Elucidating the Energetics and Effects of Solvents on Cellulose Hydrolysis Using a Polymeric Acid Catalyst
Source abstract
Abstract
A novel polymeric acid catalyst immobilized on a membrane substrate was found to possess superior catalytic activity and selectivity for biomass hydrolysis. The catalyst consists of two polymer chains, a poly(styrene sulfonic acid) (PSSA) polymer chain for catalyzing carbohydrate substrate, and a neighboring poly(vinyl imidazolium chloride) ionic liquid (PIL) polymer chain for promoting the solvation of the PSSA chain to enhance the catalytic activity. In order to elucidate the mechanism and determine the energetics of biomass catalytic processing using this unique catalyst, classical molecular dynamics (MD) coupled with metadynamics (MTD) simulations were conducted to determine the free energy surfaces (FES) of cellulose hydrolysis. The critical role that PIL plays in the catalytic conversion is elucidated. The solvation free energy and the interactions between PSSA, PIL, and cellulose chains are found to be significantly affected by the solvent.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Catalysis for Biomass Conversion · Biofuel production and bioconversion · Lignin and Wood Chemistry
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Biomedical Engineering, University of Arkansas, Fayetteville, AR 72701, USA
Funding
National Science Foundation
References (65)
Show source-provided references
1. Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines10.1016/j.pecs.2006.08.003 ↗
2. Greene, N., Celik, F.E., Dale, B., Jackson, M., Jayawardhana, K., Jin, H., Larson, E.D., Laser, M., Lynd, L., and MacKenzie, D. (2004). Growing Energy. How Biofuels Can Help End America’s Oil Dependence, Natural Resources Defense Council.
3. Bioenergy and biofuels: History, status, and perspective10.1016/j.rser.2014.10.013 ↗
4. A mini review on renewable sources for biofuel10.1016/j.biortech.2014.07.022 ↗
5. Review of evolution, technology and sustainability assessments of biofuel production10.1016/j.jclepro.2014.01.006 ↗
6. Production of first and second generation biofuels: A comprehensive review10.1016/j.rser.2009.10.003 ↗
7. Third generation biofuels from microalgae
8. Biomass pretreatment: Fundamentals toward application10.1016/j.biotechadv.2011.05.005 ↗
9. Bajpai, P. (2016). Summary of Biomass Pretreatment Methods, Pretreatment of Lignocellulosic Biomass for Biofuel Production, Springer.10.1007/978-981-10-0687-6 ↗
10. Recent updates on different methods of pretreatment of lignocellulosic feedstocks: A review10.1186/s40643-017-0137-9 ↗
11. Methods for Pretreatment of Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production10.1021/ie801542g ↗
12. Hydrolysis of Wood Cellulose with Hydrochloric Acid and Sulfur Dioxide and the Decomposition of its Hydrolytic Products10.1021/j150468a003 ↗
13. The Effect of Aqueous Hydrochloric Acid on the Cotton Cellulose III Lattice and Its Implications Concerning the Determinations of Crystallinity and Leveling-off Degree of Polymerization 210.1021/ja01647a044 ↗
14. Degradation of cotton cellulose treated with hydrochloric acid either in water or in ethanol10.1016/j.foodhyd.2008.10.005 ↗
15. The biological degradation of cellulose10.1111/j.1574-6976.1994.tb00033.x ↗
16. Hydrolysis of lignocellulosic materials for ethanol production: A review10.1016/S0960-8524(01)00212-7 ↗
17. Biological conversion of lignocellulosic biomass to ethanol10.1016/S0168-1656(97)00073-4 ↗
18. Molecular Dynamics and Metadynamics Simulations of the Cellulase Cel48F
19. Molecular dynamics simulation of the processive endocellulase Cel48F from Clostridium cellulolyticum: A novel “water-control mechanism” in enzymatic hydrolysis of cellulose10.1002/jmr.2364 ↗
20. Catalytic mechanism and origin of high activity of cellulase TmCel12A at high temperature: A quantum mechanical/molecular mechanical study10.1007/s10570-013-0011-7 ↗
21. Simulation analysis of the cellulase Cel7A carbohydrate binding module on the surface of the cellulose Iβ10.1007/s10570-013-0026-0 ↗
22. Ab initio molecular dynamics simulations of β-d-glucose and β-d-xylose degradation mechanisms in acidic aqueous solution10.1016/j.carres.2005.07.021 ↗
23. Qian, X., Nimlos, M.R., Johnson, D.K., and Himmel, M.E. (2005). Acidic Sugar Degradation Pathways, Twenty-Sixth Symposium on Biotechnology for Fuels and Chemicals, Humana Press.
24. The Effects of Water on β-d-Xylose Condensation Reactions10.1021/jp9025442 ↗
25. Free Energy Landscape for Glucose Condensation Reactions10.1021/jp1078407 ↗
26. The role of hydrogen-bonding interactions in acidic sugar reaction pathways10.1016/j.carres.2010.07.008 ↗
27. Mechanisms and Energetics for Acid Catalyzed β-d-Glucose Conversion to 5-Hydroxymethylfurfurl10.1021/jp2041982 ↗
28. Mechanisms and Energetics for Brønsted Acid-Catalyzed Glucose Condensation, Dehydration and Isomerization Reactions10.1007/s11244-012-9790-6 ↗
29. Glucose Isomerization to Fructose from ab Initio Molecular Dynamics Simulations10.1021/jp303842g ↗
30. Free Energy Surface for Brønsted Acid-Catalyzed Glucose Ring-Opening in Aqueous Solution10.1021/jp402739q ↗
31. Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent10.1016/j.carres.2014.02.010 ↗
32. Biomimetic Chemistry and Artificial Enzymes: Catalysis by Design10.1021/ar00051a008 ↗
33. Mimicking hydrogenases: From biomimetics to artificial enzymes10.1016/j.ccr.2013.12.018 ↗
34. Novel polymeric solid acid catalysts for cellulose hydrolysis10.1039/c3ra43987a ↗
35. Polymeric Solid Acid Catalysts for Lignocellulosic Biomass Fractionation10.1021/acs.iecr.7b05286 ↗
36. Glucose production from lignocellulosic biomass using a membrane-based polymeric solid acid catalyst10.1016/j.biombioe.2018.07.017 ↗
37. Escaping free-energy minima10.1073/pnas.202427399 ↗
38. Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method10.1103/PhysRevLett.100.020603 ↗
39. Metadynamics as a Tool for Exploring Free Energy Landscapes of Chemical Reactions10.1021/ar040198i ↗
40. Metadynamics10.1002/wcms.31 ↗
41. Modeling Ionic Liquids Using a Systematic All-Atom Force Field10.1021/jp0362133 ↗
42. Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: A proton conducting electrolytic component in fuel cells10.1002/jcc.21929 ↗
43. Refining classical force fields for ionic liquids: Theory and application to [MMIM][Cl]10.1039/C2CP43698A ↗
44. Generic force fields for ionic liquids10.1016/j.molliq.2013.09.001 ↗
45. Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids10.1021/ja9621760 ↗
46. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A.H. (2009). Fox, Gaussian 09, Gaussian, Inc.
47. An approach to computing electrostatic charges for molecules10.1002/jcc.540050204 ↗
48. A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: The RESP model10.1021/j100142a004 ↗
49. Application of RESP charges to calculate conformational energies, hydrogen bond energies, and free energies of solvation10.1021/ja00074a030 ↗
50. Application of the multimolecule and multiconformational RESP methodology to biopolymers: Charge derivation for DNA, RNA, and proteins10.1002/jcc.540161106 ↗
51. Application of the RESP Methodology in the Parametrization of Organic Solvents10.1021/jp9717655 ↗
52. Sun, X. (2018). Structure and Property of Polymers and Biopolymers from Molecular Dynamic Simulations, University of Arkansas.
53. Case, D., Darden, T.A., Cheatham, T.E., Simmerling, C., Wang, J., Duke, R., Luo, R., Crowley, M., Walker, R., and Zhang, W. (2010). Amber 11, University of California, San Francisco.
54. PLUMED: A portable plugin for free-energy calculations with molecular dynamics10.1016/j.cpc.2009.05.011 ↗
55. Automatic atom type and bond type perception in molecular mechanical calculations10.1016/j.jmgm.2005.12.005 ↗
56. GLYCAM06: A generalizable biomolecular force field. Carbohydrates10.1002/jcc.20820 ↗
57. Comparison of simple potential functions for simulating liquid water10.1063/1.445869 ↗
58. Stochastic Problems in Physics and Astronomy10.1103/RevModPhys.15.1 ↗
59. Cheatham, Determination of Alkali and Halide Monovalent Ion Parameters for Use in Explicitly Solvated Biomolecular Simulations10.1021/jp8001614 ↗
60. Statistical Mechanics of Fluid Mixtures10.1063/1.1749657 ↗
61. Fermentable sugars by chemical hydrolysis of biomass10.1073/pnas.0912073107 ↗
62. A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins10.1002/cssc.201000426 ↗
63. Room temperature ionic liquids as emerging solvents for the pretreatment of lignocellulosic biomass10.1002/bit.23108 ↗
64. Conversion of biomass to sugars via ionic liquid hydrolysis: Process synthesis and economic evaluation, Biofuels10.1002/bbb.1336 ↗
65. Solubility of Cellulose in Water10.1038/141332b0 ↗