Professional Education


  • Doctor of Philosophy, Stanford University, CHEM-PHD (2018)
  • Master of Science, Indian Institute of Technology, Kanpur, Chemistry (2009)

All Publications


  • Carbonate-Promoted Hydrogenation of Carbon Dioxide to Multicarbon Carboxylates. ACS central science Banerjee, A., Kanan, M. W. 2018; 4 (5): 606–13

    Abstract

    CO2 hydrogenation is a potential alternative to conventional petrochemical methods for making commodity chemicals and fuels. Research in this area has focused mostly on transition-metal-based catalysts. Here we show that hydrated alkali carbonates promote CO2 hydrogenation to formate, oxalate, and other C2+ carboxylates at elevated temperature and pressure in the absence of transition-metal catalysts or solvent. The reactions proceed rapidly, reaching up to 56% yield (with respect to CO32-) within minutes. Isotope labeling experiments indicate facile H2 and C-H deprotonations in the alkali cation-rich reaction media and identify probable intermediates for the C-C bond formations leading to the various C2+ products. The carboxylate salts are in equilibrium with volatile carboxylic acids under CO2 hydrogenation conditions, which may enable catalytic carboxylic acid syntheses. Our results provide a foundation for base-promoted and base-catalyzed CO2 hydrogenation processes that could complement existing approaches.

    View details for PubMedID 29806007

  • Carbon dioxide utilization via carbonate-promoted C-H carboxylation. Nature Banerjee, A., Dick, G. R., Yoshino, T., Kanan, M. W. 2016; 531 (7593): 215-219

    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.

    View details for DOI 10.1038/nature17185

    View details for PubMedID 26961655