Electroreduction of CO<sub>2</sub> to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency

Li, Jiachen; Kuang, Yun; Meng, Yongtao; Tian, Xin; Hung, Wei Hsuan; Zhang, Xiao; Li, Aowen; Xu, Mingquan; Zhou, Wu; Ku, Ching−Shun; Chiang, Ching-Yu; Zhu, Guanzhou; Guo, Jinyu; Sun, Xiaoming

doi:10.1021/jacs.0c00122

Cited by 179 publications

(167 citation statements)

References 43 publications

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“…Furthermore, it has more C 2+ compounds; the FE of C 2 H 6 at Cu‐foam‐ms‐1 h is 5 times higher than that of Cu‐foam, the FE of C 2 H 4 reach about 30 %, which is 2.5 times than the pristine Cu‐foam. More important the Cu‐foam‐ms‐1 h can generate C 3 and C 4 compounds, while other high CO 2 pressure experiment in the references C 1 was dominating …”

Section: Resultsmentioning

confidence: 99%

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

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The electrochemical reduction of CO 2 is a promising route to convert waste products to valuable chemicals. Search for suitable and efficient CO 2 reduction electrocatalysts with high C 2 :C 1 selectivity holds great promise. Herein, for the first time we have developed a molten salt oxidized method to modify the morphology and oxidation state of a Cu-foam catalyst. The catalyst displayed a current density of 30 mA cm À 2 (À 1.4 V versus reversible hydrogen electrode) and an ethylene/ methane ratio of 870. We provide insight into the improved performance of the catalysts by cross section scanning transmission electron microscopy and quasi in situ soft X-ray spectroscope, which show that copper oxides are surprisingly reconstructed with Cu (I) and Cu (0) on the surface during the reaction. First principle calculations also demonstrate that the partly reduced Cu 2 O (111) surface has a high reactivity and selectivity for C 2 + products. Furthermore, the molten salt treated catalysts could be applied to the direct synthesis of multi-carbon fuels, including C 3-C 4 compounds in high CO 2 pressure electrocatalytic reduction. Our results demonstrate that molten salt are both the oxidizing agent and reaction medium, which is a promising approach for synthesis of highly active CO 2 electrocatalysts, which may open a new way for industrial application.

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Section: Resultsmentioning

confidence: 99%

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

et al. 2020

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“…Metal‐ and nitrogen‐coordinated materials dispersed on carbon matrix (M–N x –C), with a high density of active sites, have attracted increased interests in the field of electrocatalytic reduction of CO 2 , due to their low cost and high abundance of raw material. [ 22–28 ] Nitrogen coordinated metal as catalytic sites that could be designable to fit the especial functionality. As is already known, the Cu–N x –C sites can have much more interaction with the oxygen of the CO 2 , which can enhance the enthalpy of the CO 2 and inhibit the HER but results in sluggish kinetics of the CO 2 + H + + e − → COOH* process.…”

Section: Figurementioning

confidence: 99%

Design of Binary Cu–Fe Sites Coordinated with Nitrogen Dispersed in the Porous Carbon for Synergistic CO₂ Electroreduction

Yun

Zhan

Wang

et al. 2020

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methods to suppress the release of CO 2 , using photo-or electrocatalysis. [7-10] Particularly, the electrocatalytic reduction can be a promising method for managing the global carbon balance and issues regarding energy generation, as it can convert CO 2 to C1 or C2 chemical products as fuel. [11,12] However, this reduction process faces significant challenges due to the chemical inertness of CO 2 , as there are high thermodynamic and kinetic barriers to obtain a successful electrocatalytic reduction of CO 2. Additionally, the CO 2-to-CO pathway is usually selected, because CO is the raw material of the Fisher-Tropsch process and other added-value hydrocarbons with wide distribution (C1-C3 products). [13-17] On the other hand, the competing hydrogen evolution reaction (HER) and the stable CO bond of CO 2 can optimize the catalytic system through the activity and selectivity during the CO 2-to-CO electrocatalytic process. [18-21] Metal-and nitrogen-coordinated materials dispersed on carbon matrix (M-N x-C), with a high density of active sites, have attracted increased interests in the field of electrocatalytic reduction of CO 2 , due to their low cost and high abundance of raw material. [22-28] Nitrogen coordinated metal as catalytic sites that could be designable to fit the especial functionality. As is already known, the Cu-N x-C sites can have much more interaction with the oxygen of the CO 2 , which can enhance the enthalpy of the CO 2 and inhibit the HER but results in sluggish kinetics of the CO 2 + H + + e − → COOH* process. [29,30] Besides, the Fe-N x-C materials are often applied in CO 2 reduction with low onset potential. Nevertheless, the desorption of *CO into the gas phase can reduce the reactivity, due to the strong binding of CO to the Fe-N x-C sites in the step of COOH* + H + + e − → CO* + H 2 O and CO* → CO+ *. [31-33] Considering the issues mentioned above, to maximize the potential of single-atom catalysts for multistep catalytic reaction, we design and synthesize biatomic active sites of Cu-Fe-N 6-C catalyst by pyrolysis of PcCu-Fe-ZIF-8 under an argon atmosphere at 1000 °C (the detail can be found in the Supporting Information). The configuration and coordination environment of the diatomic catalyst are evidenced by the aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (STEM) (AC HAADF-STEM) and X-ray adsorption spectroscopy. The experimental results show To relieve the green gas emission and involve the carbon neutral cycle, electrochemical reduction of CO 2 attracts more and more attention. Herein, a biatomic site catalyst of Cu-Fe coordinated with the nitrogen, which is doped in the carbon matrix (denoted as Cu-Fe-N 6-C), is designed. The as-obtained Cu-Fe-N 6-C exhibits higher performance than that of Cu-N-C and Fe-N-C, owing to bimetallic sites, proving synergistic functions based on different molecules and their interfaces. Cu-Fe-N 6-C shows high selectivity toward CO, with high Faradaic efficiency (98% at −0.7 V), and maintaining 98% of its in...

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“…[17,64] Particularly, Cu is the only monometallic catalysts that can produce multiple hydrocarbons as the reduction products from CO 2 RR. [65] Table 1 summarizes the catalytic performance of Co-based catalysts published so far for ECO 2 RR. We further visualized the product distribution and the corresponding catalyst types in Figure 10.…”

Section: The Reduction Product Distribution By Co-based Catalystsmentioning

confidence: 99%

Nanostructured Cobalt‐Based Electrocatalysts for CO₂Reduction: Recent Progress, Challenges, and Perspectives

Chen

Zhang

et al. 2020

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million (ppm), which is ≈50% higher than that of the pre-industrial level (280 ppm). [1] The consequent climate change (the average temperature increase of 0.8 °C above the pre-industrial level) causes global warming, one of the top environmental concerns. [2] To maintain the sustainable development of the society, the Intergovernmental Panel on Climate Change (IPCC) recently recommended the warming limit to 1.5 °C rather than 2.0 °C to reduce catastrophic climate change issues, requiring the commitment to take action to control global carbon emission. [3] Under the Paris Agreement, many countries endeavor to reduce greenhouse gas emissions gradually by 2030. [4] The carbon capture and storage (CCS) is a feasible strategy to lower the CO 2 emissions substantially. Long-term storage issues related to the leakage of CO 2 and the lack of economic incentives limited its development. [5] The CO 2 reduction reactions (CO 2 RR) that convert CO 2 into other value-added carbon products could provide a well alternative to the utilization of the captured CO 2 , which not only contributes to the mitigation of CO 2 emission but also offers useful products that can serve as fuels such as CO, HCOOH, CH 3 OH, and CH 4. [6] Moreover, the drive power of CO 2 RR could come from renewable energy resources, such as solar, wind, and hydraulic resources, which indicates that in a green concept, CO 2 RR could complete the carbon loop and potentially solve the issues of global warming and energy crisis simultaneously. [7] 1.1. Fundamental Reaction Pathways of CO 2 RR CO 2 RR is not thermodynamically and kinetically favorable. Every reduction pathway demands a certain amount of energy input. Equations (1-13) shows the reaction steps involved in CO 2 RR (in pH = 7 aqueous solution, vs Normal Hydrogen Electrode (NHE)). [8] As illustrated, it requires a significant amount of reorganizational energy between the linear molecule CO 2 and the bent radical anion − CO 2 • (Equation (1)). When coupling with proton in the reaction, the required reaction energy decreases (Equations (2-12)). Aqueous media with H 2 O molecules become ideal for providing proton into the CO 2 RR system. The reduction potential of hydrogen evolution reaction (HER) (Equation (13)) is close to that of CO 2 RR. It makes HER a competitive reaction against CO 2 RR during the reduction CO 2 reduction reaction (CO 2 RR) provides a promising strategy for sustainable carbon fixation by converting CO 2 into value-added fuels and chemicals. In recent years, considerable efforts are focused on the development of transition-metal (TM)-based catalysts for the selectively electrochemical CO 2 reduction reaction (ECO 2 RR). Co-based catalysts emerge as one of the most promising electrocatalysts with high Faradaic efficiency, current density, and low overpotential, exhibiting excellent catalytic performance toward ECO 2 RR for CO and HCOOH productions that are economically viable. The intrinsic contribution of Co and the synergistic effects in Co-hybrid catalysts play essential roles for ...

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Electroreduction of CO₂ to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency

Cited by 179 publications

References 43 publications

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

Design of Binary Cu–Fe Sites Coordinated with Nitrogen Dispersed in the Porous Carbon for Synergistic CO₂ Electroreduction

Nanostructured Cobalt‐Based Electrocatalysts for CO₂Reduction: Recent Progress, Challenges, and Perspectives

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Electroreduction of CO2 to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency

Cited by 179 publications

References 43 publications

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO2 Reduction Reaction

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO2 Reduction Reaction

Design of Binary Cu–Fe Sites Coordinated with Nitrogen Dispersed in the Porous Carbon for Synergistic CO2 Electroreduction

Nanostructured Cobalt‐Based Electrocatalysts for CO2Reduction: Recent Progress, Challenges, and Perspectives

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Electroreduction of CO₂ to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

Molten Salt Treated Cu Foam Catalyst for Selective Electrochemical CO₂ Reduction Reaction

Design of Binary Cu–Fe Sites Coordinated with Nitrogen Dispersed in the Porous Carbon for Synergistic CO₂ Electroreduction

Nanostructured Cobalt‐Based Electrocatalysts for CO₂Reduction: Recent Progress, Challenges, and Perspectives