Guiding catalytic CO<sub>2</sub> reduction to ethanol with copper grain boundaries

Cheng, Dongfang; Zhang, Gong; Li, Lulu; Shi, Xiangcheng; Zhen, Shiyu; Zhao, Zhi‐Jian; Gong, Jinlong

doi:10.1039/d3sc02647g

Cited by 10 publications

(5 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Other experimental results also suggest that Cu grain boundaries have a positive effect on the production of C 2 + oxygenates, particularly ethanol. Using joint firstprinciples calculations and experiments, Cheng et al [94] found that the undercoordinated sites with relatively longer CuÀ Cu bond lengths on grain boundaries have a strong impact on the binding strength of bidentate adsorbates, such as *COOH and *CHO. These conditions are conducive to the initial activation of CO 2 and further CO reduction, respectively.…”

Section: Morphological Evolutions Of Co2rr Electrocatalysts Using In/...mentioning

confidence: 99%

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Wang,

Ju,

Liang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

The electrochemical reductive valorization of CO2, referred to as the CO2RR, is an emerging approach for the conversion of CO2‐containing feeds into valuable carbonaceous fuels and chemicals, with potential contributions to carbon capture and use (CCU) for reducing greenhouse gas emissions. Copper surfaces and graphene‐embedded, N‐coordinated single metal atom (MNC) catalysts exhibit distinctive reactivity, attracting attention as efficient electrocatalysts for CO2RR. This review offers a comparative analysis of CO2RR on copper surfaces and MNC catalysts, highlighting their unique characteristics in terms of CO2 activation, C1/C2(+) product formation, and the competing hydrogen evolution pathway. The assessment underscores the significance of understanding structure‐activity relationships to optimize catalyst design for efficient and selective CO2RR. Examining detailed reaction mechanisms and structure‐selectivity patterns, the analysis explores recent insights into changes in the chemical catalyst states, atomic motif rearrangements, and fractal agglomeration, providing essential kinetic information from advanced in/ex‐situ microscopy/spectroscopy techniques. At the end, this review addresses future challenges and solutions related to today’s disconnect between our current molecular understanding of structure‐activity‐selectivity relations in CO2RR and the relevant factors controlling the performance of CO2 electrolyzers over longer times, at larger electrode sizes, and at higher current densities.

show abstract

Section: Morphological Evolutions Of Co2rr Electrocatalysts Using In/...mentioning

confidence: 99%

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Wang,

Ju,

Liang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

“…The low ∑ values were chosen for construction, because low ∑ boundaries tended to have lower energies than average 54 . We acknowledge the existence of various grain boundary types, and modeling all types of grain boundaries is not feasible 55 .…”

Section: Theoretical Calculationsmentioning

confidence: 99%

CO electrolysis to multicarbon products over grain boundary-rich Cu nanoparticles in membrane electrode assembly electrolyzers

Li,

Wei,

Liu

et al. 2024

Nat Commun

View full text Add to dashboard Cite

Producing valuable chemicals like ethylene via catalytic carbon monoxide conversion is an important nonpetroleum route. Here we demonstrate an electrochemical route for highly efficient synthesis of multicarbon (C2+) chemicals from CO. We achieve a C2+ partial current density as high as 4.35 ± 0.07 A cm−2 at a low cell voltage of 2.78 ± 0.01 V over a grain boundary-rich Cu nanoparticle catalyst in an alkaline membrane electrode assembly (MEA) electrolyzer, with a C2+ Faradaic efficiency of 87 ± 1% and a CO conversion of 85 ± 3%. Operando Raman spectroscopy and density functional theory calculations reveal that the grain boundaries of Cu nanoparticles facilitate CO adsorption and C − C coupling, thus rationalizing a qualitative trend between C2+ production and grain boundary density. A scale-up demonstration using an electrolyzer stack with five 100 cm2 MEAs achieves high C2+ and ethylene formation rates of 118.9 mmol min−1 and 1.2 L min−1, respectively, at a total current of 400 A (4 A cm−2) with a C2+ Faradaic efficiency of 64%.

show abstract

“…6a). [127][128][129][130] Therefore, it is widely accepted that grain boundaries play a crucial role in modulating the absorption energy barriers of intermediates, thereby promoting the formation of multi-carbon products. 57,[131][132][133][134] Grain boundaries typically form between different crystalline phases of copper with the same valence state.…”

Section: Grain Boundary Effectmentioning

confidence: 99%

Cu-based catalyst designs in CO₂ electroreduction: precise modulation of reaction intermediates for high-value chemical generation

Xie,

Jiang,

Zhu

et al. 2023

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Guiding catalytic CO₂ reduction to ethanol with copper grain boundaries

Abstract: The grain boundaries (GBs) in copper (Cu) electrocatalysts have been suggested as active sites for CO2 electroreduction to ethanol. Nevertheless, the mechanisms are still elusive. This paper describes how GBs...

Cited by 10 publications

References 51 publications

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

CO electrolysis to multicarbon products over grain boundary-rich Cu nanoparticles in membrane electrode assembly electrolyzers

Cu-based catalyst designs in CO₂ electroreduction: precise modulation of reaction intermediates for high-value chemical generation

Contact Info

Product

Resources

About

Guiding catalytic CO2 reduction to ethanol with copper grain boundaries

Abstract: The grain boundaries (GBs) in copper (Cu) electrocatalysts have been suggested as active sites for CO2 electroreduction to ethanol. Nevertheless, the mechanisms are still elusive. This paper describes how GBs...

Cited by 10 publications

References 51 publications

Electrochemical CO2 Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Electrochemical CO2 Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

CO electrolysis to multicarbon products over grain boundary-rich Cu nanoparticles in membrane electrode assembly electrolyzers

Cu-based catalyst designs in CO2 electroreduction: precise modulation of reaction intermediates for high-value chemical generation

Contact Info

Product

Resources

About

Guiding catalytic CO₂ reduction to ethanol with copper grain boundaries

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Cu-based catalyst designs in CO₂ electroreduction: precise modulation of reaction intermediates for high-value chemical generation