Covalently Modified Electrode with Pt Nanoparticles Encapsulated in

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Covalently Modified Electrode with Pt Nanoparticles Encapsulated in Porous Organic Polymer for Efficient Electrocatalysis Haobin Fang, Junxing Chen, Muhammad-Sadeeq Balogun, Yexiang Tong, and Jianyong Zhang ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b01697 • Publication Date (Web): 05 Nov 2018 Downloaded from http://pubs.acs.org on November 6, 2018

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ACS Applied Nano Materials

Covalently Modified Electrode with Pt Nanoparticles Encapsulated in Porous Organic Polymer for Efficient Electrocatalysis Haobin Fang, Junxing Chen, Muhammad-Sadeeq Balogun, Ye-Xiang Tong, and Jianyong Zhang* Sun Yat-Sen University, MOE Laboratory of Polymeric Composite and Functional Materials, School of Chemistry, School of Materials Science and Engineering, Guangzhou 510275, China. KEYWORDS: modified electrodes, porous organic polymers, Pt nanoparticles, electrocatalysis

ABSTRACT: Imidazolium-based porous organic polymer is employed to be chemically modified onto the surface of glassy carbon electrode via silane chemistry and alkylation and to support Pt nanoparticles. Pt nanoparticles with an average size of ca. 2.28 nm are loaded and the modified electrode exhibits high activity toward hydrogen evolution reaction with a low overpotential of 56 mV at 10 mA cm-2 versus the reversible hydrogen electrode, which is lower to that of commercial Pt/C, and additionally it shows long-term durability of 4000 cycles. It provides a new strategy for the development of catalytic porous electrodes with supported nanocatalysts.

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1. INTRODUCTION Efficient catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction and oxygen reduction reaction are highly desirable for electrochemical applications in water splitting, fuel cells and batteries.1-4 Pt/C is still an efficient and commercially available electrocatalyst although great endeavor has been made to exploit Pt-based materials. It is crucial to reduce the Pt loading in the designed electrocatalyst due to its limited resources and high cost.5 In this respect, downsizing Pt nanoparticles (Pt NPs) is an effective method to achieve a large proportion of active surface atoms.6-10 Metal nanoparticles supported on porous materials have been widely shown as a catalogue of highly efficient heterogeneous catalysts.11-18 Among a range of emerging porous materials, porous organic polymers (POPs) have received much attention for their chemical stability, high surface area and porosity.19-24 The structure and porosity of POPs are highly tuneable due to the cross-linking between small molecular precursors.25-29 For example, incorporation of ionic building blocks in POPs may remarkably enhance the electrostatic attraction between the porous framework and guest species carrying opposite charges.7 This strategy has been employed for imidazolium-based POPs in the in situ formation of metal NPs attributed to their excellent catalytic activity and stability.27-29 Herein, a novel porous catalytic electrode is developed by in situ modifying POPs chemically on an electrode surface, and subsequently supporting Pt NPs in the POPs. The surface of glassy carbon electrode (GCE) is modified via silane chemistry and alkylation30 by an imidazoliumbased POP synthesized via the reaction of tetrakis-[4-(1H-imidazole-1-yl)-phenyl]methane (IM) with 1,4-bis(bromomethyl)benzene (2BrB), and the POP is subsequently employed to support Pt NPs obtaining a modified electrode namely rGCE-Pt/pIM-2BrB (Figure 1). Electrocatalytic measurements and long-term stability have been investigated for rGCE-Pt/pIM-2BrB.


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Figure 1. Schematic illustration of the procedures for preparing rGCE-Pt/pIM-2BrB. 2. RESULTS AND DISCUSSION Preparation of rGCE-Pt/pIM-2BrB is shown in Scheme 1. Firstly, a polished GCE (0.07 cm2) is anodically treated via a cyclic voltammetry (CV) electrooxidation process in order to enrich oxygen-containing surface groups, e.g., -OH and -COOH groups, on the GCE surface.30 Secondly, -OH groups on the activated GCE surface is modified by -Br groups using 3bromopropyltriethoxysilane (Br(CH2)3Si(OEt)3) via alkoxysilane-hydroxylization,31 obtaining GCE-Br. Thirdly, imidazole groups of IM are alkylated on its N-atom and bridged with 2BrB and -Br group on GCE-Br to generate polymeric imidazolium porous material (pIM-2BrB) with positively charged porosity, namely GCE-pIM-2BrB.32 Then, PtCl42- is exchanged with Br-. After PtCl42- is in situ reduced by NaBH4 solution,33 Pt NPs are yielded and in the meantime


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stabilized within the porous channels of pIM-2BrB to get GCE-Pt/pIM-2BrB. At last, redundant oxygen-containing groups on the GCE surface are electroreduced by CV sweep from -1.3 to 0.7 V in a NaCl aqueous solution (0.5 mol L-1), resulting in rGCE-Pt/pIM-2BrB.30 Br

anodically treatment by CV

GCE

N

+

N

N

Si

O

O

rGCE-Pt/pIM-2BrB

Br- +N N

+

N N

N+ Br-

electroreduction by CV Pt

N N

Pt

N

+

N

Pt Br- +N N

CHCl3, 60 oC

GCE-Br

+

O

Br(CH2)3Si(OEt)3

Si O O COOH O COOH

toluene, 80 oC

0.05 M H2SO4

GCE

OH OH COOH OH COOH

IM & 2BrB

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.5 M NaCl

Si O O COOH O COOH

+

N N

1) H2PtCl6

N N Br-

+

Pt

2) NaBH4

GCE-Pt/pIM-2BrB

Br- + N N

Si O O COOH O COOH

+

N N N N+

Br-

GCE-pIM-2BrB

Scheme 1. Preparation route to rGCE-Pt/pIM-2BrB. For detailed characterization and condition optimization, Pt/pIM-2BrB was also prepared under batch conditions. The polymer was synthesized from the reaction of IM and 2BrB according to the previous report,32 subsequent anion exchange with 5.0, 2.5 or 0.8 mmol L-1 H2PtCl4 and reduction with NaBH4 produced well-dispersed Pt NPs, namely Pt/pIM-2BrB-5.0, Pt/pIM-2BrB-2.5 and Pt/pIM-2BrB-0.8, respectively. The morphology of the resulting pIM2BrB supported Pt NPs was characterized using SEM and TEM (Figure S1-S3). SEM shows that all the polymers Pt/pIM-2BrB macroscopically consist of irregular spheres with a few micrometers in diameter. TEM determines a diameter of 2.86±0.56 nm of Pt NPs for pIM-2BrB5.0, 1.92±0.33 nm for pIM-2BrB-2.5, while few Pt NPs were observed for pIM-2BrB-0.8.


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Herein pIM-2BrB-2.5 is chosen for the modification of GCE and studied in detail due to its smaller size of Pt NPs. The morphology of Pt/pIM-2BrB-2.5 loaded on GCE, namely rGCE-Pt/pIM-2BrB, was investigated (Figure 2). SEM shows the polymers are macroscopically composed of irregular interconnected polymer spheres. TEM of rGCE-Pt/pIM-2BrB scraped from the electrode determines a diameter of 2.28±0.45 nm of Pt NPs. The morphology and Pt size are similar with Pt/pIM-2BrB-2.5 synthesized under batch conditions. The loading of Pt NPs on the electrode was analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and found to be ca. 0.01 mg (per 0.07 cm2). The polymer pIM-2BrB before loading Pt NPs is amorphous as revealed by powder X-ray diffraction (XRD) (Figure S4). After the loading of Pt NPs, the strong signal at 2θ ≈ 40° is ascribed to the (111) lattice plane of Pt NPs confirming the existence of crystalline Pt NPs.17,18 In contrast to the strong signals that originate from Pt/pIM2BrB-5.0 in diffraction patterns, the signals associated with nanoparticles are too weak to be clearly observed for Pt/pIM-2BrB-2.5 and Pt/pIM-2BrB-0.8, presumably because of small size and low concentration, respectively. The existence of Pt NPs for Pt/pIM-2BrB-2.5 is confirmed by EDX and ICP-AES (Figure S5). FT-IR and solid-state 13C NMR spectra of Pt/pIM-2BrB are nearly identical to the corresponding polymers before Pt loading, indicating that their polymeric structures are well maintained (Figure S6, S7).27-29,32 X-ray photoelectron spectroscopy (XPS) of Pt/pIM-2BrB-2.5 shows that the Pt 4f region is divided into four spin-orbital pairs, suggesting that two types of surface-bound Pt species exist (Figure S8). The signals at 75.0 eV (Pt 4f5/2) and 71.4 eV (Pt 4f7/2) are assigned to Pt(0) species, while the signals at 76.4 eV (Pt 4f5/2) and 72.6 eV (Pt 4f7/2) correspond to Pt(II) species which probably result from the incomplete reduction of H2PtCl6.


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Figure 2. a,b) SEM images of rGCE-Pt/pIM-2BrB-2.5 loaded on GCE, c,d) high-resolution TEM images of rGCE-Pt/pIM-2BrB scraped from GCE, and e) particle size distribution of Pt NPs in rGCE-Pt/pIM-2BrB. Thermogravimetric analysis (TGA) of Pt-pIM-2BrB-2.5 shows that the polymer may remain thermally stable up to ca. 200 oC (Figure S9). Nitrogen physisorption at 77 K shows negligible uptake (8.1 cm3 g-1 at 1 bar) probably attributed to the charged pore channels and flexible framework, thus weak adsorbent-nitrogen interactions (Figure S10).27-29,32 In contrast, remarkably increased uptake was observed for hydrophilic MeOH. MeOH vapor sorption isotherms of Pt/pIM-2BrB-2.5 show the adsorption capacity reaches 189 cm3 g-1 (27 wt%) at 15.1 KPa and 298 K. It suggests that Pt-pIM-2BrB is ready to capture hydrophilic guests within its porous channels. The electrocatalytic activity of the modified porous electrode rGCE-Pt/pIM-2BrB was investigated by HER in an acidic electrolyte (0.5 mol L-1 H2SO4) (Figure S11). Only tiny changes were observed for LSV curves of rGCE-pIM-2BrB at different scan rates in 0.5 mol L-1


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H2SO4 when the scan rate increases from 2 to 100 mV s-1 (Figure S12), indicating efficient charge and mass transport in the electrocatalytic process.34 As exhibited in Figure 3, rGCEPt/pIM-2BrB shows an overpotential of only -56 mV at 10 mA cm-2 of HER at 50 mV s-1. The electrochemical stability of rGCE-Pt/pIM-2BrB was evaluated by durability measurements by CV from 0.0 to -1.0 V. A slight negative shift was observed for the HER polarization curves of rGCE-Pt/pIM-2BrB after a 4000 cycling test, revealing its long-term durability (Figure 3b). The present electrocatalyst has an outstanding stability in acid media, and it shows only very slow attenuation during 25 h at -0.15 V (vs. RHE) (Figure 3c). It is worth mentioning that the fluctuation of current density results from the continuous growth and release of hydrogen bubbles on the electrode surface.5 The Pt NPs of rGCE-Pt/pIM-2BrB after durability measurements show a diameter of 2.20±0.40 nm according to TEM (Figure S13) and the size does not change significantly compared with that of Pt NPs before durability measurements (2.28±0.45 nm), indicating the Pt NPs supported on pIM-2BrB are stable without aggregation during electrocatalysis. Additionally, the electrode could be reused after re-modification (Figure 4).


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0 1000 2000 3000 4000

0 GCE GCE-Pt/pIM-2BrB-Nafion GCE-Pt/C rGCE-Pt/pIM-2BrB GCE-pIM-2BrB

-20

-2

-10

-10

Current density (mA cm )

-3


0

b)

a)

-30 -40 -50 -0.4

c)

-0.3

-0.2 E (V) vs. RHE

-0.1

-20

-30

-40

-50 -0.4

0.0

-0.3

-0.2

-0.1

0.0

30

d)

0.060

0

E (V) vs. RHE

-2


38 mV dec

-10 -20 -30

0.050 0.045 37 mV dec

0.040

-1

0.030 0

5

3

10 15 Time (h)

20

-1.2

25

f)

GCE-Pt/C rGCE-Pt/pIM-2BrB

2

-0.8

-0.6 -0.4 -0.2 -2 log j (mA cm )

100

-1

Rs

60 50

-2

40

-3

30

-4

20

0.2

CPE

70

0

0.0

rGCE-Pt/pIM-2BrB GCE-Pt/C

80

1

RCT

W

10

-5 0.0

-1.0

90

-Z'' ()

-2

-1

0.035

-40

e)

0.2

GCE-Pt/C RGCE-Pt/pIM-2BrB

0.055

10

-50

0.1

E (V) vs. RHE

20


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0.2

0.4

0.6

0.8

1.0

1.2

0 10

15

20

E (V) vs. RHE

25

30 Z' ()

35

40

45

50

Figure 3. a) LSV curses of GCE, GCE-Pt/pIM-2BrB-Nafion, GCE-pIM-2BrB, GCE-Pt/C and rGCE- Pt/pIM-2BrB in 0.5 mol L-1 H2SO4 for HER, b) durability measurements with rGCEPt/pIM-2BrB during 4000 CV scans, c) chronoamperometric response of rGCE-Pt/pIM-2BrB at an applied potential of -0.15 V vs RHE at 100 mV s-1, d) Tafel curves of rGCE-Pt/pIM-2BrB and GCE-Pt/C in 0.5 mol L-1 H2SO4, e) CVs for rGCE-Pt/pIM-2BrB and GCE-Pt/C in 0.5 mol L-1


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H2SO4 at 50 mV s-1, and f) Nyquist plots of rGCE-Pt/pIM-2BrB and GCE-Pt/C in 0.5 mol L-1 H2SO4 at 0.5 V (inset shows the equivalent circuit diagram).

0

-2


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


rGCE-Pt/pIM-2BrB rGCE-Pt/pIM-2BrB re-prepared

-50 -100 -150 -200 -250 -300 -0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

E (V) vs. RHE

Figure 4. Linear sweep voltammetry for rGCE-Pt/pIM-2BrB and rGCE-Pt/pIM-2BrB that was re-prepared after destroying in 0.5 mol L-1 H2SO4. For comparison, related GCE-Pt/pIM-2BrB-Nafion, GCE-pIM-2BrB, GCE-Pt/C catalysts were also studied (Figure 3a). Pt/pIM-2BrB or Pt/C was first mixed with an ethanol solution of Nafion and then sonicated to obtain a catalyst ink. Then the ink was applied to the GCE surface and dried at ambient temperature to obtain GCE-Pt/pIM-2BrB-Nafion or GCE-Pt/C.34 Blank GCE and GCE-pIM-2BrB show no electrocatalytic activity, indicating that Pt is indispensable for HER. The effect of counter electrodes (Pt mesh and graphite) to the electrocatalytic properties was also studied. When the working electrode was GCE, GCE-Pt/C, rGCE-Pt/pIM-2BrB or rGCE-Pt/pIM-2BrB, LSV was examined in 0.5 mol L-1 H2SO4 aqueous solution at 50 mV s-1 using Pt mesh (1 cm2) or graphite electrode as the counter electrodes (Figure S14). No significant change was observed for the same material when Pt mesh or graphite counter electrode was used. GCE-Pt/pIM-2BrB-Nafion and GCE-Pt/C have overpotential of -110 mV and -65 mV, respectively, at 10 mA cm-2. In comparison, the overpotential of rGCE-Pt/pIM-2BrB is lower


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than GCE-Pt/C (-65 mV), indicating that rGCE-Pt/pIM-2BrB has outstanding electrocatalytic activity for HER. The overpotential of rGCE-Pt/pIM-2BrB is also lower than GCE-Pt/pIM2BrB-Nafion (-110 mV). The results show that the present chemically modified glassy carbon electrode with small and well-dispersed Pt NPs supported by porous materials can lower the overpotential and enhance the electrocatalytic activity of HER.35 The intrinsic kinetic rate for HER was evaluated from the Tafel slope. As displayed in Figure 3d, the Tafel slope of rGCE-Pt/pIM-2BrB (37 mV dec-1) is slightly lower than that of GCE-Pt/C (38 mV dec-1), demonstrating the efficient catalytic feature for HER. Electrochemically active surface area (ECSA) is used to assess electrochemically active sites of rGCE-Pt/pIM-2BrB and GCE-Pt/C. The ECSA is calculated based on the hydrogen desorption in the CV measured in 0.5 mol L-1 H2SO4 solution (Figure 3e) by the equation ECSA = QH/(210×WPt), where QH is the total charge (µC) for hydrogen desorption, 210 is the charge (µC cm-2 Pt) required to oxidize a monolayer of hydrogen on bright Pt surface, and WPt refers to the Pt loading (0.01 mg).36 The ECSA of rGCE-Pt/pIM-2BrB (3.29 m2 g-1) is larger than that of GCE-Pt/C (1.30 m2 g-1). The obvious ECSA enhancement of rGCE-Pt/pIM-2BrB may be attributed to the small size and welldispersed Pt NPs.36 Electrochemical impedance spectroscopy (EIS) is also used to compare the electrode activity. The Nyquist plots at 0.5 V show that rGCE-Pt/pIM-2BrB has an obviously lower fitting resistance of ca. 15 Ω than that of GCE-Pt/C (ca. 25 Ω) (Figure 3f). The lower resistance and smaller Tafel slope suggest a more favorable HER kinetics for rGCE-Pt/pIM2BrB than for GCE-Pt/C. To the best of our knowledge, the present porous electrode is among the most efficient HER electrodes in acidic medium reported thus far (Table S1).5-10,37-39 The catalytic performance enhancement may be attributed to good dispersion and stabilization of the Pt NPs in the charged pore channels of imidazolium-based POPs thus preventing their


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agglomeration and loss. Moreover the imidazolium moiety of the POPs plays a significant role in accelerating the electron transfer by means of π–π and/or cationic-π interactions, and the close contact between the electrode and well-dispersed Pt NPs linked via pIM-2BrB may probably contribute to high electron transfer between the electrode and Pt NPs.26,40,41 3. CONCLUSIONS In summary, a facile strategy is developed to modify the GCE surface via silane chemistry and alkylation by imidazolium-based porous organic polymer supported Pt NPs. The polymer is synthesized by polymerization of tetrakis-[4-(1H-imidazole-1-yl)phenyl]methane with 1,4bis(bromomethyl)benzene, and subsequent anion exchange with H2PtCl4 and reduction with NaBH4 produces well-dispersed Pt NPs. The concentration of PtCl62- affects the size of Pt NPs. A small size of 2.28 ± 0.45 nm can be obtained on the electrode with 2.5 mmol L-1 PtCl62-. LSV measurements indicate that rGCE-Pt/pIM-2BrB shows high activity toward HER with an overpotential of only 56 mV at 10 mA cm-2 (vs. RHE), which is lower than that of commercial 20% Pt/C catalyst (65 mV). The CV measurements and TEM show its long-term stability after 4000 cycles. The ECSA, Tafel plots and impedance behaviors also prove that rGCE-Pt/pIM2BrB has a great potential in HER. The present work establishes a new strategy to in situ modify the electrode surface chemically using imidazolium-based porous organic polymer, which supports and stabilizes Pt NPs, resulting in a highly efficient porous catalytic electrode for HER. The strategy is expected to work for a number of emerging porous materials, such as POPs, MOFs, and COFs. ASSOCIATED CONTENT


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Supporting Information. The following files are available free of charge. Experimental section, characterization, electrocatalytic data and summary of HER data (PDF) AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] ORCID Jianyong Zhang: 0000-0002-3297-7524 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We gratefully acknowledge the NSFC (51573216), the NSF of Guangdong Province (2017A030313057) and the FRF for the Central Universities (16lgjc66) for financial support. REFERENCES (1)

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Covalently Modified Electrode with Pt Nanoparticles Encapsulated in

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