Fe-containing nanoparticles used as effective catalysts of lignin reforming to syngas and hydrogen assisted by microwave irradiation

  • M. V. Tsodikov
  • O. G. Ellert
  • S. A. Nikolaev
  • O. V. Arapova
  • O. V. Bukhtenko
  • Yu. V. Maksimov
  • D. I. Kirdyankin
  • A. Yu. Vasil’kov
Research Paper


Active iron-containing nanosized components have been formed on the lignin surface. The metal was deposited on the lignin from an ethanol solution of Fe(acac)3 and from a colloid solution of iron metal particles obtained beforehand by metal vapor synthesis. These active components are able to absorb microwave radiation and are suitable for microwave-assisted high-rate dehydrogenation and dry reforming of lignin without addition of a carbon adsorbent, as a supplementary radiation absorbing material, to the feedstock. The dependence of the solid lignin heating dynamics on the concentration of supported iron particles was investigated. The threshold Fe concentration equal to 0.5 wt.%, providing the highest rate of sample heating up to the reforming and plasma generation temperature was identified. The microstructure and magnetic properties of iron-containing nanoparticles supported on lignin were studied before and after the reforming. The Fe3O4 nanoparticles and also core-shell Fe3O4@γ-Fe-С nanostructures are formed during the reforming of lignin samples. The catalytic performance of iron-based nanoparticles toward the lignin conversion is manifested as increasing selectivity to hydrogen and syngas, which reaches 94% at the Fe concentration of 2 wt.%. It was found that with microwave irradiation under argon, hydrogen predominates in the gas. In the СО2 atmosphere, dry reforming takes place to give syngas with the СО/Н2 ratio of ~ 0.9. In both cases, the degree of hydrogen recovery from lignin reaches 90–94%.

Graphical abstract

The microwave-supported deposition of iron on the lignin surface gives active well defined nanoparticles Fe3O4 and also core-shell Fe3O4@γ-Fe-С nanostructures. These nanocomponents provide for high-rate microwave-assisted dehydrogenation and dry reforming of lignin.


Lignin Syngas Hydrogen Microwave irradiation Nanoparticles of Fe Catalysis 



This investigation was carried out within the State Assignment of Fundamental Research to the A.V. Topchiev Institute of Petrochemical Synthesis of the RAS. The magnetic measurements were carried out within the State Assignment of Fundamental Research to the Kurnakov Institute of General and Inorganic Chemistry using the equipment of the JRC PMR IGIC RAS.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4185_MOESM1_ESM.pdf (164 kb)
ESM 1 (PDF 163 kb)


  1. Alonso DM, Bond JQ, Dumesic JA (2010) Catalytic conversion of biomass to biofuels. Green Chem 12:1493–1513CrossRefGoogle Scholar
  2. Alonso DM, Wettstein CG, Dumesic JA (2012) Bimetallic catalysts for upgrating of biomass to fuels and chemicals. Chem Soc Rev 41:8075–8098CrossRefGoogle Scholar
  3. Arapova OV, Bondarenko GN, Chistyakov AV, Tsodikov MV (2017) Vibrational spectroscopy studies of structural changes in lignin under microwave irradiation. Russ J Phys Chem A 91(9):1717–1729CrossRefGoogle Scholar
  4. Bu Q, Lei H, Wang L, Wei Y, Zhu L, Zhang X, Liu Y, Yadavalli G, Tang J (2014) Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons. Bioresour Technol 162:142–147CrossRefGoogle Scholar
  5. Carvell J, Ayieta E, Gavrin A, Ruihua C, Shah VR, Sokol P (2010) Magnetic properties of iron nanoparticle. J of Appl Phys 107:103913CrossRefGoogle Scholar
  6. David B, Pizúrová N, Schneeweiss O, Kudrle V, Jašek O, Synek P (2011) Iron-based nanopowders containing α-Fe, Fe3C, and γ-Fe particles synthesised in microwave torch plasma and investigated with Mössbauer spectroscopy. Japan J Appl Phys 50:08JF11CrossRefGoogle Scholar
  7. Durka T, Gerven TV, Stankiewicz A (2009) Microwaves in heterogeneous gas-phase catalysis: experimental and numerical approaches. Chem Eng Technol 32:1301–1312CrossRefGoogle Scholar
  8. Edwards PP, Kuznetsov VL, David WIF, Brandon NP (2008) Hydrogen and fuel cells: towards a sustainable energy future. Eng Policy 36:4356–4362CrossRefGoogle Scholar
  9. Ellert OG, Petrunenko IA, Tsodikov MV, Bukhtenko OV, Kochubey DI, Maksimov Yu V, Dominguez-Rodriguez A (1996) Study of the formation mechanism of complex oxides obtained by the sol-gel method: influence of the structure of iron, aluminium and yttrium acetylacetonate precursors on the phase composition of the ZrO2 ceramics. J Mater Chem 6:207–212CrossRefGoogle Scholar
  10. Fan L, Chen P, Zhang Y, Liu S, Liu Y, Wang Y, Dai L, Ruan R (2017) Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene with HZSM-5 and MgO for improved bio-oil yield and quality. Bioresour Technol 225:199–205CrossRefGoogle Scholar
  11. Fox MA, Dulay MT (1993) Heterogeneous photocatalysis. Chem Rev 93:341–357CrossRefGoogle Scholar
  12. Hamelink CN, Van Hooijdonk G, Faaij APC (2005) Ethanol from lignocelluloses biomass: techno-economic performance in short, middle- and long term. Biomass Bioenergy 28(4):384–410CrossRefGoogle Scholar
  13. Klabunde KJ, Li YX, Tan BJ (1991) Solvated metal atom dispersed catalysts. Chem Mater 3(1):30–39CrossRefGoogle Scholar
  14. Liu JR, Itoh M, Horikawa T, Machida K (2005) Gigahertz range electromagnetic wave absorbers made of amorphous-carbon-based magnetic nanocomposites. J Appl Phys 98:054305CrossRefGoogle Scholar
  15. Liu S, Xie Q, Zhang B, Cheng Y, Liu Y, Chen P, Ruan R (2016) Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Bioresour Technol 204:164–170CrossRefGoogle Scholar
  16. Liu W-J, Jiang H, Yu H-Q (2015) Thermochemical conversion of lignin to functional materials: a review and future directions. Green Chem 17:4888–4907CrossRefGoogle Scholar
  17. Lu B, Dong XL, Huang H, Zhang XF, Zhu XG, Lei JP, Sun JP (2008) Microwave absorbtion properties of core/shell-type iron and nickel nanoparticles. J Magn Magn Mater 320:1106–1111CrossRefGoogle Scholar
  18. Mingos DMP, Whittaker AG (1997) Microwave dielectric heating effects in chemical synthesis. In: Eldik RV, Hubbard CD (eds) Chemistry under extreme or non classical conditions, JohnWiley and sons, New York, pp 479–545Google Scholar
  19. Naumkin AV, Vasil’kov AY, Volkov IO, Smirnov VV, Nikolaev SA (2007) X-ray photoelectron spectra and structure of composites prepared via deposition of Au, Ni, and Au+Ni nanoparticles on SiO2 from colloidal solutions in triethylamine. Inorg Mater 43(4):381–385CrossRefGoogle Scholar
  20. Nogués J, Sort J, Langlais V, Skumryev V, Suriñach S, Muñoz JS, Baró MD (2005) Exchange bias in nanostructures. Phys Rep 422:65–117CrossRefGoogle Scholar
  21. Pozar D.M., 1998. Microwave engineering, second ed., John Wiley & Sons Inc., New YorkGoogle Scholar
  22. Rabinovich ML (2009) Wood hydrolysis industry in the soviet union and Russia: what can be learned from the history? The 2nd Nordic Wood Biorefinery Conference. Helsinki, Finland, pp 111–120Google Scholar
  23. Rodicheva GV, Orlovskii VP, Romanova NM, Steblevskii AV, Sukhanova GE (1996) Physicochemical investigation of Khibini apatite and its comparison to hydroxyapatite. Russ J Inorg Chem 41:728–731Google Scholar
  24. Rousselle D, Berthault A, Acher O, Bouchaud JP, Zerah PG (1993) Effective medium at finite frequency: theory and experiment. J Appl Phys 74:475–479CrossRefGoogle Scholar
  25. Rowell RM, Pettersen R, Han JS, Rowell JS, Tshabalala MA (2005) Cell wall chemistry, handbook of wood chemistry and wood composites. In: Rowell RM, editor. Boca Raton: Taylor & Francis Group, pp. 9–40Google Scholar
  26. Rubina MS, Kamitov AA, Zubavichus YV, Naumkin AV, Suzer SS, Vasil’kov AY (2016) Collagen-chitosan scaffold modifying with Au and Ag nanopatrticles: synthesis, structure and. properties, Appl Surf Sci 366:365–371CrossRefGoogle Scholar
  27. Smirnov VV, Lanin SN, Vasil'kov AY, Nikolaev SA, Murav'eva GP, Tyurina LA, Vlasenko EV (2005) Adsorption and catalytic conversion of hydrocarbons on nanosized gold particles immobilized on alumina. Russ Chem Bull 54(10):2286–2289CrossRefGoogle Scholar
  28. Snoek JL (1948) Dispersion and absorption in magnetic ferrites at frequencies above one mc/s. Physica 14(4):207–217CrossRefGoogle Scholar
  29. Tjurina LA, Smirnov VV, Potapov DA, Nikolaev SA, Esipov SE, Beletskaya IP (2004) Synthesis of cluster alkyl and aryl grignard reagents in solution. Organomet 23(6):1349–1351CrossRefGoogle Scholar
  30. Tsodikov MV, Chudakova MV, Chistyakov AV, Maksimov YV (2013) Catalytic conversion of cellulose into hydrocarbon fuel components. Neftekhim 53(6):414–420Google Scholar
  31. Tsodikov MV, Ellert OG, Nikolaev SA, Arapova OV, Konstantinov GI, Bukhtenko OV, Vasil’kov AY (2017) The role of nanosized nickel particles in microwave-assisted dry reforming of lignin. Chem Eng J 309:628–637CrossRefGoogle Scholar
  32. Tsodikov MV, Konstantinov GI, Chistyakov AV, Arapova OV, Perederii MA (2016) Utilization of petroleum residues under microwave irradiation. Chem Eng J 292:315–320CrossRefGoogle Scholar
  33. Tsodikov MV, Perederii MA, Chistyakov AV, Konstantinov GI, Kadiev KM, Khadzhiev SN (2012) High speed exhaustive utilization of petroleum residues and pollutants. Solid Fuel Chem 46:121–127CrossRefGoogle Scholar
  34. Tsodikov MV, Perederiy MA, Karaceva MS, Maksimov YV, Suzdalev IP, Gurko AA, Zhevago NK (2007) Formation of iron-containing catalysts on carbon carriers under the influence of microwave radiation. Nanotechnol Russ 1:34–39Google Scholar
  35. Vasil’kov AY, Migulin DA, Naumkin AV, Belyakova OA, Zubavichus YV, Abramchuk SS, Maksimov YV, Novichikhin SV, Muzafarov AM (2016) Hybrid materials based on core-shell polyorganosilsesquioxanes modified with iron nanoparticles. Mendeleev Commun 26:187–190CrossRefGoogle Scholar
  36. Wang T, Wang H, Chi X, Li R, Wang J (2014) Synthesis and microwave absorbtion properties of Fe-C nanofibers by electrospinning with disperse Fe nanoparticles parceled by carbon. Carbon 74:312–318CrossRefGoogle Scholar
  37. Wen FS, Zhang F, Liu ZY (2011) Investigation on microwave absorbtion properties for multiwalled carbon nanotubes /Fe/Co/Ni nanopowders as lightweight absorbers. J Phys Chem C 115(29):14025–14030CrossRefGoogle Scholar
  38. Xu J, Jiang J, Hse C, Shupe TF (2012) Renewable chemical feedstocks fromintegrated liquefaction processing of lignocellulosic materials using microwave energy. Green Chem 14:2821–2830CrossRefGoogle Scholar
  39. Xie J, Qi J, Hse C, Shupe TF (2015) Optimization for microwave-assisted directliquefaction of bamboo residue in glycerol/methanol mixtures. J For Res 26:261–265CrossRefGoogle Scholar
  40. Yunpu W, Leilei D, Liangliang F, Shaoqi S, Yuhuan L, Roger R (2016) Review of microwave-assisted lignin conversion for renewable fuels and chemicals. J Anal Appl Pyrolysis 119:104–113CrossRefGoogle Scholar
  41. Yamada Y, Yoshida H, Kouno K, Kobayashi Y (2010) Iron carbide films produced by laser deposition. J Phys: Conf Series 217:01209Google Scholar
  42. Yao Y, Falk LKL, Morjan RE, Nerushev OA, Campbell EEB (2004) Synthesis of carbon nanotube films by thermal CVD in the presence of supported catalyst particles. Part II: the nanotube film. J Mater Sci - Mater Electron 15:583–594CrossRefGoogle Scholar
  43. Zhou C-H, Xia X, Lin C-X, Tong D-S, Beltramini J (2011) Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chem Soc Rev 40:5588–5617CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • M. V. Tsodikov
    • 1
  • O. G. Ellert
    • 2
  • S. A. Nikolaev
    • 3
  • O. V. Arapova
    • 1
  • O. V. Bukhtenko
    • 1
  • Yu. V. Maksimov
    • 4
  • D. I. Kirdyankin
    • 2
  • A. Yu. Vasil’kov
    • 5
  1. 1.A.V. Topchiev Institute of Petrochemical Synthesis of the RASMoscowRussia
  2. 2.N.S. Kurnakov Institute of General and Inorganic Chemistry of the RASMoscowRussia
  3. 3.M. V. Lomonosov Moscow State UniversityMoscowRussia
  4. 4.N.N.Semenov Institute of Chemical Physics of the RASMoscowRussia
  5. 5.A. N. Nesmeyanov Institute of Organoelement Compounds of the RASMoscowRussia

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