High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts.

Nanostructured surfaces have been shown to greatly enhance the activity and selectivity of many different catalysts. Here we report a nanostructured copper surface that gives high selectivity for ethylene formation from electrocatalytic CO2 reduction. The nanostructured copper is easily formed in situ during the CO2 reduction reaction, and scanning electron microscopy (SEM) shows the surface to be dominated by cubic structures. Using online electrochemical mass spectrometry (OLEMS), the onset potentials and relative selectivity toward the volatile products (ethylene and methane) were measured for several different copper surfaces and single crystals, relating the cubic shape of the copper surface to the greatly enhanced ethylene selectivity. The ability of the cubic nanostructure to so strongly favor multicarbon product formation from CO2 reduction, and in particular ethylene over methane, is unique to this surface and is an important step toward developing a catalyst that has exclusive selectivity for multicarbon products.

[1]  M. Koper,et al.  Electrochemical reduction of carbon dioxide on copper electrodes , 2017 .

[2]  Matthew W Kanan,et al.  CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. , 2012, Journal of the American Chemical Society.

[3]  Y. Hori,et al.  Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes , 2003 .

[4]  M. Koper,et al.  Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. , 2012, Journal of the American Chemical Society.

[5]  Thomas F. Jaramillo,et al.  New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces , 2012 .

[6]  M. Koper,et al.  Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals , 2013 .

[7]  M. Koper,et al.  On-line mass spectrometry system for measurements at single-crystal electrodes in hanging meniscus configuration , 2006 .

[8]  P. Longhi,et al.  Copper in sea-water, potential-pH diagrams , 1973 .

[9]  Chunguang Chen,et al.  Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals , 2015 .

[10]  G. Griffin,et al.  Electrochemical Reduction of CO2 Using Supported Cu2O Nanoparticles , 2013 .

[11]  M. Koper,et al.  The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes , 2014 .

[12]  A. Paul Alivisatos,et al.  Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst. , 2014, Journal of the American Chemical Society.

[13]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[14]  Andrew A. Peterson,et al.  How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels , 2010 .

[15]  G. Mul,et al.  Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons. , 2014, Physical chemistry chemical physics : PCCP.

[16]  G. Olah,et al.  Anthropogenic chemical carbon cycle for a sustainable future. , 2011, Journal of the American Chemical Society.

[17]  S. Kulinich,et al.  Scalable synthesis of hollow Cu2O nanocubes with unique optical properties via a simple hydrolysis-based approach , 2013 .