Laboratory+for+Energy+and+Sustainability
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A New Strategy for the Optimal Electroreduction of CO2 to High-Value Products
-Researchers suggest that modulation of local CO2 concentration improves the selectivity, conversion rate, and electrode stability, and shed a new light on the electrochemical CO2 reduction technology for controlling emissions at a low cost.-
A KAIST research team presented three novel approaches for modulating local carbon dioxide (CO2) concentration in gas-diffusion electrode (GDE)-based flow electrolyzers. Their study also empirically demonstrated that providing a moderate local CO2 concentration is effective in promoting Carbon–Carbon (C–C) coupling reactions toward the production of multi-carbon molecules. This work, featured in the May 20th issue of Joule, serves as a rational guide to tune CO2 mass transport for the optimal production of valuable multi-carbon products.
Amid global efforts to reduce and recycle anthropogenic CO2 emissions, CO2 electrolysis holds great promise for converting CO2 into useful chemicals that were traditionally derived from fossil fuels. Many researches have been attempting to improve the selectivity of CO2 for commercially and industrially high-value multi-carbon products such as ethylene, ethanol, and 1-propanol, due to their high energy density and large market size.
In order to achieve the highly-selective conversion of CO2 into valuable multi-carbon products, past studies have focused on the design of catalysts and the tuning of local environment related to pH, cations, and molecular additives.
Conventional CO2 electrolytic systems relied heavily on an alkaline electrolyte that is often consumed in large quantities when reacting with CO2, and thus led to an increase in the operational costs. Moreover, the life span of a catalyst electrode was short, due to its inherent chemical reactivity.
In their recent study, a group of KAIST researchers led by Professor Jihun Oh from the Department of Materials Science and Engineering reported that the local CO2 concentration has been an overlooked factor that largely affects the selectivity toward multi-carbon products.
Professor Oh and his researchers Dr. Ying Chuan Tan, Hakhyeon Song, and Kelvin Berm Lee proposed that there is an intimate relation between local CO2 and multi-carbon product selectivity during electrochemical CO2 reduction reactions. The team employed the mass-transport modeling of a GDE-based flow electrolyzer that utilizes copper oxide (Cu2O) nanoparticles as model catalysts. They then identified and applied three approaches to modulate the local CO2 concentration within a GDE-based electrolytic system, including 1) controlling the catalyst layer structure, 2) CO2 feed concentration, and 3) feed flow rate.
Contrary to common intuition, the study showed that providing a maximum CO2 transport leads to suboptimal multi-carbon product faradaic efficiency. Instead, by restricting and providing a moderate local CO2 concentration, C–C coupling can be significantly enhanced.
The researchers demonstrated experimentally that the selectivity rate increased from 25.4% to 61.9%, and from 5.9% to 22.6% for the CO2 conversion rate. When a cheap milder near-neutral electrolyte was used, the stability of the CO2 electrolytic system improved to a great extent, allowing over 10 hours of steady selective production of multi-carbon products.
Dr. Tan, the lead author of the paper, said, “Our research clearly revealed that the optimization of the local CO2 concentration is the key to maximizing the efficiency of converting CO2 into high-value multi-carbon products.”
Professor Oh added, “This finding is expected to deliver new insights to the research community that variables affecting local CO2 concentration are also influential factors in the electrochemical CO2 reduction reaction performance. My colleagues and I hope that our study becomes a cornerstone for related technologies and their industrial applications.”
This work was supported by the Korean Ministry of Science and ICT (MSIT) Creative Materials Discovery Program.
Publication:
Tan, Y. C et al. (2020) ‘Modulating Local CO2 Concentration as a General Strategy for Enhancing C−C Coupling in CO2 Electroreduction’, Joule, Vol. 4, Issue 5, pp. 1104-1120. Available online at https://doi.org/10.1016/j.joule.2020.03.013
Profile: Jihun Oh, PhD
Associate Professor
jihun.oh@kaist.ac.kr
http://les.kaist.ac.kr/
Laboratory for Energy and Sustainability (LE&S)
Department of Materials Science and Engineering (MSE)
Korea Advanced Institute of Science and Technology (KAIST)
https://www.kaist.ac.kr
Daejeon 34141, Republic of Korea
Profile: Ying Chuan Tan, PhD
tanyc@kaist.ac.kr
LE&S, MSE, KAIST
Profile: Hakhyeon Song, PhD Candidate
hyeon0401@kaist.ac.kr
LE&S, MSE, KAIST
Profile: Kelvin Berm Lee, M.S. Candidate
kbl9105@kaist.ac.kr
LE&S, MSE, KAIST
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2020.06.03 View 10693 -
3D Hierarchically Porous Nanostructured Catalyst Helps Efficiently Reduce CO2
- This new catalyst will bring CO2 one step closer to serving as a sustainable energy source. -
KAIST researchers developed a three-dimensional (3D) hierarchically porous nanostructured catalyst with carbon dioxide (CO2) to carbon monoxide (CO) conversion rate up to 3.96 times higher than that of conventional nanoporous gold catalysts. This new catalyst helps overcome the existing limitations of the mass transport that has been a major cause of decreases in the CO2 conversion rate, holding a strong promise for the large-scale and cost-effective electrochemical conversion of CO2 into useful chemicals.
As CO2 emissions increase and fossil fuels deplete globally, reducing and converting CO2 to clean energy electrochemically has attracted a great deal of attention as a promising technology. Especially due to the fact that the CO2 reduction reaction occurs competitively with hydrogen evolution reactions (HER) at similar redox potentials, the development of an efficient electrocatalyst for selective and robust CO2 reduction reactions has remained a key technological issue.
Gold (Au) is one of the most commonly used catalysts in CO2 reduction reactions, but the high cost and scarcity of Au pose obstacles for mass commercial applications. The development of nanostructures has been extensively studied as a potential approach to improving the selectivity for target products and maximizing the number of active stable sites, thus enhancing the energy efficiency.
However, the nanopores of the previously reported complex nanostructures were easily blocked by gaseous CO bubbles during aqueous reactions. The CO bubbles hindered mass transport of the reactants through the electrolyte, resulting in low CO2 conversion rates.
In the study published in the Proceedings of the National Academy of Sciences of the USA (PNAS) on March 4, a research group at KAIST led by Professor Seokwoo Jeon and Professor Jihun Oh from the Department of Materials Science and Engineering designed a 3D hierarchically porous Au nanostructure with two different sizes of macropores and nanopores. The team used proximity-field nanopatterning (PnP) and electroplating techniques that are effective for fabricating the 3D well-ordered nanostructures.
The proposed nanostructure, comprised of interconnected macroporous channels 200 to 300 nanometers (nm) wide and 10 nm nanopores, induces efficient mass transport through the interconnected macroporous channels as well as high selectivity by producing highly active stable sites from numerous nanopores.
As a result, its electrodes show a high CO selectivity of 85.8% at a low overpotential of 0.264 V and efficient mass activity that is up to 3.96 times higher than that of de-alloyed nanoporous Au electrodes.
“These results are expected to solve the problem of mass transfer in the field of similar electrochemical reactions and can be applied to a wide range of green energy applications for the efficient utilization of electrocatalysts,” said the researchers.
This work was supported by the National Research Foundation (NRF) of Korea.
Image credit: Professor Seokwoo Jeon and Professor Jihun Oh, KAIST
Image usage restrictions: News organizations may use or redistribute this image, with proper attribution, as part of news coverage of this paper only.
Publication:
Hyun et al. (2020) Hierarchically porous Au nanostructures with interconnected channels for efficient mass transport in electrocatalytic CO2 reduction. Proceedings of the National Academy of Sciences of the USA (PNAS). Available online at https://doi.org/10.1073/pnas.1918837117
Profile:
Seokwoo Jeon, PhD
Professor
jeon39@kaist.ac.kr
http://fdml.kaist.ac.kr
Department of Materials Science and Engineering (MSE)
https://www.kaist.ac.kr
Korea Advanced Institute of Science and Technology (KAIST)Daejeon, Republic of Korea
Profile:
Jihun Oh, PhD
Associate Professor
jihun.oh@kaist.ac.kr
http://les.kaist.ac.kr
Department of Materials Science and Engineering (MSE)
Department of Energy, Environment, Water and Sustainability (EEWS)
KAIST
Profile:
Gayea Hyun
PhD Candidate
cldywkd93@kaist.ac.kr
http://fdml.kaist.ac.kr
Flexible Devices and Metamaterials Laboratory (FDML)
Department of Materials Science and Engineering (MSE)
KAIST
Profile:
Jun Tae Song, PhD
Assistant Professor
song.juntae@cstf.kyushu-u.ac.jp
http://www.cstf.kyushu-u.ac.jp/~ishihara-lab/
Department of Applied Chemistry
https://www.kyushu-u.ac.jp
Kyushu UniversityFukuoka, Japan
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2020.03.13 View 14892