The reaction of formic acid with RaneyTM copper

Samantha K Callear; Ian P Silverwood; Arunabhiram Chutia; C Richard A Catlow; Stewart F Parker

doi:10.1098/rspa.2016.0126

The reaction of formic acid with Raney^TM copper

Proc Math Phys Eng Sci. 2016 Apr;472(2188):20160126. doi: 10.1098/rspa.2016.0126.

Authors

Samantha K Callear¹, Ian P Silverwood², Arunabhiram Chutia², C Richard A Catlow³, Stewart F Parker⁴

Affiliations

¹ ISIS Facility, STFC Rutherford Appleton Laboratory , Chilton, Didcot OX11 0QX, UK.
² Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK; Research Complex at Harwell, STFC Rutherford Appleton Laboratory, UK Catalysis Hub, Chilton, Didcot OX11 0FA, UK.
³ Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK; Research Complex at Harwell, STFC Rutherford Appleton Laboratory, UK Catalysis Hub, Chilton, Didcot OX11 0FA, UK; Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK.
⁴ ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot OX11 0QX, UK; Research Complex at Harwell, STFC Rutherford Appleton Laboratory, UK Catalysis Hub, Chilton, Didcot OX11 0FA, UK.

Abstract

The interaction of formic acid with Raney^TM Cu proves to be complex. Rather than the expected generation of a monolayer of bidentate formate, we find the formation of a Cu(II) compound. This process occurs by direct reaction of copper and formic acid; in contrast, previous methods are by solution reaction. This is a rare example of formic acid acting as an oxidant rather than, as more commonly found, a reductant. The combination of diffraction, spectroscopic and computational methods has allowed this unexpected process to be characterized.

Keywords: copper; density functional theory; formate; methanol synthesis; neutron scattering.