Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals

Chen, Chung Shou; Handoko, Albertus D.; Wan, Jane Hui; Ma, Liang; Ren, Dan; Yeo, Boon Siang

doi:10.1039/c4cy00906a

Cited by 315 publications

(279 citation statements)

References 32 publications

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“…53,54 The electrochemical cell was formed by compartments separated by a cation-exchange membrane (Nafion  117).…”

Section: Gas Chromatography (Gc)mentioning

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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“…53,54 The electrochemical cell was formed by compartments separated by a cation-exchange membrane (Nafion  117).…”

Section: Gas Chromatography (Gc)mentioning

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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“…Copper-catalyzed CO 2 reduction to hydrocarbons was first reported by Hori in 1985 [10]. In the following decades, publications using copper electrodes [11][12][13][14][15][16][17], copper oxide electrodes [18][19][20][21], copper-containing perovskites [22], oxide-supported copper catalysts [23], halide-derived copper catalysts [24][25][26][27], copper-based alloys [28], copper-based metal-organic frameworks [29], molecular copper complexes [30], as well as alternative systems [5,[31][32][33][34][35][36] vastly increased. Also pyridine-based co-catalysis known from Pd electrodes [37] could recently be transferred to copper-based systems [38].…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

et al. 2017

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Abstract:The direct electro-reduction of CO 2 to functional molecules like ethene is a highly desirable variant of CO 2 utilization. The formation of, for example, ethene from CO 2 is a multistep electrochemical process going through various intermediates. As these intermediates are organic species, the CO 2 reducing electro-catalyst has to be competent for a variety of organic functional group transformations to yield the final product. In this work, the activity of an in situ-grown nano-structured copper catalyst towards a variety of organic functional group conversions was studied. The model reagents were selected from the product spectrum of actual CO 2 reduction reaction (CO 2 RR) experiments and from proposals in the literature. The CO 2 bulk electrolysis benchmark was conducted at 170 mAcm −2 current density with up to 43% Faradaic Efficiency (FE) for ethene and 23% FE for ethanol simultaneously. To assure relevance for application-oriented conditions, the reactivity screening was conducted at elevated current densities and, thus, overpotentials. The found reactivity pattern was then also transferred to the CO reduction reaction (CORR) under benchmark conditions yielding additional insights. The results suggest that at high current density/high overpotential conditions, also other ethene formation pathways apart from acetaldehyde reduction such as CH 2 dimerization are present. A new suggestion for a high current density mechanism will be presented, which is in agreement with the experimental observations and the found activity pattern of copper cathodes toward organic functional group conversion.

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“…The selectivity of these catalysts is dependent on structural morphology and copper oxidation state [9][10][11][12][13][14][15][16][17] . Electrochemical reduction of copper oxide catalyst films can lead to grain boundaries, undercoordinated sites and roughened surfaces that are hypothesized to be catalytically active sites 8,18 .…”

mentioning

confidence: 99%

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

et al. 2018

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As energy demand continues to increase, so too do anthropogenic carbon emissions and global temperatures. Renewable energy sources such as solar, wind and hydroelectricity displace fossil fuel carbon emissions and continue to progress to wider deployment. However, long-term (seasonal) energy storage remains a challenge that must be addressed for renewables to meet a major fraction of global energy demand 1 . Carbon dioxide electroreduction to renewable fuels and feedstocks provides an energy storage solution to the seasonal variability of renewable energy sources 2 . When coupled with carbon capture technology, the carbon dioxide reduction reaction (CO 2 RR) offers a means to close the carbon cycle.CO 2 RR electrocatalysts lower energetic barriers to CO 2 reduction by stabilizing intermediates and transition states in the multistep electrochemical reduction process 3 . Copper reduces CO 2 to a wide range of hydrocarbon products such as methane, ethylene, ethanol and propanol 4 . Unfortunately, bulk copper is not selective among various carbon products, and it also suffers Faradaic efficiency (FE) losses to the competing hydrogen evolution reaction.Among possible products, C2+ hydrocarbons are highly sought in view of their commercial value. Ethylene, for example, is a precursor to the production of polyethylene, a major plastic. Selectively producing ethylene over methane circumvents costly paraffin-olefin separation 5 . Developing catalysts that work at ambient conditions to produce C2 selectively over C1 gaseous products will increase the relevance of renewable feedstocks in the chemical sector.Oxide-derived copper is one class of catalyst that has shown enhanced CO 2 RR activity and increased selectivity towards multi-carbon products [6][7][8] . The selectivity of these catalysts is dependent on structural morphology and copper oxidation state 9-17 . Electrochemical reduction of copper oxide catalyst films can lead to grain boundaries, undercoordinated sites and roughened surfaces that are hypothesized to be catalytically active sites 8,18 . Residual oxides, proposed to play a key role in catalysis, may exist after electrochemical reduction 7 . A recent report of oxygen plasma-activated oxide-derived copper catalysts achieved an ethylene FE of 60% at − 0.9 V versus reversible hydrogen electrode (RHE) 9 , with activity attributed to the presence of Cu + species. In situ hard X-ray absorption spectroscopy (hXAS) experiments have suggested stable Cu + species exist at highly negative CO 2 RR potentials of ~− 1.0 versus RHE 9 . However, the presence of Cu + species during CO 2 RR is still the subject of debate; 7,19 and in situ tracking of the copper oxidation state with time resolution during CO 2 RR has remained elusive.Morphological effects of copper nanostructures have a significant effect on the selectivity of CO 2 RR to multi-carbon products [20][21][22][23][24] . Copper catalysts with different morphologies have been synthesized through annealing, chemical treatments on thin films, colloidal synthesis and ...

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Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals

Cited by 315 publications

References 32 publications

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

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

Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

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