Natural aloe vera derived Pt supported N-doped porous carbon: A highly durable cathode catalyst of PEM fuel cell
Graphical abstract
Introduction
Recent years has seen a huge rise in clean and efficient sustainable energy storage and conversion systems with their extensive application range [1]. The ORR is the most significant cathodic reaction in devices with major contribution in the reaction potential towards its overall performance [2]. However, the large over potential and sluggish reaction kinetics impede the practical efficiency of these devices [3,4]. Hence, it is highly anticipated towards the development of an efficient ORR catalyst with improved kinetics and stability to overcome the barriers [1,5]. At the present scenario, the most trend setting catalysts such as platinum and platinum based alloys due to their renowned ORR activity; though, the scarcity pricing, derisory reserve and deprived electrochemical stability of the Pt catalyst have considerably limited its substantial applications [[6], [7], [8]]. In spite of that, considerable optimization is required to improve the catalytic activity along with cost effectiveness and stability issues [8]. One among them is to reduce the Pt loading and use highly active catalyst support without affecting the supporting materials requirements such as low cost, good electrical conductivity, strengthened metal-support interaction, high surface area and good resistance to corrosion [[9], [10], [11], [12], [13], [14]]. Knowingly, in the past decades, carbon doped with heteroatom's such as N [[15], [16], [17], [18]], S [19], F [16,20], P [15,21], and B [22] etc. were successively proved to best able and active support materials for Pt supported catalysts in ORR and implying the feasibility of lowering Pt usage effectively [17,[23], [24], [25]]. Depending on the doping of heteroatoms and texture of porous carbon that can enhance the surface hydrophilicity and feasible the active sites creation, which leads to an increased ORR reaction kinetics [10,[14], [15], [16],21,26]. Amongst, Nitrogen (N) shows attracting dopant in the carbon matrix due to its higher electrochemical stability and electron accepting ability. Especially Pt deposited on N-doped carbon nanomaterial shows remarkable enhancement in Pt usage, activity and stability [14]. Many studies, evidence the improved stability of Pt NPs on N-doped porous carbon through the preferred active forms of N atoms [17] and form dative bond with Pt metal (N–Pt) which improves the electrochemical stability and prevents the agglomeration of Pt NPs from the support. Different categories of N-doped allotropes of carbon have been noted such as carbon nanotubes [[27], [28], [29], [30], [31]], graphene [13,[32], [33], [34]], nanocoils [35], nanofibers [10,36,37], mesoporous carbon [8,17,38], and quantum dots [18,39,40]. Amongst all, carbon with mesopores (pore size 2–50 nm) are very attractive due to their pore geometry and lofty pore volume for the faster diffusion and an efficient mass transport [41].
Recently, porous carbon derived from bio sources has been environmentally most abundant, inexpensive, also provides an excellent platform to regulate porous structure with high surface area [5,[42], [43], [44]]. The synthesis of porous carbon from biomass is achieved via pyrolysis, gasification, hydrothermal carbonization, template-based methods, and soft template [14,19,[45], [46], [47]] etc. Among all these methods, direct pyrolysis drags attention owing to template–free loom, low cost, conservational, scalable, and to prepare hierarchically porous carbon, while comparing others observe difficulties such as complex and costly instruments, use of harmful chemicals etc. [48]. Numerous reports available in the literature pertaining porous carbon derived from various biomass sources viz. Jackfruit seed [42], cotton [20,49,50], coffee beans [51], spent coffee grounds [15,16], corncob [52,53], coconut shell [54], orange peel [55], wall nut [56] and aloe vera peels [57] towards the sustainable energy storage and conversion applications. The porous carbon derived from the above sources shows great influence on the catalytic properties such as electronic conductivity, catalytic activity, charge density and tuned electron distribution by creating active sites that are favourable for ORR [5,[58], [59], [60]]. The N-doped carbon with pyridinium nitrogen has a lone pair electron, which can modify the distribution of charge into the carbon matrix, the electron donating capability and effectively weaken the O–O band [34] favourable for the adsorption and activation of oxygen, boosting the ORR process [47,61]. The graphitic N is also favourable for the active sites and with the coexistence of different kinds of N present in the carbon matrix [33,62]. The amalgamation of nitrogen into the carbon matrix functionalize the carbon and helps interaction of Pt NPs through Pt–N–C and enhance the electronic conductivity, charge transfer etc. In this point of view, aloe vera peels derived nitrogen doped carbon drags the attention due to its abundance and production availability to make an efficient electro catalyst for ORR [57].
In this work, we synthesised porous carbon from naturally available aloe vera peel with nitrogen doping as exemplary support for Pt based ORR catalyst. The Pt/N-AVC has shown high durability and excellent electrochemical activity, directly crediting to the nitrogen content and the extremely porous support material. The Pt/N-AVC catalyst even after 30,000 potential cycling, the E1/2 shows only 5 mV negative shift and there is was no sign of agglomeration or dissolution of Pt NPs from the supporting material which indicates Pt/N-AVC catalyst as an excellent high durable cathode catalyst useful for PEMFC applications.
Section snippets
Experimental section
For the preparation of porous carbon from biomass, aloe vera plant leaf was collected from a plant and aloe vera peels were dried under sunlight for 36 h to remove the moisture content. The dried peel was cut into small pieces and kept for 24 h in the oven at 80 °C. Then the peels were pyrolyzed under the nitrogen atmosphere in a temperature range of 800–1000 °C for 1 h. The resultant black materials were further purified with 5 M aqueous HNO3 and washed thoroughly with deionised (DI) water
Structure and morphology
The preparation of bio-derived porous carbon from aloe vera plant leaf and its activation process significantly influence the intrinsic and extrinsic characteristics of as-prepared carbon. Fig. 1(a) illustrate the XRD pattern of AVC and N-AVC, which shows two distinct peaks at 2ϴ value belongs to the graphitic carbon of 24° and 43° analogous to (002) and (100) planes [16]. Pt deposition on N-AVC (Pt/N-AVC) show the crystalline Pt (0) NPs with the diffraction peaks were observed at 40°, 46.5°,
Conclusions
An efficient and durable Pt supported N-doped mesoporous carbon (Pt/N-AVC) catalyst has been successfully synthesised from the naturally available Aloe Vera plant by simple pyrolysis and the reduction method. Doping N into AVC matrix, the ID/IG ratio is increasing due to more defects, which are newly created, and this leads to an increase in the specific surface area (376 m2/g) and the volume. The well dispersion of Pt NPs is seen in HR-TEM images and the presence of N, C and Pt NPs are
Acknowledgements
This work was supported by Department of Science and Technology (DST), New Delhi, India for awarding INSPIRE Faculty Award (DST/INSPIRE/04/2016/000530). One of the authors, Dr. Prabu Moni grateful to the Department of Science and Technology (DST), New Delhi, India for awarding INSPIRE Faculty Award (DST/INSPIRE/04/2016/000530). We thank Dr. N. Kalaiselvi, Director, CSIR-CECRI, for the continuous encouragement and support.
References (81)
- et al.
Emerging Pt-based electrocatalysts with highly open nanoarchitectures for boosting oxygen reduction reaction
Nano Today
(2018) - et al.
Compositing doped-carbon with metals, non-metals, metal oxides, metal nitrides and other materials to form bifunctional electrocatalysts to enhance metal-air battery oxygen reduction and evolution reactions
Chem Eng J
(2018) - et al.
New evaluation method for the effectiveness of platinum/carbon electrocatalysts under operating conditions
Electrochim Acta
(2010) - et al.
An effective electrocatalyst based on platinum nanoparticles supported with graphene nanoplatelets and carbon black hybrid for PEM fuel cells
Int J Hydrogen Energy
(2019) - et al.
Nitrogen doped mesoporous carbon supported Pt electrocatalyst for oxygen reduction reaction in proton exchange membrane fuel cells
Int J Hydrogen Energy
(2018) - et al.
Nitrogen-doped carbon dots originating from unripe peach for fluorescent bioimaging and electrocatalytic oxygen reduction reaction
J Colloid Interface Sci
(2016) - et al.
Role of phosphorus in nitrogen, phosphorus dual-doped ordered mesoporous carbon electrocatalyst for oxygen reduction reaction in alkaline media
Int J Hydrogen Energy
(2018) - et al.
Platinum on boron doped graphene as cathode electrocatalyst for proton exchange membrane fuel cells
Int J Hydrogen Energy
(2015) - et al.
Multi-walled carbon nanotubes decorated by platinum catalyst for high temperature PEM fuel cell
Int J Hydrogen Energy
(2019) - et al.
3D porous cellular NiCoO2/graphene network as a durable bifunctional electrocatalyst for oxygen evolution and reduction reactions
J Power Sources
(2018)
Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction
Appl Surf Sci
Green synthesis of nitrogen-doped graphitic carbon sheets with use of Prunus persica for supercapacitor applications
Appl Surf Sci
Highly active and stable platinum catalyst supported on porous carbon nanofibers for improved performance of PEMFC
Electrochim Acta
Sahu Fluorine-enriched mesoporous carbon as efficient oxygen reduction catalyst: understanding the defects in porous matrix and fuel cell applications
Nanoscale Adv
Facile self-assembly N-doped graphene quantum dots/graphene for oxygen reduction reaction
Electrochim Acta
Bio-derived carbon as an efficient supporting electrocatalyst for the oxygen reduction reaction
J Phys Chem Solid
Facile preparation of biomass-derived bifunctional electrocatalysts for oxygen reduction and evolution reactions
Int J Hydrogen Energy
A universal strategy for carbon–based ORR–active electrocatalyst: one porogen, two pore–creating mechanisms, three pore types
Nanomater Energy
Benefits and limitations of Pt nanoparticles supported on highly porous antimony-doped tin dioxide aerogel as alternative cathode material for proton-exchange membrane fuel cells
Appl Catal B Environ
Cotton fabric derived hierarchically porous carbon and nitrogen doping for sustainable capacitor electrode
Carbon
Electrochemical studies on corncob derived activated porous carbon for supercapacitors application in aqueous and non-aqueous electrolytes
Electrochim Acta
Porous N,P-doped carbon from coconut shells with high electrocatalytic activity for oxygen reduction: alternative to Pt-C for alkaline fuel cells
Appl Catal B Environ
Walnut shell derived porous carbon for a symmetric all-solid-state supercapacitor
Appl Surf Sci
Aloe peel-derived honeycomb-like bio-based carbon with controllable morphology and its superior electrochemical properties for new energy devices
Ceram Int
Biomass waste inspired nitrogen-doped porous carbon materials as high-performance anode for lithium-ion batteries
J Alloys Compd
Simultaneous sulfonation and reduction of graphene oxide as highly efficient supports for metal nanocatalysts
Carbon
Improved durability of Pt catalyst supported on N-doped mesoporous graphitized carbon for oxygen reduction reaction in polymer electrolyte membrane fuel cells
Carbon
Facile synthesis of boron and nitrogen-dual-doped graphene sheets anchored platinum nanoparticles for oxygen reduction reaction
Electrochim Acta
Polymer-mediated synthesis of a nitrogen-doped carbon aerogel with highly dispersed Pt nanoparticles for enhanced electrocatalytic activity
Electrochim Acta
Fabricating Pt-decorated three dimensional N-doped carbon porous microspherical cavity catalyst for advanced oxygen reduction reaction
Carbon
Enhanced oxygen reduction reaction activity of iron-containing nitrogen-doped carbon nanotubes for alkaline direct methanol fuel cell application
J Power Sources
Oxygen reduction reaction activity of platinum nanoparticles decorated nitrogen doped carbon in proton exchange membrane fuel cell under real operating conditions
Int J Hydrogen Energy
Nitrogen doped lotus stem carbon as electrocatalyst comparable to Pt/C for oxygen reduction reaction in alkaline media
Int J Hydrogen Energy
Metal-organic frameworks derived platinum-cobalt bimetallic nanoparticles in nitrogen-doped hollow porous carbon capsules as a highly active and durable catalyst for oxygen reduction reaction
Appl Catal B Environ
Probing the correlation between Pt-support interaction and oxygen reduction reaction activity in mesoporous carbon materials modified with Pt-N active sites
Electrochim Acta
Ultrathin nitrogen doped carbon layer stabilized Pt electrocatalyst supported on N-doped carbon nanotubes
Int J Hydrogen Energy
Enhanced oxygen reduction reaction of Pt deposited Fe/N-doped bimodal porous carbon nanostructure catalysts
J Catal
Platinum catalysts protected by N-doped carbon for highly efficient and durable polymer-electrolyte membrane fuel cells
Electrochim Acta
Platinum nanoparticles supported on nitrogen and fluorine co-doped graphite nanofibers as an excellent and durable oxygen reduction catalyst for polymer electrolyte fuel cells
Carbon
Catalysis with two-dimensional materials confining single atoms: concept, design, and applications
Chem Rev
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