Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance

Cheng, Tao; Xiao, Hai; Goddard, William A.

doi:10.1021/jacs.7b03300

Cited by 159 publications

(157 citation statements)

References 25 publications

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“…This stabilization is due to the electrostatic attraction between oppositely charged carbon atoms induced by the Cu + and Cu 0 interface, promoting C-C coupling 52 . We therefore concentrate on the Gibbs free energy of formation for COH* and OCCOH* as descriptors for methane formation and CO-CO dimerization to ethylene 53 . We began by constructing Cu(111) and Cu(211) slabs as model systems of flat and high-curvature Cu surfaces, respectively.…”

Section: Nature Catalysismentioning

confidence: 99%

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

et al. 2018

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As energy demand continues to increase, so too do anthropogenic carbon emissions and global temperatures. Renewable energy sources such as solar, wind and hydroelectricity displace fossil fuel carbon emissions and continue to progress to wider deployment. However, long-term (seasonal) energy storage remains a challenge that must be addressed for renewables to meet a major fraction of global energy demand 1 . Carbon dioxide electroreduction to renewable fuels and feedstocks provides an energy storage solution to the seasonal variability of renewable energy sources 2 . When coupled with carbon capture technology, the carbon dioxide reduction reaction (CO 2 RR) offers a means to close the carbon cycle.CO 2 RR electrocatalysts lower energetic barriers to CO 2 reduction by stabilizing intermediates and transition states in the multistep electrochemical reduction process 3 . Copper reduces CO 2 to a wide range of hydrocarbon products such as methane, ethylene, ethanol and propanol 4 . Unfortunately, bulk copper is not selective among various carbon products, and it also suffers Faradaic efficiency (FE) losses to the competing hydrogen evolution reaction.Among possible products, C2+ hydrocarbons are highly sought in view of their commercial value. Ethylene, for example, is a precursor to the production of polyethylene, a major plastic. Selectively producing ethylene over methane circumvents costly paraffin-olefin separation 5 . Developing catalysts that work at ambient conditions to produce C2 selectively over C1 gaseous products will increase the relevance of renewable feedstocks in the chemical sector.Oxide-derived copper is one class of catalyst that has shown enhanced CO 2 RR activity and increased selectivity towards multi-carbon products [6][7][8] . The selectivity of these catalysts is dependent on structural morphology and copper oxidation state 9-17 . Electrochemical reduction of copper oxide catalyst films can lead to grain boundaries, undercoordinated sites and roughened surfaces that are hypothesized to be catalytically active sites 8,18 . Residual oxides, proposed to play a key role in catalysis, may exist after electrochemical reduction 7 . A recent report of oxygen plasma-activated oxide-derived copper catalysts achieved an ethylene FE of 60% at − 0.9 V versus reversible hydrogen electrode (RHE) 9 , with activity attributed to the presence of Cu + species. In situ hard X-ray absorption spectroscopy (hXAS) experiments have suggested stable Cu + species exist at highly negative CO 2 RR potentials of ~− 1.0 versus RHE 9 . However, the presence of Cu + species during CO 2 RR is still the subject of debate; 7,19 and in situ tracking of the copper oxidation state with time resolution during CO 2 RR has remained elusive.Morphological effects of copper nanostructures have a significant effect on the selectivity of CO 2 RR to multi-carbon products [20][21][22][23][24] . Copper catalysts with different morphologies have been synthesized through annealing, chemical treatments on thin films, colloidal synthesis and ...

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Section: Nature Catalysismentioning

confidence: 99%

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

et al. 2018

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“…Numerous chemical modifications and nanostructuring approaches have led to improvements in product selectivity and catalytic activity. [17] Cheng et al also reported a theoretical study showing that highly active twin boundaries (TBs) on the Au surface can be superior to GBs and other defects for CO 2 RR. [2,12] Promotion of C2 products on Cu GBs has been predicted by Cheng et al, although in Li's studies the production of ethylene is low.…”

Section: Doi: 101002/adma201805405mentioning

confidence: 99%

“…[2,12] Promotion of C2 products on Cu GBs has been predicted by Cheng et al, although in Li's studies the production of ethylene is low. [17] Cheng et al also reported a theoretical study showing that highly active twin boundaries (TBs) on the Au surface can be superior to GBs and other defects for CO 2 RR. [18] Hence it would be interesting to realize Cu nanostructures with high TB for CO 2 RR.…”

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confidence: 99%

A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials

et al. 2018

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The electrochemical carbon dioxide reduction reaction (CO2RR) presents a viable approach to recycle CO2 gas into low carbon fuels. Thus, the development of highly active catalysts at low overpotential is desired for this reaction. Herein, a high‐yield synthesis of unique star decahedron Cu nanoparticles (SD‐Cu NPs) electrocatalysts, displaying twin boundaries (TBs) and multiple stacking faults, which lead to low overpotentials for methane (CH4) and high efficiency for ethylene (C2H4) production, is reported. Particularly, SD‐Cu NPs show an onset potential for CH4 production lower by 0.149 V than commercial Cu NPs. More impressively, SD‐Cu NPs demonstrate a faradaic efficiency of 52.43% ± 2.72% for C2H4 production at −0.993 ± 0.0129 V. The results demonstrate that the surface stacking faults and twin defects increase CO binding energy, leading to the enhanced CO2RR performance on SD‐Cu NPs.

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“…Thus, H 2 CO 3 decomposition likely follows a stepwise mechanism in bulk‐like water, but it might be different in other environments like an air/water interface. Goddard and coworkers have investigated multiple aspects of CO reduction on copper surfaces and copper nanoparticles with explicit water layers at different pH levels . Their studies of solvated systems were carried out using reactive force fields which significantly decrease the computational time required.…”

Section: Explicit Solvationmentioning

confidence: 99%

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

Basdogan

Maldonado

Keith

2019

WIREs Comput Mol Sci

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We provide a critical overview of progress and challenges in computationally modeling multistep reaction mechanisms relevant for catalysis and electrocatalysis.We first discuss how the chemical and materials space of energetically efficient catalysis can be explored with computational chemistry. Since reactions for renewable energy catalysis can involve acid-base chemistry and/or ions under aqueous conditions, we then summarize how solvation can be modeled with quantum chemistry schemes using implicit, mixed implicit/explicit, and fully explicit solvation modeling. We will discuss the insights (and limitations) of these solvation models primarily through the scope of understanding CO 2 reduction reaction mechanisms, but these will also be applicable for future work elucidating other reaction mechanisms of critical importance for human sustainability such as H 2 O oxidation and N 2 reduction. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis K E Y W O R D S cluster-continuum, CO 2 reduction, mixed implicit/explicit, phase diagrams, Pourbaix diagrams, solvation modeling

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Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance

Cited by 159 publications

References 25 publications

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction

A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

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