Morphological and structural differences between glucose, cellulose and lignocellulosic biomass derived hydrothermal carbons

Hydrothermal carbonization (HTC) has demonstrated that it is an effective technique for the production of functionalized carbon materials from simple carbohydrates, such as monosaccharides and disaccharides. The chemical structure of the HTC carbon has been identified in detail by means of solid-state MAS 13C NMR investigations. However, it has not yet been clearly shown what the effects are of the processing temperature and time on the chemical structure and morphology of the generated HTC carbon. This study shows, with the help of SEM, elemental and yield analysis and solid-state MAS 13C NMR, the effects of these two key variables on the final nature of the produced material, allowing the development of a mechanistic model. According to the chosen set of processing parameters, the chemical structure of the HTC carbon can be tuned from polyfuran rich in oxygen containing functional groups to a carbon network of extensive aromatic domains. The same kind of investigation using lignocellulosic biomass as a carbon precursor shows a striking difference between the HTC mechanism of glucose and cellulose. The biopolymer, when it is treated under mild hydrothermal conditions (180–280 °C), tends to react according to a reaction scheme which leads to its direct transformation into an aromatic carbon network and which has strong similarities with classical pyrolysis.

[1]  H. Spliethoff,et al.  Investigation of biomasses and chars obtained from pyrolysis of different biomasses with solid-state 13C and 23Na nuclear magnetic resonance spectroscopy , 2008 .

[2]  Alessandro Gandini,et al.  Furans in polymer chemistry , 1997 .

[3]  J. F. Haw,et al.  Carbon-13 CP/MAS NMR and FT-IR Study of Low-Temperature Lignin Pyrolysis , 1985 .

[4]  Uwe Schröder,et al.  Subcritical water as reaction environment: fundamentals of hydrothermal biomass transformation. , 2011, ChemSusChem.

[5]  K. Rissanen,et al.  The conversion from cellulose I to cellulose II in NaOH mercerization performed in alcohol–water systems: An X-ray powder diffraction study , 2007 .

[6]  Kunio Arai,et al.  Dissolution and Hydrolysis of Cellulose in Subcritical and Supercritical Water , 2000 .

[7]  Jaap J. Boon,et al.  Cellulose char structure: a combined analytical Py-GC-MS, FTIR, and NMR study , 1994 .

[8]  Markus Antonietti,et al.  Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization. , 2010, Chemical Society reviews.

[9]  O. Bobleter,et al.  Hydrothermal degradation of polymers derived from plants , 1994 .

[10]  Denise Handlarski,et al.  Green , 2007 .

[11]  W. V. Swaaij,et al.  Hydrothermal Conversion Of Biomass. II. Conversion Of Wood, Pyrolysis Oil, And Glucose In Hot Compressed Water , 2010 .

[12]  Andrew G. Glen,et al.  APPL , 2001 .

[13]  Thomas Ingram,et al.  Hydrolysis of lignocellulosic biomass in water under elevated temperatures and pressures , 2008 .

[14]  R. Meusinger,et al.  NMR of Coals and Coal Products , 1991 .

[15]  Markus Antonietti,et al.  Back in the black: hydrothermal carbonization of plant material as an efficient chemical process to treat the CO2 problem? , 2007 .

[16]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[17]  G. Gerbaud,et al.  Investigation with 13C NMR, EPR and magnetic susceptibility measurements of char residues obtained by pyrolysis of biomass , 2007 .

[18]  A. Gawlik,et al.  Biomass Conversion in Water at 330−410 °C and 30−50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways , 2003 .

[19]  Young Hee Lee,et al.  Crystalline Ropes of Metallic Carbon Nanotubes , 1996, Science.

[20]  Johnathan E. Holladay,et al.  Studying cellulose fiber structure by SEM, XRD, NMR and acid hydrolysis , 2007 .

[21]  Markus Antonietti,et al.  Structural Characterization of Hydrothermal Carbon Spheres by Advanced Solid-State MAS C-13 NMR Investigations , 2009 .

[22]  A. B. Fuertes,et al.  The production of carbon materials by hydrothermal carbonization of cellulose , 2009 .

[23]  C. Liang,et al.  Mesoporous carbon materials: synthesis and modification. , 2008, Angewandte Chemie.

[24]  G. Cody,et al.  Calculation of the 13C NMR chemical shift of ether linkages in lignin derived geopolymers , 1999 .

[25]  M. Antonietti,et al.  Coal from carbohydrates: The “chimie douce” of carbon , 2010 .

[26]  Nicole D Berge,et al.  Hydrothermal carbonization of municipal waste streams. , 2011, Environmental science & technology.

[27]  Klaus Müllen,et al.  Pyrolysis in the mesophase: a chemist's approach toward preparing carbon nano- and microparticles. , 2002, Journal of the American Chemical Society.

[28]  Markus Antonietti,et al.  Engineering Carbon Materials from the Hydrothermal Carbonization Process of Biomass , 2010, Advances in Materials.

[29]  A. C. O'sullivan Cellulose: the structure slowly unravels , 1997, Cellulose.

[30]  Andrea Kruse,et al.  Hot compressed water as reaction medium and reactant properties and synthesis reactions , 2007 .

[31]  A. Ragauskas,et al.  Cross-Polarization/Magic Angle Spinning (CP/MAS) 13C Nuclear Magnetic Resonance (NMR) Analysis of Chars from Alkaline-Treated Pyrolyzed Softwood , 2009 .

[32]  Markus Antonietti,et al.  Hydrothermal carbon from biomass : a comparison of the local structure from poly- to monosaccharides and pentoses/hexoses. , 2008 .

[33]  J. I. Seeman,et al.  A model that distinguishes the pyrolysis of d-glucose, d-fructose, and sucrose from that of cellulose. Application to the understanding of cigarette smoke formation , 2003 .

[34]  S. Capuani,et al.  13C CPMAS NMR spectroscopic analysis applied to wood characterization , 2005 .

[35]  Andrea Kruse,et al.  Hot compressed water as reaction medium and reactant. 2. Degradation reactions , 2007 .

[36]  Ferdi Schüth,et al.  Acid hydrolysis of cellulose as the entry point into biorefinery schemes. , 2009, ChemSusChem.

[37]  Taeghwan Hyeon,et al.  Recent Progress in the Synthesis of Porous Carbon Materials , 2006 .

[38]  F. Bergius Beiträge zur Theorie der Kohleentstehung , 2005, Naturwissenschaften.

[39]  Robin J. White,et al.  Porous carbohydrate-based materials via hard templating. , 2010, ChemSusChem.

[40]  M. Miki-Yoshida,et al.  Catalytic growth of carbon microtubules with fullerene structure , 1993 .

[41]  M. Delwiche,et al.  Methods for Pretreatment of Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production , 2009 .

[42]  M. Hajaligol,et al.  Observation and Characterization of Cellulose Pyrolysis Intermediates by 13C CPMAS NMR. A New Mechanistic Model , 2004 .

[43]  Richard G Compton,et al.  Metal nanoparticles and related materials supported on carbon nanotubes: methods and applications. , 2006, Small.

[44]  Michael Jerry Antal,et al.  Uncatalyzed solvolysis of whole biomass hemicellulose by hot compressed liquid water , 1992 .

[45]  Kunio Arai,et al.  Cellulose hydrolysis in subcritical and supercritical water , 1998 .