Electrochemical Reduction of CO2 to Fuels

Nicole Bernstein, Dr. Michael Janik

Department of Chemical Engineering, The Pennsylvania State University, University Park, PA

Goals and Motivation

Iron Catalysts: Carbon Reduction to Fuels: Thermal reduction of CO2 with H2 on Fe produces methane, Electrocatalytic reduction of CO2 can convert but electrochemical reduction produces only H2 (5) electricity to hydrocarbon fuels Copper metal has already been proven to produce Our goal: explain why hydrocarbons are not produced on Fe, towards defining catalyst design principles for optimal methane in CO2 reduction (1) Computational methods using Density Functional CO2 reduction to fuels Theory model reactions on the catalyst surface H+ + e+
Cu Fe Cu Cu Cu Cu

Research Objectives and Methods

Objectives: Understand what factors impede CO2 reduction to hydrocarbons on Fe. Computationally determine the relative energies of the reaction path for CO2 to hydrocarbons on an Fe (1 0 0) surface. Methods: Use of Density Functional Theory to computationally determine ground state energies of molecules in CO2 + + ne- CH CO * + nH 2 n-4+2xOx* + (2-x)H2O(g) reduction pathway through the Vienna ab-initio Simulation Package (2,3,4) Relative Energy A* (U ) = E E + (2 x)E G + eURHE RHE A* CO2,g H2O Calculations of relative energies of intermediates 2 H2
where URHE is the electrode potential on a relative hydrogen electrode scale

Comparison of Copper and Iron Catalysts

Path of Co2 Reduction: This study examines two possible paths of reduction, resulting in the production of methane or methanol Branching point occurs in the reduction of CO to either CHO or COH Copper Catalysts for Co2 Reduction: Both computationally and experimentally, Cu(111) reduces CO2 to CH4 rather than CH3OH at significant overpotentials (-1.15 VRHE) (1) The rate limiting step appears to be CO reduction to COH or COH reduction to C+H2O (1)
0

Iron Catalysts for Co2 Reduction: Experimentally, Fe fails to reduce CO2 to hydrocarbons DFT results for Fe(1 0 0) indicate favorable CO2 reduction to CO and CO reduction to CH3OH and CH4 at lower overpotential than Cu, contrary to experimental results
0 -1

-1

-2 -2 Relative Energy (eV) CO2 -3 COOH CH3OH COOH CO CHO Relative Energy (eV) -3 CH2O CH3O CO2

COOH COOH CO

COH CH2 CH3 C COH CH CH4

-4

CO

-4

CO CHO

-5 C

A*
-5

0 V-RHE -0.5 V-RHE

CH2O

-6 CH3OH CH3O -7

CH2 CH

A*

A* A*

0 V-RHE -0.5 V-RHE

CH3

-6 -8 CH4

Potential Impediments to CO2 Reduction on Iron (1 0 0)

Oxygen Buildup: On Fe (1 0 0), conversion of water to surface bound oxygen may be favorable Oxygen could bind to active sites on the surface, preventing further CO2 reduction. Carbon Buildup: xC* Cx* + (x-1)* Carbon buildup appears to be unfavorable on Fe after several preliminary calculations Hydrogen Evolution Reaction: Hydrogen Evolution is a competitive reaction on Iron, and experimentally hydrogen gas is the major product observed when CO2 reduction is attempted. H may simply outcompete CO2 derived species for active sites, limiting the rate of CO2 reduction to an undetectably small amount

2H+ + 2e- H2
CO2 hydrocarbons

X
H H H H H H H H H H H

Future Plans
Transition State Study: A clear understanding of carbon dioxide reduction is not complete without study of transition state energies Future plans involve using the climbing image nudged elastic band method to computationally determine transition states of key reactions Continued Study of Carbon Build-up: Analyze more conformations of multiple carbon atoms on Fe (1 0 0) surface

Summary and Conclusions

Iron has Potential as a Catalyst for CO2 Reduction: Computationally, the reaction pathway of CO2 reduction appears favorable Unknown factors are at play to prevent experimental success of the reaction A better understanding of CO2 reduction on Fe (1 0 0) could guide design of effective catalysts

References
(1) X. Nie, M. R. Esopi, M. J. Janik, A. Asthagiri. Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps Angew, Chem. Int. Ed. 52 (2013) 2459-2462. (2) G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) 558-561 (3) G. Kresse, J. Furthmaller, Comput. Mater. Sci. 6 (1996) 15-50. (4) G. Kresse, J. Furthmaller, Phys. Rev. B 54 (1996) 11169-11186 (5) Hori, Y. Electrochemical CO2 Reduction on Metal Electrodes. In Modern Aspects of Electrochemistry; Springer: New York, 2008; pp 89189.

Acknowledgements
NASA Pennsylvania Space Grant Consortium Women in Science and Engineering Program