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Sepia-derived N, P Co-doped Porous Carbon Spheres as Oxygen Reduction Reaction Electrocatalyst and Supercapacitor Guangyuan Ren, Yunan Li, Quanshui Chen, Yong Qian, Jugong Zheng, Yean Zhu, and Chao Teng ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b02170 • Publication Date (Web): 22 Oct 2018 Downloaded from http://pubs.acs.org on October 23, 2018

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ACS Sustainable Chemistry & Engineering

Sepia-derived N, P Co-doped Porous Carbon Spheres as Oxygen Reduction Reaction Electrocatalyst and Supercapacitor Guangyuan Ren,a, *, # Yunan Li,b, # Quanshui Chen,a Yong Qian,a Jugong Zheng,a Yean Zhu,a Chao Tengc, * a

State Key Laboratory Breeding Base of Nuclear Resources and Environment,

School

of Chemistry, Biology and Material Science, East China University of Technology, Guanglan Road No. 418, Jingkai District, Nanchang 330013, China b

School of Materials and Chemical Engineering, Zhongyuan University of Technology,

Huaihe Road No. 1, Shuanghu Economic Development District, Zhengzhou 451191, China c

College of Materials Science and Engineering, Qingdao University of Science and

Technology, Zhengzhou Road No. 53, North District of City, Qingdao 266042, China

#G.

Ren and Y. Li contributed equally to this work.

*Corresponding author

E-mail: [email protected] (G. Ren); [email protected] (C. Teng).

ACS Paragon Plus Environment

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ABSTRACT Developing economical, highly active non-precious metal electrocatalysts with good durability to substitute noble metal materials is critical for the application of energy conversion and storage devices. Herein, N, P co-doped porous carbon spheres (NPCS) derived sepia were fabricated through the simple process of pyrolysis and activation in the presence of poly(bisphenoxy)phosphazene. The NPCS showed the preferable oxygen reduction reaction (ORR) activity in KOH solution with a half-wave potentials of 0.90 V (vs RHE) and limiting current density of 6.05 mA cm-2, a longer stability and better tolerance to methanol poison compared with Pt/C catalyst. Efficient ORR activity in alkaline condition can be attributed to not only the abundant N, P dispersion, but also the hierarchical porous morphology of the carbon spheres. Moreover, as supercapacitor electrode, the NPCS also displayed a high specific capacitance of 465.2 F g-1 with a robust durability up to 10 000 cycles. The method proposed here is expected to inspire the design and preparation of advanced electrode materials due to reasonable electrochemical performance, highly cost effective, which highlights their promising applications in electrochemical energy technologies. KEYWORDS: Sepia, Electrocatalyst, Porous carbon spheres, ORR, Supercapacitor.


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Introduction Sustainable and abundant natural biomass provides plentiful materials with micro/nano structure for application in energy conversion and storage field, such as, the fuel cells and supercapacitors have captured considerable research interests owing to high efficiency, renewability and environmental friendliness.1-6 Oxygen reduction reaction (ORR) plays a vital role for developing of the fuel cells.7-8 Currently, Pt-based nanomaterials are recognized effective ORR electrocatalysts at present due to high current density and good electrochemical kinetic process.9-10 However, the expensive price, the lack of quantity in nature and the insufficient tolerance to methanol are the major hurdles impeding the further development.11-12 Therefore, researchers are inspired to use non-noble metals-based electrocatalysts as alternatives to precious metal for boosting ORR.13-18 Consequently, the transition metal-based materials have become a research focus. However, there are still many challenges of deficient stability, unhomogenious distribution of active sites and environment unfriendly due to the effect of metal.11, 19-21 Recent many reports indicate that heteroatom (N, P, S, etc.) doped carbon materials are promising as ORR catalysts and electrode materials of supercapacitors.22-29 Heteroatom doped carbon nanotubes and graphene have been widely applied in the energy storage and

conversion

field.30-35

Despite

the

outstanding

performance

of

carbon

nanotubes/graphene-based electrocatalysts and electrodes, their large-scale utilizations are severely restricted by the high cost. So far, considerable research efforts also have been devoted to polymers with micro/nano structure as promising precursors for ORR



electrocatalysts and supercapacitors due to various structures and the ability of containing heteroatoms.24-25, 36 Heteroatom doped carbon spheres with hierarchical porous structure combine the advantages such as regular geometry, high electrical conductivity, abundant porosity and tunable morphology. These innovative structures therefore present great utilitarian value for energy storage and conversion devices.37-38 Various methods have been used to fabricate precursors of porous carbon spheres, including template method and emulsion polymerization.39-40 Nevertheless, tedious process, removal of template, hazardous chemicals involvement and aggregation trouble are inevitably involved. The green, cost-effective preparation of porous carbon spheres is still a significant challenge.38 Recently, biomass derived carbon materials have been widely investigated in application of ORR and supercapacitors owing to the distinct advantages of extensive resource, reasonable cost, and convenient eco-friendly method.41-47 Biomass materials possess abundant macro-pores and volatile components integrating internally installed heteroatoms. Hierarchical porous structure and heteroatoms are introduced into the carbon network after high temperature treatment under inert gases, not only obtain a large specific surface area endowing the effective mass transport, but also improve the electrochemical performance.5, 48 Herein, we presented a template-free strategy for facile preparation of the NPCS using poly(bisphenoxy)phosphazene coated sepia as precursor, following by pre-carbonization, activation and pyrolysis process. As expected, the resultant NPCS displayed highly


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excellent electrocatalytic activities in the ORR process under the alkaline condition, the half-wave potentials (E1/2) of 0.90 V (vs RHE) was more positive than that of commercial Pt/C (0.89 V). Compared with Pt/C, the NPCS also showed a longer cycle durability and better methanol-tolerance. Furthermore, as supercapacitor electrode, the NPCS provided a high specific capacitance of 465.2 F g-1 with an excellent durability up to 10 000 cycles, comparable to literatures of carbon materials. The method of pyrolyzing sepia and poly(bisphenoxy)phosphazene provides a facile, environmental friendliness and economical avenue for fabricating heteroatom doped carbon spheres as advanced electrochemical materials for ORR and supercapacitors. Results and discussion As illustrated in Figure 1, N, P co-doped porous carbon spheres (NPCS) are obtained using natural sepia as starting materials through the processes of pre-carbonization, activation and pyrolysis. The sepia is source of C and a small part of N in the NPCS, and poly(bisphenoxy)phosphazene is mainly used as source of N, P for the NPCS. Moreover, sepia provide hierarchical porous structure in carbon matrix co-doped with N, P due to the decomposition of unstable components in sepia and activation of potassium hydroxide during pyrolysis at 900 oC in N2. For comparison, porous carbon spheres (CS) are also fabricated under the same conditions except poly(bisphenoxy)phosphazene.



Figure 1. Schematic diagram for fabrication of N, P co-doped porous carbon spheres (NPCS) using sepia as precursor.


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Figure 2. (a, b) SEM and (c) TEM images of NPCS sample, (d) TEM image and corresponding elemental distribution (C, N, and P) from EDS mapping of NPCS, (e, f) HRTEM images of NPCS. The scanning electron microscopy (SEM) images can be found in Figure 2a, b, as-prepared NPCS display sphere morphologies with the rough surface and the average size of 134 ± 6 nm. To investigate more details of morphologies, transmission electron microscopy (TEM) was applied. We can see that the NPCS surface exhibits abundant porous structure as given in Figure 2c, d. The energy-dispersive spectrometry (EDS) mapping images of NPCS correspond to C, N, P and O (Figure 2d, S1), respectively, exhibit the uniform distribution of the elements. It suggests that N, P are successfully introduced in the carbon matrix. HRTEM images of the NPCS in Figure 2e, f show the amorphous carbon feature, which is composed of randomly orientated graphitic domains.

Figure 3. (a) XPS spectra survey of the NPCS and CS. High-resolution XPS spectra of (b) N1s, (c) P2p and (d) C1s of the NPCS catalyst with deconvoluted peaks. (e) Nitrogen adsorption-desorption isotherm of the NPCS and CS, and the pore size distribution (inset).



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(f) Raman spectrum of the NPCS and CS. To examine the composition of elements of the NPCS and the CS, typical X-ray photoelectron spectroscopy (XPS) spectra were provided in Figure 3a-d and Figure S2. As expected, the peaks of N and P arise in the survey XPS spectrum of NPCS (Figure 3a) with the respective content of 3.93 and 3.54 atomic percent. There is no N and P signal in the survey XPS spectrum of CS, implying that N and P element are doped in the carbon matrix of NPCS during the process of thermal pyrolysis, these results are consistent with the elemental mapping of N and P. The high resolution N1s spectra of the NPCS display four obvious nitrogen species at 403.0, 401.1, 399.6, and 398.5 eV for oxidized N, graphitic N, pyrrolic N and pyridinic N, respectively (Figure 3b). The content of pyridinic N and graphitic N are 62 % and 21 %, respectively. In the previous report, it had been proved that both pyridinic N and graphitic N are important for carbon based materials using in ORR and supercapacitors field, which may obviously improve electrochemical activities of catalysts compared to pyrrolic N and oxidized N.18,

25, 49

The P2p fitting

spectra (Figure 3c) of the NPCS displays two peaks, which are attributable to P-C bonding (132.7 eV) and P-O bonding (133.9 eV) of the NPCS, respectively. As demonstrated in literatures, the electrocatalytic activity of the carbon materials can be promoted observably by doping of phosphorus with the larger covalent radius.24, 34, 50 The XPS C1s spectra of the NPCS are fitted into four peaks, which are assigned to C-C (284.8 eV), C-N/C-P (286.0 eV), C-O (286.7 eV) and C=O/C=N (289.0 eV), respectively (Figure 3d), it is consistent with the above conclusion of N1s, P2p and O1s peaks (Figure


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S2). Porous structure of as-prepared catalysts was further investigated by N2 adsorption-desorption method. The CS, NPCS, NPCS-800 and NPCS-1000 display the type IV isotherm (Figure 3e, Figure S3), which suggest mesoporous materials consistent with the TEM observation, and the average width of adsorption pore of NPCS is 3.7 nm, as shown in pore size distribution character (see the inset). The BET surface area of CS, NPCS, NPCS-800 and NPCS-1000 are 658, 1456, 1076 and 1609 m2 g-1, respectively. The higher specific surface area of NPCS contributes more abundant porous structure and defects, which not only facilitate electron-transfer and O2 diffusion,51-52 but also guarantee the accessibility of the reactants to the active sites, resulting in improved ORR electrocatalysis.27, 53-54 As given in Figure 3f, the Raman spectra of the NPCS and CS exhibit G band (1589 cm−1) and the D band (1344 cm−1), which correspond to the graphitic carbon and the defect mode, respectively. The ID/IG ratio is 1.08 and 1.01 for NPCS and CS respectively. The higher ID/IG ratio suggests the evident defect carbon structure of the NPCS due to pyrolysis and doping of heteroatoms, and more defective domains would offer sufficient electrochemical active sites.27, 44



Figure 4. (a) CV and (b) LSV images (obtained from RRDE measurement with rotating speeds of 1600 rpm) of the NPCS, CS and Pt/C catalysts in 0.1 M KOH solution, (c) the n of the NPCS, CS and Pt/C calculated from (b). Durability evaluation of LSV for (d) the NPCS and (e) the Pt/C towards ORR in 0.1 M KOH with rotating speeds of 1600 rpm before and after 4000 cycles. (f) i-t relation of resistance to methanol poison for NPCS and Pt/C through adding 5 mL methanol into electrolyte. The as-prepared NPCS, CS, NPCS-800, NPCS-1000, and Pt/C were applied as ORR catalysts and the electrocatalytic performance were compared through cyclic voltammetry (CV) measurement in N2- or O2-saturated 0.1 M KOH with a rate of 50 mV s–1. No obvious reduction peaks for all catalysts can be found in the N2-saturated electrolyte (Figure 4a). But three catalysts display remarkable reduction peaks in O2-saturated KOH solution. The NPCS pyrolyzed at 900 oC shows more positive potential of 0.87 V at oxygen reduction peak than those of the NPCS-800 (0.72 V), NPCS-1000 (0.83 V), CS (0.77 V) and the Pt/C (0.86 V) catalysts (Figure S4a). Furthermore, peak current density of the NPCS (1.66 mA cm–2) is superior to that of Pt/C


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(1.49 mA cm–2) and other three catalysts (Table S1). For optimizing temperature, rotating disk electrode (RDE) technology was carried out at a rate of 10 mV s–1 for NPCS, NPCS-800, NPCS-1000. As illustrated the corresponding linear sweep voltammetry (LSV) plots in Figure S4b, both of the onset potentials (Eonset) and the E1/2 of the NPCS are better than the catalysts pyrolyzed at 800 and 1000 oC (see Table S1), which indicates that the optimal pyrolyzing temperature is 900 oC. To further explore the kinetics of the ORR, the rotating ring disk electrode (RRDE) measurement was carried out in alkaline solution saturated with O2 with a rate of 10 mV s–1, corresponding curves of LSV for the NPCS and Pt/C are displayed in Figure 4b, the ring potential is set as of 1.5 V during the LSV measurement. Both of the Eonset (0.99 V) and the E1/2 (0.90 V) of the NPCS are obviously superior to those of the CS catalyst, and compared with the Pt/C, both were slightly positive as displayed in Table S1. The results of CV and LSV test suggest the kinetics performance of the NPCS to ORR is superior to the NPCS-800, NPCS-1000, CS and commercial Pt/C. The electron transfer number (n) of as-prepared catalysts and Pt/C are calculated from the results of RRDE measurement (Figure 4b) to be 3.76, 3.21, and 3.86 for the NPCS, CS, and Pt/C, respectively, as displayed in Figure 4c. The average yields of H2O2 (Figure S5) are 12.5, 38.8 and 6.8 % in the same potential range. These parameters of kinetics imply a four-electron pathway of the NPCS towards the direct formation of OH–. To evaluate the durability of the catalysts, the cycle stability experiments of NPCS and commercial Pt/C were carried out by voltage-cycling in the range of 1.1-0.3 V in 0.1 M



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KOH electrolyte at 1600 rpm , the corresponding LSV plots are displayed in Figure 4d, e. The LSV curve of NPCS is found a shift negatively of 13 mV in E1/2 after 4000 cycles, while the commercial Pt/C shows a decrease of 27 mV. In addition, as expected in the Figure 4f, the NPCS presents a better methanol-tolerance than commercial Pt/C. To investigate the potential application of NPCS as supercapacitor electrode, the CV and galvanostatic charge-discharge (GCD) measurement were performed in a three-electrode configuration. The CV curves (Figure 5a) measured at different scan rate display quasi-rectangular shape and no apparent redox peaks, demonstrating a rapid ion transfer and excellent reversible capacitive behaviors.55 As shown in Figure 5b, all GCD curves exhibit a quasi-triangular shape, implying the well-balanced charge storage ability.56 It should be noted that the discharging time become much longer than that of charging time at 1 A g-1, which could be due to the synergy of pseudocapacitance and electrochemical double-layer capacitance.57 At low current density, the nitrogen, phosphorus-containing

functional

groups

provide

a

Faradaic

pseudocapacitive

contribution to the total capacitance, which gives rise to that unusual charge/discharge curve.58 We observe a small equivalent series resistance in the Nyquist plots (Figure S6) of NPCS, which could benefit high rate capability of NPCS.59 In addition, the specific capacitance versus current density curve is illustrated in Figure 5c. At low current density of 1 A g-1, the NPCS displays a high specific capacitance of 465.2 F g-1. Even when the current density is 20 A g-1, the NPCS maintains a large capacitance of 320.0 F g-1, indicating that the NPCS electrode possesses an outstanding rate capability. These large


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capacitance values are superior, or comparable to those reported porous carbons,55, 59-61 implying the great potential of the NPCS for utilization in high-performance supercapacitors. As a control sample, the CV curves of CS also exhibit a quasi-rectangular form (Figure S7a). At the low current density of 1 A g-1, the maximum of specific capacitance for CS is only 243.5 F g-1 (Figure S7c), which demonstrates that N, P co-doping could improve the surface wettability of the NPCS electrode and provide pseudocapacitance contribution. The cycling stability curve shown in the Figure 5d was test at the current density of 20 A g-1. After 10 000 cycles, the NPCS maintains 97.0% of its initial specific capacitance, which confirms that the NPCS delivers a robust cycling durability.

Figure 5. Electrochemical properties of NPCS obtained by three-electrode method. (a) The CV curves measured from 10 to 200 mV/s. (b) The GCD curves performed at various current densities. (c) The specific capacitance as a function of current density curve. (d) The cycling stability curve measured at the current density of 20 A g-1.



To evaluate the practical application of the NPCS (CS) samples in energy storage fields, symmetric supercapacitors were also assembled by using NPCS (CS) as both positive and negative electrodes. The NPCS and CS symmetric supercapacitors exhibit rectangular shaped CV curves (Figure S8a and S8b) without apparent redox peaks at all scan rates, indicating an ideal electrochemical double-layer capacitor. The GCD curves shown in Figure S8c and Figure S8d are nearly linear and symmetric, demonstrating that the symmetric supercapacitor delivers an outstanding electrochemical reversibility. The specific capacitance versus current density diagram is illustrated in Figure S8e. At the current density of 0.5 A g-1, the NPCS symmetric device delivers a specific capacitance of 211.4 F g-1. Even when the current density is 10 A g-1, the NPCS device still has a specific capacitance of 161.0 F g-1. By contrast, at the current density of 0.5 A g-1, the CS symmetric device displays a specific capacitance of 168.6 F g-1. The Ragone plots of the symmetric supercapacitors are illustrated in Figure S8f. The NPCS device exhibits an energy density of 7.3 Wh kg-1 at the power density of 251.6 W kg-1. Even at the power density of 5 160.3 W kg-1, the device still retains an energy density of 5.6 Wh kg-1. In contrast, the CS device delivers an energy density of 5.9 Wh kg-1 when the power density is 124.9 W kg-1. Overall, the NPCS displays an outstanding ORR activity and supercapacitive performance, which could be elaborated as follows. Firstly, the 3D hierarchically porous architecture and the high specific surface area facilitate electron-transfer, O2 diffusion and shorten the diffusion distance of electrolyte ion. Moreover, the abundant N, P


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co-doping not only serves as the main active catalytic sites in the ORR process, but also facilitates

the

surface

wettability

of

the

electrode

and

provides

additional

pseudocapacitance contribution. Conclusions In summary, a green, low-cost strategy was presented for the fabrication of N, P co-doped porous carbon spheres (NPCS) as electrochemical active materials from fresh sepia along with poly(bisphenoxy)phosphazene by using the facile process of activation and pyrolysis. As biomass, sepia is the resource of C element for NPCS, notably, which provides the spherical framework with hierarchical porous microstructure. As expected, the NPCS with homogeneous N and P shows the excellent oxygen reduction activity in 0.1 M KOH with a E1/2 of 0.90 V and limiting current density of 6.05 mA cm-2 better than those of Pt/C (0.89 V, 5.36 mA cm-2, respectively), a long-term stability and better methanol-resistance than Pt/C. In addition, as supercapacitor electrode, the NPCS displays a high capacitance of 465.2 F g-1 with a robust durability up to 10 000 cycles. The high electrochemical properties are ascribed to the synergy of abundant N, P active sites with uniform dispersion and the high surface area contributed by hierarchical porous morphology of carbon spheres. In a word, this feasible procedure may provide an avenue for the development of multi-functional carbon spheres for promising applications in ORR and supercapacitor. ASSOCIATED CONTENT



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Supporting Information Experimental section, including chemicals, preparation procedure, characterization of catalysts, ORR and supercapacitors measurements. Curves of XPS, BET, EIS, CV, LSV, hydrogen peroxide percentage and supercapacitors properties. The Electrochemical data from CVs and LSVs. (PDF) AUTHOR INFORMATION *Corresponding author E-mail: [email protected] (G. Y. Ren); [email protected] (C. Teng). Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was supported by the Foundation of Jiangxi Educational Committee (GJJ160536), the NSF of Jiangxi Province (20171BAB206016, 20161BBH80052), the International

Cooperation

of

National

Science

and

Technology

of

China

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For Table of Contents Use Only Synopsis A facile and sustainable method for fabrication of N, P co-doped porous carbon spheres is developed by natural sepia as starting biomaterial for electrocatalyst. Keyword: Sepia, Electrocatalyst, Porous carbon spheres, ORR, Supercapacitor


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Sepia-derived N, P Co-doped Porous Carbon ... - ACS Publications

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