Engineering topics

Rasouli, Armin Sedighian

Publications and source records attributed to Rasouli, Armin Sedighian.

3 records

DOE OSTI2024

Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity

Improving the kinetics and selectivity of CO 2 /CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp 2 hybridization of CO (ad) , facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC–CH 2 )* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C–O, Cu–C, and C–S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation

Nitrogen-doped graphene-supported single atoms convert CO 2 to CO, but fail to provide further hydrogenation to methane – a finding attributable to the weak adsorption of CO intermediates. To regulate the adsorption energy, here we investigate the metal-supported single atoms to enable CO 2 hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO 2 -to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm –2 , while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Gold-in-copper at low *CO coverage enables efficient electromethanation of CO 2

The renewable-electricity-powered CO 2 electroreduction reaction provides a promising means to store intermittent renewable energy in the form of valuable chemicals and dispatchable fuels. Renewable methane produced using CO 2 electroreduction attracts interest due to the established global distribution network; however, present-day efficiencies and activities remain below those required for practical application. Here we exploit the fact that the suppression of *CO dimerization and hydrogen evolution promotes methane selectivity: we reason that the introduction of Au in Cu favors *CO protonation vs. C-C coupling under low *CO coverage and weakens the *H adsorption energy of the surface, leading to a reduction in hydrogen evolution. We construct experimentally a suite of Au-Cu catalysts and control *CO availability by regulating CO 2 concentration and reaction rate. This strategy leads to a 1.6× improvement in the methane:H 2 selectivity ratio compared to the best prior reports operating above 100 mA cm -2 . We as a result achieve a CO 2 -to-methane Faradaic efficiency (FE) of (56 ± 2)% at a production rate of (112 ± 4) mA cm -2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗