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Mater Renew Sustain Energy (2017) 6:19 DOI 10.1007/s40243-017-0103-7 ORIGINAL PAPER Preparation, characterization and electrocatalytic activity for oxygen reduction reaction in PEMFCs of bimetallic PdNi nanoalloy 1 2 E. F. Abo Zeid I. A. Ibrahem Received: 14 May 2017 / Accepted: 8 September 2017 / Published online: 16 September 2017 The Author(s) 2017. This article is an open access publication Abstract The modified polyol reduction method was used consequence of the bimetallic union, the electronic-struc- to prepare a carbon-supported bimetallic PdNi nanoalloys tural modifications drastically influence the catalytic per- (BMNAs). The prepared catalyst was characterized using formance of the mixed-metal catalyst systems showing X-ray diffraction and transmission electron microscopy. enhancement in specific properties at an optimum compo- The obtained data indicated that, the average particle size sition because of the synergistic effect of the composition of the alloys in the range & 20–50 nm. The morphology [6–9]. Among various non-platinum cathode catalysts, structure shows uniformly distributed particles on the palladium has attracted considerable attention due to its supported carbon surface. The catalytic activity of the promising application potential as cathode electrocatalysts compounds for oxygen reduction reaction was investigated in proton exchange membrane fuel cells (PEMFCs) by cyclic voltammetry and electrochemical polarization [10–12]. The interest in Pd is not only for the purpose to measurements in rotating disk electrodes. As a function of lower the cost of catalysts but pursuits an improved cat- time and calcination temperature, the improved activity alytic activity [13–15]. The catalytic activity of Pd can be and stability were obtained at 300 C for 3 h. modified by alloying with metals having smaller atomic size such as V, Cr, Fe, Co and Ni is particularly effective in Keywords Nanoalloy PdNi/C Electrocatalyst Oxygen enhancing the catalytic activity [16–22]. Due to the higher reduction reaction Proton exchange membrane fuel cell electronic density of nickel compared with the other metals in the first transition series, the metallic bond with palla- dium is stronger which results in increasing and improving Introduction the process of catalytic activity [23–31]. Ni is the most choice to alloy with Pd to enhance its activity and stability. Modern researches dealing with technological development In addition, the combination of Pd with Ni is expected to in the field of economics of hydrogen fuel cells have further enhance the tolerance of Pd to poisoning as Ni is an become furthermore paramount. Bimetallic nanoalloys oxophilic element [32]. (BMNAs) formed by incorporation of transition metal with The oxygen reduction reaction (ORR) in a PEMFC noble metal are found to be effective in the field of catal- cathode represents the prevalent challenge because of its ysis due to their unique role of controlling the activity, sluggish kinetics limiting the overall PEMFC performance selectivity and stability as catalysts [1–5]. As a [33, 34]. Palladium nanoalloys are being currently used to accelerate the kinetics on the cathode electrode obtaining the maximum catalytic activity towards the ORR [18, 35]. & E. F. Abo Zeid In the present work, a modified polyol reduction method esabozaid@yahoo.com; eabozaid@aun.edu.eg used to synthesize a nanostructured carbon-supported PdNi catalyst to improve the electrochemical performance of Pd Physics Department, Faculty of Science, Assiut University, catalysts. The effect of heat treatment on the stability, Assiut 71516, Egypt activity and morphology structure of the bimetallic Chemistry Department, Faculty of Science, Al-Azhar nanocatalyst are characterized by X-ray diffraction (XRD), University, Cairo, Egypt 123 19 Page 2 of 7 Mater Renew Sustain Energy (2017) 6:19 transmission electron microscopy (TEM), cyclic voltam- Electrochemical studies were performed on a poten- metry (CV), and electrochemical polarization measure- tiostat (Biologic VSP). Pt mesh counter electrode, a glassy ments in rotating disk electrodes. carbon (5 mm dia.) working electrode, and a reference electrode (Ag/AgCl, 3.5 M KCl) were used as a three electrode electrochemical cell. The glassy carbon electrode Materials and methods was polished to a mirror-like finish with 0.05 lm alumina (Buehler) before each experiment. A monolayer of the Metal salts (NH ) PdCl and NiCl 6H O was provided catalyst nanoalloy on the working electrode was prepared 4 2 4 2 2 from Daejung Chemicals and Metals Co., Ltd. (98.5%). by dispersing 1 mg of the nanocatalyst in 2 mL of deion- Ionic PDDA (35 wt% in water, molecular weight about ized water, ultrasonicating until a dark homogeneous dis- 10,000) and ethylene glycol (EG) from Samchun Pure persion is formed. 20 lL of the sample dropped by Chemical Co., Ltd. (99.5%). Sodium borohydride (NaBH ) micropipette onto the glassy carbon electrode. After drying and carbon (Vulcan XC 72R) from Kanto Chemical Co., for 15 min in the oven at 60 C. Nafion solution (20 lLof Inc. (92%). All chemicals were analytic grade and used 0.025 wt%) used to form a thin film on the catalyst without further purification. monolayer and dried at 60 C for 15 min in oven. The CV A modified polyol reduction method was used to was recorded in N -purged 0.1 M of HClO at a scan rate 2 4 -1 synthesis of carbon-supported Pd Ni bimetallic of 50 mV s between -0.2 and 0.8 V (vs. Ag/AgCl). 68 32 nanocatalyst. PdNi precursor solution was prepared as Before recording the CV, the catalyst surface was elec- -1 follows: required amounts of the metallic salts of Pd and trochemically cleaned by rapid scan rate (200 mV s ) for Ni to obtain 100 mg of bimetallic were dissolved in 50 cycles between -0.2 and 0.8 V (vs. Ag/AgCl). After deionized water. About 30 mL of ionic PDDA was added CV measurements, ORR was subsequently performed in to 30 mL of EG and sonicated for 15 min. A volume of the same potential range in O -saturated 0.1 M HClO . The 2 4 40 mL of EG refluxed at 130 C under stirring. PDDA processes were repeated at least three times to ensure and PdNi solutions were added dropwise to the EG under repeatability of the data. All the electrochemical mea- stirring for ten times with the appropriate amounts to give surements were carried out at room temperature. an atomic ratio of PDDA:Pd Ni = 7:1, after vigorous 68 32 stirring for 1 h, a reduction process of Pd and Ni ions occurred by adding a fresh solution of 200-mg NaBH in Results and discussion 40 mL of deionized water. The change of solution color from yellow to black indicates the formation of bimetallic Physical characterization of BMNAs compound. An appropriate amount of carbon (Vulcan XC 72R) was added. The mixture was kept under stirring for ICP-AES analysis was performed to detect the atomic 2 h at 130 C, and cooled to room temperature overnight, percent of the BMNA components. Ratio of Pd:Ni was and the slurry was filtered, washed with water and etha- found 68:32 and the percent of the prepared bimetallic in nol, and dried overnight in vacuum oven at 70 C. These the total weight of the electrocatalysts were found around as prepared samples are denoted as PdNi/C-ASP. To 10 wt%. To determine the alloying effect of Ni on the Pd study the effect of heat treatment on the catalytic activity, lattice, XRD was applied. Effect of calcination temperature the prepared alloy was heat treated at 300, 500, and and time on the catalyst shown in Fig. 1a, b. Figure 1a 700 C in the gas mixture of 10% H –90% Ar for 3 h, indicates XRD patterns of sample calcined at different followed by cooling to room temperature. To study the temperatures for 3 h which contains five main character- effect of calcination time, the samples were calcined for istic peaks of the fcc crystalline Pd (JCPDS Card 00-005- 1, 2, 3, 4 and 5 h at 300 C. 0681) [16], namely the planes (111), (200), (220), (311), To investigate the particle size and molecular structure of and (222), there is no peaks of Ni-containing phase is the BMNA, powder XRD diffractometer (Philips Pan ana- detected. The broad peaks at 2h = 25 are associated with lytical X-ray diffractometer in the Korea Basic Science (0 0 2) planes of the hexagonal structure of the carbon Institute using CuKa radiation k = 0.15406 nm) measure- Vulcan. From Fig. 1a, for the ASP and ASP treated at 300 ments were performed. The detailed description of the XRD and 500 C, it was observed that there are additional measurements was reported previously [16]. Inductively shifted broad peaks appeared at higher angles revealing the coupled plasma atomic emission spectrometer (ICP-AES) presence of smaller particles of bimetallic nanocrystalline. used to determine the weight percent of the catalyst com- The formation of bimetallic alloy confirmed by the ponents. Using a JEOL 2010F TEM operated at 200 keV presence of reflections corresponding to the single fcc morphological and particle distribution studies were carried phase. Due to alloying, ligament and grain size decreases, out for prepared alloys. the surface strain of Pd lattice increases and the standard 123 Mater Renew Sustain Energy (2017) 6:19 Page 3 of 7 19 (b) (a) 5 h 4 h 700 C o 3 h 500 C 300 C 2 h ASP 1 h 20 40 60 80 100 20 40 60 80 100 2θ (degree) 2θ (degree) Fig. 1 XRD patterns of the carbon-supported PdNi calcined, a at different temperatures and b at 300 C for different times sharp peak at 2h & 40 was broad [20]. The single fcc from the (111) diffraction line, XRD data (Fig. 1), using jk phase which appeared at 2h = 33 correspond to a PdNi the Scherrer equation, d ðAÞ¼ [17], and q is the b cos h -3 alloy, completely removed at 700 C (Fig. 1a) this beha- density of the PdNi alloy (*11.03 g cm ). viour related to forming a Pd-rich overlayer on the alloy The morphologies of BMNA were observed using TEM surface. (Fig. 2). As a comparison, inhomogeneous distribution of The effect of calcination time on the properties of pre- particles, with some regions showing a clear agglomera- pared samples at 300 C is shown in Fig. 1b. To study the tion, some particles with sizes in the order of few isothermal behaviour of our catalyst at optimal tempera- nanometers (&20 nm) and some others with sizes about ture, we prepared five specimens calcined at different times 50 nm can be observed in all samples after calcination at (1, 2, 3, 4 and 5 h). During calcination, as a function of various temperatures (Fig. 2a–c). The spherical shaped time it was observed that, at 3 h the diffraction broad peaks with semi aggregation and good crystallinity of NPs with shifted to higher angles, this attributed to the single phases different sizes (from 20 to 50 nm) is clearly at lower of the nanocatalyst have a thermally activated nature, this temperatures (Fig. 2a). The particle size from TEM anal- leads to a decrease of the particle size and higher surface ysis is higher than that calculated by XRD, due to inside of activity. Increase of annealing time (4 and 5 h) should lead the polycrystal grain boundaries are not exposed. Figure 2d to a better homogenization, and the cell parameter should showed a micrograph of sample calcined at 300 C for 5 h be closing to its value for the well-annealed alloy which which reflects a bad dispersion and higher agglomeration. results in an increase of particle size and decrease of sur- Ruoshi et al., published that, the addition of Ni to Pd alloy face activity (Table 1). According to the above results, we decreases the particle size, which would result in the can conclude that, the optimal temperature should be thus increase of electroactive surface areas [36]. Shen et al. [37] around 300 C for 3 h. The properties of the prepared alloy have reduced PdNi catalysts in different atomic ratios on are shown in Table 1. carbon surface using NaBH as a reductant. They had 2 -1 The active surface area S in m g was calculated using average Pd particle size of 3–3.2 nm. Pd Ni /C catalyst 1 1 the equation SðareaÞ¼ for spherical particles [16], with a Pd loading of *20 wt% showed Pd particle size of dq where d is the crystallite size (diameter) in nm obtained 3.9 nm [36]. The reduction of PdNi nanoparticles on Table 1 Properties of the prepared BMNAs by XRD Heat treatment Calcination temperature (for 3 h) Calcination time at 300 C Property ASP 300 C 500 C 700 C 1h2h 3h4h 5h APS (nm) 19.35 12.83 13.96 14.94 16.87 14.76 12.83 15.35 17.32 2 -1 S (m g ) 28.11 42.39 38.96 36.41 32.24 36.85 42.40 35.44 31.41 Intensity (a.u.) carbon vulcan (002) PdNi PdNi(111) Pd(111) PdNi(200) Pd(200) Pd(220) PdNi Pd(311) Intensity (a.u.) Carbon vulcan Pd(111) Pd(200) Pd(220) Pd(311) 19 Page 4 of 7 Mater Renew Sustain Energy (2017) 6:19 Fig. 2 TEM micrographs of the carbon-supported PdNi alloy calcined for 3 h a at 300 C, b at 500 C, c at 700 C and d at 300 C for 5 h, respectively, all of these images with 100 nm magnification Vulcan XC-72 carbon black support by formic acid and calcined at lower temperature compared to those at higher thiourea resulted in larger Pd crystal-sized particles of temperature. This indicates that the chemisorption of 4.66 nm [37]. Core/shell Ni@Pd nanoparticles supported oxygenated species on the Pd sites formed at (above 0.5 V on MWCNTs with 20 wt% total metal content and Pd:Ni vs. Ag/AgCl) inhibited at lower potential, and thus the atomic ratio of 1:1 had particle size of 6.8 nm using NaBH electrocatalytic enhancement. as a reducing agent [38]. Catalytic activity of BMNAs Electrocatalytic activity of BMNAs Figure 4 shows the single-scan voltammograms for the To evaluate the hydrogen adsorption/desorption potentials electrocatalyst coated on glassy carbon rotating disk elec- of the BMNAs, the CVs were recorded in a N -purged trode at different calcination temperatures and times, in an 0.1 M HClO solution at 27 C for electrocatalyst as a oxygen-saturated 0.1 M of HClO solution, and at ambient 4 4 function of temperature and time (Fig. 3a, b). The smaller conditions. The highest ORR activity was observed for the values of the potential range from -0.193 to -0.133 V alloy calcined at 300 C (Fig. 4a). was observed for the catalyst calcined at lower temperature This behaviour ascribed to the smaller particle size and for 3 h. The existence of smaller particles of electrocatalyst higher surface activity was obtained at lower temperatures at lower temperature for 3 h results in an increase of the (Table 1). During the calcination at lower temperature, the electrocatalytic activity and minimizes the potential range palladium atoms tend to migrate to the surface of the alloy of hydrogen adsorption/desorption processes. The starting nanoparticles because palladium and nickel exhibit a strong potential for the bimetallic oxide formation in the positive trend toward segregation due to the large segregation direction and the reduction in the negative direction is energy difference between them [18]. The catalyst consists slightly shifted to more positive potential for the catalysts of two metals, one with a low occupancy of d-orbitals (such 123 Mater Renew Sustain Energy (2017) 6:19 Page 5 of 7 19 0.08 0.08 (a) (b) 0.06 0.06 300 C 5h 3h 0.04 0.04 500 C 2h 0.02 ASP 0.02 0.00 o 0.00 700 C -0.02 -0.02 4h -0.04 -0.04 -0.06 -0.06 1h -0.08 -0.08 -0.10 -0.10 -0.12 -0.12 -0.14 -0.14 -0.16 -0.16 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 E (V vs Ag/AgCl, 3.5 M KCl) E (V vs Ag/AgCl, 3.5 M KCl) Fig. 3 CV of PdNi/C catalysts calcined a at different temperatures and b at 300 C for different times Fig. 4 Single scan voltammograms for PdNi/C catalyst calcined a at different temperatures and b at 300 C for different times as Ni) and the other with fully occupied d-orbitals (such as same temperature. For a long time the electrostatic forces Pd), the d-orbital coupling effect between them can sig- between the two metals in our alloy decreases, the particle nificantly decrease the Gibbs free energy of the electron size increase and surface area decrease leading to a lower transfer, resulting in an improvement in ORR kinetics [19]. activity of the catalyst. The synthetic methods which gave The incorporation of Ni with Pd could bring favourable best surface characteristics and high degree of the alloy at change of Pd electron structure to modify the reaction lower temperature and moderated time are favourable for kinetics for ORR on PdNi alloy, thus resulting in a higher increasing the catalytic activity. efficiency of the reduction process. Sanchez et al., reported that, the intrinsic electrocatalytic properties for the ORR of these bimetallic catalysts PdNi could be attributed to the Conclusions bifunctional effect in which the catalytic properties of each of the elements combine in a synergetic fashion to yield a A modified polyol reduction method used to prepare car- more active surface than each of the elements alone [2]. As bon-supported PdNi nanocatalyst in the presence of EG and a function of time, the electrocatalyst calcined at optimum NaBH as reducing agents. The characterizations provided temperature for 3 h, showed the highest ORR activity by ICP-AES, XRD and TEM techniques. The smaller (Fig. 4b). This behaviour is attributed to the catalyst cal- particle size (20–50 nm) and highly active surface area was cined for long times that has a larger particle size (smaller obtained at the optimum calcination conditions (300 C for surface area) compared to those at moderate periods at the 3 h). 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Materials for Renewable and Sustainable Energy – Springer Journals
Published: Nov 1, 2017
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