (TURSP-2020/03), Taif University, Taif, Saudi Arabia.
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