Doping carbon networks with phosphorus for supporting Pd in catalyzing selective oxidation of benzyl alcohol

  • Wenyao Guo
  • Shuo Niu
  • Xiaobo Ji
  • Weizhen Yu
  • Tsung-Wu Lin
  • Yifei Wu
  • Yitong Li
  • Lidong ShaoEmail author
Research Paper


A new kind of phosphorus-doped porous carbon framework (P-PCF) was synthesized using a simple and low-cost method and was used as a support material for loading Pd nanoparticles with an average diameter of 5~7 nm (Pd/P-PCF) for benzyl alcohol oxidation. Enhanced activity, selectivity, and stability were achieved over Pd/P-PCF in comparison to the undoped counterpart catalyst (Pd/PCF). Surface analysis of the fresh and reacted catalysts revealed that the selective oxidation of benzyl alcohol is favored using the Pd/P-PCF catalyst because of the modified electronic properties of Pd nanoparticles, the metal-support interactions, as well as the hydrophobic and basic surface properties of the catalyst, which originates from the phosphorus doping.

Graphical abstract


Phosphorus doping Porous carbon framework Palladium nanoparticle Selective oxidation Benzyl alcohol Nanostructured catalysts 



This work was supported by the National Natural Science Foundation of China (grant number 21403137).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4279_MOESM1_ESM.doc (384 kb)
ESM 1 (DOC 384 kb)


  1. Arrigo R, Wrabetz S, Schuster ME, Wang D, Villa A, Rosenthal D, Girsgdies F, Weinberg G, Prati L, Schlögl R, Su DS (2012) Tailoring the morphology of Pd nanoparticles on CNTs by nitrogen and oxygen functionalization. Phys Chem Chem Phys 14:10523–10532. CrossRefGoogle Scholar
  2. Batchelor-McAuley C, Shao L, Wildgoose GG, Green MLH, Compton RG (2008) An electrochemical comparison of manganese dioxide microparticles versus α and β manganese dioxide nanorods: mechanistic and electrocatalytic behaviour. New J Chem 32:1195–1203. CrossRefGoogle Scholar
  3. Chan-Thaw CE, Villa A, Katekomol P, Su D, Thomas A, Prati L (2010) Covalent triazine framework as catalytic support for liquid phase reaction. Nano Lett 10:537–541. CrossRefGoogle Scholar
  4. Chan-Thaw CE, Villa A, Veith GM, Prati L (2015) Identifying the role of N-heteroatom location in the activity of metal catalysts for alcohol oxidation. ChemCatChem 7:1338–1346. CrossRefGoogle Scholar
  5. Chen Y, Guo Z, Chen T, Yang Y (2010) Surface-functionalized TUD-1 mesoporous molecular sieve supported palladium for solvent-free aerobic oxidation of benzyl alcohol. J Catal 275:11–24. CrossRefGoogle Scholar
  6. Figueiredo JL, Pereira MFR, Freitas MMA, Órfão JJM (1999) Modification of the surface chemistry of activated carbons. Carbon 37:1379–1389. CrossRefGoogle Scholar
  7. Hasegawa G, Deguchi T, Kanamori K, Kobayashi Y, Kageyama H, Abe T, Nakanishi K (2015) High-level doping of nitrogen, phosphorus, and sulfur into activated carbon monoliths and their electrochemical capacitances. Chem Mater 27:4703–4712. CrossRefGoogle Scholar
  8. Hou H, Banks CE, Jing M, Zhang Y, Ji X (2015) Carbon quantum dots and their derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong cycle life. Adv Mater 27:7861–7866. CrossRefGoogle Scholar
  9. Huang X, Shao L, She G-W, Wang M, Chen S, Meng X-M (2012) Catalyst-free synthesis of single crystalline ZnO nanonails with ultra-thin caps. CrystEngComm 14:8330. CrossRefGoogle Scholar
  10. Kibis LS, Stadnichenko AI, Koscheev SV, Zaikovskii VI, Boronin AI (2012) Highly oxidized palladium nanoparticles comprising Pd4+ species: spectroscopic and structural aspects, thermal stability, and reactivity. J Phys Chem C 116:19342–19348. CrossRefGoogle Scholar
  11. Kopylovich MN, Ribeiro APC, Alegria ECBA, Martins NMR, Martins LMDRS, Pombeiro AJL (2015) Catalytic oxidation of alcohols: recent advances. In: Perez PJ (ed) Advances in organometallic chemistry, vol 63, pp 91–174. Google Scholar
  12. Li JD, Tian QF, Jiang SY, Zhang Y, Wu YX (2016) Electrocatalytic performances of phosphorus doped carbon supported Pd towards formic acid oxidation. Electrochim Acta 213:21–30. CrossRefGoogle Scholar
  13. Liao SX, Chi YM, Yu H, Wang HJ, Peng F (2014) Tuning the selectivity in the aerobic oxidation of cumene catalyzed by nitrogen-doped carbon nanotubes. Chemcatchem 6:555–560. CrossRefGoogle Scholar
  14. Long R, Huang H, Li Y, Song L, Xiong Y (2015) Palladium-based nanomaterials: a platform to produce reactive oxygen species for catalyzing oxidation reactions. Adv Mater 27:7025–7042. CrossRefGoogle Scholar
  15. Namdeo A, Mahajani SM, Suresh AK (2016) Palladium catalysed oxidation of glycerol—effect of catalyst support. J Mol Catal A Chem 421:45–56. CrossRefGoogle Scholar
  16. Niu S, Guo W, Lin T-W, Yu W, Wu Y, Ji X, Shao L (2017) Nanoscale Pd supported on 3D porous carbon for enhanced selective oxidation of benzyl alcohol. RSC Adv 7:25885–25890. CrossRefGoogle Scholar
  17. Otto K, Haack LP, deVries JE (1992) Identification of two types of oxidized palladium on γ-alumina by X-ray photoelectron spectroscopy. Appl Catal B Environ 1:1–12. CrossRefGoogle Scholar
  18. Parlett CMA, Bruce DW, Hondow NS, Lee AF, Wilson K (2011) Support-enhanced selective aerobic alcohol oxidation over Pd/mesoporous silicas. ACS Catal 1:636–640. CrossRefGoogle Scholar
  19. Patel MA, Luo F, Khoshi MR, Rabie E, Zhang Q, Flach CR, Mendelsohn R, Garfunkel E, Szostak M, He H (2016) P-doped porous carbon as metal free catalysts for selective aerobic oxidation with an unexpected mechanism. ACS Nano 10:2305–2315. CrossRefGoogle Scholar
  20. Prati L, Villa A, Campione C, Spontoni P (2007) Effect of gold addition on Pt and Pd catalysts in liquid phase oxidations. Top Catal 44:319–324. CrossRefGoogle Scholar
  21. Sankar M, Dimitratos N, Miedziak PJ, Wells PP, Kiely CJ, Hutchings GJ (2012) Designing bimetallic catalysts for a green and sustainable future. Chem Soc Rev 41:8099–8139. CrossRefGoogle Scholar
  22. Savara A, Chan-Thaw CE, Rossetti I, Villa A, Prati L (2014) Benzyl alcohol oxidation on carbon-supported Pd nanoparticles: elucidating the reaction mechanism. ChemCatChem 6:3464–3473. CrossRefGoogle Scholar
  23. Shao L, Lin T-W, Tobias G, Green MLH (2008) A simple method for the containment and purification of filled open-ended single wall carbon nanotubes using C60 molecules Chem Commun:2164–2166.
  24. Sharma AS, Kaur H, Shah D (2016) Selective oxidation of alcohols by supported gold nanoparticles: recent advances. RSC Adv 6:28688–28727. CrossRefGoogle Scholar
  25. Sheldon RA, Arends IWCE, ten Brink G-J, Dijksman A (2002) Green, catalytic oxidations of alcohols. Acc Chem Res 35:774–781. CrossRefGoogle Scholar
  26. Villa A, Plebani M, Schiavoni M, Milone C, Piperopoulos E, Galvagno S, Prati L (2012) Tuning hydrophilic properties of carbon nanotubes: a challenge for enhancing selectivity in Pd catalyzed alcohol oxidation. Catal Today 186:76–82. CrossRefGoogle Scholar
  27. Villa A, Dimitratos N, Chan-Thaw CE, Hammond C, Prati L, Hutchings GJ (2015) Glycerol oxidation using gold-containing catalysts. Acc Chem Res 48:1403–1412. CrossRefGoogle Scholar
  28. Wang D, Villa A, Porta F, Prati L, Su D (2008) Bimetallic gold/palladium catalysts: correlation between nanostructure and synergistic effects. J Phys Chem C 112:8617–8622. CrossRefGoogle Scholar
  29. Wang X, Sun G, Routh P, Kim DH, Huang W, Chen P (2014) Heteroatom-doped graphene materials: syntheses, properties and applications. Chem Soc Rev 43:7067–7098. CrossRefGoogle Scholar
  30. Wang Y, De S, Yan N (2016) Rational control of nano-scale metal-catalysts for biomass conversion. Chem Commun (Camb) 52:6210–6224. CrossRefGoogle Scholar
  31. Weerachawanasak P, Hutchings GJ, Edwards JK, Kondrat SA, Miedziak PJ, Prasertham P, Panpranot J (2015) Surface functionalized TiO2 supported Pd catalysts for solvent-free selective oxidation of benzyl alcohol. Catal Today 250:218–225. CrossRefGoogle Scholar
  32. Wu X, Radovic LR (2006) Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus. Carbon 44:141–151. CrossRefGoogle Scholar
  33. Wu G, Wang X, Guan N, Li L (2013) Palladium on graphene as efficient catalyst for solvent-free aerobic oxidation of aromatic alcohols: role of graphene support. Appl Catal B Environ 136-137:177–185. CrossRefGoogle Scholar
  34. Zhang H, Jin MS, Xiong YJ, Lim B, Xia YN (2013) Shape-controlled synthesis of Pd nanocrystals and their catalytic applications. Acc Chem Res 46:1783–1794. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric PowerShanghai University of Electric PowerShanghaiPeople’s Republic of China
  2. 2.College of Chemistry and Chemical EngineeringCentral South UniversityChangshaPeople’s Republic of China
  3. 3.Department of ChemistryTunghai UniversityTaichung CityTaiwan
  4. 4.Research & Development DepartmentNewford Technology Co. LtdHangzhouPeople’s Republic of China

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