The electrochemical carbon dioxide reduction reaction (CO2RR) presents a viable approach to recycle CO2gas 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 CH4production lower by 0.149 V than commercial Cu NPs. More impressively, SD‐Cu NPs demonstrate a faradaic efficiency of 52.43% ± 2.72% for C2H4production 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.
This content will become publicly available on June 11, 2025
The electrochemical carbon dioxide reduction reaction (CO2RR) is a promising approach for reducing atmospheric carbon dioxide (CO2) emissions, allowing harmful CO2to be converted into more valuable carbon‐based products. On one hand, single carbon (C1) products have been obtained with high efficiency and show great promise for industrial CO2capture. However, multi‐carbon (C2+) products possess high market value and have demonstrated significant promise as potential products for CO2RR. Due to CO2RR's multiple pathways with similar equilibrium potentials, the extended reaction mechanisms necessary to form C2+products continue to reduce the overall selectivity of CO2‐to‐C2+electroconversion. Meanwhile, CO2RR as a whole faces many challenges relating to system optimization, owing to an intolerance for low surface pH, systemic stability and utilization issues, and a competing side reaction in the form of the H2evolution reaction (HER). Ethylene (C2H4) remains incredibly valuable within the chemical industry; however, the current established method for producing ethylene (steam cracking) contributes to the emission of CO2into the atmosphere. Thus, strategies to significantly increase the efficiency of this technology are essential. This review will discuss the vital factors influencing CO2RR in forming C2H4products and summarize the recent advancements in ethylene electrosynthesis.
more » « less- PAR ID:
- 10513932
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 14
- Issue:
- 33
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Copper (Cu) remains the most important metal catalyst for the carbon dioxide reduction reaction (CO2RR) into C2products. Due to limited evidence from in situ experiments, mechanistic studies are often performed in the framework of density functional theory (DFT), using functionals at the generalized gradient approximation (GGA) level, which have fundamental difficulties to correctly describe CO adsorption and surface stability. We employ the adiabatic connection fluctuation dissipation theorem within the random phase approximation (RPA), in combination with the linearized Poisson–Boltzmann equation to describe solvation effects, to investigate the mechanism of CO2RR on the Cu(100) facet. Qualitatively different from the DFT‐GGA results, RPA results propose the formation of *OCCHO as the potential determining step towards C2products. The results suggest that it is important to use more accurate methods like RPA when modeling reactions involving multiple CO‐related species like CO2RR.
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null (Ed.)The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. Here we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (−0.50 ∼ −0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm −2 at −0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm −2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .more » « less
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