Sandwich-structured nanocomposite constructed by fabrication of exfoliation α-ZrP nanosheets and cobalt porphyrin utilized for electrocatalytic oxygen reduction
Introduction
Platinum (Pt) nanoparticles have long been regarded as the most excellent catalyst toward oxygen reduction reaction (ORR) in alkaline fuel cells. Nevertheless, the high expense of Pt catalyst which suffers from its susceptibility to time-dependent drift [1] and CO deactivation [2] limits their large-scale commercialization. Based on the problems above, two solutions were proposed: reduction of the Pt loading, and exploration of non-noble catalysts. As far as the first method is concerned, it cannot resolve the issues of high costs fundamentally. Therefore, considerable research efforts have focused on several non-noble catalysts such as carbon nanotube [3], graphene [4], phthalocyanines [5], and porphyrins [6] as promising candidates for ORR. Among them, Co-based porphyrins including CoTPP, CoTPyP [7], CoTCPP, CoTMPyP [8], and CoTMPP [9] exhibited excellent catalytic activities toward ORR. However, enzymes (including metalloporphyrins) are often expensive, sensitive to pH/temperature, and unstable in organic media, binding of enzymes on rigid inorganic matrix can partly overcome these limitations [10], and in specific cases, such binding can improve the properties of enzymes to a significant extent. α-Zr(HPO4)2·H2O (abbreviated as α-ZrP) can be the promising support matrix because of its excellent performance such as a much higher ion-exchange capacity and ease of intercalation/exfoliation, etc. compared to natural clay [11]. Therefore, some intercalation compounds of α-ZrP/hemoglobin, α-ZrP/myoglobin and α-ZrP/porphyrin, etc. were extensively reported [12], [13], [14], [15], [16], [17], [18], [19].
On the other hand, two-dimensional nanosheets derived from the layered parent materials via exfoliation process have aroused intensive attention recently on account of their extraordinary functionalities with atomic or molecular thickness [20], and the ability to serve as a building block for electrostatic layer-by-layer self-assembly [21]. The research focus of exfoliated nanosheets should be assigned to transition metal dichalcogenides (MoS2 and WS2) [22], [23], layered double hydroxides (M−Al LDHs, M = Zn, Ni, Co, Fe) [24], [25], and metal oxides (, , ) [26], [27], [28], meanwhile, delamination of α-ZrP nanosheets has also received much attention [29], [30], especially the ability to reassemble with functional guest molecules [12], [31], [32], [33]. Therefore, it is promising to realize the combination of α-ZrP nanosheets and CoTMPyP molecules for further exploration on novel functionalities of the nanocomposites.
Herein, sandwich-structured nanocomposite of α-ZrP/CoTMPyP was fabricated through electrostatic interaction between α-ZrP colloidal dispersion and cobalt porphyrin aqueous solution [34] (Fig. 1). In addition, the obtained α-ZrP/CoTMPyP hybrid film was used as a modifier on a glassy carbon electrode by simple drop-coating method to test the electrocatalytic performance toward oxygen reduction. The results indicated that oxygen was reduced to H2O2 via two-electron transfer.
Section snippets
Preparation of exfoliated α-ZrP nanosheets
As reported in previous literature [35], 3.0 g ZrOCl2·8H2O powder was dispersed into 30 ml distilled water firstly in a plastic flask, 30 ml concentrated hydrochloric acid, 3 ml hydrofluoric acid, and 9 ml phosphoric acid were added into the pre-dispersed solution above with vigorously stirring, the temperature was set at 80 °C, the resulting white precipitate was washed with distilled water three times, and dried at 50 °C overnight. Exfoliated α-ZrP nanosheets were prepared by mixing 0.1 g of
Characterization of α-ZrP/CoTMPyP hybrid thin film
α-ZrP host material was identified by XRD analysis displayed in Fig. 2. The strong and sharp diffraction peaks indicated the high crystallinity of α-ZrP original material. With respect to the formation of α-ZrP nanosheets, it should be attributed to the penetration of large TBA+ ions into the interlayer which contains positively charged nitrogen atoms with four attached alkyl groups, and expansion of the interlayer spacing to greatly weaken the interactions between neighboring sheets [36].
Conclusions
Laminar nanocomposite of α-ZrP/CoTMPyP was fabricated through a simple and rapid method named the exfoliation/restacking route. The well-dispersed and stable α-ZrP colloidal dispersion was obtained determined by a Zetasizer Nano instrument. Furthermore, the structure model of α-ZrP/CoTMPyP hybrid material was given that CoTMPyP molecule was intercalated into the host layers almost by a monolayer inclined angle of 39°. The nanocomposite prepared by the reassembly between α-ZrP nanosheets and
Acknowledgments
This work was supported by National Natural Science Foundation of China (Grant Nos. 21401062, 21201070, 51202079), Natural Science Fund of Jiangsu Province (BK2012665, BK20140447, BK20141247, SBK201220654), and University Science Research Project of Jiangsu Province (13KJB430005, 12KJD150001, 15KJB430004).
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