Morphology Manipulation of Copper Nanocrystals and Product Selectivity in the Electrocatalytic Reduction of Carbon Dioxide

Suen, Nian Tzu; Kong, Zhong Ri; Hsu, Chia‐Shuo; Chen, Hao Ming; Tung, Ching Wei; Lü, Ying; Dong, Chung Li; Shen, Chien Chang; Chung, Jen Chieh

doi:10.1021/acscatal.9b00790

Cited by 111 publications

(97 citation statements)

References 48 publications

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“…In contrast to the case of redox shuttle, the CO 2 reduction product through a conventional chronoamperometry (CA hereafter) at the same potential of −0.75 V was carbon monoxide ( Supplementary Fig. 5), which was characteristic of a copper-like behavior with the only product of CO from CO 2 RR at such potential 1,37 . The CuO x catalyst in present study gave a copper-like CO 2 RR performance once applying a higher cathodic potentials (higher than −0.95 V) where the dominant CO 2 RR product was CH 4 .…”

Section: And 2)mentioning

confidence: 95%

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

et al. 2020

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Copper electrocatalysts have been shown to selectively reduce carbon dioxide to hydrocarbons. Nevertheless, the absence of a systematic study based on time-resolved spectroscopy renders the functional agent-either metallic or oxidative Copper-for the selectivity still undecidable. Herein, we develop an operando seconds-resolved X-ray absorption spectroscopy to uncover the chemical state evolution of working catalysts. An oxide-derived Copper electrocatalyst is employed as a model catalyst to offer scientific insights into the roles metal states serve in carbon dioxide reduction reaction (CO 2 RR). Using a potential switching approach, the model catalyst can achieve a steady chemical state of half-Cu(0)and-half-Cu(I) and selectively produce asymmetric C 2 products-C 2 H 5 OH. Furthermore, a theoretical analysis reveals that a surface composed of Cu-Cu(I) ensembles can have dual carbon monoxide molecules coupled asymmetrically, which potentially enhances the catalyst's CO 2 RR product selectivity toward C 2 products. Our results offer understandings of the fundamental chemical states and insights to the establishment of selective CO 2 RR.

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Section: And 2)mentioning

confidence: 95%

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

et al. 2020

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“…Compared to the C 1 products, only few kinds of catalysts have been reported to exhibit considerable selectivity to C 2 products, of which the copper‐based materials are the most attractive, especially for ethylene . Many pioneer researchers have studied the crystal structure effects of pristine copper towards CO 2 RR, where crystal planes, nanoparticle size and edge/corner morphologies are mostly discussed .…”

Section: Introductionmentioning

confidence: 99%

“…Many pioneer researchers have studied the crystal structure effects of pristine copper towards CO 2 RR, where crystal planes, nanoparticle size and edge/corner morphologies are mostly discussed . Chen et al . demonstrated that the atomic arrangements on Cu single crystal surfaces is crucial toward product selectivity of electrocatalytic CO 2 reduction.…”

Section: Introductionmentioning

confidence: 99%

Controllable Synthesis of Leaf‐Like CuO Nanosheets for Selective CO₂ Electroreduction to Ethylene

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The carbon dioxide reduction reaction (CO 2 RR) driven by renewable electricity is a promising way to tackle the CO 2 emission woes and recycle use of CO 2 . The synthesis of electrocatalysts with high activity and selectivity for CO 2 RR to ethylene remains a great challenge. Herein, leaf-like CuO nanosheets are fabricated in situ on nitrogen-doped graphene (NG) by using a novel reduction-oxidation-reconstruction process. When used as a catalyst for the CO 2 RR in 0.1 M KHCO 3 , a high faradaic efficiency of approximately 30 % for ethylene with an ultra-high ethylene/methane ratio of 190 was achieved at À 1.3 V vs. the reversible hydrogen electrode. The SEM and TEM images confirm the leaf-like CuO nanosheets display highcurvature structures, while multiple distinguished grain boundaries constructed by CuO(110) and CuO(111) planes are verified by HRTEM. For the first time, we present a facile method to combine the high-curvature structure and the grain boundary to enhance the selectivity of the CO 2 RR to ethylene over a CuO catalyst.

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“…A similar synthesis procedure was adopted by Suen et al to prepare their Cu nanocrystals with cubic, hexarhombic dodecahedron, and octahedron‐like morphologies. [ 56 ] The group modified the standard reflux setup by performing the reaction under N 2 gas at 230 °C (or 270 °C) for 3 h. Excess n‐hexane was used to wash the additives. HRTEM images of the above‐mentioned Cu nanostructures are shown in Figure a–d.…”

Section: Synthesis Of Cu‐based Catalystsmentioning

confidence: 99%

Section: Synthesis Of Cu‐based Catalystsmentioning

confidence: 99%

Potential Link between Cu Surface and Selective CO₂ Electroreduction: Perspective on Future Electrocatalyst Designs

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Electrochemical reduction of carbon dioxide (CO2RR) product distribution has been identified to be dependent on various surface factors, including the Cu facet, morphology, chemical states, doping, etc., which can alter the binding strength of key intermediates such as *CO and *OCCO during reduction. Therefore, in‐depth knowledge of the Cu catalyst surface and identification of the active species under reaction conditions aid in designing efficient Cu‐based electrocatalysts. This progress report categorizes various Cu‐based electrocatalysts into four main groups, namely metallic Cu, Cu alloys, Cu compounds (Cu + non‐metal), and supported Cu‐based catalysts (Cu supported by carbon, metal oxides, or polymers). The detailed mechanisms for the selective CO2RR are presented, followed by recent relevant developments on the synthetic procedures for preparing Cu and Cu‐based nanoparticles. Herein, the potential link between the Cu surface and CO2RR performance is highlighted, especially in terms of the chemical states, but other significant factors such as defective sites and roughened morphology of catalysts are equally considered during the discussion of current studies of CO2RR with Cu‐based electrocatalysts to fully understand the origin of the significant enhancement toward C2 formation. This report concludes by providing suggestions for future designs of highly selective and stable Cu‐based electrocatalysts for CO2RR.

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Morphology Manipulation of Copper Nanocrystals and Product Selectivity in the Electrocatalytic Reduction of Carbon Dioxide

Cited by 111 publications

References 48 publications

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

Controllable Synthesis of Leaf‐Like CuO Nanosheets for Selective CO₂ Electroreduction to Ethylene

Potential Link between Cu Surface and Selective CO₂ Electroreduction: Perspective on Future Electrocatalyst Designs

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Morphology Manipulation of Copper Nanocrystals and Product Selectivity in the Electrocatalytic Reduction of Carbon Dioxide

Cited by 111 publications

References 48 publications

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction

Controllable Synthesis of Leaf‐Like CuO Nanosheets for Selective CO2 Electroreduction to Ethylene

Potential Link between Cu Surface and Selective CO2 Electroreduction: Perspective on Future Electrocatalyst Designs

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Product

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Controllable Synthesis of Leaf‐Like CuO Nanosheets for Selective CO₂ Electroreduction to Ethylene

Potential Link between Cu Surface and Selective CO₂ Electroreduction: Perspective on Future Electrocatalyst Designs