Nanoconfinement Allows a Less Active Cascade Catalyst to Produce More C2+ Products in Electrochemical CO2 Reduction

No Thumbnail Available
File version
Author(s)
Somerville, Samuel V
O'Mara, Peter B
Benedetti, Tania M
Cheong, Soshan
Schuhmann, Wolfgang
Tilley, Richard D
Gooding, J Justin
Griffith University Author(s)
Primary Supervisor
Other Supervisors
Editor(s)
Date
2023
Size
File type(s)
Location
License
Abstract

Enzymes with multiple distinct active sites linked by substrate channels combined with control over the solution environment near the active sites enable the formation of complex products from simple reactants via the confinement of intermediates. We mimic this concept to facilitate the electrochemical carbon dioxide reduction reaction using nanoparticles with a core that produces intermediate CO at different rates and a porous copper shell. CO2 reacts at the core to produce CO which then diffuses through the Cu to give higher order hydrocarbon molecules. By altering the rate of CO2 delivery, the activity of the CO producing site, and the applied potential, we show that the nanoparticle with lower activity for CO formation produces greater amounts of hydrocarbon products. This is attributed to a combination of higher local pH and the lower amount of CO, resulting in more stable nanoparticles. However, when lower amounts of CO2 were delivered to the core, the particles that are more active for CO formation produce more C3 products. The importance of these results is twofold. They show that in cascade reactions, more active intermediate producing catalysts do not necessarily give greater amounts of high-value products. The effect an intermediate producing active site has on the local solution environment around the secondary active site plays an important role. As the less active catalyst for producing CO also possesses greater stability, we show that nanoconfinement can be used to get the best of both worlds with regard to having a stable catalyst with high activity.

Journal Title

The Journal of Physical Chemistry C

Conference Title
Book Title
Edition
Volume

127

Issue

1

Thesis Type
Degree Program
School
Publisher link
Patent number
Funder(s)
Grant identifier(s)
Rights Statement
Rights Statement
Item Access Status
Note
Access the data
Related item(s)
Subject

Chemical sciences

Engineering

Science & Technology

Physical Sciences

Technology

Chemistry, Physical

Nanoscience & Nanotechnology

Persistent link to this record
Citation

Somerville, SV; O'Mara, PB; Benedetti, TM; Cheong, S; Schuhmann, W; Tilley, RD; Gooding, JJ, Nanoconfinement Allows a Less Active Cascade Catalyst to Produce More C2+ Products in Electrochemical CO2 Reduction, The Journal of Physical Chemistry C, 2023, 127 (1), pp. 289-299

Collections