CoChat
Sign Up
Cited by 431Carbon dioxide utilization in catalysisIonic liquids properties and applicationsCO2 Reduction Techniques and Catalysts

Carbon dioxide utilization via carbonate-promoted C–H carboxylation

Banerjee, Aanindeeta, Dick, Graham R., Yoshino, Tatsuhiko, Kanan, Matthew W.·2016·Nature
DOI 10.1038/nature17185
Open this paper in CoChat — free account

Abstract

Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

Integrity signals

Registry

Crossref · 10.1038/nature17185

Cites

30 of 30 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • The reaction of furoic acid with molten Cs2CO3 under a CO2 flow or 8 bar CO2 can give FDCA in 70-89% yield within 12 h.

    “The reaction of furoic acid with molten Cs2CO3 under a CO2 flow or 8 bar CO2 can give FDCA 2-in 70-89% yield within 12 h.”

    From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [116]

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Related

Authors
Banerjee, A., Dick, G. R., Yoshino, T., & Kanan, M. W.
Affiliations
Stanford University (US)
Corresponding author
Kanan, Matthew W.
ORCID
Venue
Nature
Publisher
Springer Science and Business Media LLC
Published
2016-03
Volume
531
Issue
7593
Pages
215-219
ISSN
  • 0028-0836 (ISSN-L)
  • 1476-4687
DOI
10.1038/nature17185
OpenAlex
W2294626429
Cited by
431
References
30
Citations by year
2026: 20 · 2025: 45 · 2024: 52 · 2023: 48 · 2022: 43 · 2021: 46 · 2020: 43 · 2019: 37 · 2018: 47 · 2017: 38 · 2016: 12
FWCI
16.12
Type
journal article
Language
en
Open access
closed
Licence
www.springer.com/tdm (tdm)
Locations
  • Nature (publishedVersion)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
Funders
Camille and Henry Dreyfus Foundation
Topics
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
  • Physical Sciences › Chemical Engineering › Catalysis › Ionic liquids properties and applications
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
Keywords
molten salts, alkali metal cations, cesium, potassium, 2-furoic acid, furan-2,5-dicarboxylic acid, bio-based feedstocks, lignocellulosic biomass, polyethylene furandicarboxylate, CO2 fixation, greenhouse gas emissions reduction, carboxylate synthesis, biomass valorization
MeSH terms
Benzene, Benzoates, Bicarbonates, Carbon, Carbon Dioxide, Cesium, Dicarboxylic Acids, Food, Furans, Hydrogen Bonding, Hydrogenation, Lignin, Potassium, Ribulose-Bisphosphate Carboxylase, Temperature, Biomass, Biomimetics, Green Chemistry Technology

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review