Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

dc.conference.date2018-07-18 to 2018-07-21
dc.conference.locationHonolulu, HI, USA
dc.conference.name40th Annual International Conference of the IEEE Engineering in Medicine and Biology Society, EMBC 2018
dc.contributor.authorDe, Sudipta
dc.contributor.authorGevers, Lieven
dc.contributor.authorEmwas, Abdul-Hamid M.
dc.contributor.authorGascon, Jorge
dc.contributor.departmentChemical Engineering Program
dc.contributor.departmentCore Labs
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentNMR
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.date.accessioned2019-03-27T06:22:51Z
dc.date.available2019-03-27T06:22:51Z
dc.date.issued2019-01-16
dc.date.published-online2019-01-16
dc.date.published-print2019-02-18
dc.description.abstractAlthough the conversion of carbon dioxide (and its derivatives) into methanol has attracted remarkable attention in the last two decades, performing this process over a heterogeneous catalyst under mild conditions is still a challenging task. We report bipyridine-functionalized iridium-based heterogeneous catalysts for the hydrogenation of formic acid to produce methanol at low temperature. The solid catalysts were obtained by postsynthetic metalation of bipyridine-functionalized organosilica nanotubes with a [Cp*Ir(H2O)3]SO4 (Cp* = η5-pentamethylcyclopentadienyl) complex. Detailed studies including N2 physisorption, TEM, XPS, and 13C CP MAS NMR confirmed the stable structures of nanotube supports and the molecular nature of the active species. The catalysts showed competitive methanol selectivities compared to their homogeneous counterpart under similar reaction conditions. Addition of strong acids (such as triflic acid) showed improved methanol selectivity, whereas the presence of free bipyridine groups was found to promote the dehydrogenation of formic acid, resulting in low methanol selectivity. The catalyst showed excellent reusability over four consecutive cycles without any significant loss in activity and maintained its heterogeneous nature in extremely high acidic environment.
dc.description.sponsorshipResearch reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).
dc.eprint.versionPost-print
dc.identifier.citationDe S, Gevers L, Emwas A-H, Gascon J (2019) Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst. ACS Sustainable Chemistry & Engineering 7: 3933–3939. Available: http://dx.doi.org/10.1021/acssuschemeng.8b05070.
dc.identifier.doi10.1021/acssuschemeng.8b05070
dc.identifier.issn2168-0485
dc.identifier.issn2168-0485
dc.identifier.journalACS Sustainable Chemistry & Engineering
dc.identifier.urihttp://hdl.handle.net/10754/631731
dc.internal.reviewer-noteEmbargo until (dd/mm/yyyy): 16/01/2020
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acssuschemeng.8b05070
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acssuschemeng.8b05070.
dc.subjectHydrogen storage
dc.subjectHydrogenation of formic acid
dc.subjectIridium-bipyridine complex
dc.subjectMethanol production
dc.subjectMolecular heterogeneous catalysis
dc.titleConversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst
dc.typeArticle
display.details.left<span><h5>Type</h5>Article<br><br><h5>Authors</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=De, Sudipta,equals">De, Sudipta</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Gevers, Lieven,equals">Gevers, Lieven</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Emwas, Abdul-Hamid M.,equals">Emwas, Abdul-Hamid M.</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0001-7558-7123&spc.sf=dc.date.issued&spc.sd=DESC">Gascon, Jorge</a> <a href="https://orcid.org/0000-0001-7558-7123" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><br><h5>KAUST Department</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Chemical Engineering Program,equals">Chemical Engineering Program</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Core Labs,equals">Core Labs</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=KAUST Catalysis Center (KCC),equals">KAUST Catalysis Center (KCC)</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=NMR,equals">NMR</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Physical Science and Engineering (PSE) Division,equals">Physical Science and Engineering (PSE) Division</a><br><br><h5>Online Publication Date</h5>2019-01-16<br><br><h5>Print Publication Date</h5>2019-02-18<br><br><h5>Date</h5>2019-01-16</span>
display.details.right<span><h5>Abstract</h5>Although the conversion of carbon dioxide (and its derivatives) into methanol has attracted remarkable attention in the last two decades, performing this process over a heterogeneous catalyst under mild conditions is still a challenging task. We report bipyridine-functionalized iridium-based heterogeneous catalysts for the hydrogenation of formic acid to produce methanol at low temperature. The solid catalysts were obtained by postsynthetic metalation of bipyridine-functionalized organosilica nanotubes with a [Cp*Ir(H2O)3]SO4 (Cp* = η5-pentamethylcyclopentadienyl) complex. Detailed studies including N2 physisorption, TEM, XPS, and 13C CP MAS NMR confirmed the stable structures of nanotube supports and the molecular nature of the active species. The catalysts showed competitive methanol selectivities compared to their homogeneous counterpart under similar reaction conditions. Addition of strong acids (such as triflic acid) showed improved methanol selectivity, whereas the presence of free bipyridine groups was found to promote the dehydrogenation of formic acid, resulting in low methanol selectivity. The catalyst showed excellent reusability over four consecutive cycles without any significant loss in activity and maintained its heterogeneous nature in extremely high acidic environment.<br><br><h5>Citation</h5>De S, Gevers L, Emwas A-H, Gascon J (2019) Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst. ACS Sustainable Chemistry & Engineering 7: 3933–3939. Available: http://dx.doi.org/10.1021/acssuschemeng.8b05070.<br><br><h5>Acknowledgements</h5>Research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).<br><br><h5>Publisher</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.publisher=American Chemical Society (ACS),equals">American Chemical Society (ACS)</a><br><br><h5>Journal</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.journal=ACS Sustainable Chemistry & Engineering,equals">ACS Sustainable Chemistry & Engineering</a><br><br><h5>Conference/Event Name</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.conference=40th Annual International Conference of the IEEE Engineering in Medicine and Biology Society, EMBC 2018,equals">40th Annual International Conference of the IEEE Engineering in Medicine and Biology Society, EMBC 2018</a><br><br><h5>DOI</h5><a href="https://doi.org/10.1021/acssuschemeng.8b05070">10.1021/acssuschemeng.8b05070</a><br><br><h5>Additional Links</h5>https://pubs.acs.org/doi/10.1021/acssuschemeng.8b05070</span>
kaust.personDe, Sudipta
kaust.personGevers, Lieven
kaust.personEmwas, Abdul-Hamid M.
kaust.personGascon, Jorge
orcid.authorDe, Sudipta
orcid.authorGevers, Lieven
orcid.authorEmwas, Abdul-Hamid M.
orcid.authorGascon, Jorge::0000-0001-7558-7123
orcid.id0000-0001-7558-7123
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