CO2+reduction
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A biohybrid system to extract 20 times more bioplastic from CO2 developed by KAIST researchers
As the issues surrounding global climate change intensify, more attention and determined efforts are required to re-grasp the issue as a state of “crisis” and respond to it properly. Among the various methods of recycling CO2, the electrochemical CO2 conversion technology is a technology that can convert CO2 into useful chemical substances using electrical energy. Since it is easy to operate facilities and can use the electricity from renewable sources like the solar cells or the wind power, it has received a lot of attention as an eco-friendly technology can contribute to reducing greenhouse gases and achieve carbon neutrality.
KAIST (President Kwang Hyung Lee) announced on the 30th that the joint research team led by Professor Hyunjoo Lee and Distinguished Professor Sang Yup Lee of the Department of Chemical and Biomolecular Engineering succeeded in developing a technology that produces bioplastics from CO2 with high efficiency by developing a hybrid system that interlinked the electrochemical CO2 conversion and microbial bio conversion methods together. The results of the research, which showed the world's highest productivity by more than 20 times compared to similar systems, were published online on March 27th in the "Proceedings of the National Academy of Sciences (PNAS)".
※ Paper title: Biohybrid CO2 electrolysis for the direct synthesis of polyesters from CO2
※ Author information: Jinkyu Lim (currently at Stanford Linear Accelerator Center, co-first author), So Young Choi (KAIST, co-first author), Jae Won Lee (KAIST, co-first author), Hyunjoo Lee (KAIST, corresponding author), Sang Yup Lee (KAIST, corresponding author)
For the efficient conversion of CO2, high-efficiency electrode catalysts and systems are actively being developed. As conversion products, only compounds containing one or up to three carbon atoms are produced on a limited basis. Compounds of one carbon, such as CO, formic acid, and ethylene, are produced with relatively high efficiency. Liquid compounds of several carbons, such as ethanol, acetic acid, and propanol, can also be produced by these systems, but due to the nature of the chemical reaction that requires more electrons, there are limitations involving the conversion efficiency and the product selection.
Accordingly, a joint research team led by Professor Hyunjoo Lee and Distinguished Professor Sang Yup Lee of the Department of Chemical and Biomolecular Engineering at KAIST developed a technology to produce bioplastics from CO2 by linking electrochemical conversion technology with bioconversion method that uses microorganisms.
This electrochemical-bio hybrid system is in the form of having an electrolyzer, in which electrochemical conversion reactions occur, connected to a fermenter, in which microorganisms are cultured. When CO2 is converted to formic acid in the electrolyzer, and it is fed into the fermenter in which the microbes like the Cupriavidus necator, in this case, consumes the carbon source to produce polyhydroxyalkanoate (PHA), a microbial-derived bioplastic.
According to the research results of the existing hybrid concepts, there was a disadvantage of having low productivity or stopping at a non-continuous process due to problems of low efficiency of the electrolysis and irregular results arising from the culturing conditions of the microbes.
In order to overcome these problems, the joint research team made formic acid with a gas diffusion electrode using gaseous CO2. In addition, the team developed a 'physiologically compatible catholyte' that can be used as a culture medium for microorganisms as well as an electrolyte that allows the electrolysis to occur sufficiently without inhibiting the growth of microorganisms, without having to have a additional separation and purification process, which allowed the acide to be supplied directly to microorganisms.
Through this, the electrolyte solution containing formic acid made from CO2 enters the fermentation tank, is used for microbial culture, and enters the electrolyzer to be circulated, maximizing the utilization of the electrolyte solution and remaining formic acid. In addition, a filter was installed to ensure that only the electrolyte solution with any and all microorganisms that can affect the electrosis filtered out is supplied back to the electrolyzer, and that the microorganisms exist only in the fermenter, designing the two system to work well together with utmost efficiency.
Through the developed hybrid system, the produced bioplastic, poly-3-hydroxybutyrate (PHB), of up to 83% of the cell dry weight was produced from CO2, which produced 1.38g of PHB from a 4 cm2 electrode, which is the world's first gram(g) level production and is more than 20 times more productive than previous research. In addition, the hybrid system is expected to be applied to various industrial processes in the future as it shows promises of the continuous culture system.
The corresponding authors, Professor Hyunjoo Lee and Distinguished Professor Sang Yup Lee noted that “The results of this research are technologies that can be applied to the production of various chemical substances as well as bioplastics, and are expected to be used as key parts needed in achieving carbon neutrality in the future.”
This research was received and performed with the supports from the CO2 Reduction Catalyst and Energy Device Technology Development Project, the Heterogeneous Atomic Catalyst Control Project, and the Next-generation Biorefinery Source Technology Development Project to lead the Biochemical Industry of the Oil-replacement Eco-friendly Chemical Technology Development Program by the Ministry of Science and ICT.
Figure 1. Schematic diagram and photo of the biohybrid CO2 electrolysis system.
(A) A conceptual scheme and (B) a photograph of the biohybrid CO2 electrolysis system. (C) A detailed scheme of reaction inside the system. Gaseous CO2 was converted to formate in the electrolyzer, and the formate was converted to PHB by the cells in the fermenter. The catholyte was developed so that it is compatible with both CO2 electrolysis and fermentation and was continuously circulated.
2023.03.30 View 6634 -
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 10696 -
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 14898