Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Biomass-derived ethanol (EtOH) and acetaldehyde (AcH) conversion to 1,3-butadiene (1,3-BD) is an alternative process for 1,3-BD production. The present investigation reports the preparation and characterization of isolated La sites introduced into the silanol nests in DeAlBEA as well as detailed studies of the mechanism and kinetics for the conversion of an EtOH–AcH mixture to 1,3-BD. La sites supported on DeAlBEA are found to be present as (≡SiO)2La–OH groups that are H-bonded with adjacent Si–OH groups, possessing high C–C coupling activity and stability, superior to state-of-the-art Y-DeAlBEA. La sites supported on silica (La-SiO2) with a similar chemical structure but no H-bonding interaction with Si–OH groups were prepared for comparison. Lewis acid La sites promote AcH aldol condensation, and the activity of such sites is nearly identical for both La-DeAlBEA and La-SiO2. The rate of C4 product formation increases by a factor of 4.8 upon addition of EtOH to the feed of AcH over La-DeAlBEA, whereas that over La/SiO2 remains unchanged. Investigation of the mechanism and kinetics of AcH aldol condensation and EtOH–AcH conversion to 1,3-BD revealed two C–C bond forming pathways─AcH aldol condensation by Lewis acid La sites and direct coupling of EtOH–AcH over H-bonded (≡SiO)2La–OH···HO–Si≡ sites. This study provides important information about the role of the local environment of isolated Lewis acid sites and their effects on the direct coupling of EtOH and AcH to form 1,3-BD.

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Publication Details

Journal
ACS Catalysis
Published
2024-10-02
DOI
https://doi.org/10.1021/acscatal.4c03935
Citations
18
Primary Topic
Zeolite Catalysis and Synthesis
Type
article
Field-Weighted Citation Impact
2.85

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article

Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Long Hao Qi, Jeffrey J. Urban, Aaron D. Sadow, Takeshi Kobayashi et al.
18 citations
ACS Catalysis
Zeolite Catalysis and Synthesis
2.85
article

Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Long Hao Qi, Jeffrey J. Urban, Aaron D. Sadow, Takeshi Kobayashi, Tingshu Yang, Huihui Chen, Chaochao Dun, Peng Tian, Débora Motta Meira, Shutao Xu, Alexis T. Bell, Yanfei Zhang, Yuting Li, Liang Qi, Haocheng Hu
article en
18 citations

Abstract

Biomass-derived ethanol (EtOH) and acetaldehyde (AcH) conversion to 1,3-butadiene (1,3-BD) is an alternative process for 1,3-BD production. The present investigation reports the preparation and characterization of isolated La sites introduced into the silanol nests in DeAlBEA as well as detailed studies of the mechanism and kinetics for the conversion of an EtOH–AcH mixture to 1,3-BD. La sites supported on DeAlBEA are found to be present as (≡SiO)2La–OH groups that are H-bonded with adjacent Si–OH groups, possessing high C–C coupling activity and stability, superior to state-of-the-art Y-DeAlBEA. La sites supported on silica (La-SiO2) with a similar chemical structure but no H-bonding interaction with Si–OH groups were prepared for comparison. Lewis acid La sites promote AcH aldol condensation, and the activity of such sites is nearly identical for both La-DeAlBEA and La-SiO2. The rate of C4 product formation increases by a factor of 4.8 upon addition of EtOH to the feed of AcH over La-DeAlBEA, whereas that over La/SiO2 remains unchanged. Investigation of the mechanism and kinetics of AcH aldol condensation and EtOH–AcH conversion to 1,3-BD revealed two C–C bond forming pathways─AcH aldol condensation by Lewis acid La sites and direct coupling of EtOH–AcH over H-bonded (≡SiO)2La–OH···HO–Si≡ sites. This study provides important information about the role of the local environment of isolated Lewis acid sites and their effects on the direct coupling of EtOH and AcH to form 1,3-BD.

ACS CatalysisVol. 14(20)
Lawrence Berkeley National Laboratory (US), Iowa State University (US), Dalian Institute of Chemical Physics (CN), Chinese Academy of Sciences (CN), Ames National Laboratory (US), Dalian National Laboratory for Clean Energy (CN), Dalian Maritime University (CN), Canadian Light Source (Canada) (CA), University of California, Berkeley (US)
U.S. Department of Energy, Canadian Light Source, Iowa State University, National Natural Science Foundation of China, Chinese Academy of Sciences, Dalian Maritime University, Office of Science, Dalian Institute of Chemical Physics, Fundamental Research Funds for the Central Universities, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Dalian National Laboratory for Clean Energy, Argonne National Laboratory
Openalex Percentile: Top 9%
Zeolite Catalysis and Synthesis
2.85
DOIOpen Access PDFOpenAlex
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