Polymer Brushes Ionic Liquid as a Catalyst for Oxygen Reduction and

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Letter

Polymer Brushes Ionic Liquid as a Catalyst for Oxygen Reduction and Oxygen Evolution Reactions Thuan Nguyen Pham Truong, Hyacinthe N. Randriamahazaka, and Jalal Ghilane ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b03158 • Publication Date (Web): 28 Dec 2017 Downloaded from http://pubs.acs.org on December 28, 2017

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ACS Catalysis

Polymer Brushes Ionic Liquid as a Catalyst for Oxygen Reduction and Oxygen Evolution Reactions Thuan Nguyen Pham Truong, Hyacinthe Randriamahazaka*, Jalal Ghilane* Université Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086 CNRS, SIELE group, 15 rue Jean Antoine de Baïf, 75013 Paris, France. ABSTRACT: Developing efficient catalysts for oxygen reduction reaction (ORR) remains an important task for future electrochemical energy applications. Here, we investigate the use of polymer brushes ionic liquid, poly(IL), as an emerging catalyst for ORR. Our results show that the poly(IL) presents a promising electrocatalytic activity which is correlated to the chemical composition and the nano-structuration of the polymer. Furthermore, we demonstrate the use of poly(IL) as a host guest platform for Pt catalyst, providing for the hybrid material a more efficient catalytic activity and tolerance to crossover reaction. In addition, we also reveal the potential use of poly(IL) and the hybrid material, poly(IL)/Pt, as an efficient bifunctional catalyst for ORR and the oxygen evolution reaction (OER).

KEYWORDS: polymer ionic liquid, electrochemistry, electrocatalysis, oxygen reduction reaction, oxygen evolution reaction.

Climate change combined with the limited availability of fossil fuels has greatly affected the world economy and ecology. Within this context, electrochemical energy storage and conversion have been proposed as a promising system.1 These energy technologies involve the oxygen reduction and evolution reactions (ORR and OER).2,3 Electro-catalysts for ORR could be classified in three categories, platinum based materials, nonprecious metals and metal-free catalysts.2 Several approaches were reported to improve the performance of the catalysts. For example, Pt alloyed with other metals such as Co, Ni, Fe or bimetallic Pt core-shell exhibited an enhanced performance and stability.4,5 For non-precious metals, composite materials proved to be able to reach performance comparable to Pt based material.5-7 Metalfree catalysts based on nanocarbon (graphene, nanotube, nanofiber, polymer, and carbon quantum dots) and doped nanocarbon materials have been demonstrated to be a good alternative as a new generation of low cost catalysts.8 However, whatever the selected catalysts they still suffer from multiple problems such as crossover effect for Pt based catalysts,9 metal dissolution along with the low conductivity of non-precious metals,10 the complicated preparation procedure for nanocarbon catalysts and the rigorous synthesis

conditions e.g. carbonization at high temperature (700-1200 °C).11 Recently, ionic liquids modified catalysts have been investigated and displayed efficient activity for ORR that was correlated to the higher O2 solubility in the ionic liquid phase.12,16 Besides that, the OER is another challenge for energy storage and conversion systems. Iridium and ruthenium oxides are the efficient electro-catalysts for the OER.17 Several reviews were devoted to the most recent achievements in the development and the design of catalysts for ORR and OER.1,18-20 The ongoing challenge is to design new catalysts that rationalize several parameters including the performance, the stability, the tolerance, and to some extent the bifunctionality. Here, we present a new approach based on polymer brushes ionic liquid, poly(IL), modified electrode to be employed as catalyst for ORR. We demonstrate that the as-prepared poly(VinylImidazolium-Methyl), poly(VImM), exhibited a promising electrocatalytic activity towards ORR. Furthermore, the latter was used as a platform to host guest a Pt catalyst and the performances of the hybrid material were investigated. Although, this work focuses on the performance of ORR on organic poly(VImM) as a metal-free catalyst and its synergy with Pt. The bi-functionality of these

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materials towards ORR and OER is further explored. Polymer ionic liquid attached onto a glassy carbon electrode was prepared using surfaceinitiated atom transfer radical polymerization (SIATRP) (Figures 1A, S1 and S2).21 The surface morphology of the generated poly(VImM) was examined by SEM and AFM. The SEM image (in inset Figures 1D and S3a) displays the presence of the bright area corresponding to unmodified gold and dark area representing the poly(VImM). The 2D-AFM image exhibits homogeneous and grainy directional structure of the poly(VImM) (Figure 1B).

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Figure 1. (A) Scheme illustrating the SI-ATRP process. (B) 3DAFM representation (C) and (D) XPS high resolution spectra for C(1s), N(1s), inset: SEM image.

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Furthermore, the 3D-AFM confirms the organization of the polymer units in a brush-like structure with an average thickness around 18 nm (Figures S3c and d). The analyses were complemented by investigating the chemical composition of the polymer using X-ray photo-electron spectroscopy (XPS). Figures 1C and 1D display the core level high resolution spectra of C(1s) and N(1s) elements. The deconvolution of the C(1s) spectra exhibits the presence of 4 components at binding energy of 285.2, 286.5, 287.2 and 288.9 eV which can be attributed to the binding energy of carbon atom derived from the C backbone (C–C), amide (C–N), –C=N group from imidazolium ring and –COO from the surface contamination, respectively.22 The main N(1s) signal appears at 401.7 eV is attributed to imine group from imidazolium ring.22 Overall, the morphological and structural analyses confirm the formation of nanostructured poly(VImM) brushes at the electrode surface. Next, the electron transfer properties at the poly(VImM) interface were evaluated in the presence of an outer-sphere and an inner-sphere redox probes. The electron transfer in an outersphere system occurs by tunneling across a thin layer of solvent, while an inner sphere system requires a strong interaction with the electrode.23 The cyclic voltammetry’s (CV’s) of modified glassy carbon with a bromide initiator layer (GC/Br initiator) and poly(VImM)/GC were performed in the presence of ferrocene methanol and potassium ferricyanide (Figure 2A). For FcMeOH, both electrodes depicted a welldefined reversible redox system with a peak-topeak separation, ∆E, of 60 mV, highlighting the presence of fast electron transfer, despite the presence of the thin initiator layer and the poly(VImM) brushes. Conversely, the CV’s responses of ferricyanide show different behaviors. Thus, on GC/Br initiator the ∆E is extremely high, 700 mV, suggesting low electron transfer rate attributed to the presence of the initiator layer that act as a barrier against the electron transfer of the inner sphere redox probe. Whereas, the CV recorded on poly(VImM)/GC exhibits a reversible electrochemical signal and shows a decrease of ∆E to 60 mV indicating fast electron transfer.


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Figure 2. (A) CV response of modified GC with initiator (GC/Br initiator) and GC/poly(VImM) electrode in the presence of FcMeOH (green curves) and K3Fe(CN)6 (blue curves) at 1 mM in 0.1 M KOH aqueous solution. (B) Electrochemical impedance spectroscopy in the presence of 1 mM K3Fe(CN)6 in 0.1 M KOH at a frequency of 100 kHz to 1 Hz. (C) and (D) SECM approach curves at bare GC and poly(VImM) using FcMeOH and K3Fe(CN)6 at 1 mM.

The reason of such behavior is linked to the poly(VImM) brush structure which has a labile anion that could be replaced by ferricyanide. The anion exchange of ferricyanide within the ionic liquid layer has been already demonstrated.24 In this situation, the ferricyanide interact strongly with the polymer film leading to anion exchange and as a consequence the incorporation of ferricyanide moieties within the polymer. The presence of ferricyanide in the vicinity of the electrode promotes the electron transfer of ferricyanide at the polymer solution interface. To confirm this result, the charge transport properties were characterized by monitoring the charge transfer resistance (RCT) at the electrode– electrolyte interface. Figure 2B shows the electrochemical impedance spectroscopy (EIS) plots at GC/Br initiator and GC/polymer electrodes in the presence of 1 mM [Fe(CN)6]3−/4− in 0.1 M KOH at a frequency of 100 kHz to 1 Hz. The RCT value for GC/Br initiator is found to be 35 kΩ while the GC/poly(VImM) displays a value around 307 Ω. This result demonstrates the fast electron transfer of the inner sphere redox probe at the polymer surface. Furthermore, scanning electrochemical microscopy, SECM, was employed to investigate the local electrochemical properties of the interface. SECM experiments investigate the local reactivity of a substrate under an ultramicroelectrode tip. The main advantage of the SECM is the ability to probe the local electrochemical activity of the surface from the solution side, tip, and without contact between the tip and the substrate. In addition, the SECM configuration allows the investigation of the surfaces at their open circuit potential (unbiased substrate). Figure 2C depicts the approach curve in the presence of FcMeOH and shows an enhancement of the current when the UME approaches the surface for both investigated surfaces. The increase of the current is related to the regeneration of FcMeOH at the electrode surface which enhance the flux of the FcMeOH in the vicinity of the UME. However, in the case of ferricyanide two different opposite behaviors were observed (Figure 2D). On GC/Br initiator electrode, the current decreases while the UME approaches the surface indicating that the backward reaction (Fe(CN)64- → Fe(CN)63- + e-) at the substrate occurs with a low electron transfer. In


ACS Catalysis

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the case of GC/poly(VImM) substrate a positive feedback is observed confirming the occurrence of the backward reaction at the polymer interface. The observed positive feedback is related to the presence of ferricyanide moieties within the poly(VImM) (after anion exchange) that promote the 2D- electron transfer. Similar SECM behavior has been reported for ferrocene attached onto silicon substrate.25 These electrochemical investigations demonstrate that the poly(VImM) brush structure enhances the electrochemical response of an inner-sphere probe. The mechanism of the oxygen reduction reaction is not well established yet, but several steps were clearly identified, including the oxygen adsorption, oxygen bond cleavage and the release of the intermediates.26 The ORR is an inner-sphere redox reaction that involve several key steps, including oxygen adsorption, O–O band splitting.26 As the poly(VImM) accelerate the electron transfer of the inner-sphere system, the electrocatalytic activities of the poly(VImM) toward the ORR was investigated. Figure 3A compares the cyclic voltammograms recorded on the bare and GC/poly(VImM) electrodes in an O2-saturated aqueous alkaline solution. The CV depicts two typical reduction waves for oxygen reduction occurring probably through the peroxide route. Compared to bare GC, the as-prepared GC/poly(VImM) shows a pronounced electrocatalytic ORR activity as attested by the positive onset potential shift (80 mV) and the increase of the peak current density (from 0.18 to 0.45 mA/cm2). Compared to the state of the art of noble-metal free catalysts, the performance of the poly(IL) is still lower.10,11 However, the observed catalytic activity combined with the facile synthesis of the polymer, in the absence of carbonization step, supports the potential use of poly(VImM) as a metal-free electrocatalyst for the ORR.

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Figure 3. (A) CV of bare GC and GC/poly(VImM) in O2saturated 0.1 M KOH solution. (B) ORR polarization curves using RDE at rotation 900 r.p.m with 10 mV/s scan rate for bare GC, GC/poly(VImM) and GC/poly(VImMM). (C) ORR polarization curves using RRDE at different rotations speeds. (D) KouteckyLevich plots for GC/poly(VImM) electrode at different potentials.


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To get more insight about the performance of the poly(VImM) toward ORR, linear sweep voltammetry (LSV) using rotating disk electrode (RDE) was performed. Figure 3B shows clearly that the GC/poly(VImM) electrode exhibits pronounced ORR electrocatalytic activity when compared to bare GC. The onset potential is 0.68 V vs. RHE and the limiting diffusion current density is 2 times higher than that of bare GC (at -0.2 V). The investigations were complemented by performing the LSV on rotating-ring disk electrode (RRDE) at various rotation rates (Figure 3C). The curves show a two reduction process, suggesting the occurrence of the ORR through consecutive two electron steps with the generation of peroxides as intermediates. The Koutecky-Levich (K-L) plot was performed to determine the number of electron, n, involved in the reduction process. Linear relationship between j-1 and ω-1/2 was observed at different potentials and the value of n varies from 3.4 to 3.6 within the potential range of 0.4 to -0.2 V (Figure 3D). These values suggest that the ORR catalyzed by the poly(VImM) involves two and four electron transfer pathways. In addition, the average yield of HO2- is about 20% within the potential range 0.6 to -0.2 V (Figure S4A). These results suggest the preferential occurrence of ORR through four-electron process. The Tafel plot (Figure S4B) shows a slope of 78 and 97 mV dec1 for GC/poly(VImM) and bare GC, respectively, demonstrating the improved kinetics and ORR performance. In the literature, metal-free catalysts involving carbon based materials and doped carbon with different heteroatoms have been reported.8 These materials were prepared using different thermal processes at temperature ranged from 700 to 1000 °C.27,28 However, in our study the poly(VImM) was used without additional heat treatments. Based on the above results, the poly(VImM) exhibits clearly an enhanced ORR activity that could be explained by two factors; explicitly the chemical composition of the poly(VImM) and the brush organization. Indeed, the origin of the catalytic properties can be attributed to the presence of nitrogen atoms (electron-rich dopant) in the imidazolium ring that induces a high electron density and as consequence generating a positive charge density of

carbon atom located in between the nitrogen atoms. The hierarchical polymer brush structure enhances the electron transfer and also the accessibility of water and oxygen.22,29 In addition, the presence of positive and negative charges within the polymer could induce several effects, including the enhancement of oxygen solubility in the vicinity of the electrode material, favor the oxygen adsorption and participate in the release of intermediates species through electrostatic interaction.30 In recent works, the covering of nanocarbon based catalysts with an ionic liquid layer showed improved ORR kinetics.31,32 In a similar way as observed in an ionic liquid, the poly(ionic liquid) could enable the formation of a preferential water channel that assist proton transportation between the imidazolium and water molecules.33 Furthermore, previous works have reported that imidazolium has acidic proton at the position 2 which could promote the interaction with oxygen molecules. Even thought, the fundamental understanding and the origin of C– H¨¨¨¨O hydrogen bond is still a matter of debate, Singh et al.34 reported that the strong interaction between the hydrogen within the imidazolium ring and oxygen atom occurred at C(2)–H. Gewirth et al. demonstrate the role of protoncoupled electron transfer (PCET) in the modulation of the ORR mechanism.35 In our case, the acidic character of the C(2)–H could act as a proton carrier and thus enhance the catalytic activity through the efficient O–O bond activation/cleavage. In order to confirm the crucial role of C(2)–H, the latter was replaced by a methyl group within the monomer structure. Next, the SI-ATRP was applied to the new monomer and the catalytic activity of poly(VImMM) was evaluated. Figure 3B, orange curve, shows a poor O2 reduction activity comparable to the bare GC electrode. This result was further confirmed by the high yield of HO2- around 70% and a number of electron transfer around 2 to 2.5 (Figures S5 A and B). Thus, the replacement of hydrogen by a methyl group at position 2 inhibits the oxygen reduction activity, confirming the important role of acidic proton on C(2) in the imidazolium. Besides, the brush organization of the poly(VImM) plays an important role in the observed catalytic activity. In additional experiments, the poly(VImM) was performed using direct electro-


ACS Catalysis

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chemical reduction leading to the formation of a homogeneous film onto GC electrode.36 Next, the ORR activity on poly(VImM) was evaluated, showing lower activity (similar to that recorded for bare GC) when compared to the polymer generated using the SI-ATRP process. This experiment evidences the important role of the brush like-structure in ORR activity. Next, the potential use of the poly(VImM) as a host guest platform for other catalysts was investigated. Thus, the platinum catalyst (commercial Pt/C) was introduced by a drop casting over the poly(VImM) and the catalytic performance of the hybrid material was investigated (Figure 4). As expected for Pt/C, the curve shows a single step plateau (Figure 4A) corresponding to the ORR reduction through 4e- process. Interestingly, when the Pt/C catalyst is supported onto poly(VImM)/GC an increase in the ORR activity is observed as attested by the positive half-wave potential shift (+40 mV) and the increase of the limiting current density from -4.5 to -5 mA cm-2. This was also confirmed by measuring the n value and the %HO2- involved in the ORR process (Figures 4B and C). As an example, at 0.3 V the n is 3.97 ± 0.02 and the % HO2- is below 1% for Pt/C/poly(VImM), while for Pt/C the n value is 3.92 ± 0.03 and the % HO2- is 3%.

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The Tafel slope, measured in the low overpotential, of Pt/C/poly(VImM) is 54 ± 4 mV dec-1 which is smaller than that of Pt/C (59 ± 3 mV dec-1) suggesting the high intrinsic catalytic activity of the hybrid material (Figure S6). The Pt based catalysts suffer from multiple limitations, including the vulnerability to the crossover effect. Within this problematic methanol tolerance of Pt/C/poly(VImM) was evaluated. The Pt/C exhibits an instantaneous relative current decay to 55% after methanol injection (Figure 4D), whereas a less pronounced variation is observed for poly(VImM) and Pt/C/poly(VImM) with a current attenuation to 85 and 75%, respectively. The Pt/C/poly(VImM) catalyst exhibits a slight improvement in ORR activity that is linked to the presence of the poly(IL). Indeed, this enhanced activity could be explained by several factors, including the synergetic effect of the hybrid catalyst, the role of the poly(VImM) in improving the interface between the Pt/C and the GC thanks to a lower charge transfer resistance and the improved dispersion of the catalyst. To bring more insight about this point, similar investigation was per-


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formed using Au nanoparticles as catalyst. It is well known that Au is an inefficient catalyst for ORR. In this experiment Au NPs were added onto poly(VImM)/GC and their ORR catalytic performances were evaluated and compared to the Au NPs deposited onto GC. Our results show that the Au NPs display oxygen reduction occurring through the peroxide route with an electron transfer number around 2.7 within a potential range 0.2 V to -0.2 V (Figure S7). However, for drop cast AuNPs onto poly(VImM)/GC a higher catalytic activity is observed (Figure S7A) and the onset potential is shifted by 150 mV compared to AuNPs/GC catalyst. In addition, the electron transfer number for the hybrid catalyst is found to be around 3.5 over a potential range 0.5 to -0.2 V (Figure S7B). These results confirm the presence of a synergetic effect between the AuNPs and the poly(VImM). The electrocatalytic performances of the Pt/C/poly(VImM) were investigated in acidic media. Figure 5A shows the LSV curves for Pt/C/poly(VImM) at various rotation speeds in 0.1 M HClO4.

The curves exhibit a reduction plateau suggesting a diffusion controlled regime within the potential range of 0.3 to 0.6 V. Figure 4B shows improved catalytic activity of Pt/C/poly(VImM) for ORR when compared to the Pt/C as attested by the positive potential shift 25 mV along with the increase of the limiting current density. Furthermore, the n value and the %H2O2 of Pt/C/poly(VImM) are found to be 4 and 0.1% over the potential range 0.9 to 0.3V (Figure S8), confirming that the ORR in acidic media occurs exclusively via a 4e- pathway (O2 + 4H+ + 4e- → 2H2O). Beside the ORR, the oxygen evolution reaction (OER) is another important reaction for energy storage and conversion systems. The challenge within this topic is to find bi-functional catalysts presenting an efficient catalytic activity toward the ORR and OER.37 The electrocatalytic activity for the OER of the as-prepared poly(VImM) and after incorporation of Pt/C was evaluated in alkaline solution. 0.4

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Figure 6. (A) OER polarization curves at 10 mV/s and 1600 r.p.m. in O2-saturated 0.1 M KOH solution recorded on bare GC, poly(VImM), Pt/C and Pt/C/poly(VImM). (B) LSV plots comparing the ORR and OER at Pt/C and Pt/C/poly(VImM) catalyst.


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Figure 6A shows that the poly(VImM) has a small catalytic activity when compared to bare GC, but lower than that observed for Pt/C which is an inefficient catalyst for OER. One has to note that even if the poly(VImM) displays catalytic activity, it is still far below than the iridium and ruthenium oxide catalysts. More interestingly, the hybrid material based on Pt/C/poly(VImM) exhibits pronounced catalytic activity compared to Pt/C. Figure 6B compares the catalytic activity of Pt/C and Pt/C/poly(VImM) in alkaline media. The Pt/C/poly(VImM) offered higher current densities and lower overpotentials for both ORR and OER reactions when compared to Pt/C. The overpotential of the hybrid material at 2 mA cm-2 is almost 200 mV lower than that for Pt/C. For similar reasons as described above, the enhancement of the OER activity could be linked to the chemical composition and to the surface organization in brush-like structure of the poly(VImM). In the literature carbon based catalysts have been investigated for OER, thus, nitrogen-doped carbon (N/C) nanomaterials exhibit notable activity.38 This activity was linked to the carbon (adjacent to N atom) carrying positive charge that favor the adsorption of OH-. In our case, the OER activity can be attributed to the presence of nitrogen (electron-rich dopant) in imidazolium generating a high electron density and as consequence generating a positive charge density of carbon that adsorb OH- and thus accelerating the catalytic cycle of OER. In summary, poly(IL) could be used as a new class of electrocatalyst for the ORR. The catalytic activity was demonstrated to be linked to the brush-like structure and to the chemical composition, including a positive charge density of carbon atoms adjacent to nitrogen atoms and also proton carrier in the imidazolium ring. Furthermore, the poly(IL) was successfully used as a host guesting platform for conventional Pt/C catalyst, providing a synergetic effect as attested by a higher electrocatalytic activity and tolerance to methanol injection. The hybrid material was also demonstrated to be a suitable as a catalyst for the ORR in acidic media. Finally, the poly(IL)/Pt shows a potential use as a bifunctional catalyst for ORR and OER. This study provides simple and new strategies for preparing poly(IL) based catalyst or hybrid materials that combine the

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poly(IL) and other metal catalysts. We anticipate that the simple preparation of poly(IL) and the capability to design wide ranges of task-specific poly(IL) can provide a new class of materials for energy applications. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Experimental and additions results.

AUTHOR INFORMATION Corresponding Author [email protected]; paris-diderot.fr

hyacinthe.randria@univ-

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT We acknowledge support from the CNRS, SATT IDF Innov and doctoral school (ED388). The authors thank Dr. Philippe Decorse for performing the XPS measurements and for the valuable discussions.

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Polymer Brushes Ionic Liquid as a Catalyst for Oxygen Reduction and

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