Protecting Copper Oxidation State via Intermediate Confinement for Selective CO<sub>2</sub> Electroreduction to C<sub>2+</sub> Fuels

Yang, Peng‐Peng; Zhang, Xiaolong; Gao, Fei‐Yue; Zheng, Ya‐Rong; Niu, Zhuang‐Zhuang; Yu, Xingxing; Liu, Ren; Wu, Zhe; Qin, Shuai; Chi, Liping; Duan, Yu; Ma, Tao; Zheng, Xusheng; Zhu, Junfa; Wang, Huijuan; Gao, Min‐Rui; Yu, Shu‐Hong

doi:10.1021/jacs.0c01699

Cited by 513 publications

(372 citation statements)

References 62 publications

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“…From this perspective, pore size was considered to have a significant impact on the catalytic performance of porous catalysts. [78,79] Among the various methods to synthesize indium-based catalysts, electrodeposition is a facile one that has been most frequently used. The substrate where metallic indium is to be deposited has been found to affect the catalyst morphologies.…”

Section: Morphologymentioning

confidence: 99%

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

Zhu

Han

2020

ChemCatChem

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Electrochemical reduction of CO2 (CO2RR) is a promising solution to mitigate the ever‐increasing global carbon emission. Indium‐based catalysts have been extensively studied for catalyzing the production of formate, CO, and even multi‐carbon molecules from CO2. Rational design of the catalyst, however, is urgently needed to further improve the activity, selectivity, and stability for the sake of commercialization. Herein, we comprehensively reviewed recent progresses on the indium based CO2RR catalysts. Specifically, aspects regarding the nature of active sites, reaction mechanism, and the impact of operating conditions are overviewed. The reported indium‐based monometallic and bimetallic catalysts in the literature are summarized, as well. Future directions should be focused on the understanding of catalyst system during the reaction and under industrial‐relevant conditions.

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Section: Morphologymentioning

confidence: 99%

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

Zhu

Han

2020

ChemCatChem

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“…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 ]…”

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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“…Cu catalysts in different oxidation states (Cu 0 , Cu 1+ , and Cu 2+ ) are all active toward C 1 and C 2+ product formations in ECO 2 RR, while the specific product selectivity varies depending on the certain type of the Cu catalysts. [ 125 ] The ECO 2 RR product selectivity is facet‐dependent for Cu‐based catalysts. For example, {100} of Cu cubes prefers ethylene formation, while {111} of Cu octahedral prefers methane formation.…”

Section: The “Firework” Between Co and Other Materialsmentioning

confidence: 99%

“…[ 127 ] Nanoscaled defects on Cu can enrich the reaction intermediates (*CO and *OCCO) and hydroxyl ions on the electrocatalyst, thus promoting C−C coupling for ethylene formation. [ 125,128 ] Organic molecules or metal complexes can also functionalize Cu catalysts with the other binding interactions that may tune the stability of the reaction intermediates, improving catalytic performance by increasing FE, as well as decreasing overpotential. [ 31b ] Oxygenates of Cu catalysts play important roles in ECO 2 RR for C 2+ productions.…”

Section: The “Firework” Between Co and Other Materialsmentioning

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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Protecting Copper Oxidation State via Intermediate Confinement for Selective CO₂ Electroreduction to C₂₊ Fuels

Cited by 513 publications

References 62 publications

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

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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Protecting Copper Oxidation State via Intermediate Confinement for Selective CO2 Electroreduction to C2+ Fuels

Cited by 513 publications

References 62 publications

Recent Advances in Electrochemical CO2 Reduction on Indium‐Based Catalysts

Recent Advances in Electrochemical CO2 Reduction on Indium‐Based Catalysts

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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Protecting Copper Oxidation State via Intermediate Confinement for Selective CO₂ Electroreduction to C₂₊ Fuels

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

Recent Advances in Electrochemical CO₂ Reduction on Indium‐Based Catalysts

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