Next Article in Journal
Activation of Peroxymonosulfate by Fe, O Co-Embedded Biochar for the Degradation of Tetracycline: Performance and Mechanisms
Previous Article in Journal
Boosting Benzene’s Ozone Catalytic Oxidation at Mild Temperatures over Highly Dispersed Ag-Doped Mn3O4
Previous Article in Special Issue
Characterization of Equilibrium Catalysts from the Fluid Catalytic Cracking Process of Atmospheric Residue
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 14
Issue 9
10.3390/catal14090555
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Spartina alterniflora-Derived Carbons for High-Performance Oxygen Reduction Reaction (ORR) Catalysts

by
Xinmeng Hao
,
Yougui Zhou
,
Lihua Guo
,
Huipeng Li
,
Hong Shang
* and
Xuanhe Liu
*
School of Science, China University of Geosciences, Beijing 100083, China
*
Authors to whom correspondence should be addressed.
Catalysts 2024, 14(9), 555; https://doi.org/10.3390/catal14090555
Submission received: 11 July 2024 / Revised: 31 July 2024 / Accepted: 22 August 2024 / Published: 24 August 2024
(This article belongs to the Special Issue Porous Materials as Efficient Catalysts: Synthesis, Characterization and Applications)
Browse Figures
Versions Notes

Abstract

:
Being an alien species, Spartina alterniflora has occupied the living space of native animals and plants, causing irreversible damage to the environment. Converting Spartina alterniflora into carbon or its derivatives offers a valuable solution to manage both invasive biomass and an energy shortage. Herein, through a simple activation process, we successfully prepared Spartina alterniflora-derived carbon (SAC) and its N-doped derivative SANC, and used them as metal-free catalysts for an oxygen reduction reaction (ORR). SAC exhibits good electrochemical performance and holds significant potential in catalysis. After N-doping by melamine as a nitrogen source, electronegativity is redistributed in SANC, leading to enhanced performance (a half-wave potential of 0.716 V vs. RHE, and a four-electron transfer pathway with a H2O2 yield of only 2.05%). This work presents a straightforward and cost-effective approach to the usage of obsolete invasive biomass and shows great potential in energy generation.

1. Introduction

With rapid growth of the global economy and increasing human activities, energy consumption has steadily risen in recent years. Fossil fuels are the main resource to provide energy. However, fossil fuels are non-renewable and excessive use can cause significant environmental pollution [1,2]. Therefore, it is urgently important to develop new materials and technologies in energy storage and conversion [3,4,5]. As efficient energy conversion devices, fuel cells play a crucial role in addressing power shortages by converting intermittent energy sources into stable, clean electricity [6,7]. An oxygen reduction reaction is vital during the process of electrochemical energy storage and conversion in fuel cells [8]. However, the efficiency of the ORR is significantly limited by the slow reaction kinetics of oxygen species [9]. As a result, various efforts have been made to develop ORR catalysts [10,11,12]. A commercial Pt/C catalyst has excellent catalytic performance [13,14,15]; however, as a noble metal, Pt is scarce and has a steeply rising price. Consequently, Pt-free ORR electrocatalysts with low cost and high activity need to be widely explored [16,17,18].
Metal-free electrocatalysts with good stability and high conductivity have been investigated in the past few years [19,20]. Among these materials, carbons and carbon-based catalysts have attracted significant attention due to their promising catalytic activity [21,22]. Importantly, the performance of carbons can be easily regulated by heteroatom doping (N, S, Fe, Co, and so on) or by forming composites with other molecules or materials [23,24,25,26]. The carbon element is the most fundamental component of living organisms. As a natural, rich, and renewable high-carbon resource, biomass has many advantages in synthesizing various carbon materials [27,28]. Converting biomass into valuable chemicals and biochar offers an effective method to deal with extensive biomass waste [29,30,31]. Carbon materials made of biomass have been widely studied for their potential in electrocatalysis and as supercapacitors and electrodes for batteries. This includes carbon materials such as hibiscus calyx [32], waste-kapok flower [33], platycladus orientalis tree-cone [34], waste-reed straw [35], rice husk [36], corn cob [37], and palm fruit [38]. As a coastal invasive species, Spartina alterniflora has strong vitality and is recognized as a global threat to biodiversity and the environment [39,40]. Especially in China, the growth rate of the area occupied by Spartina alterniflora was 2.17 km2 per year in the east coast from 2016 to 2021 [41], making it urgently needed to explore more prevention and treatment methods. Upon activation and carbonization, the porous carbon material derived from Spartina alterniflora can be used as an electrode for a high-performance Na-ion battery with a reversible high capacity of 265 mA h g−1 at a current density of 20 mA g−1 and with an excellent rate performance [42], demonstrating its high economic value in next-generation high energy density batteries. This can be attributed to the hollowed structure of Spartina alterniflora, which can expose more surfaces and defects.
In this paper, Spartina alterniflora-derived carbon SAC and its N-doped derivative SANC were successfully prepared through a straightforward activation process (Scheme 1) and post-doping method by melamine as a nitrogen source. Due to their porous structure and abundant active defects, the as-prepared carbon materials can be used as metal-free catalysts for the ORR. Both of the materials indicate mainly a four-electron transfer pathway, with a H2O2 yield of only 3.93% for SAC and 2.05% for SANC. Impressively, SANC presents a more positive potential (0.7156 V vs. RHE) and faster kinetics (100 mV dec−1) and charge transfer process than SAC according to electrochemical measurements. The improvement was attributed to the structural defects and distributed active sites from N-doping, which benefit the acceleration of the ORR reaction [43,44]. Compared to other carbon materials in Table S1, Spartina alterniflora-derived carbon SAC and SANC showed great potential as ORR catalysts. The exploration of utilizing Spartina alterniflora for ORR electrocatalysis provides an approach to retard the environmental problems derived from obsolete invasive biomass and benefit energy storage and conversion.

2. Results and Discussion

2.1. Characterization of SAC and SANC

The two carbon materials from Spartina alterniflora were thoroughly characterized by various measurements. Figure 1 shows the morphologies of SAC and SANC. Typically, carbons from biomass mostly presented amorphous characteristics [45]. This is also true for carbons derived from Spartina alterniflora. It can be seen that SAC and SANC materials presented a rough surface (Figure 1a for SAC and Figure 1c for SANC), which can increase structural defects and expose more active sites. After heteroatom doping, the hierarchically porous structure and abundant N active sites benefited the improvement of surface/interface contact, electron transfer, and conductivity. In irregular carbon blocks, there was no significant difference after N-doping in TEM (Figure 1b for SAC and Figure 1d for SANC) images. From EDS elemental mapping in Figure 1e,f and Figure S1, it can be clearly seen that the N element was uniformly distributed among the carbon, indicating that N was successfully doped into the SAC material. It is generally believed that N-doping can influence electrochemical behavior and improve the conductivity of carbons [46]. Thus, SANC may have more advantages in energy storage and conversion.
Their amorphous nature was also concluded from XRD spectra (Figure 2a). All the XRD patterns showed a broad peak at 20–25°, presenting relatively low-degree graphitization [47]. In the Raman spectrum of SAC, there was a D-band at 1330 cm−1 (corresponding to defects of the carbon material) and a G-band at around 1580 cm−1 (corresponding to the graphite carbon structure) [48]. For SANC, after N-doping, it also exhibited similar peaks. However, the relative strength ratio (ID/IG) was changed. According to the calculated result, the ID/IG value of SANC (0.94) was larger than that of SAC (0.92), indicating that N-doping can increase the structural defects of carbon [49]. The chemical composition of the surface was further investigated by XPS (Figure 2c). For SAC, only C 1s and O 1s peaks with a content of 85.4% and 14.45% can be observed. As shown in Figures S2 and S3, the high-resolution C 1s spectrum of SAC material can be divided into four peaks at 284.6, 285.13, 286.24, and 289.01 eV, corresponding to C=C, C−C, C−O, and O−C=O, respectively. For the high-resolution O 1s spectrum of SAC, there were three peaks at 531.46 (C=O), 532.62 (C−O), and 533.31 eV (HO−C=O). After post N-doping by melamine, there was a clear N1s peak in the XPS of SANC with a content of 2.79%. The high-resolution C1s can be deconvoluted into five fitted peaks at 284.08, 284.68, 285.33, 286.48, and 288.78 eV, corresponding to the configurations of C=C, C−C, C=N, C−O, and O−C=O, respectively. The high-resolution N1s spectrum can be deconvoluted into three peaks at 398.90, 399.87, and 401.43 eV, corresponding to pyridinic nitrogen, pyrrolic nitrogen, and graphitic nitrogen, respectively. In SANC, the high-resolution O1s can be deconvoluted into four fitted peaks at 531.21, 532.19, 533.17, and 533.92 eV, respectively, corresponding to the configurations of C=O, C−OH, C−O, and O=C−OH. Oxygen was uniformly distributed in the carbon materials derived from Spartina alterniflora with a content of 14.45% for SAC and 12.94% for SANC, respectively. With the oxygen-containing groups, the amorphous structure of the carbons would maintain stability during the converted treatment [50].

2.2. Electrocatalytic Performance of SAC and SANC

The electrocatalytic activities of SAC and SANC were first evaluated in 0.1 M KOH solution with N2 or O2 saturation by cyclic voltammetry (CV) at a scan rate of 10 mV s−1. From the CV curves in Figure 3a,b, no distinct redox peaks were observed in the N2-saturated solution for SAC and SANC, while obvious cathodic peaks appeared in the O2-saturated solution. It can be seen in Figure 3c that the potential of the cathodic peak for SANC (0.6986 V vs. RHE) was slightly more positive than that of SAC (0.6926 V vs. RHE), demonstrating that SANC showed better catalytic activity. This was further confirmed by linear sweep voltammetry (LSV) measurements. As shown in Figure 3d–f, SANC exhibited a subtle positive half-wave potential (0.7156 V vs. RHE) compared to SAC (0.7116 V vs. RHE), along with a slightly higher limiting current value of 6.192 mA cm−2 under a rotation rate of 1600 rpm. The CV and LSV results suggest that N-doped carbon material SANC outperforms SAC in terms of electrocatalytic performance, emphasizing the advantage of N-doping in facilitating the oxygen reduction reaction.
Figure 4a,b show Koutecky–Levich (K-L) plots of SAC and SANC at various working potentials. Accordingly, per O2 molecule, the electron transfer number was calculated as 3.84 for SAC and 4.00 for SANC in Figure 4c, indicating a predominant four-electron transfer pathway in the ORR process. The Tafel slopes (Figure 4d) further supported these results, with values of 154 mV dec−1 for SAC and 100 mV dec−1 for SANC, indicating faster kinetics for SANC in the electrocatalytic ORR process [51]. Additionally, the electron transfer numbers and peroxide yields of the two catalysts were also determined using RRDE linear sweep voltammograms (Figure 4e), with SAC exhibiting an electron transfer number of 3.92 and SANC showing 3.96 (Figure S4). The H2O2 yields were calculated as 3.93% and 2.05% for SAC and SANC (Figure S5), respectively. In Figure S6, the cycling performance of SAC and SANC catalysts were compared by conducting chronoamperometry measurements. After continuous testing of 3000 s at 0.7 V vs. RHE, SANC remained at 72.7% of its original current density, whereas the current density of SAC only retained 65.5%. The results indicated that the SANC electrode had better stability toward the ORR than that of the SAC electrode. The improvement was attributed to the distributed active sites by N-doping, which can act as electron acceptors and facilitate electron transfer efficiency and conductivity [52,53].
Figure 4f shows electrochemical impedance spectroscopy (EIS) of SAC and SANC electrodes. The ion adsorption kinetics and charge transfer resistance (Rct) can be concluded by the high-frequency semicircles in the spectra [54]. SANC displayed a smaller semicircle, indicating faster ion adsorption kinetics and charge transfer compared to SAC, which was in accordance with the results of the Tafel plots. The Warburg length for SANC in the middle frequency indicated its faster ion diffusion and transportation [47] compared to SAC. According to the superior ORR electrocatalytic performance of SANC, it can effectively confirm the importance of N-doping and the excellent ORR electrocatalytic properties of carbon materials based on obsolete Spartina alterniflora.

3. Materials and Methods

3.1. Reagents and Materials

Spartina alterniflora was obtained from the east coast of China. Ethanol was purchased from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). Sodium hydroxide (NaOH), potassium hydroxide (KOH), and hydrochloric acid (HCl) were purchased from Beijing Chemical Reagent Co. Ltd. (Beijing, China). Melamine was purchased from Innochem (Beijing, China). Without further purification, all chemical reagents were used as received.

3.2. Material Synthesis

Firstly, the chopped Spartina alterniflora underwent thorough washing with distilled water and ethanol several times. After drying, a high-speed multifunctional grinder was employed to grind the Spartina alterniflora into powder. Subsequently, the powder was placed in a tube furnace and heated at 500 °C for 2 h under an Ar atmosphere. Then, the pre-carbonized product was combined with NaOH (mass ratio 1:1). The mixture was activated at 600 ℃, followed by neutralizing the pH with 0.1 mol L−1 HCl. The SAC material was successfully obtained after the filtration and drying process. For the preparation of its N-doped material SANC, the raw material Spartina alterniflora was initially pre-carbonized at 500 °C for 2 h. And then, melamine was mixed into the pre-carbonized carbon materials and carbonized to prepare SANC.

3.3. Characterization

An Empyrean diffractometer (Malvern Panalytical, Malvern, UK), utilizing CuKa radiation with an output power of 1.6 kW at a voltage of 40 kV, was employed to characterize X-ray diffraction (XRD) spectra. Raman spectra were measured using a Renishaw-2000 Raman spectrometer (Wotton-under-Edge, UK) equipped with an Ar laser at 473 nm. X-ray photoelectron spectroscopy (XPS) spectra were obtained using a Thermo Scientific ESCALab 250Xi apparatus (Boston, MA, USA) with 200 W monochromated AlKa radiation. Scanning electron microscopy (SEM) images and energy dispersive spectra (EDS) were captured using a Hitachi Model S-4800 field emission scanning electron microscope (Ibaraki, Japan). Transmission electron microscopy (TEM) images were acquired using a H-7700 electron microscope with an accelerating voltage of 100 kV.

3.4. Electrochemical Measurement

The oxygen reduction performance of the catalysts was tested using a CHI-760E Shanghai Chenhua Electrochemical Workstation (Shanghai, China), including cyclic voltammetry, linear sweep voltammetry, rotating ring disk electrode testing, and electrochemical impedance spectroscopy. CV and LSV were tested within a potential window of −1–0.2 V with a scan rate of 10 mV s−1 in 0.1 M KOH solution saturated with N2 or O2. EIS was measured at an open circuit voltage with frequencies ranging from 0.01 Hz–100 kHz with an amplitude of 5 mV. EIS was analyzed using Z-view software (Solartron Analytical, Farnborough, UK). The most popular method of after-the-scan compensation was used, and the experimental data were manually corrected with a solution resistance according to the electrochemical impedance spectroscopy.

4. Conclusions

In summary, carbon material SAC and its N-doped derivative SANC were successfully prepared via a simple activation process from the obsolete Spartina alterniflora. Benefiting from their abundant pore structures and defects, the carbon materials exhibited excellent electrocatalytic performance when utilized as metal-free catalysts for ORR. Impressively, after post N-doping by melamine as the nitrogen source, the uniformly distributed N active sites (pyridinic nitrogen, pyrrolic nitrogen, and graphitic nitrogen) in SANC effectively improved the charge transfer and ion diffusion/transport process, and contributed to the acceleration of the ORR. Thus, SANC possessed a half-wave potential of 0.716 V vs. RHE and a four-electron transfer pathway with a H2O2 yield of only 2.05% with faster kinetics. This work offers a cost-effective solution for addressing the ecological damage caused by Spartina alterniflora and creates high economic values through the utilization of obsolete biomass.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal14090555/s1, Figure S1: Oxygen elemental mapping of SANC material. Figure S2: High-resolution C 1 s XPS spectrum of SAC. Figure S3: High-resolution O 1 s XPS spectrum of SAC. Figure S4: Electron transfer number of SAC and SANC from RRDE voltammograms. Figure S5: H2O2 yield calculated from the RRDE for SAC and SANC catalysts. Figure S6: Chronoamperometric response for SAC and SANC in O2-saturated 0.1 M KOH aqueous solution. Table S1: Reported carbon electrocatalysts for ORR. Refs. [55,56,57,58] are cited in Supplementary Materials.

Author Contributions

Conceptualization, H.S. and X.L.; methodology, X.H. and H.S.; software, X.H.; validation, X.H., Y.Z., L.G., and H.L.; formal analysis, X.H., Y.Z., L.G., and H.L.; investigation, X.H., Y.Z., L.G., and H.L.; resources, X.H., Y.Z., L.G., and H.L.; data curation, X.H., Y.Z., L.G., and H.L.; writing—original draft preparation, X.H. and H.S.; writing—review and editing, H.S. and X.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China, grant number 22001240. Beijing Young Elite Scientist Sponsorship Program by Bast and the large instruments and equipment sharing platform of China University of Geosciences (Beijing) are gratefully acknowledged.

Data Availability Statement

The data presented in this study are available upon request from the corresponding authors.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Omer, A.M. Energy, environment and sustainable development. Renew. Sustain. Energy Rev. 2008, 12, 2265–2300. [Google Scholar] [CrossRef]
  2. Bose, B.K. Global warming: Energy, environmental pollution, and the impact of power electronics. IEEE Ind. Electron. Mag. 2010, 4, 6–17. [Google Scholar] [CrossRef]
  3. Zhang, C.; Yang, Y.; Liu, X.; Mao, M.; Li, K.; Li, Q.; Zhang, G.; Wang, C. Mobile energy storage technologies for boosting carbon neutrality. Innovation 2023, 4, 100518. [Google Scholar] [CrossRef]
  4. Chen, S.; Tao, R.; Guo, C.; Zhang, W.; Liu, X.; Yang, G.; Guo, P.; Sun, G.; Liang, J.; Lu, S. A new trick for an old technology: Ion exchange syntheses of advanced energy storage and conversion nanomaterials. Energy Storage Mater. 2021, 41, 758–790. [Google Scholar] [CrossRef]
  5. Amiri, A.; Shahbazian-Yassar, R. Recent progress of high-entropy materials for energy storage and conversion. J. Mater. Chem. A 2020, 9, 782–823. [Google Scholar] [CrossRef]
  6. Boudghene Stambouli, A.; Traversa, E. Fuel cells, an alternative to standard sources of energy. Renew. Sustain. Energy Rev. 2002, 6, 295–304. [Google Scholar] [CrossRef]
  7. Abdelkareem, M.A.; Elsaid, K.; Wilberforce, T.; Kamil, M.; Sayed, E.T.; Olabi, A. Environmental aspects of fuel cells: A review. Sci. Total Environ. 2020, 752, 141803. [Google Scholar] [CrossRef] [PubMed]
  8. Zhao, W.; Xu, G.; Dong, W.; Zhang, Y.; Zhao, Z.; Qiu, L.; Dong, J. Progress and perspective for in situ studies of oxygen reduction reaction in proton exchange membrane fuel cells. Adv. Sci. 2023, 10, 2300550. [Google Scholar] [CrossRef]
  9. Dey, S.; Mondal, B.; Chatterjee, S.; Rana, A.; Amanullah, S.; Dey, A. Molecular electrocatalysts for the oxygen reduction reaction. Nat. Rev. Chem. 2017, 0098, 2397–3358. [Google Scholar] [CrossRef]
  10. Luo, X.; Wu, W.; Wang, Y.; Li, Y.; Ye, J.; Wang, H.; Jiang, Q.; Zhou, Z.; Li, Y.C.; Wang, Y.; et al. Relay catalysis of multi-sites promotes oxygen reduction reaction. Adv. Funct. Mater. 2023, 33, 2215021. [Google Scholar] [CrossRef]
  11. Zhang, X.; Xu, Y.; Liu, Y.; Wei, Y.; Lan, F.; Wang, J.; Liu, X.; Wang, R.; Yang, Y.; Chen, J. Improving oxygen reduction reaction by cobalt iron-layered double hydroxide layer on nickel-metal organic framework as cathode catalyst in microbial fuel cell. Bioresour. Technol. 2023, 392, 130011. [Google Scholar] [CrossRef] [PubMed]
  12. Liu, M.; Liu, S.; Cui, C.; Miao, Q.; He, Y.; Li, X.; Xu, Q.; Zeng, G. Construction of catalytic covalent organic frameworks with redox-active sites for the oxygen reduction and the oxygen evolution reaction. Angew. Chem. Int. Ed. 2022, 61, e202213522. [Google Scholar] [CrossRef]
  13. Huang, L.; Wei, M.; Qi, R.; Dong, C.; Dang, D.; Yang, C.; Xia, C.; Chen, C.; Zaman, S.; Li, F.; et al. An integrated platinum-nanocarbon electrocatalyst for efficient oxygen reduction. Nat. Commun. 2022, 13, 6703. [Google Scholar] [CrossRef]
  14. Tian, X.L.; Xu, Y.Y.; Zhang, W.; Wu, T.; Xia, B.Y.; Wang, X. Unsupported platinum-based electrocatalysts for oxygen reduction reaction. ACS Energy Lett. 2017, 2, 2035–2043. [Google Scholar] [CrossRef]
  15. Liu, J.; Jiao, M.; Lu, L.; Barkholtz, H.M.; Li, Y.; Wang, Y.; Jiang, L.; Wu, Z.; Liu, D.; Zhuang, L.; et al. High performance platinum single atom electrocatalyst for oxygen reduction reaction. Nat. Commun. 2017, 8, 15938. [Google Scholar] [CrossRef]
  16. Sivaraman, R.; Opulencia, M.J.C.; Majdi, A.; Patra, I.; Kadhem Abid, M.; Hammid, A.T.; Derakhshandeh, M. Design a promising non-precious electro-catalyst for oxygen reduction reaction in fuel cells. Int. J. Hydrogen Energy 2022, 48, 6308–6316. [Google Scholar] [CrossRef]
  17. Friedman, A.; Mizrahi, M.; Levy, N.; Zion, N.; Zachman, M.; Elbaz, L. Application of molecular catalysts for the oxygen reduction reaction in alkaline fuel cells. ACS Appl. Mater. Interfaces 2021, 13, 58532–58538. [Google Scholar] [CrossRef] [PubMed]
  18. Shimizu, K.; Sepunaru, L.; Compton, R.G. Innovative catalyst design for the oxygen reduction reaction for fuel cells. Chem. Sci. 2016, 7, 3364–3369. [Google Scholar] [CrossRef]
  19. Xiang, Q.; Yin, W.; Liu, Y.; Yu, D.; Wang, X.; Li, S.; Chen, C. A study of defect-rich carbon spheres as a metal-free electrocatalyst for an efficient oxygen reduction reaction. J. Mater. Chem. A 2017, 5, 24314–24320. [Google Scholar] [CrossRef]
  20. Long, X.; Li, D.; Wang, B.; Jiang, Z.; Xu, W.; Wang, B.; Yang, D.; Xia, Y. Heterocyclization strategy for construction of linear conjugated polymers: Efficient metal-free electrocatalysts for oxygen reduction. Angew. Chem. Int. Ed. 2019, 58, 11369–11373. [Google Scholar] [CrossRef]
  21. Hu, C.; Paul, R.; Dai, Q.; Dai, L. Carbon-based metal-free electrocatalysts: From oxygen reduction to multifunctional electrocatalysis. Chem. Soc. Rev. 2021, 50, 11785–11843. [Google Scholar] [CrossRef]
  22. Fu, A.; Xiao-qing, B.; Xiao-yang, D.; Zi-zai, M.; Xiao-guang, W. Carbon-based metal-free oxygen reduction reaction electrocatalysts: Past, present and future. New Carbon Mater. 2022, 37, 338–354. [Google Scholar]
  23. Ren, G.; Chen, S.; Zhang, J.; Zhang, N.; Jiao, C.; Qiu, H.; Liu, C.; Wang, H. N-doped porous carbon spheres as metal-free electrocatalyst for oxygen reduction reaction. J. Mater. Chem. A 2021, 9, 5751–5758. [Google Scholar] [CrossRef]
  24. Oh, J.; Park, S.; Jang, D.; Shin, Y.; Lim, D.; Park, S. Metal-free N-doped carbon blacks as excellent electrocatalysts for oxygen reduction reactions. Carbon 2019, 145, 481–487. [Google Scholar] [CrossRef]
  25. Ma, Z.H.; Han, Y.; Wang, X.; Sun, G.W.; Li, Y. Lignin-derived hierarchical porous flower-like carbon nanosheets decorated with biomass carbon quantum dots for efficient oxygen reduction. Colloids Surf. A 2022, 652, 129818. [Google Scholar] [CrossRef]
  26. Wang, M.; Chen, Y.; Zhao, S.S.; Zhao, C.K.; Wang, G.X.; Wu, M.B. Nitrogen-doped hierarchical porous carbons derived from biomass for oxygen reduction reaction. Front. Chem. 2023, 11, 1218451. [Google Scholar] [CrossRef] [PubMed]
  27. Zhang, S.; Jiang, S.; Huang, B.; Shen, X.; Chen, W.; Zhou, T.; Cheng, H.; Cheng, B.; Wu, C.; Li, W.; et al. Sustainable production of value-added carbon nanomaterials from biomass pyrolysis. Nat. Sustain. 2020, 3, 753–760. [Google Scholar] [CrossRef]
  28. Hu, X.; Nango, K.; Bao, L.; Li, T.; Hasan, M.D.M.; Li, C. High yields of solid carbonaceous materials from biomass. Green Chem. 2019, 21, 1128–1140. [Google Scholar] [CrossRef]
  29. Srivastava, R.K.; Shetti, N.P.; Reddy, K.R.; Kwon, E.E.; Nadagouda, M.N.; Aminabhavi, T.M. Biomass utilization and production of biofuels from carbon neutral materials. Environ. Pollut. 2021, 276, 116731. [Google Scholar] [CrossRef]
  30. Yuancheng, H.; Zheng, T.; Siyu, Z.; Hong, W.; Yougen, T.; Dan, S.; Haiyan, W. Renewable waste biomass-derived carbon materials for energy storage. J. Phys. D Appl. Phys. 2022, 55, 1250834. [Google Scholar]
  31. Elyasi, S.; Saha, S.; Hameed, N.; Mahon, P.J.; Juodkazis, S.; Salim, N. Emerging trends in biomass-derived porous carbon materials for hydrogen storage. Int. J. Hydrogen Energy 2024, 62, 272–306. [Google Scholar] [CrossRef]
  32. Wang, X.; Yan, D.; Liu, L.; Xu, K.; Zhong, J. Biomass-derived activated carbon nanoarchitectonics with hibiscus flowers for high-performance supercapacitor electrode applications. Chem. Eng. Technol. 2022, 45, 649–657. [Google Scholar]
  33. Zheng, L.; Chen, M.; Liang, S.; Lü, Q. Oxygen-rich hierarchical porous carbon derived from biomass waste-kapok flower for supercapacitor electrode. Diam. Relat. Mater. 2021, 113, 108267. [Google Scholar] [CrossRef]
  34. Nagaraj, M.; Sadhasivam, T.; Sol, B.S.; Athibala, M.; Yu, R.C.; Tae, H.O.; Yoong, A.K. N-doped defect-rich porous carbon nanosheets framework from renewable biomass as efficient metal-free bifunctional electrocatalysts for HER and OER application. Renew. Energy 2023, 222, 119801. [Google Scholar]
  35. Zhao, J.; Wu, W.; Jia, X.; Xia, T.; Li, Q.; Zhang, J.; Wang, Q.; Zhang, W.; Lu, C. High-value utilization of biomass waste: From garbage floating on the ocean to high-performance rechargeable Zn–MnO2 batteries with superior safety. J. Mater. Chem. A 2020, 8, 18198–18206. [Google Scholar] [CrossRef]
  36. Rybarczyk, M.K.; Peng, H.; Tang, C.; Lieder, M.; Zhang, Q.; Titirici, M. Porous carbon derived from rice husks as sustainable bioresources: Insights into the role of micro-/mesoporous hierarchy in hosting active species for lithium-sulphur batteries. Green Chem. 2016, 18, 5169–5179. [Google Scholar] [CrossRef]
  37. Deli, L.; Qidong, Y.; Zhe, C.; Fengtian, Z.; Chen, L.; Sheng, H. High-efficiency phenol removal by novel biomass-based alginate composite hydrogel. Chem. Phys. Lett. 2023, 826, 140676. [Google Scholar]
  38. Susanto, S.; Nurtono, T.; Widiyastuti, W.; Yeh, M.H.; Setyawan, H. Controlling N-doping nature at carbon aerogels from biomass for enhanced oxygen reduction in seawater batteries. ACS Omega 2024, 9, 13994–14004. [Google Scholar] [CrossRef]
  39. Patten, K.; O’Casey, C.; Metzger, C. Large-scale chemical control of smooth cordgrass (spartina alterniflora) in Willapa Bay, WA: Towards eradication and ecological restoration. Invasive Plant Sci. Manag. 2017, 10, 284–292. [Google Scholar] [CrossRef]
  40. Zhao, Z.; Xu, Y.; Yuan, L.; Li, W.; Zhu, X.; Zhang, L. Emergency control of spartina alterniflora re-invasion with a chemical method in Chongming Dongtan, China. Water Sci. Eng. 2020, 13, 24–33. [Google Scholar] [CrossRef]
  41. Qiu, Z.Q.; Mao, D.H.; Feng, K.D.; Wang, M.; Xiang, H.X.; Wang, Z.M. High-Resolution Mapping Changes in the Invasion of Spartina Alterniflora in the Yellow River Delta. IEEE J. Sel. Top. Appl. Earth Obs. Remote Sens. 2022, 15, 6445–6455. [Google Scholar] [CrossRef]
  42. Cheng, H.; Tang, Z.; Luo, X.; Zheng, Z. Spartina alterniflora-derived porous carbon using as anode material for sodium-ion battery. Sci. Total Environ. 2021, 777, 146120. [Google Scholar] [CrossRef]
  43. Wang, S.T.; Chen, Y.; Zhao, Y.L.; Wei, G.Y.; Li, D.L.; Liu, X.P. Mesopore-dominated N, S co-doped carbon as advanced oxygen reduction reaction electrocatalysts for Zn-air battery. J. Mater. Sci. 2022, 57, 19431–19446. [Google Scholar] [CrossRef]
  44. Zhan, Y.; Yu, X.; Cao, L.; Zhang, B.; Wu, X.; Xie, F.; Zhang, W.; Chen, J.; Xie, W.; Mai, W.; et al. The influence of nitrogen source and doping sequence on the electrocatalytic activity for oxygen reduction reaction of nitrogen doped carbon materials. Int. J. Hydrogen Energy 2016, 41, 13493–13503. [Google Scholar] [CrossRef]
  45. Dong, X.; Huayang, Y.; Heng, L.; Peng, H.; Qun, L.; Yuanpeng, W. Carbon-based and carbon-supported nanomaterials for the catalytic conversion of biomass: A review. Environ. Chem. Lett. 2022, 20, 1719–1744. [Google Scholar]
  46. Zhou, X.; Wang, P.; Zhang, Y.; Wang, L.; Zhang, L.; Zhang, L.; Xu, L.; Liu, L. Biomass based nitrogen-doped structure-tunable versatile porous carbon materials. J. Mater. Chem. A 2017, 25, 12958–12968. [Google Scholar] [CrossRef]
  47. Sunwen, X.; Wenhan, G.; Ning, C.; Lin, S.; Hewen, Z.; Wang, L.; Xu, C.; Jian, Z.; Yingquan, C.; Haiping, Y.; et al. Synthesis and application in oxygen reduction reaction of N-doping porous graphitic carbon from biomass waste. Fuel Process. Technol. 2021, 224, 107028. [Google Scholar]
  48. Zhang, P.; Fan, J.; Wang, Y.; Dang, Y.; Heumann, S.; Ding, Y. Insights into the role of defects on the Raman spectroscopy of carbon nanotube and biomass-derived carbon. Carbon 2024, 222, 118998. [Google Scholar] [CrossRef]
  49. Jiang, L.; van Dijk, B.; Wu, L.; Maheu, C.; Hofmann, J.P.; Tudor, V.; Koper, M.T.M.; Hetterscheid, D.G.H.; Schneider, G.F. Predoped oxygenated defects activate nitrogen-doped graphene for the oxygen reduction reaction. ACS Catal. 2021, 12, 173–182. [Google Scholar] [CrossRef]
  50. Quan, H.; Fan, X.; Wang, W.; Gao, W.; Dong, Y.; Chen, D. Hierarchically porous carbon derived from biomass: Effect of mesopore and heteroatom-doping on electrochemical performance. Appl. Surf. Sci. 2018, 460, 8–16. [Google Scholar] [CrossRef]
  51. Cao, Y.; Sun, Y.; Zheng, R.; Wang, Q.; Li, X.; Wei, H.; Wang, L.; Li, Z.; Wang, F.; Han, N. Biomass-derived carbon material as efficient electrocatalysts for the oxygen reduction reaction. Biomass Bioenergy 2022, 168, 106676. [Google Scholar] [CrossRef]
  52. Wei, W.; Ge, H.; Huang, L.; Kuang, M.; Al-Enizi, A.M.; Zhang, L.; Zheng, G. Hierarchically tubular nitrogen-doped carbon structures for the oxygen reduction reaction. J. Mater. Chem. A 2017, 5, 13634–13638. [Google Scholar] [CrossRef]
  53. Quílez-Bermejo, J.; Pérez-Rodríguez, S.; Torres, D.; Canevesi, R.; Morallón, E.; Cazorla-Amorós, D.; Celzard, A.; Fierro, V. Nitrogen sites prevail over textural properties in N-doped carbons for the oxygen reduction reaction. J. Colloid Interface Sci. 2023, 654, 446–453. [Google Scholar] [CrossRef] [PubMed]
  54. Fernandes, D.M.; Mestre, A.S.; Martins, A.; Nunes, N.; Carvalho, A.P.; Freire, C. Biomass-derived nanoporous carbons as electrocatalysts for oxygen reduction reaction. Catal. Today 2019, 357, 269–278. [Google Scholar] [CrossRef]
  55. Liu, W.T.; Wu, X. Ligin-derived graphene-like ultrathin carbon materials for ORR catalysis. J. Phys. Conf. Ser. 2024, 2749, 012003. [Google Scholar] [CrossRef]
  56. Girimonte, A.; Stefani, A.; Mucci, C.; Giovanardi, R.; Marchetti, A.; Innocenti, M.; Fontanesi, C. Electrochemical performance of metal-free carbon-based catalysts from different hydrothermal carbonization treatments for oxygen reduction reaction. Nanomaterials 2024, 14, 173. [Google Scholar] [CrossRef]
  57. Zhang, W.Z.; Dijk, B.V.; Wu, L.F.; Maheu, C.; Tudor, V.; Hofmann, J.P.; Jiang, L.; Hetterscheid, D.; Schneider, G.F. Role of vacancy defects and nitrogen dopants for the reduction of oxygen on graphene. ACS Catal. 2024, 14, 11065–11075. [Google Scholar] [CrossRef]
  58. Yang, Z.; Gao, Y.; Zuo, L.L.; Long, C.; Yang, C.Y.; Zhang, X.F. Tailoring heteroatoms in conjugated microporous polymers for boosting oxygen electrochemical reduction to hydrogen peroxide. ACS Catal. 2023, 13, 4790–4798. [Google Scholar] [CrossRef]
Catalysts 14 00555 sch001
Scheme 1. Schematic diagram of the synthesis of SAC carbon material.
Scheme 1. Schematic diagram of the synthesis of SAC carbon material.
Catalysts 14 00555 sch001
Catalysts 14 00555 g001
Figure 1. (a,b) SEM and TEM images of SAC; (c,d) SEM and TEM images of SANC; (e,f) elemental mapping of SANC.
Figure 1. (a,b) SEM and TEM images of SAC; (c,d) SEM and TEM images of SANC; (e,f) elemental mapping of SANC.
Catalysts 14 00555 g001
Catalysts 14 00555 g002
Figure 2. (a) XRD of SAC and SANC; (b) Raman spectra of SAC and SANC; (c) XPS spectra of SAC and SANC; (d–f) high-resolution C 1 s, N1s, and O 1 s spectra of SANC.
Figure 2. (a) XRD of SAC and SANC; (b) Raman spectra of SAC and SANC; (c) XPS spectra of SAC and SANC; (d–f) high-resolution C 1 s, N1s, and O 1 s spectra of SANC.
Catalysts 14 00555 g002
Catalysts 14 00555 g003
Figure 3. (a,b) CV curves of SAC and SANC in 0.1 M KOH electrolyte with N2 and O2 saturation at a scanning rate of 10 mV s−1; (c) comparison of CV curves for SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at a scanning rate of 10 mV s−1; (d,e) LSV curves of SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at different rotation rates from 400 to 1600 rpm; (f) comparison of LSV curves for SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at 1600 rpm.
Figure 3. (a,b) CV curves of SAC and SANC in 0.1 M KOH electrolyte with N2 and O2 saturation at a scanning rate of 10 mV s−1; (c) comparison of CV curves for SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at a scanning rate of 10 mV s−1; (d,e) LSV curves of SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at different rotation rates from 400 to 1600 rpm; (f) comparison of LSV curves for SAC and SANC in 0.1 M KOH electrolyte with O2 saturation at 1600 rpm.
Catalysts 14 00555 g003
Catalysts 14 00555 g004
Figure 4. (a,b) Koutecky−Levich plots of SAC and SANC under different applied potentials; (c) electron transfer numbers of SAC and SANC; (d) Tafel slope diagrams of SAC and SANC; (e) RRDE voltammograms for SAC and SANC with O2-saturated 0.1 M KOH solution at 1600 rpm at a scanning rate of 10 mV s−1; (f) electrochemical impedance spectra of SAC and SANC.
Figure 4. (a,b) Koutecky−Levich plots of SAC and SANC under different applied potentials; (c) electron transfer numbers of SAC and SANC; (d) Tafel slope diagrams of SAC and SANC; (e) RRDE voltammograms for SAC and SANC with O2-saturated 0.1 M KOH solution at 1600 rpm at a scanning rate of 10 mV s−1; (f) electrochemical impedance spectra of SAC and SANC.
Catalysts 14 00555 g004
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Hao, X.; Zhou, Y.; Guo, L.; Li, H.; Shang, H.; Liu, X. Spartina alterniflora-Derived Carbons for High-Performance Oxygen Reduction Reaction (ORR) Catalysts. Catalysts 2024, 14, 555. https://doi.org/10.3390/catal14090555

AMA Style

Hao X, Zhou Y, Guo L, Li H, Shang H, Liu X. Spartina alterniflora-Derived Carbons for High-Performance Oxygen Reduction Reaction (ORR) Catalysts. Catalysts. 2024; 14(9):555. https://doi.org/10.3390/catal14090555

Chicago/Turabian Style

Hao, Xinmeng, Yougui Zhou, Lihua Guo, Huipeng Li, Hong Shang, and Xuanhe Liu. 2024. "Spartina alterniflora-Derived Carbons for High-Performance Oxygen Reduction Reaction (ORR) Catalysts" Catalysts 14, no. 9: 555. https://doi.org/10.3390/catal14090555

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop