Sandwich-structured nanocomposite constructed by fabrication of exfoliation α-ZrP nanosheets and cobalt porphyrin utilized for electrocatalytic oxygen reduction
Graphical abstract
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).
References (44)
- et al.
J. Power Sources
(2007) - et al.
J. Electroanal. Chem.
(1999) Comp. Biochem. Physiol. A
(1997)- et al.
Microporous Mesoporous Mater.
(2004) - et al.
Microporous Mesoporous Mater.
(2008) - et al.
Polyhedron
(2003) - et al.
Mater. Lett.
(2015) - et al.
Microporous Mesoporous Mater.
(2005) - et al.
J. Inorg. Nucl. Chem.
(1968) - et al.
J. Solid State Chem.
(2006)
Catal. A Chem.
J. Catal.
Microporous Mesoporous Mater.
J. Mol. Catal. A Chem.
J. Mol. Catal. A Chem.
J. Mol. Catal. A Chem.
Chem. Rev.
Science
ACS Nano
J. Phys. Chem. C
Langmuir
J. Electrochem. Soc.
Cited by (16)
One-pot ball-milling preparation of cetylpyridinium chloride/α-zirconium phosphate composite for simultaneous detection of ascorbic acid and dopamine
2021, Journal of Alloys and CompoundsCitation Excerpt :It has a weight loss of 37% below 450 °C, which corresponds to the decomposition of intercalated CPC. The decomposition temperature of CPC is enhanced, which may be due to the protective effect of the α-ZrP gallery [24]. Generally, AA and DA coexist in biological systems, it is a major target to distinguish them selectively in electrochemical analysis.
A sandwich-structured, layered CoTMPyP/Sr<inf>2</inf>Nb<inf>3</inf>O<inf>10</inf> nanocomposite for simultaneous voltammetric determination of dopamine and ascorbic acid
2020, Journal of Electroanalytical ChemistryCitation Excerpt :In recent years, research on porphyrin complexes has attracted attention, thanks to the application of metalloporphyrins and their derivatives in photovoltaic energy [16], catalysis [17] and medicine [18]. However, metal porphyrins and their derivatives are expensive [19] and are sensitive to conditions such as temperature, pH and organic media [20]. Layered perovskite oxides exhibit a wealth of physical and chemical properties including photocatalysis [21], ionic conductance [22], electrochemical stability [23], magnetic properties [24] and piezoelectricity [25].
FeNi-based bimetallic MIL-101 directly applicable as an efficient electrocatalyst for oxygen evolution reaction
2019, Microporous and Mesoporous MaterialsCitation Excerpt :Electrochemical water decomposition provides a clean and effective way to produce pure hydrogen on a large scale [4,5]. The oxygen evolution reaction (OER), which plays an important role in various energy storage and conversion processes, is considered to be the main bottleneck preventing effective water decomposition for hydrogen generation [6–8]. Moreover, the anodic OER is a four-electron transfer (4OH− → 2H2O + O2 + 4e−).
A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction
2017, Applied Surface ScienceCitation Excerpt :Therefore, a great deal of research has been carried out to develop highly active cobalt complexes which could work efficiently in aqueous solutions. Cobalt porphyrins have also been previously demonstrated to act as efficient photocatalyst for HER [8,9] and electrocatalysts for the oxygen reduction reaction [10–12] and oxygen evolution reaction [13]; while the exploration of cobalt porphyrins based HER electrocatalysts has received much less attention. Dong et al. [14] developed metalloporphyrin-polyoxometalate hybrid films by the layer-by-layer method and investigated their catalytic properties for HER in acid media.
From biomass chitin to mesoporous nanosheets assembled loofa sponge-like N-doped carbon/g-C<inf>3</inf>N<inf>4</inf> 3D network architectures as ultralow-cost bifunctional oxygen catalysts
2017, Microporous and Mesoporous MaterialsCitation Excerpt :Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the key electrode processes for a variety of air-based sustainable energy technologies such as metal-air batteries, regenerative fuel cells and water splitting [1–4]. However, the sluggish kinetics of ORR and OER limit the efficiency of these technologies and stand in the way of their wide commercialization [4–7]. Therefore, the catalysts, especially bifunctional catalysts that unify the efficient catalytic activities of both OER and ORR, are crucial in the field of air-based energy technologies [8].