Urchin-like Ni@N-doped carbon composites with Ni nanoparticles encapsulated in N-doped carbon nantubes as high-efficient electrocatalyst for oxygen evolution reaction
Graphical abstract
Urchin-like Ni@N-doped carbon composites (Ni–N–C species) derived from nickel tetraaminophthalocyanine via electrospinning and carbonization. The fabricated sea urchin-like composite has special a structure and there are many bamboo-like N-doped carbon nanotubes (CNTs) encapsulated Ni nanoparticles on its surface. It is obviously that the urchin-like structure significantly increased the specific surface area and the number of exposed active sites. The catalyst has superior performance in OER shows a low overpotentials of 305 mV (vs. Saturated Calomel Electrode, SCE) at the 10 mV cm−2 in 1.0 M KOH and a small Tafel slope of 95 mV·dec−1.
Introduction
With the development of the times, people have more and more demands for sustainable new energy, among which the water splitting to produce hydrogen is an ideal development prospect. As an important step in the electrolysis of water and metal-air batteries, the oxygen evolution reaction has attracted more and more attention [1,2]. Nevertheless, the practical application of OER is limited due to its slow reaction kinetics and high overpotential [3]. To overcome such obstacles, many catalysts have been designed through theoretical research [4,5]. At present, the best OER catalysts are still limited to precious metal oxides, such as RuO2 or IrO2 [6,7]. However, their expensive price and limited reserves have restricted their applications in practice. Therefore, how to develop an efficient and inexpensive OER catalyst is of current interest [[8], [9], [10], [11], [12]].
Nowadays, the electrocatalysts containing transition metal components have been considered to be one of the most applicable electrocatalytic materials to replace precious metal catalysts, such as Ni, Fe, Co and their derivatives, MoS2, MoC, MnO2. [[13], [14], [15], [16], [17], [18], [19], [20]] However, these materials have disadvantages such as poor conductivity and easy agglomeration, which lead to a decrease in electrocatalytically active sites and affect the transfer of electrons of electrocatalysis [21]. Recently, there have been many reports that the composite of transition metal and carbon can solve the above problem [[22], [23], [24], [25], [26], [27], [28], [29]]. For instance, Zhang and coworkers prepared Co or CoO nanoparticle encapsulated in N-doped carbon (Co/CoO@Co–N–C) by pyrolysis polypyrrole and shrimp shell transformed carbon nanodot complexes, which shows an overpotential of 370 mV at the 10 mV cm−2 [22]. Liu and coworkers synthesized Ni nanoparticle immobilized in N doping reduced graphene oxide (Ni/N-rGO), exhibited an overpotential of 590 mV at the current density of 10 mV cm−2 and a Tafel slope of 138 mV·dec−1 [28]. By dispersing the transition metal or its compounds and encapsulating them in the carbon matrix, the agglomeration of the nanoparticles can be effectively reduced, and the graphitized carbon also makes up for the lack of conductivity of the transition metal materials. Phthalocyanine is a kind of organic macrocyclic compound and its structure is similar to that of porphyrins such as haemoglobin and chlorophyll [[30], [31], [32], [33], [34]]. Its pyrolysis products are suitable transition metals/carbon composites, which owns the excellent electrocatalytic effect for oxygen reduction reactions(ORR) and CO2 reduction [[35], [36], [37], [38], [39], [40], [41], [42], [43]]. However, there are few studies focus on the application of these materials in OER.
In this work, we demonstrate a highly efficient OER catalyst based on urchin-like Ni@N-doped carbon composites (Ni–N–C species) derived from nickel tetraaminophthalocyanine via electrospinning and carbonization. The fabricated sea urchin-like composite has special a structure and there are many bamboo-like N-doped carbon nanotubes (CNTs) encapsulated Ni nanoparticles on its surface. It is obviously that the urchin-like structure significantly increased the specific surface area and the number of exposed active sites. The catalyst has superior performance in OER shows a low overpotentials of 305 mV (vs. Saturated Calomel Electrode, SCE) at the 10 mV·cm−2in 1.0 M KOH and a small Tafel slope of 76 mV·dec−1. Additionally, our catalyst also exhibits long-term electrochemical durability. Our research broadens the application of transition metal/carbon composites derived from phthalocyanine compounds to high-efficiency electrocatalysts to highly efficient electrocatalysts.
Section snippets
Chemicals and materials
Nickel tetraaminophthalocyanine (NiPc) was purchased from J&K Scientific Ltd(China). Poly(methyl methacrylate) (PMMA, Mw ≈ 350,000) was got from Sigma-Aldrich(American). RuO2 and N, N-dimethylformamide (DMF) were purchased from Aladdin Industrial Corporation(China). Nafion solution (D520-5%, Dupont) was purchased from Tianjin aiweixin Corporation(China). All the chemicals and reagents have not been further purified.
Preparation of Ni–N–C electrocatalyst
To obtain the nanofibres, a precursor solution was prepared. Firstly, 0.4 g NiPc
Morphological and structural analysis
The method of preparing Ni–N–C species is illustrated in Fig. 1. Firstly, NiPc/PMMA nanofibres were prepared by electrospinning. Then the nanofibres precursor was placed in a tube furnace and calcinated at 800 °C in nitrogen atmosphere. The nanofibres gradually broke down and formed block mass because PMMA decomposed at high temperatures. Meanwhile the carbon substance was catalyzed by nearby nickel particles and bamboo-like carbon nanotubes were grown in situ. Finally, carbon substance mass
Conclusions
Putting briefly, we demonstrated a simple means to prepare urchin-like Ni–N–C composites based electrocatalyst. The Ni–N–C species required only 305 mV to transmit a galvanic current of 10 mA/cm2 with long-lasting electrochemical hold and the Tafel slope was 76 mV·dec−1 only. This work showed a simple route to construct high-efficient OER catalysts with earth-abundant substance.
Conflicts of interest
The authors declare no conflicts of interest.
Acknowledgements
This work was financially supported by National Natural Science Foundation of China (No.51774245), Applied Basic Research Program of Science and Technology Department of Sichuan Province (No.2018JY0517), Sichuan Province sci-tech Supported project (2015RZ0023), Research Center of Energy Polymer Materials and Youth science and technology creative group fund of Southwest Petroleum University (2015CXTD03).
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