Microchimica Acta

, Volume 184, Issue 5, pp 1417–1426 | Cite as

Graphene micro-aerogel based voltammetric sensing of p-acetamidophenol

  • Li Ruiyi
  • Liu Ling
  • Li Zaijun
  • Gu Zhiguo
  • Wang Guangli
  • Liu Junkang
Original Paper


The authors describe a method for the fabrication of graphene micro-aerogels (GMA) using a multiple emulsion as a soft template. A mixed surfactant consisting of polymannitol oleate ester and polyoxyethylene castor oil was dissolved in toluene. An aqueous dispersion of graphene oxide was dropped into the above solution to produce a water-in-oil-in-water multiple emulsion. Hydrazine was used to reduce the graphene oxide. The partly reduced sheets of graphene oxide diffuse into the oil phase due to their low polarity. This induces the self-assembly of graphene sheets at the oil-water interface to finally form GMA. Following freeze drying and thermal annealing at 900 °C under Ar/H2, GMA is obtained which possesses a microcapsule-like structure, high electrical conductivity (3250 S m−1), a large specific surface (1253 m2 g−1) and a well-defined porous structure. A glassy carbon electrode modified with the GMA shows ultrahigh sensitivity for the electrochemical detection of p-acetamidophenol. The differential pulse voltammetric peak current increases linearly over the 1 × 10−8 to 8.0 × 10−5 M p-acetamidophenol concentration range, and the detection limit is 5.7 × 10−9 M (at an S/N ratio of 3). The sensitivity is much better than that of sensors based on the use of graphene, graphene aerogel, or high density graphene aerogel. The method was successfully applied to the determination of p-acetamidophenol in tablets. The study also provides promising prospects in terms of graphene aerogel materials with improved electrochemical performance in electrocatalysis, supercapacitors and lithium ion batteries.

Graphical abstract

Schematic presentation of the fabrication of graphene micro aerogels (GMAs) using a multiple emulsion as soft template. GMAs possess microcapsule-like structure and excellent electron transfer activity. The sensor based on GMA shows ultrahigh sensitivity for the voltammetric detection of p-acetamidophenol.


Aerogel Paracetamol Differential pulse voltammetry Microcapsules Water-in-oil-in-water emulsion Drug analysis 



The authors acknowledge the financial support from the National Natural Science Foundation of China (No. 21576115), Prospective Joint Research Project: Cooperative Innovation Fund (No. BY2015019-26) and MOE & SAFEA for the 111 Project (B13025).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2017_2148_MOESM1_ESM.doc (603 kb)
ESM 1 (DOC 603 kb)


  1. 1.
    Zhang JJ, Li RY, Li ZJ, Liu JK, Gu ZG, Wang GL (2014) Synthesis of nitrogen-doped activated graphene aerogel/gold nanoparticles and its application for electrochemical detection of hydroquinone and o-dihydroxybenzene. Nanoscale 6:5458–5466CrossRefGoogle Scholar
  2. 2.
    Krittayavathananon A, Sawangphruk M (2016) Electrocatalytic oxidation of ethylene glycol on palladium coated on 3D reduced graphene oxide aerogel paper in alkali media: effects of carbon supports and hydrodynamic diffusion. Electrochim Acta 212:237–246CrossRefGoogle Scholar
  3. 3.
    Sawangphruk M, Srimuk P, Chiochan P, Krittayavathananon A, Luanwuthi S, Limtrakul J (2013) High- performance supercapacitor of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper. Carbon 60:109–116CrossRefGoogle Scholar
  4. 4.
    Krittayavathananon A, Srimuk P, Luanwuthi S, Sawangphruk M (2014) Palladium nanoparticles decorated on reduced graphene oxide rotating disk electrodes toward ultrasensitive hydrazine detection: effects of particle size and hydrodynamic diffusion. Anal Chem 86:12272–12278CrossRefGoogle Scholar
  5. 5.
    Sawangphruk M, Krittayavathananon A, Chinwipas N, Srimuk P, Vatanatham T, Limtrakul S, Foord JS (2013) Ultraporous palladium supported on graphene-coated carbon fiber paper as a highly active catalyst electrode for the oxidation of methanol. Fuel Cells 13:881–888Google Scholar
  6. 6.
    Lampraserthun P, Krittayavathananon A, Sawangphruk M (2016) N-doped reduced graphene oxide aerogel coated on carboxyl-modified carbon fiber paper for high-performance ionic-liquid supercapacitors. Carbon 102:455–461CrossRefGoogle Scholar
  7. 7.
    Yang XQ, Liu AR, Zhao YW, Lu HJ, Zhang YJ, Wei W, Li Y, Liu SQ (2015) Three-dimensional macroporous polypyrrole-derived graphene electrode prepared by the hydrogen bubble dynamic template for supercapacitors and metal-free catalysts. ACS Appl Mater Interfaces 7:23731–23740CrossRefGoogle Scholar
  8. 8.
    Ren HB, Shi XP, Zhu JY, Zhang Y, Bi YT, Zhang L (2016) Facile synthesis of N-doped graphene aerogel and its application for organic solvent adsorption. J Mater Sci 51:6419–6427CrossRefGoogle Scholar
  9. 9.
    Yang J, Zhang EW, Li XF, Zhang YT, Qu J, Yu ZZ (2015) Cellulose/graphene aerogel supported phase change composites with high thermal conductivity and good shape stability for thermal energy storage. Carbon 98:50–57CrossRefGoogle Scholar
  10. 10.
    Lu JS, Zhang YJ, Li HN, Yu JC, Liu SQ (2014) Electrochemically driven drug metabolism via a CyP1A2-UGT1A10 bienzyme confined in a graphene anno-cage. Chem Commun 50:13896–13899CrossRefGoogle Scholar
  11. 11.
    Lim MB, Hu M, Manandhar S, Sakshaug A, Strong A, Riley L, Pauzauskie PJ (2015) Ultrafast sol-gel synthesis of graphene aerogel materials. Carbon 95:616–624CrossRefGoogle Scholar
  12. 12.
    Xiao F, Yang SX, Zhang ZY, Liu HF, Xiao JW, Wan L, Luo J, Wang S, Liu YQ (2015) Scalable synthesis of freestanding sandwich-structured graphene/polyaniline/graphene nanocomposite paper for flexible all-solid-state supercapacitor. Sci Rep UK 5(1–7):9359CrossRefGoogle Scholar
  13. 13.
    Ye SB, Feng JC (2014) Self-assembled three-dimensional hierarchical graphene/polypyrrole nanotube hybrid aerogel and its application for supercapacitors. ACS Appl Mater Interfaces 6:9671–9679CrossRefGoogle Scholar
  14. 14.
    Bei HX, Li RY, Li ZJ, Liu JK, Gu ZG, Wang GL (2015) Fabrication of a high density graphene aerogel– gold nanostar hybrid and its application for the electrochemical detection of hydroquinone and o- dihydroxybenzene. RSC Adv 5:54211–54219CrossRefGoogle Scholar
  15. 15.
    Li RY, Liu L, Bei HX, Li ZJ (2016) Nitrogen-doped multiple graphene aerogel/gold nanostar as the electrochemical sensing platform for ultrasensitive detection of circulating free DNA in human serum. Biosens Bioelectron 79:457–466CrossRefGoogle Scholar
  16. 16.
    Li RY, Wang JJ, Liu L, Liu ZJ (2016) Ultrasensitive direct detection of dsDNA using a glassy carbon electrode modified with thionin-functionalized multiple graphene aerogel and gold nanostars. Microchim Acta 183:1641–1649CrossRefGoogle Scholar
  17. 17.
    Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339CrossRefGoogle Scholar
  18. 18.
    Oda K, Sato Y, Katayama S, Ito A, Ohgitani T (2004) Separation and characterization of adjuvant oligosaccharide oleate ester derived from product mixture of mannitol-oleic acid esterification. Vaccine 22:2812–2821CrossRefGoogle Scholar
  19. 19.
    Gutierrez MC, Ferrer ML, del Monte F (2008) Ice-templated materials: sophisticated structures exhibiting enhanced functionalities obtained after unidirectional freezing and ice-segregation-induced self-assembly. Chem Mater 20:634–648CrossRefGoogle Scholar
  20. 20.
    Nguyen DD, Suzuki S, Kato S, To BD, Hsu CC, Murata H, Rokuta E, Tai NH, Yoshimura M (2015) Macroscopic, freestanding, and tubular graphene architectures fabricated via thermal annealing. ACS Nano 9:3206–3214CrossRefGoogle Scholar
  21. 21.
    Gao LB, Ren WC, Xu HL, Jin L, Wang ZX, Ma T, Ma LP, Zhang ZY, Fu Q, Peng LM, Bao XH, Cheng HM (2012) Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum. Nat Commu 3: 699–1–699-7.Google Scholar
  22. 22.
    Li Y, Umasankar Y, Chen SM (2009) Polyaniline and poly(flavin adenine dinucleotide) doped multi-walled carbon nanotubes for p-acetamidophenol sensor. Talanta 79:486–492CrossRefGoogle Scholar
  23. 23.
    Yuan X, Yuan D, Zeng F, Zou W, Tzorbatzoglou F, Tsiakaras P, Wang Y (2013) Preparation of graphitic mesoporous carbon for the simultaneous detection of hydroquinone and catechol. Appl Catal B Environ 129:367–374CrossRefGoogle Scholar
  24. 24.
    Du-Vall SH, McCreery RL (1999) Control of catechol and hydroquinone electron-transfer kinetics on native and modified glassy carbon electrodes. Anal Chem 71:4594–4602CrossRefGoogle Scholar
  25. 25.
    Daneshvar L, Rounaghi GH, Tarahomi S (2016) Voltammetric paracetamol sensor using a gold electrode made from a digital versatile disc chip and modified with a hybrid material consisting of carbon nanotubes and copper nanoparticles. Microchim Acta 183:3001–3007CrossRefGoogle Scholar
  26. 26.
    Karimi-Maleh H, Hatami M, Moradi R, Khalilzadeh MA, Amiri S, Sadeghifar H (2016) Synergic effect of Pt-Co nanoparticles and a dopamine derivative in a nanostructured electrochemical sensor for simultaneous determination of N-acetylcysteine, paracetamol and folic acid. Microchim Acta 183:2957–2964CrossRefGoogle Scholar
  27. 27.
    Sadok I, Tyszczuk-Rotko K, Nosal-Wiercinska A (2016) Bismuth particles Nafion covered boron-doped diamond electrode for simultaneous and individual voltammetric assays of paracetamol and caffeine. Sensor Actuat B-Chem 235:263–272CrossRefGoogle Scholar
  28. 28.
    Tefera M, Geto A, Tessema M, Admassie S (2016) Simultaneous determination of caffeine and paracetamol by square wave voltammetry at poly(4-amino-3-hydroxynaphthalene sulfonic acid)- modified glassy carbon electrode. Food Chem 210:156–162CrossRefGoogle Scholar
  29. 29.
    Kalambate PK, Srivastava AK (2016) Simultaneous voltammetric determination of paracetamol, cetirizine and phenylephrine using a multiwalled carbon nanotube-platinum nanoparticles nanocomposite modified carbon paste electrode. Sensors Actuators B 233:237–248CrossRefGoogle Scholar
  30. 30.
    Luo J, Ma Q, Wei W, Zhu Y, Liu R, Liu XY (2016) Synthesis of water-dispersible molecularly imprinted Electroactive nanoparticles for the sensitive and selective paracetamol detection. ACS Appl Mater Interfaces 8:21028–21038CrossRefGoogle Scholar
  31. 31.
    Tadayon F, Naghinejad R, Daneshinejad H (2016) A sensitive and selective electrochemical method for the simultaneous determination of dopamine and paracetamol based on a multiwalled carbon nanotubes/poly(l-lysine)-modified glassy carbon electrode. Chem Lett 45:1006–1008CrossRefGoogle Scholar
  32. 32.
    Liu L, Lv HY, Wang CY, Ao ZM, Wang GX (2016) Fabrication of the protonated graphitic carbon nitride nanosheets as enhanced electrochemical sensing platforms for hydrogen peroxide and paracetamol detection. Electrochim Acta 206:259–269CrossRefGoogle Scholar
  33. 33.
    Hinostroza Ramos JV, Matos Morawski FD, Haas Costa TM, Pereira Dias SL, Benvenutti EV, Menezes EWD, Arenas LT (2015) Mesoporous chitosan/silica hybrid material applied for development of electrochemical sensor for paracetamol in presence of dopamine. Microporous Mesoporous Mater 217:109–118CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Wien 2017

Authors and Affiliations

  • Li Ruiyi
    • 1
  • Liu Ling
    • 1
  • Li Zaijun
    • 1
    • 2
  • Gu Zhiguo
    • 1
  • Wang Guangli
    • 1
  • Liu Junkang
    • 1
  1. 1.School of Chemical and Material EngineeringJiangnan UniversityWuxiChina
  2. 2.Key Laboratory of Food Colloids and BiotechnologyMinistry of EducationWuxiChina

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