Pt (1 1 1) quantum dot engineered Fe-MOF nanosheet arrays with porous core-shell as an electrocatalyst for efficient overall water splitting
Graphical abstract
Introduction
With the increasing of environmental pollution and the rapid consumption of fossil fuels, it is of most significant for our humanity to develop sustainable and eco-friendly clean energy [1], [2], [3]. Hydrogen is considered to be an ideal clean energy to replace traditional fossil fuels [4], [5], [6]. Among the techniques of producing hydrogen, electrochemical water splitting is one of the relatively efficient and clean methods for large-scale hydrogen production [7], [8]. It is required to develop highly active bifunctional electrocatalysts to reduce the influence of slow reaction kinetics for high overpotentials [9], [10]. Currently, Pt is regarded as the state-of-the-art catalytic material for HER, because water molecules could effectively be adsorbed by Pt to form Pt-Had in active sites [11], [12]. Moreover, the (1 1 1) plane of Pt was more active than other plane of Pt, particularly when it is combined with other metals as Pt-based bimetallic or polymetal metals electrocatalyst [13], [14]. Pt nanoparticle has high surface energy, however, it is easy aggregated to cause performance degradation [15]. To a certain extent, the stability of Pt is also affected by its high surface energy when it is used for a long time under strong alkali conditions [16]. In addition, the widespread application of Pt has been limited by the high cost [17], [18], [19]. One of the effective ways to solve these problems is constructing a core-shell structure with Pt nanoparticles as the core and the other material as the shell [20], [21].
Metal-organic framework (MOF) could form coordination functional groups and unsaturated metal ion centers in the form of self-assembly by connecting organic ligands with metal ions. As a function material, MOF is considered to have an immeasurable application prospect for electrocatalysis, due to its high porosity, large surface area and good stability [22], [23], [24], [25]. Moreover, the porous MOF provides an opportunity to fabricate core-shell structures. He et al. [26] reported a core-shell Ag @ MOF-5 nanoparticles for highly selective sensing property, and Ag nanoparticles were dispersed in excellent form in MOF-5. Other researchers had also explored coat nanoparticles on MOF materials to achieve uniform dispersion and excellent properties of small nanoparticles [27], [28], [29], [30]. Therefore, when the core-shell structure is formed by coating Pt with MOF, the quantum dot Pt could be evenly dispersed in MOF. Thus, the content of Pt usage can be drastically reduced. In additional, MOF in shell as electron conductor will shorten diffusion distance between charges and electrolyte ions to fast charge transport [31]. Meanwhile, the Pt QDs in core structure with different feature can change the interface contact of core-shell structure differently [32]. However, MOF particles are easily aggregated during the preparation process at high temperature, which makes the formed MOF aggregates unfavorable to the electronic conductivity in electrocatalytic reaction [33], [34], [35]. To resolve the problem, in situ growth of MOF materials on Ni foam (NF) at low temperature could prevent particle aggregation and maintain the orientation of MOF [36], [37], [38], [39]. Cai et al. [40] reported one-dimensional MOF nanorod arrays which were grown on NF, showing excellent electrical conductivity. Zhang et al. [37] adopted two-dimensional MOF nanosheets which were grown on NF, and it had been proved improving the adsorption of water molecules onto the catalyst and promoting gas diffusion to enhance the electrocatalytic performance. In addition, metal Ni in the NF could bond with Fe species to increase the active sites for OER [34], [41]. So, it will be an interesting idea if the electrocatalyst could be prepared by introducing Fe into Pt QDs @MOF on NF electrode. Thus, the Fe-MOF as an electron conductor in shell would improve the electron transfer rate and play a major role for OER in the MOF system on NF. What’s more, Fe-MOF would provide the opportunity for the formation excellent dispersion of ultralow Pt QDs in core to increase the stability and active sites of Pt for HER under alkaline conditions. To the best of our knowledge, core-shell Pt QDs @Fe-MOF nanosheet arrays in situ growth on NF for overall water splitting has rarely been reported.
In this work, we successfully synthesized Pt QDs @Fe-MOF with a porous cuboids structure on NF by a facile one-step hydrothermal treatment. The Pt QDs cores uniformly were coated with Fe-MOF nanosheet arrays shell. The Pt DQs @ Fe-MOF/NF only needed the 1.84 μg cm−2 of content of Pt to achieve a current density of 100 mA cm−2 at 191 mV for HER, which is the lowest noble metal content electrocatalyst reported so far. Moreover, the Pt DQs @ Fe-MOF/NF with the porous cuboids core-shell structure exhibited remarkable activity and stability for overall water splitting. Therefore, it has a promising future in electrocatalysis for water splitting in industrial practice.
Section snippets
Reagents and materials
NF was provided by Shanghai Zhonghui Foam Aluminum Products Co. Ltd (Shanghai, China). Chloroplatinic acid hexahydrate (H2PtCl6) was obtained from Aladdin Reagent (Shanghai) Co. Ltd. FeCl3·6H2O, terephthalic acid, N, N-Dimethylformamide (DMF) hydrochloric acid (HCl), potassium hydroxide (KOH), and ethanol were obtained from Nanning Blue Sky Experimental Equipment Co. Ltd (Nanning, China). All chemical regents were in the analytical grade and used without further purification. Deionized water
Material characterizations
The self-assembled porous cuboids of core-shell Pt DQs@Fe-MOF nanosheets arrays on NF were synthesized via a facile one-step hydrothermal treatment (Scheme 1). XRD patterns of NF, Fe-MOF/NF and Pt DQs @Fe-MOF/NF are shown in Fig. 1. The characteristic diffraction peaks of NF were located at 44.369°, 51.594° and 76.082°, corresponding to the (1 1 1), (2 0 0) and (2 2 0) planes of Ni, respectively (PDF No. 01-1258). Moreover, the three characteristic diffraction peaks shown in Fe-MOF/NF and Pt
Conclusion
In this work, self-assembly porous cuboids of core-shell Pt DQs @Fe-MOF nanosheets arrays supported on NF were synthesized by a facile one-step hydrothermal treatment with in situ grown. The Pt QDs cores uniformly are coated with Fe-MOF nanosheet arrays shell for efficient overall water splitting. The Pt DQs @Fe-MOF/NF had efficient catalytic performance and excellent stability, due to the special porous core-shell MOF structure and the (1 1 1) plane of Pt QDs, which effectively promoted the
Acknowledgements
This work was financially supported by the National Science Foundation of China (Nos. 21367002, 51707021), Guangxi Natural Science Foundation (Nos. 2016GXNSFAA380212, 2017GXNSFBA198186, 2018GXNSFAA294062 and 2018GXNSFAA281290), China Postdoctoral Science Foundation Grant (No. 2018M633295) , and Young Teachers Innovation Cultivation Program (BRP180261) from Guangxi Bossco Environmental Protection Technology Co., Ltd., and Open Fund of Guangxi Key Laboratory of Clean Pulp & Papermaking and
References (65)
- et al.
Bimetal-decorated nanocarbon as a superior electrocatalyst for overall water splitting
J. Power Sour.
(2018) - et al.
Tailoring the structure of clew-like carbon skeleton with 2D Co-MOF for advanced Li-S cells
Appl. Surf. Sci.
(2019) - et al.
Self-supported cobalt nitride porous nanowire arrays as bifunctional electrocatalyst for overall water splitting
Electrochim. Acta
(2018) - et al.
Fabrication of Pt nanoparticles on nitrogen-doped carbon/Ni nanofibers for improved hydrogen evolution activity
J. Colloid Interf. Sci.
(2018) - et al.
Confined distribution of platinum clusters on MoO2 hexagonal nanosheets with oxygen vacancies as a high-efficiency electrocatalyst for hydrogen evolution reaction
Nano Energy
(2019) - et al.
MOF-derived metal/carbon materials as oxygen evolution reaction catalysts
Inorg. Chem. Commun.
(2018) - et al.
Metal-organic-framework template-derived hierarchical porous CoP arrays for energy-saving overall water splitting
Electrochim. Acta
(2018) - et al.
Glycine derivative-functionalized metal-organic framework (MOF) materials for Co(II) removal from aqueous solution
Appl. Surf. Sci.
(2019) - et al.
Self-supported yolk–shell nanocolloids towards high capacitance and excellent cycling performance
Nano Energy
(2015) - et al.
Modern progress in metal-organic frameworks and their composites for diverse applications
Micropor. Mesopor. Mater.
(2017)
Synergistically well-mixed MOFs grown on nickel foam as highly efficient durable bifunctional electrocatalysts for overall water splitting at high current densities
Nano Energy
Template-directed growth of well-aligned MOF Arrays and derived self-supporting electrodes for water splitting
Chem
Pt/Fe-NF electrode with high double-layer capacitance for efficient hydrogen evolution reaction in alkaline media
Int. J. Hydrogen Energy
Hydrogen peroxide biosensor based on chitosan/2D layered double hydroxide composite for the determination of H2O2
Bioelectrochemistry
Enhancing electrocatalytic total water splitting at few layer Pt-NiFe layered double hydroxide interfaces
Nano Energy
Highly selective detection of Pb2+ by a nanoscale Ni-based metal–organic framework fabricated through one-pot hydrothermal reaction
Sensor. Actuat. B: Chem.
Preparation of MOF(Fe) and its catalytic activity for oxygen reduction reaction in an alkaline electrolyte
Chin. J. Catal.
Resin modified MIL-53 (Fe) MOF for improvement of photocatalytic performance
Appl. Catal., B: Environ.
Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting
Nano Energy
Fine-sized Pt nanoparticles dispersed on PdPt bimetallic nanocrystals with non-covalently functionalized graphene toward synergistic effects on the oxygen reduction reaction
Electrochim. Acta
Hybrid cobalt-based electrocatalysts with adjustable compositions for electrochemical water splitting derived from Co2+-loaded MIL-53(Fe) particles
Electrochim. Acta
The comprehensive understanding of as an evaluation parameter for electrochemical water splitting
Small Methods
Layered trichalcogenidophosphate: a new catalyst family for water splitting
Nano-Micro Lett.
Stability and catalytic performance of reconstructed Fe3O4(001) and Fe3O4(110) surfaces during oxygen evolution reaction
J. Phys. Chem. C
Phosphorus-doped Co3O4 nanowire array: a highly efficient bifunctional electrocatalyst for overall water splitting
ACS Catal.
In situ fabrication of heterostructure on nickel foam with tuned composition for enhancing water-splitting performance
Small
Electronic structure tuning in Ni3FeN/r-GO aerogel toward bifunctional electrocatalyst for overall water splitting
ACS Nano
Noble metal-free nanocatalysts with vacancies for electrochemical water splitting
Small
Ultrafine Pt nanoparticle-decorated pyrite-type CoS2 nanosheet arrays coated on carbon cloth as a bifunctional electrode for overall water splitting
Adv. Energy Mater.
Unlocking the door to highly active ORR catalysts for PEMFC applications: polyhedron-engineered Pt-based nanocrystals
Energ. Environ. Sci.
Pt (111) quantum dot decorated flower-like αFe2O3 (104) thin film nanosheets as a highly efficient bifunctional electrocatalyst for overall water splitting
J. Mater. Chem. A
Metals@MOFs – loading MOFs with metal nanoparticles for hybrid functions
Eur. J. Inorg. Chem.
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