Electrocatalytic reduction of CO2 in neat and water-containing imidazolium-based ionic liquids

Papasizza, Marco; Yang, Xiaohui; Cheng, Jun; Cuesta, Ángel

doi:10.1016/j.coelec.2020.04.004

Cited by 29 publications

(28 citation statements)

References 46 publications

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“…[429] This approach speeds up the calculation and can be applied to larger and complex systems including electrolyte. [430][431][432][433] Machine learning is emerging as a promising computational tool for screening efficient catalysts based on experimental results and DFT calculations. Modeling catalyst surface chemistry is a multistep Figure 12.…”

Section: Carbon Dioxide Reduction Reactionmentioning

confidence: 99%

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Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

138

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With the increase in energy demand and worldwide natural environment crises, it is imperative to develop green and sustainable energy systems to produce clean fuels and chemicals, which can replace fossil fuels and reduce carbon dioxide emissions. [1][2][3] A promising strategy is to develop advanced electrochemical technologies that can convert some common molecules (e.g., water, carbon dioxide, and nitrogen) into high-value chemical products (e.g., hydrogen, hydrocarbons, oxygenates, ammonia, and carbonates). [4][5][6][7] The important energy-related electrocatalytic reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), carbon dioxide reduction reaction (CO 2 RR), are the key conversion routes. In the complex processes for the electrocatalytic reactions, an efficient, highly selective, and stable electrocatalyst plays a pivotal role in speeding up the reaction kinetics and decreasing the overpotential, [5,8,9] which can enhance the sustainable energy conversion efficiency. Over the past few decades, tremendous progresses have been made in the establishment of electrocatalysts preparation and fundamental catalytic mechanisms. [6,7,[9][10][11][12][13][14][15][16][17][18] Nevertheless, those breakthroughs still stay at the stage of experimental synthesis and lack of indepth understanding of fundamental principles of the active site on the catalyst surface and catalytic reactions mechanisms, which seriously limits the development of efficient catalysts. Researchers are full of enthusiasm about preparation of advanced catalysts with ideal properties, expecting to establish the composition-structure-function relationships. Density functional theory (DFT) calculations are based on quantum mechanics, which can calculate the electronic structure of the whole catalytic system. It is probably the most powerful computational approach to investigate the structure-activity relationships of electrocatalysts at atomic level. With the rapid advances of computer technology, DFT calculations have created tremendous opportunities in shedding light on the electrocatalytic mechanisms and predicting promising catalysts. [19,20] Identification of the active sites and understanding of the reaction mechanisms are the two key aspects for the study of electrocatalytic reactions. [21] For the former, the experimental approach for identifying active sites is indirect by prepared specified catalysts and establishing definite correlations between catalytic performances and controllable factors. [22,23] Actually, many intermediate states of electrocatalytic

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Section: Carbon Dioxide Reduction Reactionmentioning

confidence: 99%

“…[ 429 ] This approach speeds up the calculation and can be applied to larger and complex systems including electrolyte. [ 430‐433 ]…”

Section: Perspectives and Outlookmentioning

confidence: 99%

Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

138

View full text Add to dashboard Cite

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“…However, CO 2 conversion without a catalyst is not possible due to the high thermodynamic stability of CO 2 (Δ G f ° = −400 kJ mol –1 ) . Electrocatalysis of CO 2 is a promising approach, e.g., for the production of ethanol or formic acid as fuel carriers and has recently gained considerable attention. ,− However, in aqueous electrolytes, substantial overpotentials for reduction of CO 2 exists and CO 2 reduction can compete with hydrogen evolution reactions and thus impair CO 2 electrocatalysis. The origin of existing overpotentials lies partly in the formation of a CO 2 radical anion as a necessary reaction intermediate …”

Section: Introductionmentioning

confidence: 99%

Cations of Ionic Liquid Electrolytes Can Act as a Promoter for CO₂ Electrocatalysis through Reactive Intermediates and Electrostatic Stabilization

Ratschmeier

Braunschweig

2021

J. Phys. Chem. C

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Room-temperature ionic liquids (IL) play an important role in lowering CO onset potentials for CO2 reduction reactions (CO2RR), but the reaction mechanism is still controversial. Using in operando IR absorption spectroscopy and in situ sum-frequency generation spectroscopy, we provide new information on the role of the cation for CO2RR. For this purpose, we have investigated CO2RR on polycrystalline Pt electrodes using 1-butyl-3-methylimidazolium [BMIM], 1-butyl-2,3-dimethylimidazolium [BMMIM], and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [BMPyrr][NTf2] with 10 and 500 mM H2O. Cyclic voltammetry indicates CO2RR reduction activity for all three systems, with the highest current densities for [BMMIM][NTf2]. Spectroscopic investigation revealed a CO onset potential of −0.7 V vs. standard hydrogen electrode for [BMMIM/BMPyrr][NTf2], which is independent of the variation of the H2O concentration and where CO formation can occur via an electrostatically stabilized CO2 radical anion. On the other hand, [BMIM][NTf2] shows a strong dependence on H2O with an onset potential of −0.4 V at 500 mM H2O and the formation of an imidazolium-2-carboxylic acid as a reactive intermediate.

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“…The mechanism of the reduction of CO 2 to HCOOH is still controversial after more than 40 years of study. [4][5][6][7][8][9][10][11][12][13][14][15] Hori and co-workers [1,2] suggested that CO 2adsorbs on the electrode surface through its carbon atom, and that whether CO or HCOOH is the final product of the 2-electron reduction depends on the corresponding adsorption energy. Figure 1 is an illustration of these two reaction pathways.…”

Section: Introductionmentioning

confidence: 99%