Selective electrochemical conversion of CO2 to C2 hydrocarbons

Gonçalves, Moutinho; Gomes, Adriano S. O.; Condeço, José; Fernandes, R.; Pardal, Tiago; Sequeira, C. A. C.; Branco, Joaquim B.

doi:10.1016/j.enconman.2009.08.002

Cited by 74 publications

(46 citation statements)

References 12 publications

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“…Since some early reports over 30 years ago, copper has been known as a complicated electrocatalyst with unique catalytic properties, due to its capability of electrochemical reduction of CO 2 into a variety of gaseous products, alcohols, and other organic products. In 1985, Hori et al reported several catalysts with different main products for the first time .…”

Section: Reaction Pathways Of the Cu‐based Electrocatalystsmentioning

confidence: 99%

Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction

et al. 2018

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The continuous increase of CO2 concentration in the atmosphere has been imposing an imminent threat for global climate change and environmental hazards. In recent years, the electrochemical or photochemical conversion of CO2 into value‐added chemicals or fuels has received significant attention, as it may enable an attractive means to mitigate the atmospheric CO2 concentration and complete the imbalanced carbon‐neutral energy cycle, as well as create renewable energy resources for human use. Among the different electrocatalysts being studied, Cu‐based materials have been demonstrated as the only category of candidates that allows the conversion of CO2 into a variety of reducing products, including carbon monoxide, hydrocarbons, and alcohols. Herein, the reaction pathways for different Cu‐based catalysts for C1 and C2+ products are introduced. Then, different parameters in tuning Cu‐based electrocatalysts are summarized and discussed, including the morphologies, compositions, crystal facets, and oxide derivation. In addition, various types of parameters for CO2 electroreduction are also described, particularly the option of electrolytes such as aqueous, ionic liquids, and organic solutions. Finally, the current challenges are discussed and the potential strategies to facilitate the future development of CO2 electroreduction are summarized.

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Section: Reaction Pathways Of the Cu‐based Electrocatalystsmentioning

confidence: 99%

Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction

et al. 2018

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“…In particular, Cu-based electrodes, due to their high overpotential for hydrogen evolution, have been the focus of many studies. It has been reported that the main products on a Cu-based electrode are hydrocarbons such as methane and ethylene in aqueous electrolytes [10][11][12]. Hori et al [13][14][15][16], who pioneered a series of experimental investigations into the mechanism of CO 2 electrochemical reduction on a copper-based electrode, suggested that the electrochemical reduction of CO 2 proceeds through CO or COderived intermediates, with the main products being CH 4 , C 2 H 4 and alcohols.…”

Section: Introductionmentioning

confidence: 98%

A DFT study of CO2 electrochemical reduction on Pb(211) and Sn(112)

et al. 2015

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Electrochemical reduction of CO 2 has the benefit of turning greenhouse gas emissions into useful resources. We performed a comparative study of the electrochemical reduction of CO 2 on stepped Pb(211) and Sn(112) surfaces based on the results of density functional theory slab calculations. We mapped out the potential energy profiles for electrochemical reduction of CO 2 to formate and other possible products on both surfaces. Our results show that the first step is the formation of the adsorbed formate (HCOO*) species through an Eley-Rideal mechanism. The formate species can be reduced to HCOO  through a oneelectron reduction in basic solution, which produces formic acid as the predominant product. The respective potentials of forming HCOO* are predicted to be 0.72 and 0.58 V on Pb and Sn. Higher overpotentials make other reaction pathways accessible, leading to different products. On Sn(112), CO and CH 4 can be generated at 0.65 V following formate formation. In contrast, the limiting potential to access alternative reaction channels on Pb(211) is 1.33 V, significantly higher than that of Sn. electrochemical reduction, reaction mechanism, carbon dioxide, formate, DFT

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“…7 Also, the behavior of a Cu layer obtained by in situ electroredution of dissolved CuSO 4 salt (1.0 mmol L -1 , Merck) was also studied since Cu is one component of the Cu 4 Sn/C nanoalloy material that is the central focus of the present investigation. 52 For all electrochemical measurements, a platinum wire and a silver/silver chloride electrode (Ag/AgCl/Cl -) were used as counter and reference electrodes, respectively. Cyclic voltammograms were recorded at 1 or 10 mV s -1 , and chronoamperometry were carried out at different potentials, depending on the experiment, according to the potential range for which the CO 2 reduction takes place.…”

Section: Differential Electrochemical Mass Spectrometry (Dems) Experimentioning

confidence: 99%

Investigation of Electrocatalysts for Selective Reduction of CO2 to CO: Monitoring the Reaction Products by on line Mass Spectrometry and Gas Chromatography

Camilo¹,

Silva²,

Lima³

2017

J. Braz. Chem. Soc.

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The carbon dioxide electrocatalytic reduction is central for the development of regenerative cycles of electrochemical energy conversion and storage. Herein, the gaseous products of the CO 2 electroreduction were monitored by using an electrochemical cell on line coupled to a differential electrochemical mass spectrometer (DEMS), aiming at searching for electrocatalysts with high selectivity for CO formation. The results showed that, among the studied materials, the Cu 4 Sn/C alloy nanoparticles were stable during potentiostatic polarizations as revealed by in situ X-ray absorption spectroscopy (XAS), and the on line DEMS measurements showed the production of CO, suppression of methane and ethylene formations, and diminishing of the hydrogen evolution reaction, in relation to that on pure Cu 2 O-Cu/C. The faradaic efficiencies for CO formation were 13 and 23% for Cu 4 Sn/C and Au/C (a known electrocatalyst for CO), respectively, determined by experiments of in line gas chromatography (GC). The selectivity of Cu 4 Sn/C for CO formation was ascribed to the role of Sn atoms on stabilizing adsorbed HCOO intermediates, and hindering further hydrogenation, letting CO free for desorption. These results are expected to be used as a guide for further development of electrocatalysts with a fine-tuning of composition for increasing the faradaic efficiency of CO 2 electroreduction to CO.Keywords: CO 2 electrochemical reduction, on line DEMS, in line GC, CO formation, Cu 4 Sn/C alloy IntroductionConcomitantly with the growth of the world population, the energy demand is increasing. To satisfy this scenario, fossil fuels, such as oil, coal and natural gas, are being exhaustively used. Unfortunately, together to the dependence on these fuels, large amounts of carbon dioxide (CO 2 ) are emitted into the environment and, so, this is not a sustainable cycle. This has initiated research projects to investigate efficient processes for using the available CO 2 in the atmosphere. The electrochemical reduction of carbon dioxide is, in principle, an efficient manner that can be explored. In this context, the electroreduction of CO 2 to fuels with high-energy density or to industrial chemicals, that can be further processed to produce useful fuels, such as CO, using photovoltaic panels, with the consecutive utilization as fuel in fuel cells, would define a sustainable or regenerative cycle. [1][2][3][4][5][6][7] In the case of performing the CO 2 electroreduction to CO in parallel with the water electroreduction (or the hydrogen evolution reaction (HER)), the mixture CO + H 2 (syngas) is produced. 8,9 In the chemical industry, CO/H 2 mixtures are reacted to form methanol or other liquid fuels, such as diesel, by using the Fischer-Tropsch process. 10 The CO 2 electrochemical reduction can be productselective by using different electrocatalysts. However, even for two-electron products, it is decisive to know the kinetically important steps of the studied reaction. Also, synthesizing an optimized electrocatalyst that do not catalyze undesi...

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Selective electrochemical conversion of CO2 to C2 hydrocarbons

Cited by 74 publications

References 12 publications

Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction

Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction

A DFT study of CO2 electrochemical reduction on Pb(211) and Sn(112)

Investigation of Electrocatalysts for Selective Reduction of CO2 to CO: Monitoring the Reaction Products by on line Mass Spectrometry and Gas Chromatography

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Selective electrochemical conversion of CO2 to C2 hydrocarbons

Cited by 74 publications

References 12 publications

Nanostructured Copper‐Based Electrocatalysts for CO2 Reduction

Nanostructured Copper‐Based Electrocatalysts for CO2 Reduction

A DFT study of CO2 electrochemical reduction on Pb(211) and Sn(112)

Investigation of Electrocatalysts for Selective Reduction of CO2 to CO: Monitoring the Reaction Products by on line Mass Spectrometry and Gas Chromatography

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Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction

Nanostructured Copper‐Based Electrocatalysts for CO₂ Reduction