TY - JOUR
T1 - Electrocatalyst Design for Direct Borohydride Oxidation Guided by First Principles
AU - Rostamikia, Gholamreza
AU - Patel, Romesh J.
AU - Merino-Jimenez, Irene
AU - Hickner, Michael
AU - Janik, Michael J.
N1 - Funding Information:
This work was supported by the National Science Foundation, grant no. CBET-1264104.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/9
Y1 - 2017/2/9
N2 - Density functional theory (DFT) calculations are used to propose a Au-Cu binary metal catalyst for the electrochemical borohydride oxidation reaction (BOR), which is evaluated experimentally and observed to show enhanced oxidation activity relative to a pure Au electrode. Our previous work has applied DFT methods to determine the BOR mechanism and elucidate the key reaction steps that dictate catalyst activity and selectivity to complete oxidation. A balanced initial adsorption strength of the borohydride anion is essential for an active and selective catalyst. Adsorption must be strong enough to provide a reasonable coverage of surface species and promote B-H bond dissociation but not so strong as to promote easy dissociation and provide a high coverage of surface H atoms that result in H2 evolution. Borohydride adsorption energetics were evaluated for a series of close-packed pure metal surfaces. Copper catalysts appear encouraging but are not electrochemically stable under reaction conditions. Gold-copper alloys are predicted to show increased activity compared to a pure gold electrode while maintaining the selectivity to direct oxidation and increasing the stability compared to pure Cu. DFT results suggest an approximately 0.2 V decrease in the overpotential for borohydride oxidation on a Au2Cu(111) electrode compared to that on a Au(111) electrode. This DFT-predicted reduction in overpotential is realized experimentally. Electrodeposition was used to prepare AuCu electrodes, and their borohydride oxidation electrokinetics were examined by linear sweep voltammetry. An 88.5% gold and 11.5% copper sample demonstrated an overpotential reduction of 0.17 V compared to a pure Au electrode. The binding energy and adsorption free energy of BH4- over other surface alloys are also examined to further identify promising BOR electrodes. (Chemical Equation Presented).
AB - Density functional theory (DFT) calculations are used to propose a Au-Cu binary metal catalyst for the electrochemical borohydride oxidation reaction (BOR), which is evaluated experimentally and observed to show enhanced oxidation activity relative to a pure Au electrode. Our previous work has applied DFT methods to determine the BOR mechanism and elucidate the key reaction steps that dictate catalyst activity and selectivity to complete oxidation. A balanced initial adsorption strength of the borohydride anion is essential for an active and selective catalyst. Adsorption must be strong enough to provide a reasonable coverage of surface species and promote B-H bond dissociation but not so strong as to promote easy dissociation and provide a high coverage of surface H atoms that result in H2 evolution. Borohydride adsorption energetics were evaluated for a series of close-packed pure metal surfaces. Copper catalysts appear encouraging but are not electrochemically stable under reaction conditions. Gold-copper alloys are predicted to show increased activity compared to a pure gold electrode while maintaining the selectivity to direct oxidation and increasing the stability compared to pure Cu. DFT results suggest an approximately 0.2 V decrease in the overpotential for borohydride oxidation on a Au2Cu(111) electrode compared to that on a Au(111) electrode. This DFT-predicted reduction in overpotential is realized experimentally. Electrodeposition was used to prepare AuCu electrodes, and their borohydride oxidation electrokinetics were examined by linear sweep voltammetry. An 88.5% gold and 11.5% copper sample demonstrated an overpotential reduction of 0.17 V compared to a pure Au electrode. The binding energy and adsorption free energy of BH4- over other surface alloys are also examined to further identify promising BOR electrodes. (Chemical Equation Presented).
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U2 - 10.1021/acs.jpcc.6b12159
DO - 10.1021/acs.jpcc.6b12159
M3 - Article
AN - SCOPUS:85013844934
VL - 121
SP - 2872
EP - 2881
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 5
ER -