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: A broad and historical view of different aspects and their complex interplay in CO2R catalysis on Cu is taken, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices.
Abstract: To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.
2,055 citations
TL;DR: A comparative analysis of electrocatalyst and carbon emissions assessment of CO2 products such as ethylene, ethanol, and carbon monoxide shows that electrocatalytic production has the potential to yield the greatest reduction in carbon emissions, provided that a steady supply of clean electricity is available.
Abstract: Electrocatalytic transformation of carbon dioxide (CO2) and water into chemical feedstocks offers the potential to reduce carbon emissions by shifting the chemical industry away from fossil fuel dependence. We provide a technoeconomic and carbon emission analysis of possible products, offering targets that would need to be met for economically compelling industrial implementation to be achieved. We also provide a comparison of the projected costs and CO2 emissions across electrocatalytic, biocatalytic, and fossil fuel-derived production of chemical feedstocks. We find that for electrosynthesis to become competitive with fossil fuel-derived feedstocks, electrical-to-chemical conversion efficiencies need to reach at least 60%, and renewable electricity prices need to fall below 4 cents per kilowatt-hour. We discuss the possibility of combining electro- and biocatalytic processes, using sequential upgrading of CO2 as a representative case. We describe the technical challenges and economic barriers to marketable electrosynthesized chemicals.
1,234 citations
TL;DR: In this article, the authors review recent advances and challenges in the understanding of electrochemical CO2 reduction and discuss existing models for the initial activation of CO2 on the electrocatalyst and their importance for understanding selectivity.
Abstract: The electrocatalytic reduction of carbon dioxide is a promising approach for storing (excess) renewable electricity as chemical energy in fuels. Here, we review recent advances and challenges in the understanding of electrochemical CO2 reduction. We discuss existing models for the initial activation of CO2 on the electrocatalyst and their importance for understanding selectivity. Carbon–carbon bond formation is also a key mechanistic step in CO2 electroreduction to high-density and high-value fuels. We show that both the initial CO2 activation and C–C bond formation are influenced by an intricate interplay between surface structure (both on the nano- and on the mesoscale), electrolyte effects (pH, buffer strength, ion effects) and mass transport conditions. This complex interplay is currently still far from being completely understood. In addition, we discuss recent progress in in situ spectroscopic techniques and computational techniques for mechanistic work. Finally, we identify some challenges in furthering our understanding of these themes. Electrocatalytic reduction of CO2 to fuels could be used as an approach to store renewable energy in the form of chemical energy. Here, Birdja et al. review current understanding of electrocatalytic systems and reaction pathways for these conversions.
1,141 citations
04 Mar 2019
TL;DR: In this article, the authors discuss strategies to achieve high selectivity towards multicarbon products via rational catalyst and electrolyte design, focusing on findings extracted from in situ and operando characterizations.
Abstract: The CO2 electroreduction reaction (CO2RR) to fuels and feedstocks is an attractive route to close the anthropogenic carbon cycle and store renewable energy. The generation of more reduced chemicals, especially multicarbon oxygenate and hydrocarbon products (C2+) with higher energy densities, is highly desirable for industrial applications. However, selective conversion of CO2 to C2+ suffers from a high overpotential, a low reaction rate and low selectivity, and the process is extremely sensitive to the catalyst structure and electrolyte. Here we discuss strategies to achieve high C2+ selectivity through rational design of the catalyst and electrolyte. Current state-of-the-art catalysts, including Cu and Cu–bimetallic catalysts, as well as some alternative materials, are considered. The importance of taking into consideration the dynamic evolution of the catalyst structure and composition are highlighted, focusing on findings extracted from in situ and operando characterizations. Additional theoretical insight into the reaction mechanisms underlying the improved C2+ selectivity of specific catalyst geometries and compositions in synergy with a well-chosen electrolyte are also provided. The electrochemical reduction of carbon dioxide to fuels and feedstocks has received increased attention over the past few years. In this Review, Roldan Cuenya and co-workers discuss strategies to achieve high selectivity towards multicarbon products via rational catalyst and electrolyte design.
719 citations
TL;DR: A catalyst:ionomer bulk heterojunction (CIBH) architecture that decouples gas, ion, and electron transport and achieves CO2 electroreduction on copper in 7 M potassium hydroxide electrolyte with an ethylene partial current density at 45% cathodic energy efficiency.
Abstract: Electrolysis offers an attractive route to upgrade greenhouse gases such as carbon dioxide (CO2) to valuable fuels and feedstocks; however, productivity is often limited by gas diffusion through a liquid electrolyte to the surface of the catalyst. Here, we present a catalyst:ionomer bulk heterojunction (CIBH) architecture that decouples gas, ion, and electron transport. The CIBH comprises a metal and a superfine ionomer layer with hydrophobic and hydrophilic functionalities that extend gas and ion transport from tens of nanometers to the micrometer scale. By applying this design strategy, we achieved CO2 electroreduction on copper in 7 M potassium hydroxide electrolyte (pH ≈ 15) with an ethylene partial current density of 1.3 amperes per square centimeter at 45% cathodic energy efficiency.
659 citations
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