Carbon dioxide conversion into hydrocarbon fuels on defective graphene-supported Cu nanoparticles from first principles

Lim, Dong‐Hee; Jo, Jun Ho; Shin, Dongyun; Wilcox, Jennifer; Ham, Hyung Chul; Nam, Suk Woo

doi:10.1039/c3nr06539a

Cited by 156 publications

(123 citation statements)

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“…Lim et al predicted a strong interaction between Cu nanoparticles and carbon, and we expect that to extend to CNS as well. [12] We expect that the strong interaction provides an environment in which a mechanism involving reactive sites on both the Cu surface and on the N-doped CNS may dominate.…”

Section: Resultsmentioning

confidence: 99%

“…[8] Polycrystalline Cu foil produces a mixture of compounds in CO 2 -saturated aqueous solutions that are dominated either by H 2 at low overpotential, or by CO and HCOO À at high overpotential, or by hydrocarbons and multi-carbon oxygenates at the most extreme potentials. [9,11] Theoretical studies predict that graphene-supported Cu nanoparticles would enhance catalytic activity due to the strong Cu -graphene interaction via defect sites, [12] which would stabilize the intermediates from CO 2 reduction and improve selectivity towards hydrocarbon products as methane and methanol at lowered overpotential. Early studies revealed that the electrode surface was dominated by adsorbed CO during the CO 2 reduction and that CO acted as intermediate in the production of hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

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High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

et al. 2016

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Though carbon dioxide is a waste product of combustion, it can also be a potential feedstock for the production of fine and commodity organic chemicals provided that an efficient means to convert it to useful organic synthons can be developed. Herein we report a common element, nanostructured catalyst for the direct electrochemical conversion of CO 2 to ethanol with high Faradaic efficiency (63 % at À1.2 V vs RHE) and high selectivity (84 %) that operates in water and at ambient temperature and pressure. Lacking noble metals or other rare or expensive materials, the catalyst is comprised of Cu nanoparticles on a highly textured, N-doped carbon nanospike film. Electrochemical analysis and density functional theory (DFT) calculations suggest a preliminary mechanism in which active sites on the Cu nanoparticles and the carbon nanospikes work in tandem to control the electrochemical reduction of carbon monoxide dimer to alcohol.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

et al. 2016

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Section: Inducing Adsorption Sites With Oxophilicitymentioning

confidence: 98%

Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO₂

Sun

2016

Advanced Energy Materials

349

277

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and selectively produce carbon-containing products from CO 2 with reasonably low overpotentials and low cost.From the theoretical point of view, electrochemical CO 2 reduction, similar to many other electrochemical energy conversion processes on metal surfaces, comprise of multiple concerted or sequential proton-electron transfer reactions. In 2004, Nørskov et al. [2] developed a concise and effective scheme to understand the origin of the overpotential, which was denoted as the computational hydrogen electrode (CHE) model. They claimed that due to the relative low proton transfer barriers, the kinetic aspects in the proton transfer was omitted, and the rate-determining step was the one with the most positive free energy change ΔE max . To make the free energy of the rate-determining step become zero, a limiting potentialneeds to be applied. If we denote the equilibrium potential of a given electrochemical reaction as U eq , the overpotential wouldThe overpotential thereby originates from the relative stability between certain adsorbed intermediates. For example, the overpotential for 4-electron oxygen reduction reaction (ORR) is ascribed to the high adsorption free energy barrier of *OOH on the weak binding materials or the high desorption free energy barrier of *OH on the strong binding materials. [3] Similarly, when excluding the Tafel mechanism, the overpotential for hydrogen evolution reaction (HER) originates from either the high adsorption free energy barrier of *H (Volmer step) or the high desorption barrier of the same intermediate (Heyrovsky step). [4] Based on the Sabatier principle, [5] when the maximum electrocatalytic activity is reached in these reactions, the binding of the reaction intermediates should be neither too strong nor too weak. In HER, where only *H is emerged as the reaction intermediate, it is easier to achieve a maximum reactivity with negligible overpotential because the binding energy of *H is not limited and can be tuned freely. If the binding energy of *H on a certain material renders the adsorption free energy of *H close to zero, the overpotential will be negligible. Such an electroactive electrode for HER indeed exists, say the platinum electrode. However, for electrocatalytic reactions with multiple proton-electron transfer steps, the case is much more complex. The overpotential cannot be lowered to a negligible value because the relative The increasing concentration of CO 2 in the atmosphere, and the resulting environmental problems, call for effective ways to convert CO 2 into valuable fuels and chemicals for a sustainable carbon cycle. In such a context, CO 2 electrocatalytic reduction has been hotly studied due to the merits of ambient operational conditions and easy control of the reaction process by changing the applied potential. Among the various systems studied, Cu and Au are found to possess the highest Faradaic efficiency toward cathodic electrocatalytic conversion of CO 2 to hydrocarbons and CO, respectively. However, both of them suffer from large overpotentials ...

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“…Lim et al used DFT to study Cu nanoparticles (Cu 55 ; diameter of approximately 0.9 nm) on a defective graphene system. [106] The Cu 55 exhibited strong adsorption on the graphene with adsorption energy of -4.26 eV. This was attributed to the dangling bonds of carbon atoms adjacent to the 5-8-5 vacancy site interacting with the copper atoms and is thought to be key in preventing sintering of the nanoparticles.…”

Section: Nanostructured Carbon Supportsmentioning

confidence: 99%

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂

Vasileff

Zheng

Qiao

2017

Advanced Energy Materials

351

222

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The electrochemical reduction of CO2 to useful molecules offers an elegant technological solution to current energy security and sustainability issues because it sequesters carbon from the atmosphere, provides an energy storage solution for intermittent renewable sources, and can be used to produce fuels and industrial chemicals. Nanostructured carbon materials have been extensively used to catalyse some key electrochemical processes because of their excellent electrical conductivity, chemical stability, and abundant active sites. This progress report focuses on nanostructured carbon materials, namely graphene materials, carbon nanotubes, porphyrin materials, nanodiamond, and glassy carbon, which have recently shown promise as high performing CO2 reduction electrocatalysts and supports. Along with discussion regarding materials synthesis, structural characterisation, and electrochemical performance characterisation techniques used, this report will discuss the findings of recent computational CO2RR studies which have been key to elucidating active sites and reaction mechanisms, and developing strategies to break conventional scaling relationships. Lastly, challenges and future perspective of these carbon‐based materials for CO2 reduction applications will be given. Much work is still required to realise the commercial viability of the technology, but advanced experimental techniques coupled with theoretical calculations are expected to facilitate future development of the technology.

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Carbon dioxide conversion into hydrocarbon fuels on defective graphene-supported Cu nanoparticles from first principles

Cited by 156 publications

References 40 publications

High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO₂

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂

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Carbon dioxide conversion into hydrocarbon fuels on defective graphene-supported Cu nanoparticles from first principles

Cited by 156 publications

References 40 publications

High‐Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

High‐Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO2

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO2

Contact Info

Product

Resources

About

High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

High‐Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle/N‐Doped Graphene Electrode

Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO₂

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂