Mechanistic Insights into the Reduction of CO<sub>2</sub> on Tin Electrodes using in Situ ATR-IR Spectroscopy

Baruch, Maor F.; Pander, James E.; White, J. L.; Bocarsly, Andrew Bruce

doi:10.1021/acscatal.5b00402

Cited by 444 publications

(477 citation statements)

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“…This problem has been neglected for the study of CO 2 reduction until Chen et al reported their experiments [23]. Baruch et al studied the electrochemical reduction of CO 2 on Sn cathode by utilizing in situ attenuated total reflectance infrared spectroscopy, and found that the peaks attributed to a surface-bound monodentate tin carbonate species (intermediate of CO 2 reduction) only appeared at potentials where CO 2 reduction was observed, and disappeared when the tin surface was chemically etched to remove surface oxide [24]. In this work, the CV and the electrolysis results illustrate that Sn electrode possessing oxide layer shows excellent catalytic activity for CO 2 reduction, and the Sn electrode removed its oxide layer shows poor catalytic activity for CO 2 reduction but hydrogen evolution reaction accelerates.…”

Section: Resultsmentioning

confidence: 99%

“…Chen et al reported that Sn/SnO x layer on Ti substrate is highly selective towards CO and HCOOH compared to pure Sn, and they obtained the highest faradaic efficiency of 95% for CO 2 reduction (40% for producing formate and 55% for producing CO) at −0.7 V vs. RHE [23]. Baruch et al studied the electrochemical reduction of CO 2 on Sn cathode and reported that a metastable oxide layer presented on the surface of the Sn cathode under reducing potentials [24].…”

Section: Introductionmentioning

confidence: 99%

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Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

Zhang

Lei

2015

Applied Surface Science

123

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

Zhang

Lei

2015

Applied Surface Science

123

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“…SnO 2 /C has low H 2 production (metal with high hydrogen overpotential), and catalyzes the CO 2 electrochemical reduction to CO (Figure 7e). Actually, previously published works have found that, even at negative potentials, tin may exist as tin hydroxide 69 and the main product of the CO 2 electroreduction is formate ions, 14 being CO a parallel or secondary product (formate cannot be detected be DEMS). So, part of the electrochemical current for SnO 2 /C observed in Figure 7a is spent in the production of formate ions, which is not counted in the present study, explaining the lowest ionic currents for CO and H 2 .…”

Section: Electrochemical Experiments Electrocatalytic Reduction Of Comentioning

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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“…Studies on tin 5,6 and indium 7,8 have demonstrated the importance of a hydrated oxide layer, either native or anodized, which can interact with CO 2 to form a surface-bound carbonate species that is implicated as an essential intermediate. Other research has shown that a size-dependence exists on gold, 9,10 palladium, 11 silver, 10,12,13 and tin oxide 14 nanoparticles for the conversion of CO 2 , with an optimum diameter less than 10 nm but typically greater than 2 nm.…”

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confidence: 99%

Enhanced Carbon Dioxide Reduction Activity on Indium-Based Nanoparticles

White

Bocarsly

2016

J. Electrochem. Soc.

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104

105

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Nanoparticles of indium, indium hydroxide, and indium oxide were synthesized and evaluated for their electrocatalytic abilities in the reduction of CO 2 to formate. These nanoparticles were characterized with several microscopic and spectroscopic techniques in order to investigate their structure and surface features. Their electrochemical behavior was also probed through voltammetry and bulk electrolysis. faradaic efficiencies approaching 100% were achieved on these particles at potentials as positive as −1.3 V vs. Ag/AgCl, which represents a significant decrease in the overpotential compared to that observed using bulk indium electrodes. The nanostructuring of the particles and the partial surface oxidation of the indium nanoparticles to yield catalytic surface indium hydroxide species are implicated in the high efficiencies at low overpotentials. Recent decades have seen the rapid rise in the amounts of carbon dioxide, a greenhouse gas, present in both the atmosphere and the oceans, as well as a concomitant increase in global temperatures. 1This heating trend is predicted to amplify if net CO 2 emissions from fossil fuels continue to grow unabated, leading to a mean surface temperature increase of up to 4• C by 2100. 2 Therefore, a move away from fossil fuels toward renewable sources of energy such as wind and solar is essential for the long-term maintenance of the environment.The reduction of carbon dioxide to fuels and chemicals is an important component of a future energy portfolio based on renewable sources that seeks to mitigate carbon levels. The formation of useful chemicals from CO 2 rather than petroleum decreases the net CO 2 emissions and reduces reliance on oil. Generating high energy density carbon-based fuels, though only carbon-neutral and not carbonnegative, aids in load-leveling with intermittent power sources, leading to the production of fuels during periods of high output and the consumption during periods of low output.The electrochemical reduction of CO 2 on metal electrodes in aqueous solution has been studied for decades.3 Heavy post-transition metals, including indium, tin, lead, and bismuth yield predominantly formate, with small amounts of CO and H 2 as well. These metals have high overpotentials for water reduction, which allows them to be more selective for CO 2 reduction than most transition metals. However, the CO 2 reduction overpotentials are also fairly large, typically on the order of 1 V, significantly decreasing the energy efficiency of conversion. These metals have been proposed to reduce CO 2 in a oneelectron rate-determining step to the weakly adsorbed or free CO 2•− radical anion, which can then be protonated and reduced by another electron to yield formate.3 However, the formal redox potential for this process is −1.85 V vs. SHE, 4 considerably more negative than the potentials at which products are formed.Recent, more in-depth investigations on the mechanism of formate production on these metals have led to a greater understanding of the role of surface species in th...

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Mechanistic Insights into the Reduction of CO₂ on Tin Electrodes using in Situ ATR-IR Spectroscopy

Cited by 444 publications

References 37 publications

Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

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

Enhanced Carbon Dioxide Reduction Activity on Indium-Based Nanoparticles

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Mechanistic Insights into the Reduction of CO2 on Tin Electrodes using in Situ ATR-IR Spectroscopy

Cited by 444 publications

References 37 publications

Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate

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

Enhanced Carbon Dioxide Reduction Activity on Indium-Based Nanoparticles

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Mechanistic Insights into the Reduction of CO₂ on Tin Electrodes using in Situ ATR-IR Spectroscopy