Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO<sub>2</sub>reduction reaction on copper electrodes

Gao, Shuting; Xiang, Shi‐Qin; Shi, Jianwu; Zhang, Wei; Zhao, Liu−Bin

doi:10.1039/c9cp06824d

Cited by 19 publications

(33 citation statements)

References 70 publications

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“…Based on Marcus charge transfer theory, the activation energy is calculated by reorganization energy and Gibbs free‐energy change as Equation (3). Under the equilibrium potential (the Gibbs free‐energy change equals 0), the activation energy is only determined by the reorganization energy of the reactants ( λ R ) and the reorganization energy of the products ( λ P ) [40,45–47] . We draw the contour map of activation barrier as a function of λ R and λ P at equilibrium potential.…”

Section: Resultsmentioning

confidence: 99%

“…A displaced‐distorted oscillator model based on classic Marcus theory is proposed to calculate the activation barrier of a concerted proton–electron transfer process, which is expressed as the following Equation : [45–47]

true E_{a} = {(\frac{- \sqrt{λ_{normalR}} + \sqrt{\frac{λ_{normalR}}{λ_{normalP}} ([], λ_{R} + Δ G ((), \frac{λ_{normalR}}{λ_{normalP}} - 1))}}{(\frac{λ_{R}}{λ_{P}} - 1)})}^{2}

…”

Section: Methodsmentioning

confidence: 99%

“…The reaction barriers were composed of reaction free‐energy change and reorganization energy. Therefore, it is closer to an actual NRR process and capable to explore the influencing factors of reaction barriers [46,47] …”

Section: Introductionmentioning

confidence: 99%

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Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Shi

Xiang

et al. 2021

ChemSusChem

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Electrochemical reduction of nitrogen to produce ammonia at moderate conditions in aqueous solutions holds great prospect but also faces huge challenges. Considering the high selectivity of Au‐based materials to inhibit competitive hydrogen evolution reaction (HER) and high activity of transition metals such as Fe and Mo toward the nitrogen reduction reaction (NRR), it was proposed that Au‐based alloy materials could act as efficient catalysts for N2 fixation based on density functional theory simulations. Only on Mo3Au(111) surface the adsorption of N2 is stronger than H atom. Thermodynamics combined with kinetics studies were performed to investigate the influence of composition and ratio of Au‐based alloys on NRR and HER. The binding energy and reorganization energy affected performance for the initial N2 activation and hydrogenation process. By considering the free‐energy diagram, the computed potential‐determining step was either the first or the fifth hydrogenation step on metal catalysts. The optimum catalytic activity could be achieved by adjusting atomic proportion in alloys to make all intermediate species exhibit moderate adsorption. Free‐energy diagrams of N2 hydrogenation via Langmuir‐Hinshelwood mechanism and hydrogen evolution via Tafel mechanism were compared to reveal that the Mo3Au surface showed satisfactory catalytic performance by simultaneously promoting NRR and suppressing HER. Theoretical simulations demonstrated that Au‐Mo alloy materials could be applied as high‐performance electrocatalysts for NRR.

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Section: Resultsmentioning

confidence: 99%

true E_{a} = {(\frac{- \sqrt{λ_{normalR}} + \sqrt{\frac{λ_{normalR}}{λ_{normalP}} ([], λ_{R} + Δ G ((), \frac{λ_{normalR}}{λ_{normalP}} - 1))}}{(\frac{λ_{R}}{λ_{P}} - 1)})}^{2}

…”

Section: Methodsmentioning

confidence: 99%

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Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Shi

Xiang

et al. 2021

ChemSusChem

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“…Diverse products were investigated from the reduction of CO 2 , as methanol, ethanol, and acetone, but just methanol was identified and quantified in all reactions. Before the discussion of the results, it is important to mention that some recent studies have showed that the rate of methanol production is largely dependent on the electrocatalytic activity of deposited copper crystal surfaces, and it increases in the following order, Cu(111) < Cu(100) < Cu(110) < Cu(211) [65]. This difference in electrocatalytic activity is attributed to the surface and solvation effects that directly influence on the activation barriers for the electrochemical charge transfer and the reaction driving force (Gibbs energy).…”

Section: Photoelectrocatalytic Reduction Of Co 2 On Nt/tio 2 With Copper Oxidesmentioning

confidence: 99%

“…Although Cu 2 O nanoparticles exhibit octahedral shape and expose more photoactive surfaces, the (111) crystal facet has low faradaic efficiency performance on the formation of radical intermediates that leads methanol production when compared with CuO (110) surfaces, which are in majority in NT/TiO 2 -CuO (lactic acid) (Fig. 4) [65].…”

Section: Photoelectrocatalytic Reduction Of Co 2 On Nt/tio 2 With Copper Oxidesmentioning

confidence: 99%

Contribution of CuxO distribution, shape and ratio on TiO2 nanotubes to improve methanol production from CO2 photoelectroreduction

Almeida

Pacheco

Brito

et al. 2020

J Solid State Electrochem

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Many studies are focused on the development of materials for converting carbon dioxide into multicarbon oxygenates such as methanol and ethanol, because of their higher energy density and wider applicability. In this work, TiO 2 nanotubes (NT/TiO 2 ) were modified with Cu x O nanoparticles in order to investigate the contribution of different ratio of Cu 2 O/CuO and its distribution over NT/TiO 2 for CO 2 photoelectro-conversion to methanol. The photoelectrodes were built by anodization process to obtain NT/TiO 2 layer, and the decoration with Cu x O hybrid system was carried out by electrodeposition process, using Na 2 SO 4 or acid lactic as electrolyte, followed by annealing at different temperatures. X-ray photoelectron spectroscopy analysis revealed the predominance of Cu +1 and Cu +2 at 150°C and 300°C, respectively. X-ray diffraction and scanning electron microscopy indicated that under lactic acid solution, the oxide nanoparticles exhibited small size, cubic shape, and uniform distribution on the nanotube wall. While under Na 2 SO 4 electrolyte, large nanoparticles with two different morphologies, octahedral and cubic shapes, were deposited on the top of the nanotubes. All modified electrodes converted CO 2 in methanol in different quantities, identified by gas chromatograph. However, the NT/TiO 2 modified with CuO/Cu 2 O (80:20) nanoparticles using lactic acid as electrolyte showed better performance in the CO 2 reduction to methanol (0.11 mmol L −1 ) in relation to the other electrodes. In all cases, a blend among the structures and nanoparticle morphologies were achieved and essential to create new site of reactions what improved the use of light irradiation, minimization of charge recombination rate and promoted high selectivity of products.Keywords CO 2 photoelectroreduction . Hybrid TiO 2 -Cu x O photocatalysts . p-n heterojunction . Electrolyte design . Methanol formation

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Toward Unifying the Mechanistic Concepts in Electrochemical CO₂ Reduction from an Integrated Material Design and Catalytic Perspective

Bagchi

Roy

Sarma

et al. 2022

Adv Funct Materials

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Electrocatalytic CO2 reduction (eCO2RR) is one of the avenues with most potential toward achieving sustainable energy economy and global climate change targets by harvesting renewable energy into value‐added fuels and chemicals. From an industrial standpoint, eCO2RR provides specific advantages over thermochemical and photochemical pathways in terms of much broader product scope, high product specificity, and easy adaptability to the renewable electricity infrastructure. However, unlike water electrolyzers, the lack of suitable cathode materials for eCO2RR impedes its commercialization due to material design challenges. The current state‐of‐the‐art catalysts in eCO2RR suffer largely from low reaction rates, insufficient C2+ product selectivity, high overpotentials, and industrial‐scale stability. Overcoming the scientific and applied technical hurdles for commercial realization demands a holistic integration of catalytic designs, deep mechanistic understanding, and efficient process engineering. Special emphasis on mechanistic understanding and performance outcome is sought to guide the future design of eCO2RR catalysts that can play a significant role in closing the anthropogenic carbon loop. This article provides an integrative approach to understand principles of robust eCO2RR catalyst design superimposed with underlying mechanistic projections which strongly depend on experimental conditions viz. choice of electrolyte, reactor and membrane design, pH of the solvent, and partial pressure of the CO2.

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Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO₂reduction reaction on copper electrodes

Abstract: The electrochemical reduction of CO2 is a promising route for converting intermittent renewable energy into storable fuels and useful chemical products.

Cited by 19 publications

References 70 publications

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Contribution of CuxO distribution, shape and ratio on TiO2 nanotubes to improve methanol production from CO2 photoelectroreduction

Toward Unifying the Mechanistic Concepts in Electrochemical CO₂ Reduction from an Integrated Material Design and Catalytic Perspective

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Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO2reduction reaction on copper electrodes

Abstract: The electrochemical reduction of CO2 is a promising route for converting intermittent renewable energy into storable fuels and useful chemical products.

Cited by 19 publications

References 70 publications

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Contribution of CuxO distribution, shape and ratio on TiO2 nanotubes to improve methanol production from CO2 photoelectroreduction

Toward Unifying the Mechanistic Concepts in Electrochemical CO2 Reduction from an Integrated Material Design and Catalytic Perspective

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Theoretical understanding of the electrochemical reaction barrier: a kinetic study of CO₂reduction reaction on copper electrodes

Toward Unifying the Mechanistic Concepts in Electrochemical CO₂ Reduction from an Integrated Material Design and Catalytic Perspective