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Title: Investigating the impact of micropore volume of aminosilica functionalized SBA-15 on catalytic activity for amine-catalyzed reactions

Abstract

Mesoporous materials such as SBA-15 are used in many applications since the materials are robust and have tunable properties. Whereas these materials are thought to be ideal, the materials are complex with the common synthesis methods producing materials that contain micropores. This work will investigate the impact of micropores on catalytic activity of aminosilica materials. For comparison, materials are formed using a standard method that produces materials with micropores (REG-SBA-15) and using a modified method that produces materials with negligible micropore volume (NMP-SBA-15). After grafting the calcined support with an aminosilane (either (N-methyl amino propyl) trimethoxy silane (denoted as 2°Am) or (N,N-diethyl-3-amino propyl) trimethoxy silane (3°Am)), catalytic testing experiments reveal that NMP-SBA-15 functionalized materials are more active than REG-SBA-15 functionalized materials for a range of reactions. The reactions include (a) glucose isomerization where amines interacting with surface silanols limit catalytic activity and (b) aldol and Knoevenagel chemistry where amine-silanol interactions increase the reaction rate. For aldol chemistry, the observed difference in rate is further investigated using site quantification experiments. Interestingly, the results reveal that three types of sites exist for each material, including sites that are (1) highly active, (2) intermediate active, and (3) inactive. Additionally, NMR experiments indicate thatmore » amines immobilized on REG-SBA-15 supports are less mobile than amines on NMP-SBA-15. For REG-SBA-15, the materials are found to have aminosilanes that have limited mobility and the largest fraction of inactive sites, which suggests that the inactive catalytic sites are in the micropores. Overall, the design of highly active catalytic materials can be achieved using materials that have limited micropore volumes.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [1]
+ Show Author Affiliations
  1. The Ohio State Univ., Columbus, OH (United States)
  2. Ames Lab., Ames, IA (United States)
  3. The Ohio State Univ., Columbus, OH (United States); National Taiwan Univ., Taipei (Taiwan)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; American Chemical Society Petroleum Research Fund; National Science Foundation (NSF); Ohio State University Institute for Materials Research; USDOE
OSTI Identifier:
1899321
Alternate Identifier(s):
OSTI ID: 1890234
Report Number(s):
IS-J-10,938
Journal ID: ISSN 0021-9517
Grant/Contract Number:  
AC02-07CH11358; ACS-PRF 55946-DNI5; NSF 1653587; NSF 2015669; OSU IMR FG0211; EMR-G00018
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 414; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aldol reaction and condensation; aminosilica; knoevenagel condensation; glucose isomerization; micropores; SBA-15

Citation Formats

Deshpande, Nitish, Chen, Jee-Yee, Kobayashi, Takeshi, Cho, Eun Hyun, Pineault, Hannah, Lin, Li-Chiang, and Brunelli, Nicholas A. Investigating the impact of micropore volume of aminosilica functionalized SBA-15 on catalytic activity for amine-catalyzed reactions. United States: N. p., 2022. Web. doi:10.1016/j.jcat.2022.09.016.
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Deshpande, Nitish, Chen, Jee-Yee, Kobayashi, Takeshi, Cho, Eun Hyun, Pineault, Hannah, Lin, Li-Chiang, & Brunelli, Nicholas A. Investigating the impact of micropore volume of aminosilica functionalized SBA-15 on catalytic activity for amine-catalyzed reactions. United States. https://doi.org/10.1016/j.jcat.2022.09.016
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Deshpande, Nitish, Chen, Jee-Yee, Kobayashi, Takeshi, Cho, Eun Hyun, Pineault, Hannah, Lin, Li-Chiang, and Brunelli, Nicholas A. Sat . "Investigating the impact of micropore volume of aminosilica functionalized SBA-15 on catalytic activity for amine-catalyzed reactions". United States. https://doi.org/10.1016/j.jcat.2022.09.016. https://www.osti.gov/servlets/purl/1899321.
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@article{osti_1899321,
title = {Investigating the impact of micropore volume of aminosilica functionalized SBA-15 on catalytic activity for amine-catalyzed reactions},
author = {Deshpande, Nitish and Chen, Jee-Yee and Kobayashi, Takeshi and Cho, Eun Hyun and Pineault, Hannah and Lin, Li-Chiang and Brunelli, Nicholas A.},
abstractNote = {Mesoporous materials such as SBA-15 are used in many applications since the materials are robust and have tunable properties. Whereas these materials are thought to be ideal, the materials are complex with the common synthesis methods producing materials that contain micropores. This work will investigate the impact of micropores on catalytic activity of aminosilica materials. For comparison, materials are formed using a standard method that produces materials with micropores (REG-SBA-15) and using a modified method that produces materials with negligible micropore volume (NMP-SBA-15). After grafting the calcined support with an aminosilane (either (N-methyl amino propyl) trimethoxy silane (denoted as 2°Am) or (N,N-diethyl-3-amino propyl) trimethoxy silane (3°Am)), catalytic testing experiments reveal that NMP-SBA-15 functionalized materials are more active than REG-SBA-15 functionalized materials for a range of reactions. The reactions include (a) glucose isomerization where amines interacting with surface silanols limit catalytic activity and (b) aldol and Knoevenagel chemistry where amine-silanol interactions increase the reaction rate. For aldol chemistry, the observed difference in rate is further investigated using site quantification experiments. Interestingly, the results reveal that three types of sites exist for each material, including sites that are (1) highly active, (2) intermediate active, and (3) inactive. Additionally, NMR experiments indicate that amines immobilized on REG-SBA-15 supports are less mobile than amines on NMP-SBA-15. For REG-SBA-15, the materials are found to have aminosilanes that have limited mobility and the largest fraction of inactive sites, which suggests that the inactive catalytic sites are in the micropores. Overall, the design of highly active catalytic materials can be achieved using materials that have limited micropore volumes.},
doi = {10.1016/j.jcat.2022.09.016},
journal = {Journal of Catalysis},
number = ,
volume = 414,
place = {United States},
year = {Sat Sep 24 00:00:00 EDT 2022},
month = {Sat Sep 24 00:00:00 EDT 2022}
}
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