Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts

Handle URI:
http://hdl.handle.net/10754/604946
Title:
Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts
Authors:
Chen, Jiawei; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Chen, Eugene Y.-X.
Abstract:
This contribution reports the first example of highly selective reduction of CO2 into CH4 via tandem hydrosilylation with mixed main-group organo-Lewis acid (LA) catalysts [Al(C6F5)3 + B(C6F5)3] {[Al] + [B]}. As shown by this comprehensive experimental and computational study, in this unique tandem catalytic process, [Al] effectively mediates the first step of the overall reduction cycle, namely the fixation of CO2 into HCOOSiEt3 (1) via the LA-mediated C=O activation, while [B] is incapable of promoting the same transformation. On the other hand, [B] is shown to be an excellent catalyst for the subsequent reduction steps 2–4, namely the hydrosilylation of the more basic intermediates [1 to H2C(OSiEt3)2 (2) to H3COSiEt3 (3) and finally to CH4] through the frustrated-Lewis-pair (FLP)-type Si–H activation. Hence, with the required combination of [Al] and [B], a highly selective hydrosilylative reduction of CO2 system has been developed, achieving high CH4 production yield up to 94%. The remarkably different catalytic behaviors between [Al] and [B] are attributed to the higher overall Lewis acidity of [Al] derived from two conflicting factors (electronic and steric effects), which renders the higher tendency of [Al] to form stable [Al]–substrate (intermediate) adducts with CO2 as well as subsequent intermediates 1, 2 and 3. Overall, the roles of [Al] and [B] are not only complementary but also synergistic in the total reduction of CO2, which render both [Al]-mediated first reduction step and [B]-mediated subsequent steps catalytic.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Selective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts 2016 Journal of the American Chemical Society
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
4-Apr-2016
DOI:
10.1021/jacs.6b01497
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
This work was supported by the US National Science Foundation (NSF- CHE- 1507702) for the study carried out at Colorado State University and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST. We thank Boulder Scientific Co. for the research gift of B(C6F5)3.
Is Supplemented By:
Chen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446069: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrd7; DOI:10.5517/ccdc.csd.cc1kjrd7; HANDLE:http://hdl.handle.net/10754/624555; Chen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446070: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrf8; DOI:10.5517/ccdc.csd.cc1kjrf8; HANDLE:http://hdl.handle.net/10754/624556
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.6b01497
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorChen, Jiaweien
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorChen, Eugene Y.-X.en
dc.date.accessioned2016-04-10T13:42:39Zen
dc.date.available2016-04-10T13:42:39Zen
dc.date.issued2016-04-04en
dc.identifier.citationSelective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalysts 2016 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.6b01497en
dc.identifier.urihttp://hdl.handle.net/10754/604946en
dc.description.abstractThis contribution reports the first example of highly selective reduction of CO2 into CH4 via tandem hydrosilylation with mixed main-group organo-Lewis acid (LA) catalysts [Al(C6F5)3 + B(C6F5)3] {[Al] + [B]}. As shown by this comprehensive experimental and computational study, in this unique tandem catalytic process, [Al] effectively mediates the first step of the overall reduction cycle, namely the fixation of CO2 into HCOOSiEt3 (1) via the LA-mediated C=O activation, while [B] is incapable of promoting the same transformation. On the other hand, [B] is shown to be an excellent catalyst for the subsequent reduction steps 2–4, namely the hydrosilylation of the more basic intermediates [1 to H2C(OSiEt3)2 (2) to H3COSiEt3 (3) and finally to CH4] through the frustrated-Lewis-pair (FLP)-type Si–H activation. Hence, with the required combination of [Al] and [B], a highly selective hydrosilylative reduction of CO2 system has been developed, achieving high CH4 production yield up to 94%. The remarkably different catalytic behaviors between [Al] and [B] are attributed to the higher overall Lewis acidity of [Al] derived from two conflicting factors (electronic and steric effects), which renders the higher tendency of [Al] to form stable [Al]–substrate (intermediate) adducts with CO2 as well as subsequent intermediates 1, 2 and 3. Overall, the roles of [Al] and [B] are not only complementary but also synergistic in the total reduction of CO2, which render both [Al]-mediated first reduction step and [B]-mediated subsequent steps catalytic.en
dc.description.sponsorshipThis work was supported by the US National Science Foundation (NSF- CHE- 1507702) for the study carried out at Colorado State University and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST. We thank Boulder Scientific Co. for the research gift of B(C6F5)3.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b01497en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.6b01497.en
dc.titleSelective Reduction of CO2 to CH4 by Tandem Hydrosilylation with Mixed Al/B Catalystsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USAen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, I-84084, Fisciano, Italyen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByChen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446069: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrd7en
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1kjrd7en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624555en
dc.relation.isSupplementedByChen, J., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1446070: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kjrf8en
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1kjrf8en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624556en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.