Self-nitrogen-doped carbon materials derived from the petioles and blades of apricot leaves as metal-free catalysts for selective oxidation of aromatic alkanes

Abstract

Carbon materials with tailorable structures and superior properties have great potential applications in environmental protection, energy conversion, and catalysis. Plant biomass as abundant and green non-toxic raw materials has been considered as good precursors for synthesizing heteroatom-doped carbon materials. However, few studies have been reported on the different natures of carbon materials derived from different parts of the same plant biomass. In this study, we prepared carbon materials from the petioles and blades of apricot leaves by direct pyrolysis without additives. Detailed characterizations indicate that these two carbon materials are similar in element composition and graphitization degree, but differ greatly in surface area and pore volume. These differences can be attributed to the different contents of inorganic salts, vascular bundles, and proteins in petioles and blades. When used as catalysts for the oxidation of ethylbenzene, the petiole-derived carbon shows better catalytic performance than the blades derived carbon due to its high surface area, large average pore size, and doped nitrogen atoms. Furthermore, the carbon catalysts derived from the petioles and blades of poplar leaves and parasol tree leaves show the same difference in catalytic reaction, implying that the above-mentioned conclusion is rather universal, which can provide reference for the synthesis of carbon materials from leaves.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. 1.

    Liu J, Wickramaratne NP, Qiao SZ, Jaroniec M (2015) Molecular-based design and emerging applications of nanoporous carbon spheres. Nat Mater 14:763–774

    CAS  Google Scholar 

  2. 2.

    Liu TY, Zhang F, Song Y, Li Y (2017) Revitalizing carbon supercapacitor electrodes with hierarchical porous structures. J Mate Chem A 5:17705–17733

    CAS  Google Scholar 

  3. 3.

    Tang L, Liu YI, Wang JJ, Zeng GM, Deng YC, Dong HR, Feng HP, Wang JJ, Peng B (2018) Enhanced activation process of persulfate by mesoporous carbon for degradation of aqueous organic pollutants: electron transfer mechanism. Appl Catal B Environ 231:1–10

    CAS  Google Scholar 

  4. 4.

    Su DS, Wen GD, Wu SC, Peng F, Schlogl R (2017) Carbocatalysis in liquid-phase reactions. Angew Chem Int Ed 56:936–964

    CAS  Google Scholar 

  5. 5.

    Chen B, Wang LY, Dai W, Shang SS, Lv Y, Gao S (2015) Metal-free and solvent-free oxidative coupling of amines to imines with mesoporous carbon from macrocyclic compounds. ACS Catal 5:2788–2794

    CAS  Google Scholar 

  6. 6.

    Ma WJ, Wang N, Tong TZ, Zhang LJ, Lin KYA, Han XJ, Du YC (2018) Nitrogen, phosphorus, and sulfur tri-doped hollow carbon shells derived from ZIF-67@poly (cyclotriphosphazene-co-4,4′-sulfonyldiphenol) as a robust catalyst of peroxymonosulfate activation for degradation of bisphenol A. Carbon 137:291–303

    CAS  Google Scholar 

  7. 7.

    Li MM, Xu F, Li HR, Wang Y (2016) Nitrogen-doped porous carbon materials: promising catalysts or catalyst supports for heterogeneous hydrogenation and oxidation. Catal Sci Technol 6:3670–3693

    CAS  Google Scholar 

  8. 8.

    Hu CG, Dai LM (2019) Doping of carbon materials for metal-free electrocatalysis. Adv Mater 31:1804672

    Google Scholar 

  9. 9.

    Yang ZZ, Liu ZH, Zhang HY, Yu B, Zhao YF, Wang H, Ji GP, Chen Y, Liu XW, Liu ZM (2017) N-Doped porous carbon nanotubes: synthesis and application in catalysis. Chem Commun 53:929–932

    CAS  Google Scholar 

  10. 10.

    Xu ZX, Zhuang XD, Yang CQ, Cao J, Yao ZQ, Tang YP, Jiang JZ, Wu DQ, Feng XL (2016) Nitrogen-doped porous carbon superstructures derived from hierarchical assembly of polyimide nanosheets. Adv Mater 28:1981–1987

    CAS  Google Scholar 

  11. 11.

    Wang X, Li YW (2016) Nanoporous carbons derived from MOFs as metal-free catalysts for selective aerobic oxidations. J Mater Chem A 4:5247–5257

    CAS  Google Scholar 

  12. 12.

    Srinivas G, Krungleviciute V, Guo ZX, Yildirim T (2014) Exceptional CO2 capture in a hierarchically porous carbon with simultaneous high surface area and pore volume. Energy Environ Sci 7:335–342

    CAS  Google Scholar 

  13. 13.

    Titirici MM, Antonietti M (2010) Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization. Chem Soc Rev 39:103–116

    CAS  Google Scholar 

  14. 14.

    Dutta S, Bhaumik A, Wu KCW (2014) Hierarchically porous carbon derived from polymers and biomass: effect of interconnected pores on energy applications. Energy Environ Sci 7:3574–3592

    CAS  Google Scholar 

  15. 15.

    Li YJ, Wang GL, Wei T, Fan ZJ, Yan P (2016) Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors. Nano Energy 19:165–175

    CAS  Google Scholar 

  16. 16.

    Wang ZH, Shen DK, Wu CF, Gu S (2018) State-of-the-art on the production and application of carbon nanomaterials from biomass. Green Chem 20:5031–5057

    CAS  Google Scholar 

  17. 17.

    White RJ, Budarin V, Luque R, Clark JH, Macquarrie DJ (2009) Tuneable porous carbonaceous materials from renewable resources. Chem Soc Rev 38:3401–3418

    CAS  Google Scholar 

  18. 18.

    Jiang SF, Ling LL, Chen WJ, Liu WJ, Li DC, Jiang H (2019) High efficient removal of bisphenol A in a peroxymonosulfate/iron functionalized biochar system: mechanistic elucidation and quantification of the contributors. Chem Eng J 359:572–583

    CAS  Google Scholar 

  19. 19.

    Zhao L, Baccile N, Gross S, Zhang YJ, Wei W, Sun YH, Antonietti M, Titirici MM (2010) Sustainable nitrogen-doped carbonaceous materials from biomass derivatives. Carbon 48:3778–3787

    CAS  Google Scholar 

  20. 20.

    Patel MA, Luo FX, Khoshi MR, Rabie E, Zhang Q, Flach CR, Mendelsohn R, Garfunkel E, Szostak M, He HX (2016) P-doped porous carbon as metal free catalysts for selective aerobic oxidation with an unexpected mechanism. ACS Nano 10:2305–2315

    CAS  Google Scholar 

  21. 21.

    Gao SY, Wei XJ, Fan H, Li LY, Geng KR, Wang JJ (2015) Nitrogen-doped carbon shell structure derived from natural leaves as a potential catalyst for oxygen reduction reaction. Nano Energy 13:518–526

    CAS  Google Scholar 

  22. 22.

    Biswal M, Banerjee A, Deo M, Ogale S (2013) From dead leaves to high energy density supercapacitors. Energy Environ Sci 6:1249–1259

    CAS  Google Scholar 

  23. 23.

    Gao SY, Geng KR, Liu HY, Wei XJ, Zhang M, Wang P, Wang JJ (2015) Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction. Energy Environ Sci 8:221–229

    CAS  Google Scholar 

  24. 24.

    Desclos-Theveniau M, Coquet L, Jouenne T, Etienne P (2015) Proteomic analysis of residual proteins in blades and petioles of fallen leaves of Brassica napus. Plant Biol 17:408–418

    CAS  Google Scholar 

  25. 25.

    Schreiner RP, Scagel CF (2017) Leaf blade versus petiole nutrient tests as predictors of nitrogen, phosphorus, and potassium status of ‘pinot noir’ grapevines. HortScience 52:174–184

    CAS  Google Scholar 

  26. 26.

    Srivastava RP, Dixit P, Singh L, Verma PC, Saxena G (2018) Comparative morphological and anatomical studies of leaves, stem, and roots of Selinum vaginatum C. B. Clarke and Selinum tenuifolium Wall. Flora 248:54–60

    Google Scholar 

  27. 27.

    Sun YB, Liu K, Hou C, Liu J, Huang RK, Cao CY, Song WG (2019) Nitrogen, sulfur co-doped carbon materials derived from the leaf, stem and root of amaranth as metal-free catalysts for selective oxidation of aromatic hydrocarbons. Chemcatchem 11:1010–1016

    CAS  Google Scholar 

  28. 28.

    Gong YN, Li DL, Luo CZ, Fu Q, Pan CX (2017) Highly porous graphitic biomass carbon as advanced electrode materials for supercapacitors. Green Chem 19:4132–4140

    CAS  Google Scholar 

  29. 29.

    Zhou X, Wang PL, Zhang YG, Zhang XM, Jiang YF (2016) From waste cotton linter: a renewable environment-friendly biomass based carbon fibers preparation. ACS Sustain Chem Eng 4:5585–5593

    CAS  Google Scholar 

  30. 30.

    Li TF, Luo G, Liu KH, Li X, Sun DM, Xu L, Li YF, Tang YW (2018) Encapsulation of Ni3Fe nanoparticles in n-doped carbon nanotube-grafted carbon nanofibers as high-efficiency hydrogen evolution electrocatalysts. Adv Funct Mater 28:1805828

    Google Scholar 

  31. 31.

    Yuan Y, Ding YJ, Wang CH, Xu F, Lin ZS, Qin YY, Li Y, Yang ML, He XD, Peng QY, Li YB (2016) Multifunctional stiff carbon foam derived from bread. ACS Appl Mater Interfaces 8:16852–16861

    CAS  Google Scholar 

  32. 32.

    Wang YM, Lin XJ, Liu T, Chen H, Chen S, Jiang ZJ, Liu J, Huang JL, Liu ML (2018) Wood-derived hierarchically porous electrodes for high-performance all-solid-state supercapacitors. Adv Funct Mater 28:1806207

    Google Scholar 

  33. 33.

    Lei W, Deng YP, Li GR, Cano ZP, Wang XL, Luo D, Liu YS, Wang DL, Chen ZW (2018) Two-dimensional phosphorus-doped carbon nanosheets with tunable porosity for oxygen reactions in zinc-air batteries. ACS Catal 8:2464–2472

    CAS  Google Scholar 

  34. 34.

    Wang QC, Ji YJ, Lei YP, Wang YB, Wang YD, Li YY, Wang SY (2018) Pyridinic-N-dominated doped defective graphene as a superior oxygen electrocatalyst for ultrahigh-energy-density zn-air batteries. ACS Energy Lett 3:1183–1191

    CAS  Google Scholar 

  35. 35.

    Bian HY, Gao Y, Yang YQ, Fang GG, Dai HQ (2018) Improving cellulose nanofibrillation of waste wheat straw using the combined methods of prewashing, p-toluenesulfonic acid hydrolysis, disk grinding, and endoglucanase post-treatment. Bioresour Technol 256:321–327

    CAS  Google Scholar 

  36. 36.

    Wang Y, Jin X, Pan Y, Li JM, Guo NN, Wang RW (2018) Facile conversion of radish to nitrogen-doped mesoporous carbon as effective metal-free oxygen reduction electrocatalysts. Chemnanomat 4:954–963

    CAS  Google Scholar 

  37. 37.

    Wang XL, Xiang Q, He B, Nie J, Yin W, Fa HB, Chen CG (2018) A promising graphitic N-dominated porous carbon catalyst derived from lotus leaves for oxygen reduction reaction. Ionics 24:3601–3609

    CAS  Google Scholar 

  38. 38.

    Qian WJ, Sun FX, Xu YH, Qiu LH, Liu CH, Wang SD, Yan F (2014) Human hair-derived carbon flakes for electrochemical supercapacitors. Energy Environ Sci 7:379–386

    CAS  Google Scholar 

  39. 39.

    Zhang JA, Song Y, Kopec M, Lee J, Wang ZY, Liu SY, Yan JJ, Yuan R, Kowalewski T, Bockstaller MR, Matyjaszewski K (2017) Facile aqueous route to nitrogen-doped mesoporous carbons. J Am Chem Soc 139:12931–12934

    CAS  Google Scholar 

  40. 40.

    Zhao R, Xia W, Lin C, Sun JL, Mahmood A, Wang QF, Qiu B, Tabassum H, Zou RQ (2017) A pore-expansion strategy to synthesize hierarchically porous carbon derived from metal-organic framework for enhanced oxygen reduction. Carbon 114:284–290

    CAS  Google Scholar 

  41. 41.

    Wen GD, Wu SC, Li B, Dai CL, Su DS (2015) Active sites and mechanisms for direct oxidation of benzene to phenol over carbon catalysts. Angew Chem Int Ed 54:4105–4109

    CAS  Google Scholar 

  42. 42.

    Prati L, Bergna D, Villa A, Spontoni P, Bianchi CL, Hu T, Romar H, Lassi U (2018) Carbons from second generation biomass as sustainable supports for catalytic systems. Catal Today 301:239–243

    CAS  Google Scholar 

  43. 43.

    Li XH, Wang XC, Antonietti M (2012) Solvent-free and metal-free oxidation of toluene using O2 and g-C3N4 with nanopores: nanostructure boosts the catalytic selectivity. ACS Catal 2:2082–2086

    CAS  Google Scholar 

  44. 44.

    Wu ZY, Xu SL, Yan QQ, Chen ZQ, Ding YW, Li C, Liang HW, Yu SH (2018) Transition metal-assisted carbonization of small organic molecules toward functional carbon materials. Sci Adv 4:eaat0788

    CAS  Google Scholar 

  45. 45.

    Huang RK, Cao CY, Liu J, Sun DP, Song WG (2019) N-Doped carbon nanofibers derived from bacterial cellulose as an excellent metal-free catalyst for selective oxidation of arylalkanes. Chem Commun 55:1935–1938

    Google Scholar 

  46. 46.

    Liu SJ, Cui LT, Peng ZY, Wang JJ, Hu YJ, Yu A, Wang HN, Peng P, Li FF (2018) Eco-friendly synthesis of N,S co-doped hierarchical nanocarbon as a highly efficient metal-free catalyst for the reduction of nitroarenes. Nanoscale 10:21764–21771

    CAS  Google Scholar 

  47. 47.

    Hu XW, Long Y, Fan MY, Yuan M, Zhao H, Ma JT, Dong ZP (2019) Two-dimensional covalent organic frameworks as self-template derived nitrogen-doped carbon nanosheets for eco-friendly metal-free catalysis. Appl Catal B Environ 244:25–35

    CAS  Google Scholar 

  48. 48.

    Qi W, Yan PQ, Su DS (2018) Oxidative dehydrogenation on nanocarbon: insights into the reaction mechanism and kinetics via in situ experimental methods. Acc Chem Res 51:640–648

    CAS  Google Scholar 

  49. 49.

    Liu L, Zhu YP, Su M, Yuan ZY (2015) Metal-free carbonaceous materials as promising heterogeneous catalysts. Chemcatchem 7:2765–2787

    CAS  Google Scholar 

  50. 50.

    Sun YB, Cao CY, Liu C, Liu J, Zhu YN, Wang XS, Song WG (2017) Nitrogen-doped hollow carbon spheres derived from amination reaction of fullerene with alkyl diamines as a carbon catalyst for hydrogenation of aromatic nitro compounds. Carbon 125:139–145

    CAS  Google Scholar 

  51. 51.

    Yang SL, Peng L, Huang PP, Wang XS, Sun YB, Cao CY, Song WG (2016) Nitrogen, phosphorus, and sulfur co-doped hollow carbon shell as superior metal-free catalyst for selective oxidation of aromatic alkanes. Angew Chem Int Ed 55:4016–4020

    CAS  Google Scholar 

  52. 52.

    Wang J, Ma QQ, Wang YQ, Li ZH, Li ZH, Yuan Q (2018) New insights into the structure-performance relationships of mesoporous materials in analytical science. Chem Soc Rev 47:8766–8803

    CAS  Google Scholar 

Download references

Acknowledgements

We thank the Natural Science Foundation of Shandong Province (ZR2018LB009, ZR2018LB020), National Natural Science Foundation of China (NSFC 21801180), and the Science Foundation of Shandong Province for Excellent Young Scholars (ZR2017JL015) for financial support. The instrumental analysis was performed at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS), and Shiyanjia Lab (http://www.shiyanjia.com). We also thank Jian Liu and Conghua Qi for support.

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Yongbin Sun or Kun Liu.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 568 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Sun, Y., Hao, J., Zhu, X. et al. Self-nitrogen-doped carbon materials derived from the petioles and blades of apricot leaves as metal-free catalysts for selective oxidation of aromatic alkanes. Carbon Lett. 30, 133–141 (2020). https://doi.org/10.1007/s42823-019-00078-0

Download citation

Keywords

  • Carbon
  • Heterogeneous catalysis
  • Petioles and blades
  • Metal-free
  • Selective oxidation