te. When the TEOS was added at high rates, the mean size and standard deviation of the silicacoated nanoparticles were 653 nm and 56 nm, respectively, based on total of 226 nanoparticles (Figure 2(c)). A TEM image of SiMNPs obtained after dropwise addition of the TEOS is shown in Figure 2(d). The mean size of SiMNPs was 3.5 nm with a standard deviation of 1.6 nm based on 629 nanoparticles. The mean size of SiMNPs aggregates was 2.2 µm with a standard deviation of 0.3 µm. Acid functionalization changed the dispersability of the nanoparticles because larger aggregates were found after this step. The material functionalized with PFS acid groups showed a bimodal distribution; the smaller distribution could be attributed to silica-coated

Figure 2. TEM images of (a) cobalt iron oxide (CoFe2O4) nanoparticles; (b) CoFe2O4 aggregates of nanoparticles; (c) SiMNPs synthesized at high addition rates of TEOS; and (d) SiMNPs synthesized at low addition rates of TEOS.

iron oxide that escaped the functionalization. The smaller material had a mean of 2.3 (±0.1) µm, which is the same as that obtained for silica-coated iron oxide aggregates. The functionalization with PFS had promoted the formation of larger aggregates with a mean size of 74.0 (±4.1) µm. AS nanoparticles also showed a bimodal distribution with mean diameter of 13. (±2.5) µm for the larger aggregates and mean diameter of 0.8 (±0.1) µm for the smaller aggregates.

FTIR spectra for acid-functionalized nanoparticles are shown in Figure 3. The broad band in the wavelength 500 - 600 cm–1 appears in all the spectra. This band has been associated to Fe-O bonds [44,45]. The bands at 820 and 960 cm–1 in SiMNPs, AS, and PFS spectra have been attributed to the stretching vibrations of Si–O–Si and Si–O–H groups [46]. Similarly, a broad band at 1120 cm–1 from the Si–O bond appears in all these spectra [47]. The peak at 1370 cm–1 has been assigned to the O=S=O stretching vibrations [48-51]. The peaks at 1425 cm–1 in the spectra of AS and PFS nanoparticles have been attributed to undissociated SO3H groups [48,50]. The peaks at 1080, 1150, and 1190 cm–1 in the spectrum of PFS nanoparticles have been assigned to the C-F bond [52-54]. The results from FTIR analysis showed that all of the nanoparticles had the functional groups expected.

XPS profiles for PFS and AS functionalized nanoparticles were used to analyze their atomic concentration (Figure 4). A peak at 104 - 108 eV was observed for both acid-functionalized nanoparticles. This peak is associated with silicon bonds from the silica layer that covers the CoFe2O4 nanoparticles [51,55]. The peaks associated with carbon, silicon, and sulfur were observed in the AS spectrum. The surface composition of both PFS and AS nanoparticles is shown in Table 1. For AS, the C/Si theoretical value was calculated from the molecular formula of the propylsulfonic acid attached to the silica surface as 3. The C/Si ratio of 3.4 from the XPS experiment agrees with the theoretical value. The C/S ratio of 26.6 was much larger than the theoretical value, which is also 3.0. The large amount of carbon with respect to sulfur suggests that the loss of the sulfonic acid groups might have occurred during the synthesis procedure. The peaks that correspond to F, O, C, S, and Si were found in the XPS profiles for PFS nanoparticles. As in the AS case, the C/S ratio of 10.4 was greater than the theoreticcal value of 3.0. The large amount of carbon also suggests the loss of the sulfonic acid group during the synthesis procedure; however, the ratio of fluorine to carbon (0.8) was lower than expected (3.0), which indicates that the acid sulfonic group leached out along with other fluorine atoms of the HFP sultone moieties.

The thermal decomposition scans of the nanoparticles before and after acid functionalization were used to evaluate the thermal stability of the nanoparticles and

Figure 3. FTIR spectra of CoFe2O4, SiMNPs, AS-SiMNPs, and PFS-SiMNPs after synthesis. All the samples were dried at 45˚C under vacuum before taking the spectra.

Figure 4. XPS profiles of PFS and AS nanoparticles.

Table 1. Atomic concentration and organic load of the acidfunctionalized nanoparticles.

their total organic loading (Figure 5). The DTA curves show that the drying step occurred before the samples reached 150˚C. SiMNPs had absorbed more water than the acid-functionalized nanoparticles. The moisture content of SiMNPs, AS, and PFS nanoparticles was 3.9%, 2.6%, and 2.6%, respectively. The incorporation of alkylsulfonic and perfluoroalkylsulfonic acids groups increased

Figure 5. TG/DTA profiles of SiMNP, PFS, and AS functionalized nanoparticles.

the hydrophobicity of the nanoparticles. Similar results were found during functionalization of silica with perfluoroalkylsulfonic acid [51]. An increase in the hydrophobic properties of the nanoparticles can affect their dispersability in the biomass slurry and could promote aggregation of nanoparticles, thus reducing the available area for the reaction. The TGA profile of SiMNPs showed a total weight loss of 4.2% during heating from 150˚C to 800˚C. The weight loss between 150˚C and 400˚C was 1.7% and it has been attributed to bound water. The weight loss at temperatures higher than 400˚C was measured as 2.5% and it has been explained as the weight lost due to a ferrite crystallization process [44,56]. PFS and AS nanoparticles showed similar thermal stabilities; when heated to 450˚C, PFS nanoparticles lost 22% of their weight, or about 60% of their original organic content; AS lost 10% of their weight, or about 55% of their original organic content. The first derivative profile for PFS nanoparticles shows four peaks at 225˚C, 292˚C, 417˚C, and 492˚C, which indicates that the perfluoroalkylsulfonic acid group splits into smaller moieties. The sulfonic acid groups and the CF2-chains decompose at different temperatures [51]. The first derivative profile for AS nanoparticles shows a main peak at 437˚C that corresponds to the alkyl-sulfonic acid. The left shoulder on this peak could be attributed to mercapto-propyl groups that were not completely oxidized to the sulfonic acid [57]. The total organic content was counted as the total mass lost between 150˚C and 600˚C; these values can be seen in Table 1 along with the number of acid sites on the nanoparticles. The hydronium ion concentration per mass of catalyst was calculated from the values of total organic content on the nanoparticles and the surface sulfur concentration.

3.2. Biomass Pretreatment

Table 2 shows the biomass composition on a dry mass basis, and the total hemicellulose sugars recovered at 80˚C and 160˚C from wheat straw are shown in Figure 6.

At temperatures as low as 80˚C, solubilization of hemicellulose rather than cellulose hydrolysis is expected [8]. The amount of sugars solubilized (24.0% ± 1.1%) at 80˚C in the presence of PFS nanoparticles was greater

Figure 6. Wheat straw hemicelluloses recovered after pretreatment with PFS and AS acid-functionalized nanoparticles. The left columns correspond to results of the experiments carried out at 80˚C for 24 h with a catalyst load of 1.5% and biomass load of 2.5%. Results of the experiments carried out at 160˚C for 2 h with a catalyst load of 0.25% and biomass load of 2.5% are shown in the right columns. The error bars represent the standard errors of two replicate experiments.

Table 2. Whole biomass composition.

than the sugars released from the control (7.7% ± 0.8%); but the amount of hemicelluloses recovered with AS (9.1% ± 1.7%) was not significantly different from the control. PFS experiments used 2 mmol H+/L based on the values obtained for organic content and sulfur atomic concentration; this is equivalent to using 0.02% (w/w) sulfuric acid solutions. By a similar calculation, the load of AS nanoparticles provides 1.02 mmol H+/L, which is equivalent to using 0.01% (w/w) sulfuric acid solutions. Hemicellulose yield of 20% can be considered moderate because low temperature and acidity levels were used. Complete (100%) hemicellulose solubilization requires temperatures higher than 160˚C using 1% sulfuric acid [8]. Previous work reported that complete xylan solubilization was reached at 130˚C using 3% (w/w) sulfuric acid solutions for 4 h [58]. Higher temperatures have been used (180˚C - 220˚C) for hemicellulose hydrolysis with acid concentrations between 0% to 0.1% sulfuric acid (w/w) [59-61].

Very few monosaccharides were obtained after pretreatment of biomass with PFS or AS nanoparticles. PFS and AS solubilized the xylan fraction into its monomeric form at very low levels: 3.5% ± 0.1%, 1.0% ± 0.2% at 80˚C. Xylose monomer units were not detected in the solution for the control experiment. In the experiments carried out at 160˚C, only 0.3% and 1.2% of the original xylan was found in the solution as xylose for PFS and AS nanoparticles, respectively. From the initial arabinan, 49.5% ± 2.1% and 57.9% ± 11.2% was found as arabinose monomer in the pretreatment liquor of AS and PFS nanoparticles. In the control experiment, 36.0% ± 1.6% of arabinan was hydrolyzed to the monomeric form. These results agree with previous findings in which acidfunctionalized amorphous carbon was used to hydrolyze cellulose, the yield of monomers was only 4%, and most of the sugars obtained were in oligomeric form [49]. About 30% monomers yield was obtained from loblolly pine hemicelluloses using 1% sulfuric acid at 150˚C and 60% at 200˚C [62]. At 160˚C, the low percentage of xylose found in the solution could be explained by degradation of the xylose units to other products such as furfural and formic acid [63-67]; in this experiment, 16.0% ± 0.2%, 20.0% ± 1.3%, and 15.7% ± 1.2% of the original xylan was found in solution as furfural for AS, PFS, and control, respectively (Figure 7). Formic acid was also found in the pretreatment liquor, but it may have been a degradation product of either cellulose or xyloglucans. The results of this paper agree with the hemicellulose hydrolysis models proposed in the literature [59,68-71]. These models suggest that either hemicelluloses or xylan are made of two different fractions that are hydrolyzed at different rates, one slow and one fast. In the present work, the fast-hydrolyzing fraction of hemicellulose is degraded to decomposition products, and that is why very few

Figure 7. Wheat straw hemicelluloses solubilized after pretreatment with PFS and AS acid-functionalized nanoparticles. The pretreatment was carried out at 160˚C for 2 h with a catalyst load of 0.25% and biomass load of 2.5%. The error bars represent the standard errors of two replicate experiments.

monomers were found in the pretreatment liquor. The slow-hydrolyzing fraction is found in solution as oligomers or remains in the non-hydrolyzed solid fraction.

In the experiments performed at high temperature, a 0.25% (w/w) catalyst load was used; the PFS and AS nanoparticle dispersions are equivalent to using 0.003% and 0.002% (w/w) sulfuric acid solutions, respectively. The total hemicellulose (oligosaccharides and monosaccharides) recovered from wheat straw at 160˚C reached 46.3% ± 0.4% and 45.0% ± 1.2% using PFS and AS, respectively. The control experiment recovered 35.0% ± 1.8% of the original hemicellulose in the wheat straw sample. Most of the sugars found in solution came from the xylan fraction 38.6% ± 0.9% and 40.4% ± 0.2% using AS and PFS, respectively. Hemicellulose solubilization could have been affected by the buffering effect of the biomass, which has been said could reduce 1% (w/w) acid concentration in half [8]. Low acid levels are frequently used along with high temperatures; hemicellulose conversions of up to 97% (w/w) have been reported when using 0.1% (w/w) sulfuric acid at 180˚C, but still more than 50% was oligomers of hemicellulose [72]. In a another study, 96% (w/w) conversion of hemicellulose was obtained with 0.8% (w/v) sulfuric acid from yellow poplar sawdust at 175˚C [61]. PFS and AS nanoparticles converted 66.3% ± 1.7% and 61.0% ± 1.2% of the hemicelluloses at acid levels 50 and 400 fold lower than those acid sulfuric solutions at 160˚C.

PFS and AS nanoparticles gave similar amounts of recovered hemicellulose; and both catalysts gave more sugars than the control. A better performance of PFS nanoparticles was expected because perfluorosulfonic acids are known as superacids and can be more acidic than sulfuric acid [27,48,73]. The acid strength of these acids has been explained by the electron-withdrawing properties of the Fluorine atoms [74], but the leveling effect of water could have an effect on the catalytic activity of PFS nanoparticles [74]. Nanoparticles functionalized with alkyl-sulfonic acid show a significant improvement on hemicelluloses solubilization when using 160˚C instead of 80˚C, although the acid loading for this catalyst was relatively low. Similar acid capacity was reported previously for propyl-sulfonic acid-functionalized materials [38]. Low catalytic activity also could have been a consequence of the low water affinity observed for this catalyst in TGA experiments. These results agree with the findings of Van Rhijn et al. [75], who synthesized mesoporous silicas functionalized with propylsulfonic acid and obtained moisture contents of less than 1%. The aggregation of both PFS and AS nanoparticles also could have an effect on their capacity to hydrolyze hemicelluloses due to a considerable reduction of their surface area; however, the attachment of PFS and AS acid functions could have stabilized the acid and allowed moderate levels of hemicellulose hydrolysis compared with sulfuric acid solutions of similar acid strength.

4. Conclusion

Acid-functionalized magnetic nanoparticles were synthesized as catalysts for pretreatment and hydrolysis of lignocellulosic feedstock. TEM images confirmed that the synthesis of cobalt spinel ferrite yielded particles with diameters less than 10 nm. Coating the cobalt spinel ferrite particles did not significantly change the size distribution of the nanoparticles, although some particles agglomerated upon coating. FTIR and XPS spectra confirmed the covalent bonding between the magnetic core and the silica layer and the presence of sulfonic acid groups following functionalization. Analysis of sugars in the liquid fraction after pretreatment revealed a significant amount of oligosaccharides compared with the hydro-thermolysis when using PFS or AS nanoparticles at 160˚C. The acid-functionalized nanoparticles broke down the non-soluble polysaccharides into oligomeric forms.

5. Acknowledgements

This project is supported by the NSF award CNET- 1033538 and the NSF EPSCoR Kansas Center for Solar Energy Research. This material is also based upon work supported by NSF Grant # 0903701: “Integrating the Socioeconomic, Technical, and Agricultural Aspects of Renewable and Sustainable Biorefining Program awarded to Kansas State University.” Contribution number 12- 367-J from the Kansas Agricultural Experiment Station.

REFERENCES

  1. Renewable Fuels Association, “2010 Ethanol Industry Outlook,” 2010.
  2. Senate and House of Representatives of the United States of America in Congress, “Energy Indepence and Security Act,” 2007.
  3. Office of the Biomass Program, “Biomass: Multi-Year Program Plan, U.S. DOE,” 2010.
  4. S. Iborra, A. Corma and G. Huber, “Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering,” Chemical Reviews, Vol. 106, No. 9, 2006, pp. 4044-4098. doi:10.1021/cr068360d
  5. C. E. Wyman and B. J. Goodman, “Biotechnology for Production of Fuels, Chemicals, and Materials from Biomass,” Applied Biochemistry and Biotechnology, Vol. 39-40, No. 1, 1993, pp. 41-59. doi:10.1007/BF02918976
  6. R. Preston, “Fibrillar Units in the Structure of Native Cellulose,” Discussions of the Faraday Society, Vol. 11, No. 11, 1951, pp. 165-170. doi:10.1039/df9511100165
  7. O. Bobleter, “Hydrothermal Degradation of Polymers Derived from Plants,” Progress in Polymer Science, Vol. 19, No. 5, 1994, pp. 797-841. doi:10.1016/0079-6700(94)90033-7
  8. J. D. McMillan, “Pretreatment of Lignocellulosic Biomass,” In: M. E. Himmel, J. O. Baker and R. P. Overend, Eds., Enzymatic Conversion of Biomass for Fuels Production, American Chemical Society, 1994, pp. 292-294. doi:10.1021/bk-1994-0566.ch015
  9. N. Rodrussamee, N. Lertwattanasakul, K. Hirata, S. Limtong and T. Kosaka, “Growth and Ethanol Fermentation Ability on Hexose and Pentose Sugars and Glucose Effect Under various Conditions in Thermotolerant Yeast Kluyveromyces Marxianus,” Applied Microbiology and Biotechnology, Vol. 90, No. 4, 2011, pp. 1573-1586. doi:10.1007/s00253-011-3218-2
  10. F. M. Girio, C. Fonseca, F. Carvalheiro, L. C. Duarte and S. Marques, “Hemicelluloses for Fuel Ethanol: A Review,” Bioresource Technology, Vol. 101, No. 13, 2010, pp. 4775-4800. doi:10.1016/j.biortech.2010.01.088
  11. L. Olsson, H. R. Soerensen, B. P. Dam, H. Christensen and K. M. Krogh, “Separate and Simultaneous Enzymatic Hydrolysis and Fermentation of Wheat Hemicellulose with Recombinant Xylose Utilizing Saccharomyces Cerevisiae,” Applied Biochemistry and Biotechnology, Vol. 129, No. 1-3, 2006, pp. 117-129. doi:10.1385/ABAB:129:1:117
  12. A. Bacic and B. Stone, “A (1 → 3)-Linked and (1 → 4)- Linked Beta-D-Glucan in the Endosperm Cell-Walls of Wheat,” Carbohydrate Research, Vol. 82, No. 2, 1980, pp. 372-377. doi:10.1016/S0008-6215(00)85713-4
  13. V. Menon, G. Prakash and M. Rao, “Enzymatic Hydrolysis and Ethanol Production using Xyloglucanase and Debaromyces Hansenii from Tamarind Kernel Powder: Galactoxyloglucan Predominant Hemicellulose,” Journal of Biotechnology, Vol. 148, No. 4, 2010, pp. 233-239. doi:10.1016/j.jbiotec.2010.06.004
  14. R. de Vries and J. Visser, “Aspergillus Enzymes Involved in Degradation of Plant Cell Wall Polysaccharides,” Microbiology and Molecular Biology reviews, Vol. 65, No. 4, 2001, pp. 497-522. doi:10.1128/MMBR.65.4.497-522.2001
  15. J. Vincken, W. York, G. Beldman and A. Voragen, “Two General Branching Patterns of Xyloglucan, XXXG and XXGG,” Plant Physiology, Vol. 114, No. 1, 1997, pp. 9-13. doi:10.1104/pp.114.1.9
  16. A. Matsushika, H. Inoue, K. Murakami, O. Takimura and S. Sawayama, “Bioethanol Production Performance of Five Recombinant Strains of Laboratory and Industrial Xylose-Fermenting Saccharomyces Cerevisiae,” Bioresource Technology, Vol. 100, No. 8, 2009, pp. 2392-2398. doi:10.1016/j.biortech.2008.11.047
  17. J. Song and D. Wei, “Production and Characterization of Cellulases and Xylanases of Cellulosimicrobium Cellulans Grown in Pretreated and Extracted Bagasse and Minimal Nutrient Medium M9,” Biomass Bioenergy, Vol. 34, No. 12, 2010, pp. 1930-1934. doi:10.1016/j.biombioe.2010.08.010
  18. C. Q. Zhang, W. Qi, F. Wang, Q. Li and R. X. Su, “Ethanol from Corn Stover using SSF: An Economic Assessment,” Energy Sources Part B: Economics, Planning and Policy, Vol. 6, No. 2, 2011, pp. 136-144.
  19. D. Y. Corredor, X. S. Sun, J. M. Salazar, K. L. Hohn and D. Wang, “Enzymatic Hydrolysis of Soybean Hulls using Dilute Acid and Modified Steam-Explosion Pretreatments,” Journal of Biobased Materials and Bioenergy, Vol. 2, No. 1, 2008, pp. 43-50. doi:10.1166/jbmb.2008.201
  20. E. Viola, F. Nanna, E. Larocca, M. Cardinale, D. Barisano and F. Zimbardi, “Acid Impregnation and Steam Explosion of Corn Stover in Batch Processes,” Industrial Crops and Products, Vol. 26, No. 2, 2007, pp. 195-206. doi:10.1016/j.indcrop.2007.03.005
  21. U.S. Department of Energy, “Concentrated Acid Hydrolysis,” 2006. http://www1.eere.energy.gov/biomass/printable_versions/concentrated_acid.html
  22. Y. Lee and S. Kim, “Diffusion of Sulfuric Acid within Lignocellulosic Biomass Particles and its Impact on Dilute-Acid Pretreatment,” Bioresource Technology, Vol. 83, No. 2, 2002, pp. 165-171. doi:10.1016/S0960-8524(01)00197-3
  23. N. S. Mosier, C. M. Ladisch and M. R. Ladisch, “Characterization of Acid Catalytic Domains for Cellulose Hydrolysis and Glucose Degradation,” Biotechnology and Bioengineering, Vol. 79, No. 6, 2002, pp. 610-618. doi:10.1002/bit.10316
  24. K. Cejpek, J. Velisek and O. Novotny, “Formation of Carboxylic Acids during Degradation of Monosaccharides,” Czech Journal of Food Science, Vol. 26, No. 2, 2008, pp. 113-131.
  25. J. Delgenes, “Effects of Lignocellulose Degradation Products on Ethanol Fermentations of Glucose and Xylose by Saccharomyces Cerevisiae, Zymomonas Mobilis, Pichia Stipitis, and Candida Shehatae,” Enzyme and Microbial Technology, Vol. 19, No. 3, 1996, pp. 220-225. doi:10.1016/0141-0229(95)00237-5
  26. J. M. Oliva, M. J. Negro and F. Saez, “Effects of Acetic Acid, Furfural and Catechol Combinations on Ethanol Fermentation of Kluyveromyces Marxianus,” Process Biochemistry, Vol. 41, No. 5, 2006, pp. 1223-1228. doi:10.1016/j.procbio.2005.12.003
  27. A. Corma and H. Garcia, “Silica-Bound Homogeneous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis.” Advanced Synthesis & Catalysis, Vol. 348, No. 12-13, 2006, pp. 1391-1412. doi:10.1002/adsc.200606192
  28. M. A. Harmer, Q. Sun, A. J. Vega, W. E. Farneth, A. Heidekum and W. F. Hoelderich, “Nafion Resin-Silica Nanocomposite Solid Acid Catalysts. Microstructure-Processing-Property Correlations,” Green Chemistry, Vol. 2, No. 1, 2000, pp. 7-14. doi:10.1039/a907892d
  29. M. Yurdakoc, M. Akcay, Y. Tonbul and K. Yurdakoc, “Acidity of Silica-Alumina Catalysts by Amine Titration using Hammett Indicators and FT-IR Study of Pyridine Adsorption,” Turkish Journal of Chemistry, Vol. 23, No. 3, 1999, pp. 319-327.
  30. J. A. Bootsma and B. H. Shanks, “Cellobiose Hydrolysis Using Organic-Inorganic Hybrid Mesoporous Silica Catalysts,” Applied Catalysis A-General, Vol. 327, No. 1, 2007, pp. 44-51.doi:10.1016/j.apcata.2007.03.039
  31. P. L. Dhepe, M. Ohashi, S. Inagaki, M. Ichikawa and A. Fukuoka, “Hydrolysis of Sugars Catalyzed by WaterTolerant Sulfonated Mesoporous Silicas,” Catalysis Letters, Vol. 102, No. 3-4, 2005, pp. 163-169. doi:10.1007/s10562-005-5850-x
  32. A. Onda, T. Ochi and K. Yanagisawa, “Selective Hydrolysis of Cellulose into Glucose Over Solid Acid Catalysts,” Green Chemistry, Vol. 10, No. 10, 2008, pp. 1033-1037. doi:10.1039/b808471h
  33. K. Shimizu, H. Furukawa, N. Kobayashi, Y. Itaya and A. Satsuma, “Effects of Bronsted and Lewis Acidities on Activity and Selectivity of Heteropolyacid-Based Catalysts for Hydrolysis of Cellobiose and Cellulose,” Green Chemistry, Vol. 11, No. 10, 2009, pp. 1627-1632. doi:10.1039/b913737h
  34. P. Dhepe and R. Sahu, “A Solid-Acid-Based Process for the Conversion of Hemicellulose,” Green Chemistry, Vol. 12, No. 12, 2010, pp. 2153-2156. doi:10.1039/c004128a
  35. A. Bell, “The Impact of Nanoscience on Heterogeneous Catalysis,” Science, Vol. 299, No. 5613, 2003, pp. 1688- 1691. doi:10.1126/science.1083671
  36. V. Polshettiwar and R. Varma, “Green Chemistry by Nano-Catalysis,” Green Chemistry, Vol. 12, No. 5, 2010, pp. 743-754. doi:10.1039/b921171c
  37. M. Zhang, B. L. Cushing and C. J. O’Connor, “Synthesis and Characterization of Monodisperse Ultra-Thin SilicaCoated Magnetic Nanoparticles,” Nanotechnology, Vol. 19, No. 8, 2008, pp. 1-5. doi:10.1088/0957-4484/19/8/085601
  38. C. S. Gill, B. A. Price and C. W. Jones, “Sulfonic AcidFunctionalized Silica-Coated Magnetic Nanoparticle Catalysts.” Journal of Catalysis, Vol. 251, No. 1, 2007, pp. 145-152. doi:10.1016/j.jcat.2007.07.007
  39. P. D. Stevens, J. Fan, H. M. R. Gardimalla, M. Yen and Y. Gao, “Superparamagnetic Nanoparticle-Supported Catalysis of Suzuki Cross-Coupling Reactions.” Organic Letters, Vol. 7, No. 11, 2005, pp. 2085-2088. doi:10.1021/ol050218w
  40. N. T. S. Phan and C. W. Jones, “Highly Accessible Catalytic Sites on Recyclable Organosilane-Functionalized Magnetic Nanoparticles: An Alternative to Functionalized Porous Silica Catalysts,” Journal of Molecular Catalysis A: Chemical, Vol. 253, No. 1-2, 2006, pp. 123-131. doi:10.1016/j.molcata.2006.03.019
  41. A. J. Rondinone, A. C. S. Samia and Z. J. Zhang, “Superparamagnetic Relaxation and Magnetic Anisotropy Energy Distribution in CoFe2O4 Spinel Ferrite Nanocrystallites,” Journal of Physical Chemistry B, Vol. 103, No. 33, 1999, pp. 6876-6880.doi:10.1021/jp9912307
  42. A. Sluiter, B. Hames, R. Ruiz, et al., “Determination of Structural Carbohydrates and Lignin in Biomass,” 2008. http://www.nrel.gov/biomass/pdfs/42618.pdf
  43. A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter and D. Templeton, “Determination of Sugars, Byproducts, and Degradation Products in Liquid Fraction Process Samples,” 2008. http://www.nrel.gov/biomass/pdfs/42623.pdf
  44. J. Silva, W. de Brito and N. Mohallem, “Influence of Heat Treatment on Cobalt Ferrite Ceramic Powders,” Materials Science Engineering B: Solid-State Materials for Advanced Technology, Vol. 112, No. 2-3, 2004, pp. 182-187.
  45. M. Naseri, E. Saion, H. Ahangar, A. Shaari and M. Hashim, “Simple Synthesis and Characterization of Cobalt Ferrite Nanoparticles by a Thermal Treatment Method,” Journal of Nanomaterials, Vol. 2010, 2010, pp. 1-8. doi:10.1155/2010/907686
  46. X. S. Zhao, G. Q. Lu and X. Hu, “Characterization of the Structural and Surface Properties of Chemically Modified MCM-41 Material,” Microporous and Mesoporous Materials, Vol. 41, 2000, pp. 37-47.
  47. M. Colilla, I. Izquierdo-Barba, S. Sanchez-Salcedo, J. Fierro, J. Hueso and M. Vallet-Regi, “Synthesis and Characterization of Zwitterionic SBA-15 Nanostructured Materials,” Chemistry of Materials, Vol. 22, No. 23, 2010, pp. 6459-6466. doi:10.1021/cm102827y
  48. M. Alvaro, A. Corma, D. Das, V. Fornes and H. Garcia, “Nafion-Functionalized Mesoporous MCM-41 Silica shows High Activity and Selectivity for Carboxylic Acid Esterification and Friedel-Crafts Acylation Reactions,” Journal of Catalysis, Vol. 231, No. 1, 2005, pp. 48-55. doi:10.1016/j.jcat.2005.01.007
  49. S. Suganuma, K. Nakajima, M. Kitano, D. Yamaguchi, H. Kato, S. Hayashi and M. Hara, “Hydrolysis of Cellulose by Amorphous Carbon Bearing SO3H, COOH, and OH Groups,” Journal of the American Chemical Society, Vol. 130, No. 38, 2008, pp. 12787-12793. doi:10.1021/ja803983h
  50. R. Buzzoni, S. Bordiga, G. Ricchiardi, G. Spoto and A. Zecchina, “Interaction of H2O, CH3OH, (CH3)2O, CH3CN, and Pyridine with the Superacid Perfluorosulfonic Membrane Nafion: An IR and Raman Study,” Journal of Physical Chemistry, Vol. 99, No. 31, 1995, pp. 11937- 11951. doi:10.1021/j100031a023
  51. G. Blanco Brieva, J. Campos Martin, M. de Frutos and J. Fierro, “Preparation, Characterization, and Acidity Evaluation of Perfluorosulfonic Acid-Functionalized Silica Catalysts,” Industrial Engineering Chemistry Research, Vol. 47, No. 21, 2008, pp. 8005-8010.doi:10.1021/ie800221f
  52. T. H. Kim, Y. H. Im and Y. B. Hahn, “Plasma Enhanced Chemical Vapor Deposition of Low Dielectric Constant SiCFO Thin Films,” Chemical Physics Letters, Vol. 368, No. 1-2, 2003, pp. 36-40. doi:10.1016/S0009-2614(02)01715-3
  53. J. Scaranto, A. P. Charmet and S. Giorgianni, “IR Spectroscopy and Quantum-Mechanical Studies of the Adsorption of CH2CClF on TiO2,” Journal of Physical Chemistry C, Vol. 112, No. 25, 2008, pp. 9443-9447. doi:10.1021/jp801075n
  54. C. Biloiu, I. A. Biloiu, Y. Sakai, Y. Suda and A. Ohta, “Amorphous Fluorocarbon Polymer (a-C: F) Films obtained by Plasma Enhanced Chemical Vapor Deposition from Perfluoro-Octane (C8F18) Vapor I: Deposition, Morphology, Structural and Chemical Properties,” Journal of Vacuum Science & Technology A, Vol. 22, No. 4, 2004, pp. 1158-1165. doi:10.1116/1.1759354
  55. K. Zavadil, N. Armstrong and C. Peden, “Reactions at the Interface between Multi-Component Glasses and Metallic Lithium Films,” Journal of Materials Research, Vol. 4, No. 4, 1989, pp. 978-989. doi:10.1557/JMR.1989.0978
  56. K. Senapati, C. Borgohain and P. Phukan, “Synthesis of Highly Stable CoFe2O4 Nanoparticles and Their Use as Magnetically Separable Catalyst for Knoevenagel Reaction in Aqueous Medium,” Journal of Molecular Catalysis A, Vol. 339, No. 1-2, 2011, pp. 24-31. doi:10.1016/j.molcata.2011.02.007
  57. S. Hamoudi, S. Royer and S. Kaliaguine, “Propyland Arene-Sulfonic Acid Functionalized Periodic Mesoporous Organosilicas,” Microporous and Mesoporous Materials, Vol. 71, No. 1-3, 2004, pp. 17-25. doi:10.1016/j.micromeso.2004.03.009
  58. F. Carvalheiro, L. Duarte, R. Medeiros and F. Girio, “Optimization of Brewery’s Spent Grain Dilute-Acid Hydrolysis for the Production of Pentose-Rich Culture Media,” Applied Biochemistry and Biotechnology, Vol. 113, 2004, pp. 1059-1072. doi:10.1385/ABAB:115:1-3:1059
  59. S. E. Jacobsen and C. E. Wyman, “Xylose Monomer and Oligomer Yields for Uncatalyzed Hydrolysis of Sugarcane Bagasse Hemicellulose at Varying Solids Concentration,” Industrial Engineering Chemistry Research, Vol. 41, No. 6, 2002, pp. 1454-1461. doi:10.1021/ie001025+
  60. C. E. Wyman, B. E. Dale, R. T. Elander, M. Holtzapple, M. R. Ladisch and Y. Y. Lee, “Coordinated Development of Leading Biomass Pretreatment Technologies,” Bioresource Technology, Vol. 96, No. 18, 2005, pp. 1959-1966. doi:10.1016/j.biortech.2005.01.010
  61. S. Allen, D. Schulman, J. Lichwa, M. Antal and E. Jennings, “A Comparison of Aqueous and Dilute-Acid Single-Temperature Pretreatment of Yellow Poplar Sawdust,” Industrial Engineering Chemistry Research, Vol. 40, No. 10, 2001, pp. 2352-2361. doi:10.1021/ie000579+
  62. T. Marzialetti, C. Sievers and P. Agrawal, “Dilute Acid Hydrolysis of Loblolly Pine: A Comprehensive Approach,” Industrial Engineering Chemistry Research, Vol. 47, No. 19, 2008, pp. 7131-7140. doi:10.1021/ie800455f
  63. A. Corma, S. Iborra and A. Velty, “Chemical Routes for the Transformation of Biomass into Chemicals,” Chemical Reviews, Vol. 107, No. 6, 2007, pp. 2411-2502. doi:10.1021/cr050989d
  64. B. Girisuta, L. Janssen and H. Heeres, “A Kinetic Study on the Conversion of Glucose to Levulinic Acid,” Chemical Engineering Research and Design, Vol. 84, No. 5, 2006, pp. 339-349. doi:10.1205/cherd05038
  65. G. Bonn and O. Bobleter, “Determination of the Hydrothermal Degradation Products of D-(U-14C) Glucose and D-(U-14C) Fructose by TLC,” Journal of Radioanalytical Chemistry, Vol. 79, No. 2, 1983, pp. 171-177. doi:10.1007/BF02518929
  66. A. P. Dunlop, “Furfural Formation and Behavior,” Industrial Engineering Chemistry, Vol. 40, No. 2, 1948, pp. 204-209. doi:10.1021/ie50458a006
  67. M. J. Antal, T. Leesomboon, W. S. Mok and G. N. Richards, “Mechanism of Formation of 2-Furaldehyde from D-Xylose,” Carbohydrate Research, Vol. 217, 1991, pp. 71-85. doi:10.1016/0008-6215(91)84118-X
  68. F. Carrasco and C. Roy, “Kinetic-Study of Dilute-Acid Prehydrolysis of Xylan-Containing Biomass,” Wood Science and Technology, Vol. 26, No. 3, 1992, pp. 189-208. doi:10.1007/BF00224292
  69. R. Torget and T. Hsu, “Two-Temperature Dilute-Acid Prehydrolysis of Hardwood Xylan using a Percolation Process,” Applied Biochemistry and Biotechnology, Vol. 45-46, 1994, pp. 5-21. doi:10.1007/BF02941784
  70. S. B. Kim, Y. Y. Lee and R. Torget, “Kinetics in Acid-Catalyzed Hydrolysis of Hardwood Hemicellulose,” Biotechnology & Bioengineering Symposium, Vol. 17, 1987, pp. 71-84.
  71. K. Grohmann, R. Torget and M. Himmel, “Optimization of Dilute Acid Pretreatment of Biomass,” Biotechnology & Bioengineering Symposium, Vol. 15, 1986, pp. 59-80.
  72. C. Liu and C. E. Wyman, “Effect of the Flow Rate of a Very Dilute Sulfuric Acid on Xylan, Lignin, and Total Mass Removal from Corn Stover,” Industrial & Engineering Chemistry Research, Vol. 43, No. 11, 2004, pp. 2781-2788. doi:10.1021/ie030754x
  73. J. Grondin, R. Sagnes and A. Commeyras, “Perfluorosulfonic Acids-3. Hammett Acidity Functions of Perfluoroalkanesulfonic Acids and of their Mixtures with SbF5,” Bulletin de la Société Chimique de France, No. 11, 1976, pp. 1779-1783.
  74. A. Corma, D. Das, V. Fornes, H. Garcia and M. Alvaro, “Single-Step Preparation and Catalytic Activity of Mesoporous MCM-41 and SBA-15 Silicas Functionalized with Perfluoroalkylsulfonic Acid Groups Analogous to Nafion (R),” Chemical Communications, No. 8, 2004, pp. 956-957.
  75. W. M. Van Rhijn, D. E. De Vos, B. F. Sels, W. D. Bossaert and P. A. Jacobs, “Sulfonic Acid Functionalized Ordered Mesoporous Materials as Catalysts for Condensation and Esterification Reactions,” Chemical Communications Cambridge, Vol. 1998, No. 3, 1998, pp. 317- 318. doi:10.1039/a707462j

NOTES

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