Selective Heterogeneous CO2 Electroreduction to Methanol

Catalytic electroreduction of carbon dioxide to useful chemical feedstocks is an environmentally and technologically important process, yet the low energy efficiency and difficulty in controlling product selectivity are great challenges. The reason for part of the latter is that there are presently no catalyst design principles to selectively control CO2 electroreduction toward a desired product. In this work, as a first attempt, we suggest combining a few criteria (CO binding energy, OH binding energy, and H binding energy) that can be collectively used as activity- and selectivity-determining descriptors to preferentially produce methanol over methane from CO2 electroreduction. We then apply these concepts to near-surface alloys (NSAs) to propose efficient and selective CO2 electrochemical reduction catalysts to produce methanol. The W/Au alloy is identified as a promising candidate to have increased catalyst efficiency (decreased CO2 reduction overpotential and increased overpotential for unwanted hydr...

[1]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[2]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[3]  J. Wilcox,et al.  Carbon dioxide conversion into hydrocarbon fuels on defective graphene-supported Cu nanoparticles from first principles. , 2014, Nanoscale.

[4]  Xin Wang,et al.  A review on the electrochemical reduction of CO2 in fuel cells, metal electrodes and molecular catalysts , 2014 .

[5]  W. Yim,et al.  Ozone Oxidation of Single Walled Carbon Nanotubes from Density Functional Theory , 2009 .

[6]  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.

[7]  Narendra K. Gupta,et al.  Electrochemical reduction of CO2 to hydrocarbons to store renewable electrical energy and upgrade biogas , 2007 .

[8]  J. Nørskov,et al.  Scaling relationships for adsorption energies on transition metal oxide, sulfide, and nitride surfaces. , 2008, Angewandte Chemie.

[9]  Harold H. Kung,et al.  Methanol production and use , 1994 .

[10]  Egill Skúlason,et al.  The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations , 2010 .

[11]  J. Nørskov,et al.  Computational high-throughput screening of electrocatalytic materials for hydrogen evolution , 2006, Nature materials.

[12]  M. Mavrikakis,et al.  Alloy catalysts designed from first principles , 2004, Nature materials.

[13]  Daniel R. Cohn,et al.  Alcohol Fueled Heavy Duty Vehicles Using Clean, High Efficiency Engines , 2010 .

[14]  Y. Hori,et al.  Adsorption of CO accompanied with simultaneous charge transfer on copper single crystal electrodes related with electrochemical reduction of CO2 to hydrocarbons , 1995 .

[15]  Joseph H. Montoya,et al.  Electroreduction of Methanediol on Copper , 2013, Catalysis Letters.

[16]  Zhipan Liu,et al.  General trends in the barriers of catalytic reactions on transition metal surfaces , 2001 .

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

[18]  M. Neurock,et al.  First-principles study of the role of solvent in the dissociation of water over a Pt-Ru alloy , 2003 .

[19]  J. Nørskov,et al.  Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals , 1999 .

[20]  Andrew A. Peterson,et al.  Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts , 2012 .

[21]  Y. Hori,et al.  Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution , 1990 .

[22]  Thomas Bligaard,et al.  Trends in the exchange current for hydrogen evolution , 2005 .

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

[24]  J. Nørskov,et al.  Hydrogen evolution over bimetallic systems: understanding the trends. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[25]  Toshio Tsukamoto,et al.  Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media , 1994 .

[26]  Kristian Sommer Thygesen,et al.  Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene , 2013 .

[27]  I. Chorkendorff,et al.  CO2 Electroreduction on Well-Defined Bimetallic Surfaces: Cu Overlayers on Pt(111) and Pt(211) , 2013 .

[28]  Jiujun Zhang,et al.  A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. , 2014, Chemical Society reviews.

[29]  Jean-Michel Savéant,et al.  Catalysis of the electrochemical reduction of carbon dioxide. , 2013, Chemical Society reviews.

[30]  G. Olah,et al.  Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons. , 2009, The Journal of organic chemistry.

[31]  Ture R. Munter,et al.  Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. , 2007, Physical review letters.

[32]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode , 2004 .

[33]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

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

[35]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[36]  Y. Hori,et al.  Electrochemical CO 2 Reduction on Metal Electrodes , 2008 .

[37]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[38]  Karen Chan,et al.  Molybdenum Sulfides and Selenides as Possible Electrocatalysts for CO2 Reduction , 2014 .

[39]  John-Paul Jones,et al.  Recycling of carbon dioxide to methanol and derived products - closing the loop. , 2014, Chemical Society reviews.

[40]  John Kitchin,et al.  Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces , 2011 .

[41]  G. Karlberg,et al.  Density-functional based modeling of the intermediate in the water production reaction on Pt(111). , 2004, Physical review letters.

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

[43]  Ib Chorkendorff,et al.  Enabling direct H2O2 production through rational electrocatalyst design. , 2013, Nature materials.

[44]  Andrew A. Peterson,et al.  Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces , 2011 .

[45]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[46]  M. G. Evans,et al.  The activation energy of diene association reactions , 1938 .

[47]  Jan Rossmeisl,et al.  Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites , 2014 .

[48]  Ib Chorkendorff,et al.  Design of an active site towards optimal electrocatalysis: overlayers, surface alloys and near-surface alloys of Cu/Pt(111). , 2012, Angewandte Chemie.