CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
18 May 2018-Science (American Association for the Advancement of Science)-Vol. 360, Iss: 6390, pp 783-787
TL;DR: A copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO2 to ethylene with 70% faradaic efficiency at a potential of −0.55 volts versus a reversible hydrogen electrode (RHE).
Abstract: Carbon dioxide (CO 2 ) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO 2 to ethylene with 70% faradaic efficiency at a potential of −0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO 2 reduction and carbon monoxide (CO)–CO coupling activation energy barriers; as a result, onset of ethylene evolution at −0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.
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TL;DR: In this paper, a self-powered hybrid CO2 electrolysis is demonstrated by the coupling of a Mg anode to a nanoporous Ag cathode in 0.6 m NaCl or seawater.
Abstract: Oceans are regarded as a sink for anthropogenic CO2; as such seawater provides an attractive electrolyte for electrochemical CO2 reduction to value-added carbon-based fuels and chemical feedstocks. However, the composition of seawater is inherently complex, containing multiple cations and anions that may participate in the CO2 electroreduction reaction. Herein, examination of a nanoporous Ag electrocatalyst in seawater reveals a significant influence of calcium ions on the electrochemical CO2 reduction performance. Under the applied cathodic potential and in the presence of CO2, calcium ions in the seawater result in calcium carbonate deposition onto the nanoporous Ag, reducing active sites for CO2 electroreduction. Mitigation of calcification would promote a stable CO2 electrolysis in seawater. A first proof-of-concept self-powered hybrid CO2 electrolysis is demonstrated by the coupling of a Mg anode to a nanoporous Ag cathode in 0.6 M NaCl or seawater. A spontaneous oxidation of a Mg alloy at the anode drives cathodic reduction of AgCl to nanoporous Ag, which electrocatalytically reduces CO2 to CO. Combining galvanic and electrolytic properties in a single electrochemical cell offers a general approach for designing hybrid self-powered electrolysers. Strategies to overcome calcification such as removal of calcium from the seawater and development of anti-calcifying electrocatalysts are needed to promote practicability of seawater as an electrolyte in CO2 electroreduction technology.
14 citations
TL;DR: In this paper , the authors summarized recent progress in the electrochemical synthesis of catalytic materials such as single atoms, spherical and shaped nanoparticles, nanosheets, nanowires, core-shell nanostructures, layered nanomaterials, dendritic nanostructure, hierarchically porous nanstructures as well as composite materials.
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28 Dec 2020
TL;DR: In this article, a design strategy and syntactic strategies for C3 chemicals, such as acetone in CO2 reduction reaction, are presented. But the design strategies are limited to Cu-based materials and therefore it is highly desirable to devise design strategies and synt...
Abstract: Electrocatalysts for C3 chemicals, such as acetone in CO2 reduction reaction, are predominantly limited to Cu-based materials. Therefore, it is highly desirable to devise design strategies and synt...
13 citations
TL;DR: In this article, an integrated photo-electrochemical architecture was proposed to supply electricity directly to the photosynthetic electron transfer chain (PETC) in living cyanobacteria.
Abstract: Nature's biocatalytic processes are driven by photosynthesis, whereby photosystems I and II are connected in series for light-stimulated generation of fuel products or electricity. Externally supplying electricity directly to the photosynthetic electron transfer chain (PETC) has numerous potential benefits, although strategies for achieving this goal have remained elusive. Here we report an integrated photo-electrochemical architecture which shuttles electrons directly to PETC in living cyanobacteria. The cathode of this architecture electrochemically interfaces with cyanobacterial cells that have a lack of photosystem II activity and cannot perform photosynthesis independently. Illumination of the cathode channels electrons from an external circuit to intracellular PETC through photosystem I, ultimately fueling cyanobacterial conversion of CO2 into acetate. We observed acetate formation when supplying both illumination and exogenous electrons under intermittent conditions (e.g., in a 30 s supply plus 30 min interval condition of both light and exogenous electrons). The energy conversion efficiency for acetate production under programmed intermittent LED illumination (400–700 nm) and exogenous electron supply reached ca. 9%, when taking into account the number of photons and electrons received by the biotic system, and ca. 3% for total photons and electrons supplied to the cyanobacteria. This approach is applicable for generating various CO2 reduction products by using engineered cyanobacteria, one of which has enabled electrophototrophic production of ethylene, a broadly used hydrocarbon in the chemical industry. The resulting bio-electrochemical hybrid has the potential to produce fuel chemicals with numerous potential advantages over standalone natural and artificial photosynthetic approaches.
13 citations
TL;DR: In this article, the authors proposed to use metal-free carbon catalysts for the reverseduction of CO2 to value-added chemicals using single N-doped carbons.
13 citations
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TL;DR: An improved way of estimating the local tangent in the nudged elastic band method for finding minimum energy paths is presented, and examples given where a complementary method, the dimer method, is used to efficiently converge to the saddle point.
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