Design and fabrication of Fe2O3/FeP heterostructure for oxygen evolution reaction electrocatalysis
Introduction
The extensive use of fossil fuels is the major cause of the burgeoning environmental and energy crisis. The introduction of more sustainable methods of generating energy is urgently needed to overcome energy crises [1], [2]. The transformation of our reliance on petrochemicals towards renewable energy sources is significant [3], [4]. Hydrogen is the best source of clean renewable energy [5], [6]. Due to the fact that when it is formed and burned, only water is produced as a by-product and has a carbon dioxide-free system. The reforming process produces 90% hydrogen, which contains impurities and is not very efficient, but is still one of the largest sources of hydrogen production [7]. Hence, the development of clean energy is important in modern times due to environmental changes and the depletion of fossil fuel reservoirs. To fulfill the global demand for clean energy and to counter the decline in fossil fuel production, electrocatalytic water splitting is a promising and suitable solution [8], [9], [10]. The electrochemical splitting of water is one of the most important ways of producing hydrogen and a promising solution to meet the global energy demand [11], [12], [13]. The currently most effective and well-known electrocatalysts for water splitting are precious metals-based oxides, especially IrO2 and RuO2 [14]. However, their inadequacy and high cost limit their practical application considerably [15].
In view of the limited availability of precious metals and the higher manufacturing costs of these metals-based catalysts, it is highly desirable to design and synthesize earth-abundant and cost-effective non-noble metal-based catalysts for OER [16], [17]. Metal phosphides have recently been shown high activity as non-toxic electrocatalysts in OER. Considerable efforts have been made to synthesize metal phosphides, especially MoP, FeP, CoP and Ni2P as the best substitutes for noble metals-based catalysts for OER due to their long-term stability[18]. Niu et al. reported on hierarchical heterostructure of CoP-FeP as a bifunctional high-performance and durable electrocatalyst for OER and HER in various electrolytes [19]. Ray et al. grew the Fe-coated nickel-cobalt-phosphide nanoplates in carbon material and investigated the electrochemical splitting of water in a basic environment [20]. Fang et al. reported on the metal-organic framework-template synthesis of bimetallic selenides for OER [21]. Lei et al. manufactured an electrocatalyst by embedding FeCo in a matrix of N-doped carbon nanotubes/carbon nanosheets for the oxygen reduction reaction and OER [22]. Zhang et al. reported on a NiFe-MOF electrocatalyst for OER [23].
A rational design of a Fe2O3/FeP heterostructure based on inexpensive and earth-abundant Fe metal for OER is reported here. In the heterostructure, the interaction of Fe2O3 and FeP effectively changes the electronic structure of Fe2O3 and FeP and leads to increased intrinsic catalytic activity towards OER. An overpotential of 264 mV is required for the fabricated Fe2O3/FeP heterostructure to drive the OER with a current density of 10 mAcm-2 and a low Tafel slope value of 47 mV/dec in 1.0 M potassium hydroxide solution. The results provide useful guidelines for developing the low-cost and earth-abundant electrocatalysts for OER.
Section snippets
Materials
Iron chloride hexahydrate (FeCl3.6H2O,>98%) was purchased from Spectrum Chemicals. Potassium hydroxide (KOH, 99%) was bought from Grace Chemicals. Nafion solution (5 wt%), red phosphorus (P4, 98%) and ethanol (C2H5OH, 99.9%) were purchased from Sigma Aldrich. Sodium hydroxide (99%) was purchased from Daejung chemicals. All chemicals were used as received.
Synthesis of electrocatalysts
The hydrothermal method was used to synthesize catalysts. For iron oxide synthesis, 25 mL of 0.5 M FeCl3.6 H2O solution was kept under
Structural analysis
XRD studies were conducted to confirm the crystal structures of electrocatalysts [25]. Fig. 1 presents the XRD patterns of Fe2O3, FeP and Fe2O3/FeP electrocatalysts. The diffraction peaks in the XRD spectrum of Fe2O3 at 2θ= 24.10°, 33.02°, 35.61°, 40.81°, 49.57°, 54.13°, 57.68°, 62.51°, and 64.15° attributed to the lattice plane of (012), (104), (110), (113), (024), (116), (122), (214), and (300), respectively of rhombohedrally centered hexagonal phase [26], [27] (JCPDS No. 33–0664). X-ray
Conclusions
In summary, we have synthesized an efficient OER catalyst on the basis of a Fe2O3/FeP heterostructure, which starts oxygen evolution at an applied potential of 1.49 V (vs. RHE) and generates an OER current density of 10 mAcm-2 at only 264 mV overpotential. This improved OER performance is associated with the presence of holes in the framework of the electrocatalyst, which serve as a reservoir for an electrolyte that increases the OER performance. Moreover, the large surface area with many
CRediT authorship contribution statement
Iqbal Ahmad: Conceptualization, Experimentation, Supervision, Investigation, Resources, Methodology. Jawad Ahmed: Experimentation, Formal analysis. Saima Batool: Experimentation, Formal analysis, Writing – review & editing. Muhammad Nadeem Zafar: Formal analysis, Writing – review & editing. Amna: Formal analysis, Writing – review & editing. Zahidullah: Formal analysis, Writing – review & editing. Muhammad Faizan Nazar: Formal analysis, Writing – review & editing. Anwar Ul-Hamid: Formal
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.
Acknowledgments
The author (Alaa Dahshan) extends his appreciation to the Deanship of Scientific Research at King Khalid University for funding this work through research groups program under grant number (RGP.2/89/42).
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Authors have equal contribution in this research work