A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis
A systematic and structure-agnostic method for identifying heterogeneous activity of solid acids for catalyzing cellulose hydrolysis is presented. The basis of the method is preparation of a supernatant liquid by exposing the solid acid to reaction conditions and subsequent use of the supernatant li...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-11-01
|
| Series: | Sustainable Chemistry |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2673-4079/2/4/36 |
| _version_ | 1797500488709570560 |
|---|---|
| author | Maksim Tyufekchiev Jordan Finzel Ziyang Zhang Wenwen Yao Stephanie Sontgerath Christopher Skangos Pu Duan Klaus Schmidt-Rohr Michael T. Timko |
| author_facet | Maksim Tyufekchiev Jordan Finzel Ziyang Zhang Wenwen Yao Stephanie Sontgerath Christopher Skangos Pu Duan Klaus Schmidt-Rohr Michael T. Timko |
| author_sort | Maksim Tyufekchiev |
| collection | DOAJ |
| description | A systematic and structure-agnostic method for identifying heterogeneous activity of solid acids for catalyzing cellulose hydrolysis is presented. The basis of the method is preparation of a supernatant liquid by exposing the solid acid to reaction conditions and subsequent use of the supernatant liquid as a cellulose hydrolysis catalyst to determine the effects of in situ generated homogeneous acid species. The method was applied to representative solid acid catalysts, including polymer-based, carbonaceous, inorganic, and bifunctional materials. In all cases, supernatant liquids produced from these catalysts exhibited catalytic activity for cellulose hydrolysis. Direct comparison of the activity of the solid acid catalysts and their supernatants could not provide unambiguous detection of heterogeneous catalysis. A reaction pathway kinetic model was used to evaluate potential false-negative interpretation of the supernatant liquid test and to differentiate heterogeneous from homogeneous effects on cellulose hydrolysis. Lastly, differences in the supernatant liquids obtained in the presence and absence of cellulose were evaluated to understand possibility of false-positive interpretation, using structural evidence from the used catalysts to gain a fresh understanding of reactant–catalyst interactions. While many solid acid catalysts have been proposed for cellulose hydrolysis, to our knowledge, this is the first effort to attempt to differentiate the effects of heterogeneous and homogeneous activities. The resulting supernatant liquid method should be used in all future attempts to design and develop solid acids for cellulose hydrolysis. |
| first_indexed | 2024-03-10T03:04:33Z |
| format | Article |
| id | doaj.art-28154c1215724cbaa34882162cb54656 |
| institution | Directory Open Access Journal |
| issn | 2673-4079 |
| language | English |
| last_indexed | 2024-03-10T03:04:33Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Sustainable Chemistry |
| spelling | doaj.art-28154c1215724cbaa34882162cb546562023-11-23T10:35:36ZengMDPI AGSustainable Chemistry2673-40792021-11-012464566910.3390/suschem2040036A New Method for Solid Acid Catalyst Evaluation for Cellulose HydrolysisMaksim Tyufekchiev0Jordan Finzel1Ziyang Zhang2Wenwen Yao3Stephanie Sontgerath4Christopher Skangos5Pu Duan6Klaus Schmidt-Rohr7Michael T. Timko8Department of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Civil and Environmental Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USADepartment of Chemistry, Brandeis University, 415 South Street, Waltham, MA 02453, USADepartment of Chemistry, Brandeis University, 415 South Street, Waltham, MA 02453, USADepartment of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USAA systematic and structure-agnostic method for identifying heterogeneous activity of solid acids for catalyzing cellulose hydrolysis is presented. The basis of the method is preparation of a supernatant liquid by exposing the solid acid to reaction conditions and subsequent use of the supernatant liquid as a cellulose hydrolysis catalyst to determine the effects of in situ generated homogeneous acid species. The method was applied to representative solid acid catalysts, including polymer-based, carbonaceous, inorganic, and bifunctional materials. In all cases, supernatant liquids produced from these catalysts exhibited catalytic activity for cellulose hydrolysis. Direct comparison of the activity of the solid acid catalysts and their supernatants could not provide unambiguous detection of heterogeneous catalysis. A reaction pathway kinetic model was used to evaluate potential false-negative interpretation of the supernatant liquid test and to differentiate heterogeneous from homogeneous effects on cellulose hydrolysis. Lastly, differences in the supernatant liquids obtained in the presence and absence of cellulose were evaluated to understand possibility of false-positive interpretation, using structural evidence from the used catalysts to gain a fresh understanding of reactant–catalyst interactions. While many solid acid catalysts have been proposed for cellulose hydrolysis, to our knowledge, this is the first effort to attempt to differentiate the effects of heterogeneous and homogeneous activities. The resulting supernatant liquid method should be used in all future attempts to design and develop solid acids for cellulose hydrolysis.https://www.mdpi.com/2673-4079/2/4/36biomasscellulosecellulose hydrolysissolid acidsolid acid catalyst |
| spellingShingle | Maksim Tyufekchiev Jordan Finzel Ziyang Zhang Wenwen Yao Stephanie Sontgerath Christopher Skangos Pu Duan Klaus Schmidt-Rohr Michael T. Timko A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis Sustainable Chemistry biomass cellulose cellulose hydrolysis solid acid solid acid catalyst |
| title | A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis |
| title_full | A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis |
| title_fullStr | A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis |
| title_full_unstemmed | A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis |
| title_short | A New Method for Solid Acid Catalyst Evaluation for Cellulose Hydrolysis |
| title_sort | new method for solid acid catalyst evaluation for cellulose hydrolysis |
| topic | biomass cellulose cellulose hydrolysis solid acid solid acid catalyst |
| url | https://www.mdpi.com/2673-4079/2/4/36 |
| work_keys_str_mv | AT maksimtyufekchiev anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT jordanfinzel anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT ziyangzhang anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT wenwenyao anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT stephaniesontgerath anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT christopherskangos anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT puduan anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT klausschmidtrohr anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT michaelttimko anewmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT maksimtyufekchiev newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT jordanfinzel newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT ziyangzhang newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT wenwenyao newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT stephaniesontgerath newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT christopherskangos newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT puduan newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT klausschmidtrohr newmethodforsolidacidcatalystevaluationforcellulosehydrolysis AT michaelttimko newmethodforsolidacidcatalystevaluationforcellulosehydrolysis |