Large-Scale Fabrication of Hollow Pt3Al Nanoboxes and Their

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Large-scale fabrication of hollow Pt3Al nanoboxes and their electrocatalytic performance for hydrogen evolution reaction Qiang Li, Bin Wei, Yue Li, Junyuan Xu, Junjie Li, Lifeng Liu, and Francis Leonard Deepak ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00372 • Publication Date (Web): 13 May 2019 Downloaded from http://pubs.acs.org on May 21, 2019

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ACS Sustainable Chemistry & Engineering

Large-scale fabrication of hollow Pt3Al nanoboxes and their electrocatalytic performance for hydrogen evolution reaction

Qiang Lia, Bin Weib, Yue Lic, Junyuan Xub,*, Junjie Lib,d* Lifeng Liub, and Francis Leonard Deepakb a

School of Mechanical Engineering, University of Shanghai for Science and Technology, Shanghai 200093, P. R. China

b International

Iberian Nanotechnology Laboratory (INL), Avenida Mestre Jose Veiga, Braga 4715-330, Portugal

c

Center of Chemistry, Chemistry Department, University of Minho, Gualtar Campus, Braga, 4710-057, Portugal.

d

CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS; Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. Email: [email protected] (J. J. Li); [email protected] (J. Y. Xu)

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ABSTRACT: Hollow structuring and alloying have been known to be effective methods to improve physicochemical properties and create new functionalities of nanomaterials. However, it is technically difficult to fabricate hollow alloyed intermetallic compound nanostructures, which are emerging as promising electrocatalysts for water splitting, in a controllable and scalable manner using current wet chemical routes. Here, we report a simple method allowing for large-scale fabrication of hollow Pt3Al nanoparticles using a melt-spinning and subsequent self-templating etching route. We demonstrate that upon etching both microstructure and phase composition changed, leading to the transformation of Al-rich PtAl6 intermetallic compound ribbons to interconnected hollow nanoparticles of Pt-rich Pt3Al with sizes varying from 4 to 22 nm. The electrochemical measurement shows that the hollow Pt3Al intermetallic nanoparticles have better electrocatalytic activity and catalytic stability than commercial Pt/C catalysts for the hydrogen evolution reaction in alkali media, showing that the hollow Pt3Al nanobox can be used as potential cathode catalysts for water splitting. The facile melt-spinning and self-templating etching route can be readily extended to fabricate other noble metal-based alloy hollow nanostructures on a large scale for various applications. Keywords: hollow nanostructures, alloying, Pt3Al, intermetallic compound, hydrogen evolution reaction.


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INTRODUCTION Hollow and porous nanostructures have received considerable attention for their various applications in catalysis, energy-conversion and storage.1-6 The first hollow structure based on silica was reported by Caruso and co-workers in 1998, since then, various hollow nano- or/and microstructures with different morphologies such as ellipsoids, cubes, rods, and wires, have been successfully fabricated via the template approach. Specifically, the following templating strategies have been employed so far: (1) hard templating which involves coating a layer of desired materials on the surface of a hard template with specific shapes, followed by selective removal of the template to obtain the hollow structure;10-14 (2) soft templating during which soft matters such as gas bubbles, emulsion,15-17 and vesicles/micelles,18-19 are utilized as templates; (3) self-templating which is developed based on different principles, including Ostwald ripening,1, 20 galvanic replacement,21 Kirkendall effect22 and surface-protected etching23-24. However, most hollow structures fabricated by these strategies are metal oxides or chalcogenides and carbon spheres,25-29 and it remains a technical challenge to fabricate hollow noble metal-transition metal intermetallic compound nanostructures, particularly on a large scale. Herein, we report a simple and highly efficient self-templating etching route that allows us to fabricate hollow noble metal-based intermetallic nanoparticles on a large scale. The platinumaluminum (Pt-Al) alloy was chosen for the model system considering the potential applications of Pt-based nanoparticles in water splitting as cathode materials. The hollow Pt3Al nanoboxes were prepared by self-templating etching induced phase and microstructure transformation of melt-spun Al-rich PtAl6 nanoboxes. The obtained hollow Pt3Al nanoboxes were studied as the catalyst for hydrogen evolution reaction (HER) in alkali media and demonstrated a good



electrocatalytic activity for HER with η10 = 38 mV and good stability, better than the commercial Pt/C catalysts.

EXPERIMENTAL SECTIONS Preparation and characterization of hollow Pt3Al nanoboxes Platinum-aluminium ingots (Pt3Al97) with a stoichiometric ratio of 3 : 97 were prepared by non-consumable arc melting of Pt (99.99%, mass.%) and Al (99.99%, mass.%) in high-purity argon (Ar). The alloyed ingots were then spun into ribbons with a width of approximately 1500 µm and a thickness of 30 µm through a single-roller melting-spinning process in argon atmosphere. Subsequently, the alloyed ribbons were etched in 1 M NaOH for several days to obtain hollow Pt3Al nanoparticles. The resultant black products were centrifuged, washed with deionized water for 6 times and dried at about 25 oC for further use. The crystal structure of the obtained products was characterized by X-ray diffraction (XRD), which was implemented on a X'Pert PRO diffractometer (PANalytical) working at 45 kV with Cu Kα radiation. The morphology and composition of the obtained products were investigated by transmission electron microscope (TEM), scanning TEM (STEM) along with energy dispersive spectroscopy (EDS) on a double corrected transmission electron microscope operating at 200 kV (FEI Themis 60 – 300, equipped with a Super-X EDS detector and both image Cs and probe correctors), offering an unprecedented opportunity to probe sub-Ångström-resolution crystal structures.30-33 Electrochemical measurement


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The electrodes for catalytic tests were prepared by carrying out the following steps: (1) 5 mg of catalysts were dispersed into a solution containing ethanol (950 μL) and Nafion (50 μL) by ultrasonication for 2 hours. (2) the fabricated catalyst ink (50 μL) was transferred onto a polished glassy carbon electrode, and the exposed area was about 0.78 cm2, leading to a loading of ca. 0.3 mg cm-2. (3) The electrode was then dried naturally for about 20 mins in air. Subsequently, the glassy carbon was used for electrocatalytic measurements in a three-electrode system on a Biologic VMP-3 potentiostat/galvanostat in 1.0 M NaOH as working electrode. The saturated calomel electrode and graphite rod were used as reference and counter electrodes, respectively. It is worthy to note that the saturated calomel electrode was calibrated using platinum as working electrode in a Ar/H2-saturated H2SO4 solution (0.5 M) before the electrochemical tests. Based on the measured potentials, the potentials versus RHE are obtained from the following equation:34 ERHE = ESCE + 0.059 × pH + 0.241

(1)

Cyclic voltammetry (CV) was performed at a scan rate of 5 mV s-1 in the potential range of 0.2 to 0.2 V vs RHE. To compensate for the voltage drop between the reference and working electrodes, iR-correction (85%) was made through a single-point high-frequency impedance measurement.34 The Impedance measurement was implemented at -0.03 V vs RHE in the frequency range of 105 to 0.01 Hz with a 10 mV sinusoidal perturbation. The stability was probed through continuous CV scanning in the range of -0.1 – 0 V vs RHE at a sweep rate of 50 mV s-1. The stability was evaluated using the overpotentials at a current density of 10 mA cm-2 from the different voltammetry cycles. RESULTS AND DISCUSSION



a

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Figure 1. a. Schematic illustration of the fabrication of hollow Pt3Al nanoboxes from Al-rich PtAl6 nanoparticles using the melt-spinning and subsequent self-templating etching route. Insets show the HAADF-STEM images of individual PtAl6 (red frame) and hollow Pt3Al (blue frame) nanoboxes. b. XRD patterns of the as-spun PtAl6 and hollow Pt3Al nanoparticles. For reference, the standard XRD patterns of Al (JCPDS No. 04-0787), PtAl6 (JCPDF No. 47-0981) and Pt3Al (JCPDS No. 29-0070) are also given. Inset shows a digital photograph of the obtained hollow Pt3Al nanobox powders at a gram level. Fig. 1a shows the schematic of the fabrication of hollow Pt-rich Pt3Al nanoboxes from Al-rich PtAl6 nanoparticles using the self-templating etching induced phase transformation strategy. The alloying ribbons were fabricated by a single-roller melting-spinning method in argon atmosphere and have a width of approximately 1500 µm and a thickness of 30 µm (see Experimental details in ESI†). X-ray diffraction (XRD, Fig. 1b) confirmed that the as-spun ribbons consist of a


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mixture of crystalline Al (JCPDS No. 04-0787) and orthorhombic PtAl6 alloy (JCPDF No. 470981). Hollow Pt3Al nanoboxes were obtained by soaking the as-spun Pt3Al97 ribbons (consisting of PtAl6 nanoboxes embedded in Al matrix) in 1 M NaOH solution. Upon etching, the initial shiny intermetallic ribbons were converted into a large amount of black powders (Fig. 1b, inset). Inset images in Fig. 1a are the low magnification high-angle annular-dark-field scanning transmission electron microscopy (HAADF-STEM) images for PtAl6 (red box in Fig. 1a) and hollow Pt3Al (blue box in Fig. 1a) nanoboxes. The XRD examination of the black powder products shows three diffraction peaks at 2θ = 40.3°, 47.4° and 69.3°, which can be exclusively assigned to the (111), (200) and (220) planes of tetragonal Pt3Al intermetallic compound (JCPDS No. 29-0070), respectively, indicating that the crystalline Al phase was completely dissolved during etching and the PtAl6 phase was transformed into tetragonal Pt3Al structure likely due to the atomic rearrangement under corrosion conditions. To further investigate the microstructure and chemical composition of PtAl6 nanoparticles obtained by melt-spinning, we performed transmission electron microscopy (TEM) studies. The bright-field TEM images (Fig. 2a-b) clearly show the solid box-like structure, the size of which ranges from ~ 10 to ~ 40 nm. High resolution TEM imaging (HR-TEM, Fig. 2c) and its FastFourier-Transform (FFT) analysis (Fig. 2d) confirm the formation of orthorhombic PtAl6 intermetallic compound, which is embedded in the Al matrix. The elemental distribution was examined using energy-dispersive X-ray mapping in the high-angle annular-dark-field STEM (HAADF-STEM) mode. EDS mapping study verified that individual nanobox is composed of Pt and Al (Fig. S1, ESI†), and EDS mapping illustrated that Pt is uniformly distributed over the nanobox and the PtAl6 nanobox is embedded in the Al matrix (Fig. 2f-g).



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Figure 2. TEM (a-c) and FFT (d) images revealing the box morphology for the PtAl6 nanoparticles in the alloy ribbons before chemical etching. HAADF-STEM image (e) and EDS mapping of Pt (f), Al (g) and combined map (h) confirming the chemical compositions of the PtAl6 nanobox in the alloy ribbons. Interestingly, along with the crystallographic phase transformation, interesting morphology transformation was also observed: all the initial solid PtAl6 nanoboxes were converted into hollow nanoparticles. Fig. 3 shows the morphology and microstructure of the obtained Pt3Al hollow nanoboxes, where the hollow interiors can be clearly resolved in the low-magnification bright-field TEM images (Fig. 3a-b). HR-TEM imaging shows an inter-planar spacing of 2.22 Å, corresponding to the (111) crystal planes of tetragonal Pt3Al intermetallic compound (Fig. 3c). The corresponding FFT electron diffraction (FFT-ED) pattern reveals the polycrystalline nature of the formed Pt3Al nanoboxes, as shown in Fig. S2. The specimen was further investigated in the HAADF-STEM mode (Fig. 3d-f). Due to the intensity of each atomic column in HAADF-STEM image (where the intensity is directly proportional to Z~1.7 (Z: atomic


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number)), the atom columns can be identified directly based on atomic models.35-39 The highresolution HAADF-STEM image in the marked region in Fig. 3f matches well with the atomic models of Pt3Al along [110] direction (Fig. S3, ESI†), which corroborates the tetragonal structure of the formed Pt3Al nanocrystals. To show the hollow structure more clearly, we analyzed the change of intensity along with an individual hollow nanoparticle in HAADF-STEM image, as shown in Fig. S4, where the hollow interior is found to be ca. 8 nm out of the 14 nm Pt3Al nanocrystal. To understand the size distribution, we carried out a statistical analysis based on a low-magnification HAADF-STEM image, as shown in Fig. S5 (ESI†). The histogram shows a size distribution of the formed hollow Pt3Al nanoboxes from 4 to 22 nm. The chemical composition of hollow Pt3Al nanoparticles was further examined by EDS elemental mapping (Fig. 3g-j), which confirms that Pt and Al are evenly distributed over the hollow nanoparticles, indicating the formation of an uniform alloy. The quantitative analyses of chemical compositions based on corresponding EDS spectrum data (Fig. S6) show the atomic ratio of Pt : Al = 74.93 : 25.07 in Pt3Al nanoboxes (Table S1), which is close to the composition of Pt3Al, further confirming the chemical structure of Pt3Al. EDS line-scan was further performed across a single hollow nanoparticle, illustrating a hollow structure and verifying a Pt-rich surface (Fig. 3k and 3l). According to the TEM characterizations on PtAl6 and Pt3Al, and the self-templating etching mechanisms40, the evolution of the Pt3Al hollow structure should be related to the surfaceprotected hollowing process, as shown in Fig. S7. At the initial stage of chemical etching, the formed Pt-rich Pt3Al structures can stabilize the box morphology and greatly reduce the rate of surface etching. However, it allows the production of small openings on the particle surface, allowing the inward diffusion of the etchant.40 Accordingly, the interior structure can be removed much quicker than the surface layer, inducing structural shrink and producing hollow structures.



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Figure 3. TEM (a-c) and HAADF-STEM (d-f) images revealing the hollow Pt3Al nanobox structure. HAADF-STEM images (g and l), EDS mapping (h-j) and EDS line scan profile (k), confirming the chemical compositions of the hollow Pt3Al nanoboxes. The electrocatalytic performance of hollow Pt3Al nanostructures was investigated for the HER in 1.0 M NaOH solution using CV and electrochemical impedance spectroscopy (EIS).23 As a comparison, the HER activity of commercial Pt/C (20 wt % Pt) catalysts was also measured. The


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overpotential needed to deliver a current density of 10 mA cm-2 (i.e., η10) has been widely used as a performance indicator of electrocatalysts.29,

41-42

As shown in Fig. 4a, the hollow Pt3Al

nanoboxes need a η10 of 38 mV to afford the HER catalytic current density of 10 mA cm-2, lower than that of the commercial Pt/C nanoparticles (η10 = 52 mV). The HER reaction kinetics are analyzed by the Tafel plot (Fig. 4b). The Tafel slope of hollow Pt3Al nanoparticles is 38 mV dec1,

which is smaller than that of the commercial Pt/C nanocatalysts (41 mV dec-1). Besides, the

faradaic efficiency was used to evaluate the real HER performance.43 The faradaic efficiency of Pt3Al catalysts was monitored at 10 mA cm-2, which show an efficiency very close to 100% (Fig.S8). The HER kinetics of Pt3Al were also investigated by EIS analysis (Fig. 4c). The charge transfer resistance (Rct) of Pt3Al is 9.2 Ω, substantially lower than the 14.5 Ω of commercial Pt/C catalysts. The electrocatalytic stability is an important performance indicator to consider for applications in practical water splitting. As shown in Fig. 4d, after continuous 1500 cycles of CV scans in -0.1 – 0 V, the η10 of hollow Pt3Al nanoparticles only increased by 22.0 mV (from 38 to 60 mV), remarkably lower than the 46 mV increase (from 52 mV to 98 mV) for commercial Pt/C catalysts, indicating much better stability for the HER. Based on the STEM characterizations of commercial Pt/C and Pt-rich Pt3Al nanocatalysts before and after HER stability test (Fig. S9), it is evident that the hollow Pt3Al nanoboxes show good morphology and size stability after long time electrochemical measurement, which are better than the commercial Pt/C catalysts. The potential increase presumably results from local dissolution of the catalysts, as revealed by the inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis, where some Pt (average content: 2 ppm from Pt/C vs 0.8 ppm from Pt3Al) and Al (average content:0.3 ppm from Pt3Al) was etched during the stability test.



Hence, the better catalytic stability of hollow Pt3Al nanoboxes can be attributed to their more stable structure than the commercial Pt/C catalysts. 0.06 a 0 b 0.05

-10

Pt/C in 1.0 M NaOH Pt3Al in 1.0 M NaOH

0.04 Pt/C in 1.0 M NaOH

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Pt3Al in 1.0 M NaOH

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Ts, 41 mV dec

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Pt3Al in 1.0 M NaOH

Pt3Al in 1.0 M NaOH

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Figure 4. HER performance of Pt3Al with the commercial Pt/C catalyst in NaOH (1.0 M). a. iR corrected polarization curves. b. Tafel plot. c. EIS measured at -0.03 V vs RHE. d. Stability tests. CONCLUSIONS In summary, we report a simple self-templating etching strategy enabling the preparation of hollow Pt3Al nanoparticles on a large scale (at gram levels). This was accomplished by simply soaking Al-rich Pt3Al97 ribbons obtained by melt-spinning in an alkaline solution. The free corrosion of Al results in both crystal phase and morphology transformation, leading to the formation of a large amount of Pt-rich Pt3Al hollow, box-like structures with size distribution from 4 to 22 nm. The hollow Pt3Al nanoboxes show good electrochemical activity and catalytic stability for the HER in alkali media, better than commercial Pt/C catalysts. The facile meltspinning and subsequent chemical etching route could be readily extended to fabricate other noble-metal based hollow alloy nanostructures for various important applications.


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ASSOCIATED CONTENT Supporting Information. The support information is available from the ACS Publications website or from the author. EDS spectrum of the obtained PtAl6 nanobox; HRTEM image and the corresponding FFT electron diffraction (FFT-ED) pattern of the fabricated hollow Pt3Al nanobox; HAADF-STEM image, atomic models and intensity profiles of tetragonal Pt3Al; lowmagnification HAADF-STEM image and size distribution of the obtained hollow Pt3Al nanoboxes; EDS spectrum of Pt3Al; schematic diagram for the transformation PtAl6 nanobox into hollow Pt3Al nanobox; Faradaic efficiency of the Pt3Al catalysts; STEM images of Pt/C and Pt3Al catalysts before and after stability measurement; the quantitative analysis of the chemical composition of Pt3Al based on EDS spectrum.

AUTHOR INFORMATION Corresponding Author *Email:

[email protected] (J. J. Li); [email protected] (J. Y. Xu).

Author Contributions All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT JJL and FLD acknowledge the financial support by the N2020: Nanotechnology based functional solutions (NORTE-45-2015-02). L.F.L acknowledges the FCT Investigator grant awarded by the Portuguese Foundation of Science and Technology (grant no. IF/01595/2014).



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For Table of Contents Use Only SYNOPSIS We report a simple method allowing for large-scale fabrication of hollow Pt3Al nanoboxes using a self-templating etching route and investigate their applications in water splitting for the hydrogen evolution reaction.

TOC

The hollow Pt3Al nanobox fabricated by self-templating etching method exhibit outstanding electrocatalytic activity and good long-term stability toward the HER in alkali media.


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Large-Scale Fabrication of Hollow Pt3Al Nanoboxes and Their

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