Triton X-100 Mediated One-pot Solution Phase Synthesis of Au@PtCo/C Nanoparticles with Enhanced Oxygen Reduction Performance in Fuel Cells

doi:10.21203/rs.3.rs-4868334/v1

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Triton X-100 Mediated One-pot Solution Phase Synthesis of Au@PtCo/C Nanoparticles with Enhanced Oxygen Reduction Performance in Fuel Cells

https://doi.org/10.21203/rs.3.rs-4868334/v1

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Au doped PtCo/C (Au@PtCo/C) as an oxygen reduction reaction (ORR) catalyst is synthesized using a facile single step solution phase synthesis method with Triton X-100 as a mediator guiding the shape and size of the metal nanoparticles. The spherical shaped nanoparticles of 2–4 nm were uniformly dispersed over the porous carbon support accounting for an electrochemical active surface area (ECSA) of 52 m²/g_Pt. It was observed that at 0.9V, the mass activity (I_m) of Au@PtCo/C catalyst is 0.57 A/mg_Pt which is 4 times higher in relation to commercial Pt/C catalyst. While evaluating in real time PEMFC configuration under acidic environment, this catalyst delivers a peak power density of 1.33 W/cm² at a current density of 3.43 A/cm² with H₂/O₂ feeds under ambient pressure, thus emerging as a promising electrocatalyst for fuel cell applications.

Since ancient times, the precious metals such as Platinum(Pt), Silver (Ag) and Gold (Au) have received acknowledgement as metals invaluable to human use.[1] Contemporarily, their outstanding stability, distinctive physicochemical features and unique surface properties persistently make them crucial for a wide range of applications for the industry such as cracking of petroleum,[2] treatment of exhausts,[3] nano medicinal applications[4] and off late as electrocatalysts for sustainable energy conversion.[5–8] Amidst the precious metals, the Pt metal has been well recognised for its superior activity[9–11] and prolonged durability, [12, 13]when used in the catalysis of the oxygen reduction reaction (ORR) owing to its optimum work function essential for such electron transfer reactions. ORR, is essentially sluggish in nature,[14–16] occurs in the cathodic region in proton exchange membrane fuel cells (PEMFC) and is the spine behind the smooth functioning of the hydrogen powered electric vehicles.[10, 17] With a swift rise in the need for larger PEMFC stacks in electric vehicles and other such heavy-duty applications, the need of the hour is to efficiently utilize every ounce of the available Pt resources.[17] In recent times, Pt nanoparticles, anchored on different types of carbon support has evolved to be the best catalyst and is used commercially.[18] However, the use of Pt is surrounded by a huge setback in terms of cost and availability, with the higher cost and scarcity of Pt posing major challenges in its successful commercialization.[19–21]

To address this need, several approaches have been made over decades pertaining to the generation of Pt reliant electrocatalysts namely (a) Pt nanoparticles; (b) Pt alloys; (c) atomically distributed Pt; (d) Pt core shell structures; among which the Pt based alloys have drawn the interest of researchers significantly. Alloying ushers in several advantages such as cost cutting, without compromising on the superior activity and durability. Moreover, alloying also aids in deferring the strengths of the bonds formed between the electrocatalyst and the ORR intermediates, making it optimum as required to ensure a fast ORR kinetics. [22] Initially Pt monometallic electrocatalyst was used and then with time, the bimetallic alloys of Pt began to gain significant limelight. A wide range of transition metals like Co, Pd, Ni, V, Cr, Cu, Au, Fe, Mn, Cr etc were deployed for this purpose.[23–32] By virtue of alloying, several structural changes are incorporated in Pt that affect the strain on its d-band and consequently, on the coordination number, both crucial in promoting the higher performance and prolonged durability of the catalysts. [30, 31] Several theoretical reports also suggest that the transition metals used while alloying with Pt prove to be instrumental in lowering the d-band centre through electronic effect and compressive strain. [32] As a result of this, the interaction between the adsorbed intermediates of ORR (O*, OH*, OOH*) and the catalysts tend to become feebler, and are removed, eventually exposing higher number of surface-active sites. [33–39] Several other experimental studies also show that the origin of such high ORR activity can also be traced back to various other factors such as the dual functional nature of the catalytic surface, [40–45] shortening of the Pt-Pt bond distance caused by lattice shrinkage, [43] formation of an adlayer of Pt metal on the surface of the nanocluster, [46, 47] and segregation effect. [48] Consequent to this, a surfeit of methodologies like coprecipitation, wet chemical method, nanoengineered synthesis, solid state method, annealing, sputtering, electrodeposition, dealloying etc. have been used and reported for years as useful methods for the synthesis of such Pt reliant electrocatalysts. [29, 41, 49–54]. However, although these catalysts with bimetallic compositions have collected significant research interest both from the purview of laboratory research as well as development of technology, the exact reason responsible for the enhanced electrochemical activity still remains a topic of much debate among researchers. [55–57]

Herein, we report the synthesis of Au doped PtCo/C following a facile single pot solution phase synthesis method. Alloying with a smaller sized 3d metal like Co, brings in morphological changes, while doping of Au on Pt further modifies the electronic structure of the latter. [58] The alloyed Co atoms remain deep seated in the lattice structure of Pt, generating compressive strain that eventually narrows down the Pt-Pt bond distance. The electronegativity value of Pt and Co are 2.28 and 1.88 respectively.[38, 59] This ensures a faster filling and down shifting of the Pt d-band in the presence of Co which further increases the number of catalytically active sites while simultaneously reducing the bond strength of the bonded oxygenated intermediates (-OH and -OOH) by virtue of the electronic charge transfer from Co to Pt. [60] This helps the Pt atoms in the Au@PtCo/C alloys to revert back to their initial oxidation state, accounting for an increased stability. [53] Thus, the ameliorating impact of alloying and doping form the backbone of the improved ORR performance of the synthesized catalyst. The present work elucidates the performance of PtCo/C doped with 0.6% Au as a potential ORR electrocatalyst.

The Au- doped nanoparticles were synthesized following a one pot solution phase method. Typically, 4 ml of Triton X-100 was added to 10 ml of a solution containing oleyl amine (OAm): oleic acid (OA): ethylene glycol (EG) = 2:2:1. To the solution, 0.05 M HAuCl₄ (0.1 ml), 0.05 M K₂PtCl₄ (0.45 ml), and 0.05M CoCl₂ (0.45 ml) were added. Finally, ketjenblack carbon (~ 20% metal loading) and 44 mg of ascorbic acid was poured into the reactant mixture. Then it was kept for sonication for half an hour to ensure a homogenous dissolution. After this the solution was kept for refluxing at 160°C continuously for 5 h in order to promote the complete conversion of Pt (II) to Pt (0). The sample obtained after reflux was washed several times with both ethanol and water. It was then left for drying at 60°C and designated as Au@PtCo/C. The advantage of this method is that it is equally suited for large scale synthesis of catalysts with a desired size and shape. It is noteworthy here that the Triton X-100 used in the synthetic procedure helps in increasing the porosity of the carbon, while also directing the formation of spherical nanoparticles. The OAm used in the synthesis procedure has a crucial role in directing the eventual structure of the synthesised nanoparticles. OAm is essentially a long chain primary alkyl amine, that behaves as a donor of electrons, exhibiting highly basic nature and also has a higher affinity to the metallic centres by virtue of its amine (-NH₂) group.[61] This results in a stronger bond formation between the Pt and the N atoms of OAm that hastens the process of reduction. The details of the materials used and those of the physical and electrochemical characterizations have been provided in the supporting information.

Figure 1 displays the comparison between the powdered XRD patterns of Au@PtCo/C and Pt/C. The role of Au can be vividly observed in the formation of the catalyst. All the peaks are observed at a 2θ values higher than those of Au/C as seen in literature[62] and lower than those of Pt/C indicating successful alloy formation. The atomic radii of Au are higher than that of Pt while Co is smaller sized than Pt. Thus, the shifting of all the peak positions in comparison to commercial Pt/C can be explained. [63] The most intense peak of the electrocatalyst is that of the (111) plane which lies at a 2θ value of 39.6°, an intermediate between that of the Au (111) plane and Pt (111) plane of a face centred cubic lattice structure (fcc).[64, 65] A similar trend is also observed for the (002), (220) and (311) planes. Lastly, the broad peak observed at 2θ = 25° is due to the presence of the carbon support in the catalyst.

The morphology of the Au@PtCo/C catalyst was analysed using HRSEM and HRTEM. Figure 2 illustrates the uniform distribution of the Au@PtCo/C nanoparticles on the porous carbonaceous support. As observed in Fig. 2 (a), the nanoparticles obtained were mainly spherical, in shape. This morphology was further confirmed using the HRTEM images as depicted in Fig. 2 (b-d). The uniformly distributed spherical nanoparticles had an average size ranging between 2–4 nm. In Fig. 2d, the HRTEM image of one single such nanoparticle shows the interplanar distance to be equal to 0.22 nm that well correlates with the Pt (111) plane observed from XRD results. However, this d-spacing so obtained was lower than that observed in pure Pt/C which is 0.23 nm. This alteration in the value of d-spacing can be well justified by the formation of the alloy of Pt with smaller sized Co atom in Au@PtCo/C.

The composition of elements and the consequent chemical environment present on the surface of the electrocatalyst was studied using XPS. Thus, the deconvoluted spectra corresponding to Au 4f, Pt 4f, C 1s and Co 2p have been depicted in Fig. 3 (a-d). Explicitly, Fig. 3 (a) elucidates a doublet of spin orbit coupled peaks appearing at 84.0 eV and 87.9 eV corresponding to Au 4f_7/2 and Au 4f_5/2 of Au (0) state respectively. In Fig. 3 (b), two different spin orbit coupled doublets are visible which correspond to two different oxidation states of Pt. The peaks visible at 71.3 eV and 74.7 eV correspond to the Pt4f_7/2 and Pt4f_5/2 of ground state Pt (0). The other doublet reappearing at 72.1 eV and 75.4 eV are due to the presence of any residual unreduced Pt (II). The higher intense Pt (0) peak when compared to Pt (II) is essential in realising the higher electrocatalytic performance as it is these metallic Pt sites that act as the catalytically active ORR sites. Moreover, the slight drift in the XPS peak can be equated to the changes in the energy of the fermi level, work function and position of d-band centre. The presence of an atom of a different electronegativity around Pt can be attributed to a partial transfer of charge that reshuffles and alters the normal distribution of electrons in Pt. Figure 3(c) illustrates the C1s spectrum, attributed to the support present in the Au@PtCo/C. The peaks observed at 284.6 eV can be well assigned to the presence of the C-C bond corresponding to the sp² carbon.[30, 31, 61, 66] Finally, the Co 2p spectrum after deconvolution has been depicted in Fig. 3(d), where, at 783.2 eV and 797.1 eV the 2p_3/2 and 2p_1/2 peaks of Co can be observed. The signal to noise ratio in this case was observed to be higher, may be due to the lower content of metallic Co in the finally prepared electrocatalyst.

The electrochemical performance of Au@PtCo/C has been depicted in Fig. 5. Explicitly, Fig. 5(a) shows the CV of Au@PtCo/C recorded at a sweeping speed of 100 mV/s in an N₂ saturated HClO₄ solution (0.1M), while the CV of Pt/C, recorded under identical conditions has been depicted in the inset. Primarily there are two main factors guiding the electrochemical behaviour of the Au@PtCo/C nanoparticles. To begin with, from several previously reported literature it can be well concluded that the embedding of Co particles into the lattice of Pt brings in electronic changes in the latter. This in turn decreases the binding energy of the oxygenated intermediates residing on the surface of the catalyst and consequently their coverage on the surface decreases sharply. This helps to generate more active Pt sites that remain available for the further incoming O₂ or H₂O molecules.[67] Next, from several studies conducted and reported previously, it has been established that the catalytic performance of the electrocatalysts per unit surface area tends to decrease proportionately with the decrease in the size of the nanocrystals. This is due to the growth and increase of the catalytically inactive planes of Pt around the edges and corners of the nanoparticles at the expense of the most active (111) plane.[68] In every CV, there was a forward positive potential sweep from 0.1V to 1.2 V Vs RHE followed by a reverse sweep backwards from 1.2 V to 0.1V Vs RHE. In the process, two distinctive potential windows were observed that correspond to the under potential adsorption and desorption of hydrogen (H⁺ + e⁻ = H_upd), as expected in case of any polycrystalline nanoparticle of Pt. The other potential window lies beyond 0.6 V and it is indicative of the coverage of the electrocatalytic surface by a layer of hydroxide formed on it (2H₂O = OH_ad +H₃O⁺ +e⁻). As observed, the voltammogram shows a response similar to that observed in case of Pt/C, although the hydrogen adsorption/desorption region is relatively lower. This is due to the presence of the alloyed Co also on the surface of the catalyst. The electrochemically active surface area (ECSA) per unit weight was found to be 51.5 m²/g_Pt and 83.4 m²/g_Pt for Au@PtCo/C and Pt/C respectively. These values were calculated from the area of the H_upd zone, after making the necessary corrections pertaining to the formation of double layer and then normalizing it to a value of 0.21 mC/cm², which corresponds to the charge required by a monolayer of hydrogen to get adsorbed on the surface of any clean polycrystalline Pt.[47] Fig. 5(b) depicts the LSV curve of Au@PtCo/C recorded at 1600 rpm at a scanning velocity of 10 mV/s in an HClO₄ solution (0.1M, O₂ saturated) while the inset depicts the LSV of Pt/C recorded under similar conditions. [42] The ORR activities of the catalysts were quantified at a potential of 0.9V vs RHE to avoid any interference incurred from the mass-transport loss occurring at high current densities. The limiting current obtained was also well within a margin of 10% from the theoretically derived value using the Levich Eq. (5.7 mA/cm²) which indicates a negligibly low Nafion or carbon support contribution. As anticipated, Au@PtCo/C catalyst exhibited a single reduction curve of a mixed kinetic-diffusion guided region between the potential window of 0.75V to 1.0V Vs RHE. This was succeeded by a flatter wave of diffusion limited current ranging in the window between 0.2V to 0.7V. Au@PtCo/C depicts marginally better behaviour initially as compared to Pt/C. The presence of Au as a dopant result in the generation of an electronic coupling effect that tends to significantly weaken the π- bonds present in the adsorbed O₂.[37] The intrinsic properties of Au@PtCo/C such as the I_m (A/mg_Pt), and I_s (mA/ cm²_Pt) were calculated from the Koutecky-Levich equation after normalisation of the kinetic current (i_k) value obtained to Pt loading and to the actual geometric area possessed by the electrode in use respectively. The I_m of Au@PtCo/C obtained is 0.57 A/mg_Pt (I_m of Pt = 0.14 A/mg_Pt ) and the I_s value obtained is 1.1 mA/cm²_Pt (I_s for Pt/C = 0.18 mA/cm²_Pt)

In order to test the withstanding power of Au@PtCo/C, the catalyst was exposed to potential cycling and the electrochemical performance of the catalyst was recorded after 10k cycles. As observed in Fig. 4(c), the stability test carried out on Au@PtCo/C revealed an improvement in the electrocatalytic performance after 10k cycles. It was interesting to notice that 27% increment in the value of ECSA was observed at the completion of 10k cycles. This increment in the value of ECSA can be well explained through the temporary rise in the dispersion of Pt atoms on the surface or also by the rearrangement of atoms or by the removal of other Co atoms from the catalyst’s surface that exposes a higher number of active sites. Under prolonged exposure to the harsh acidic medium, the Co atoms leach out, so the lower layers of atoms are exposed, thereby opening up fresh active sites for the adsorption of oxygen. The exposure of newer active sites upon potential cycling can be further reinstated by the improved ORR performance of Au@PtCo/C as observed in the linear sweep voltammogram depicted in Fig. 4(d). The E_1/2 shifts positively by 30 mV indicating that the modification in the geometry of the alloy nanoparticles coupled with the electronic rearrangement is responsible for this improved ORR performance. The I_m and I_s of Au@PtCo/C evaluated at the end of 10k cycles at 0.9 V were 0.87 A/mgPt and 1.6 mA/cm²_Pt respectively. This better ORR activity of Au@PtCo/C is attributed to the ameliorated synergistic effect occurring between Pt, Co and Au.

Morphological analysis of the coin shaped Au@PtCo/C nanoparticles was taken after 10k cycles. As observed in Fig. 5(a-b), the HRTEM images were observed to show minimal change in morphology after 10k cycles, although coalescence of the particles is visible which, again, is a commonly observed phenomenon in the acidic medium. The HRTEM image of a single Au@PtCo/C nanoparticle as seen in Fig. 5(b), shows a d-spacing of 0.229 nm, which indicates the retention of the (111) plane of Pt even after 10k potential cycles. This minor difference in d-spacing suggests the occurrence of changes intrinsically in the nanoparticle on account of potential cycling.

The performance of Au@PtCo/C was further tested under the actual conditions of fuel cell both under a H₂/O₂ and H₂/Air environment. A lower overpotential was observed in the activation region with the open circuit voltage recorded to be 0.93V. The polarisation was studied for a higher current density of 4.5A/cm² to check the mass transfer losses of the catalyst. There was minimal fall in the voltage even at higher current, indicating the superiority of the catalyst in fuel cell conditions. In an H₂/O₂ environment, the peak power density was observed to be 1.33 W/cm² at a current density of 3.43 A/cm². On the other hand, when the polarisation was measured under a H₂/Air environment, the peak power density obtained was observed to be 0.78 W/cm² at a current density of 2.26 A/cm² as observed in Fig. 6. These results indicate that Au@PtCo/C can be potentially used as an efficient catalyst for ORR in the fuel cells for further studies.

To conclude, a facile, single pot solution phase synthesis method was deployed to produce Au@PtCo/C nanoparticles. The Au@PtCo/C electrocatalyst shows improved ORR performance even after 10k potential cycles. Doping of the PtCo/C alloy with Au, leads to a synergistic effect that eventually modifies the structural and electronic design of the fcc crystal lattice structure. We firmly believe that the use of such a facile synthesis strategy, involving the combination of doping and alloying would eventually be of immense help in overcoming the losses incurred in PEMFCs.

Conflict of Interest

The authors declare no conflict of interest

Author Contribution

P.M: Methodology, WritingS.D; S.S. : Collection of literature, Writing, EditingA.S. : Editing, SupervisionA.K.S: Final Editing, Resources, SupervisionAll authors have reviewed the final manuscript.

Acknowledgement

P.M. is indebted to Science and Engineering Research Board (SERB), Govt of India for the National Post-Doctoral fellowship (PDF/2023/000873/CS) for the research funding. P.M., S.K., and A.K.S also express sincere gratitude to Central Electrochemical Research Institute (CECRI), CSIR Madras Complex and S.S. and A.S. is grateful to SRM Institute of Science and Technology for providing a research environment and the requisite research facilities for the smooth functioning of the work

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Triton X-100 Mediated One-pot Solution Phase Synthesis of Au@PtCo/C Nanoparticles with Enhanced Oxygen Reduction Performance in Fuel Cells

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Experimental section Synthesis of Au-doped PtCo/C nanoparticles (Au@PtCo/C)

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