CO<sub>2</sub> electroreduction to fuels on mesoporous carbon-embedded copper nanoparticles

Şahin, Nihat Ege; Silva, Wanderson O.; Camilo, Mariana R.; Ticianelli, Édson Antônio; Lima, Fabio H. B.; Parmentier, Julien; Comminges, Clément; Napporn, Têko W.; Kokoh, K. Boniface

doi:10.1039/d0se01025a

Cited by 6 publications

(5 citation statements)

References 56 publications

(55 reference statements)

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“…The results presented in Figure 4 establish our procedure as a dependable and sensitive analysis technique for fast MS quantification of CO in a CO 2 RR gas mixture. Comparing the four different metal catalysts shows the contrasting selectivities known from the literature: Pt generates almost exclusively H 2 , [17] Ag and Au are most efficient towards CO, [18] Cu is the only one of the four metals enabling further reduction to lower oxidation states of C [2b,14,19] . Clear trends are also obtained when for a given metal the overpotential is varied, with both overall yield and product composition affected.…”

Section: Resultsmentioning

confidence: 99%

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

Englhard

Bachmann

2023

Chemistry Methods

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The reduction of CO2 in water can yield a variety of volatile products mixed with the starting material and often dinitrogen as an inert gas. While mass spectrometry is ideally suited to the quantitative analysis of gases in low concentrations, the simultaneous detection is usually performed with a preliminary chromatographic separation. In its absence, the mass spectrometric signal at m/z=28 can be due to CO, CO2, and N2. Here, we demonstrate that ionizing the mixture of reaction products under 16 eV results in the selective detection of CO at m/z=28, at the complete exclusion of CO2 and N2. This method is applicable to headspace analysis after a bulk electrolysis and delivers product compositions as they depend on catalyst and applied potential. Furthermore, its immediate nature also enables the experimentalist to perform, in real time, a direct monitoring of the reaction products generated during cyclic voltammetry.

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Section: Resultsmentioning

confidence: 99%

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

Englhard

Bachmann

2023

Chemistry Methods

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“…The CO 2 electrolysis measurements were conducted in a typical H‐type electrochemical cell equipped by a bi‐potentiostat (AUTOLAB‐PGSTAT302 N) with Ag|AgCl, KCl sat. reference electrode described elsewhere [48] . As CO 2 and CO can interact with both Cu and Pd, we consider that it is not accurate to take into account only Pd in the calculation of the electrode active surface.…”

Section: Methodsmentioning

confidence: 99%

“…reference electrode described elsewhere. [48] As CO 2 and CO can interact with both Cu and Pd, we consider that it is not accurate to take into account only Pd in the calculation of the electrode active surface. Therefore, in cyclic voltammetry and electrolysis experiments, the current densities were normalized with the metal loading (CuPd) deposited on the conducting substrate.…”

Section: Co 2 Reduction Electrolysis and Product Analysismentioning

confidence: 99%

CO₂‐to‐HCOOH Electrochemical Conversion on Nanostructured Cu_xPd_100−x/Carbon Catalysts

et al. 2021

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Selective electrochemical conversion of CO 2 to HCOOH is obtained at the surface of a carbon-supported bimetallic cathode material composed of copper and palladium nanoparticles. Polycrystalline copper or large copper particles are well-known to catalyze CO 2 reduction to hydrocarbons at relatively negative potentials, or when their surface is covered by copper oxides (Cu 2 O and CuO). Cu-based materials modified by various palladium contents (0 < × < 100), were synthesized by using the microwave-assisted polyol method to serve as a cathode in the selective CO 2 -into-HCOOH transformation. Here-in, we developed a targeted preparation route toward the metal content/catalytic activity relationship correlating atomic ratio with faradaic efficiency (FE) to formate formation (ca. 60 % FE) at À 0.72 V vs. RHE, which represents a 703 mV overpotential at pH = 7. Consequently, the occurrence of this reduction reaction slows down the parallel H 2 production from the solvent consumption, while the neighboring CuÀ Pd provides excellent activity and a good efficiency toward CO 2 reduction via the hydridation of the CO 2 molecule to orientate the reaction to formate rather than carbon monoxide or H 2 evolution.

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“…The possibility to convert CO 2 into high value-added chemicals and simultaneously removing this polluting gas from the atmosphere, reducing its concentration in the air, has been arising great interest worldwide. Therefore, the electrochemical CO 2 reduction reaction also has been investigated by EC-MS [58][59][60][61][62][63][64][65] to characterize the products and their dependence on the applied potential, and evaluate the performance of new electrocatalysts. However, the investigation of the electroreduction of CO 2 by EC-MS faces some challenges, since the reagent itself, CO 2 , is a dissolved gaseous species and, so, it has a low concentration around the electrode surface.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Mass Spectrometry: Evolution of the Cell Setup for On‐Line Investigation of Products and Screening of Electrocatalysts for Carbon Dioxide Reduction

et al. 2022

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One of the most important current topics in the renewable and sustainable energy scenario is the CO2 electro‐reduction reaction (CO2RR), which is an alternative and important route for its conversion into various high value‐added chemicals, therefore making up a CO2 recycling process. Despite its importance and the works already developed in this field, many challenges still need to be overcome for CO2RR to reach high values of efficiency and selectivity. This is even more challenging considering that this reaction occurs with the transfer of several electrons, making the investigation and elucidation of the reaction mechanism a real need. Thus, several characterization techniques have been employed, and specially, the on‐line Electrochemical Mass Spectrometry (EC‐MS) technique emerges as a powerful tool, thus making possible to improve the understanding of reaction pathways, through the identification of products and intermediaries, and allowing the screening of electrocatalyst potentials for CO2RR. Herein, we present the evolution of adaptations of general electrochemical cell designs for the study of the CO2RR.

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CO₂ electroreduction to fuels on mesoporous carbon-embedded copper nanoparticles

Abstract: Electrochemical carbon dioxide reduction reaction (CO2RR) process can allow the production of chemicals under ambient conditions on nanostructured copper materials. However, reaction selectivity is still main drawback due to the...

Cited by 6 publications

References 56 publications

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

CO₂‐to‐HCOOH Electrochemical Conversion on Nanostructured Cu_xPd_100−x/Carbon Catalysts

Electrochemical Mass Spectrometry: Evolution of the Cell Setup for On‐Line Investigation of Products and Screening of Electrocatalysts for Carbon Dioxide Reduction

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CO2 electroreduction to fuels on mesoporous carbon-embedded copper nanoparticles

Abstract: Electrochemical carbon dioxide reduction reaction (CO2RR) process can allow the production of chemicals under ambient conditions on nanostructured copper materials. However, reaction selectivity is still main drawback due to the...

Cited by 6 publications

References 56 publications

Quantification of CO and Further CO2 Reduction Products by On‐line Mass Spectrometry

Quantification of CO and Further CO2 Reduction Products by On‐line Mass Spectrometry

CO2‐to‐HCOOH Electrochemical Conversion on Nanostructured CuxPd100−x/Carbon Catalysts

Electrochemical Mass Spectrometry: Evolution of the Cell Setup for On‐Line Investigation of Products and Screening of Electrocatalysts for Carbon Dioxide Reduction

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CO₂ electroreduction to fuels on mesoporous carbon-embedded copper nanoparticles

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

Quantification of CO and Further CO₂ Reduction Products by On‐line Mass Spectrometry

CO₂‐to‐HCOOH Electrochemical Conversion on Nanostructured Cu_xPd_100−x/Carbon Catalysts