Br-Doped CuO Multilamellar Mesoporous Nanosheets with Oxygen Vacancies and Cetyltrimethyl Ammonium Cations Adsorption for Optimizing Intermediate Species and Their Adsorption Behaviors toward CO<sub>2</sub> Electroreduction to Ethanol with a High Faradaic Efficiency

Zhang, Wuzhengzhi; Ding, Lianchun; Sun, Weipei; Wu, Zhengcui; Chen, Zheng; Gao, Feng

doi:10.1021/acs.inorgchem.1c02102

Cited by 16 publications

(24 citation statements)

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“…In this reaction system, the Ag NPs/CuO MNSs heterostructure was constructed on a Cu foil through twostep solution-phase reactions under normal atmospheric temperature. In the first step, CuO MNSs were grown via the "partial dissolution and self-assembly" process, 39 In our special Ag NPs/CuO MNSs heterostructure, the CuO MNSs with rough edges favored gas infiltration, while Ag NPs loading expanded the active sites for CO 2 molecule adsorption. The electrons were transferred from Ag to Cu in Ag NPs/CuO MNSs, enabling CO 2 molecules to adsorb on Cu sites at the interfacial boundaries of CuO.…”

Section: Resultsmentioning

confidence: 99%

“…In this reaction system, the Ag NPs/CuO MNSs heterostructure was constructed on a Cu foil through two-step solution-phase reactions under normal atmospheric temperature. In the first step, CuO MNSs were grown via the “partial dissolution and self-assembly” process, from Cu(OH) 2 mesoporous nanobelts (Cu(OH) 2 MNBs) to thin Cu(OH) 2 mesoporous nanobelts, then MNSs of CuO and Cu(OH) 2 mixed phases, and finally CuO MNSs, as shown in Figure S12. Briefly, S 2 O 8 2– ions oxidized Cu(0) on the Cu foil into Cu 2+ ions; then, Cu 2+ ions coordinated with the NH 3 molecules generated from the reaction of NH 4 + ions and OH – ions to produce [Cu(NH 3 ) 4 ] 2+ complex ions.…”

Section: Resultsmentioning

confidence: 99%

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Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

et al. 2021

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It is an ongoing pursuit for researchers to precisely control the catalyst’s surface for high-performance CO2 electrochemical reduction (CO2ER). In this work, CuO mesoporous nanosheets (CuO MNSs) with rough edges decorated by small Ag nanoparticles (Ag NPs) with a tunable amount of Ag were synthesized on a Cu foil at normal atmospheric temperature through two-step solution-phase reactions for CO2ER to CO. In this special Ag NPs/CuO MNSs heterostructure, the mesoporous CuO NSs with rough edges favored gas infiltration, while decorated Ag NPs expanded the active sites for CO2 molecule adsorption. Ag NPs endowed Ag NPs/CuO MNSs with good electrical conductivity and promoted the adsorbed CO2 molecules to obtain electrons from the catalyst. Especially, the Ag–CuO interface stabilized the *COOH intermediate with strong bonding, which is important in boosting CO2ER to CO. The optimal Ag1.01%/CuO can catalyze CO2ER to CO with a Faradaic efficiency of 91.2% and a partial current density of 10.5 mA cm–2 at −0.7 V. Moreover, it exhibited prominent catalytic stability, retaining 97.8% of the initial current density and 97.6% of the original Faradaic efficiency for CO after 12 h of testing at −0.7 V. Notably, the Faradaic efficiency of CO on Ag1.01%/CuO can retain over 80% in the potential area from −0.6 to −0.9 V, embodying its high selectivity for CO. This work develops precious metal/metal oxide heterostructures with a low precious metal loading for efficacious CO2ER to CO and beyond.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

et al. 2021

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“…The liquid product was detected by 1 H NMR spectroscopy, where 100 μL of dimethyl sulfoxide (DMSO, 100 ppm (v/v) deuterium substituted water) was mixed with 500 μL of electrolyte. Liquid product Faradaic efficiency is calculated according to eq . , where n i is the number of moles of product, I represents current, t is the electrolysis time, and z i is the number of transferred electrons.…”

Section: Methodsmentioning

confidence: 99%

Metal–Organic Framework-Derived BiIn Bimetallic Oxide Nanoparticles Embedded in Carbon Networks for Efficient Electrochemical Reduction of CO₂ to Formate

et al. 2022

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Bismuth-based catalysts exhibit excellent activity and selectivity for the electroreduction of carbon dioxide (CO 2 ). However, single-component bismuth-based catalysts are not satisfactory for the electrochemical reduction of CO 2 to formic acid, mainly due to their high hydrogen production, low electrical conductivity, and small catalytic current density. Herein, we used a coordination strategy to recombine Bi and In at the molecular level to form Bi/In bimetallic metal−organic frameworks (MOFs), which were then calcined to obtain MOF-derived Bi/In bimetallic oxide nanoparticles embedded in carbon networks. Thanks to the synergistic effect of bimetallic components, high specific surface area, suitable pore size distribution, and high electrical conductivity of the carbon network, the material exhibits excellent activity and selectivity for electroreduction of CO 2 to formate. In H-type electrolyzers, the formate Faradaic efficiency reaches 91% at −0.9 V (vs RHE) and does not decrease significantly within 48 h. In situ Fourier transform infrared spectroscopy confirms the reaction intermediates and reveals that CO 2 electroreduction is dominant by the *OCHO pathway.

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“…Nonmetallic doping has also been proved to be beneficial for electrocatalysis. Zhang et al synthesized multilamellar mesoporous CuO nanosheets through Br − doping and cetyltriammonium (CTA + ) cation adsorption, [97] where the Br − dopants not only tuned the electronic structure of the catalyst to the optimal state, but also reduced the activation energy of CO 2 molecules and adjusted the intermediate species and their adsorption state, which facilitated the conversion of the *OCH 2 CH 3 intermediate to C 2 H 5 OH (Figure 10a).…”

Section: Defect Engineeringmentioning

confidence: 99%

Section: Defect Engineeringmentioning

confidence: 99%

Emerging 2D Copper‐Based Materials for Energy Storage and Conversion: A Review and Perspective

Ren

Wang

Chen

et al. 2022

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extensive interest, [1][2][3] such as SCs, [4] rechargeable ion batteries, [5] water splitting, [6] metal-air batteries, [7] and CO 2 RR. [8] However, the practical applications of SCs and rechargeable ion batteries are limited by low energy density and low power density, respectively. [9,10] The multiple-electron transfer reactions in water splitting have posed a significant challenge that limits the catalytic efficiency and cycle stability. [11] At present, the urgent issue of metal-air battery is to design high-performance bifunctional electrodes. [12] For CO 2 RR, the technical realization is limited by the activity and selectivity of the catalyst, and the selectivity of its product beyond that of CO. [13,14] In these electrochemical devices, electrodes represent the core component, which dictates the efficiency, energy and power density, as well as catalytic activity and durability.Since the birth of graphene, 2D materials have attracted great attention due to their unique electrochemical, mechanical, and optical properties and diverse applications, as manifested in over 3000 academic papers each year. [15,16] 2D materials possess some structural advantages over the 0D and 1D counterparts by interlayer gap bonding and weak out-of-plane Van der Waals interaction, which provides an interesting platform for energy storage and conversion research. [17,18] So far, the 2D material family mainly includes transition metal dichalcogenides, transition metal carbides, layered metal oxides, layered double hydroxides and other graphene-like materials, such as black phosphorus. Of these, copper-based materials have received extensive attention because of high natural abundance, low price, high strength, arc erosion resistance, easy preparation of various nanoshapes, wear resistance, etc. (Figure 1), [19,20] leading to excellent electrochemical performance and advancement of electrochemical energy storage and conversion (Figure 2). For example, with a large surface area and potential size effect, CuO nanostructures, a p-type semiconductor, have excellent physical and chemical properties for SCs, as well as interesting magnetic and superhydrophobic properties, as compared with other metal oxides, such as TiO 2 , ZnO, WO 3 , and SnO 2 . [21] Cu-S compounds are a promising lithium cathode with a high energy density and long cycling stability. [22] Cu-Se is also considered as a novel cathode 2D materials have shown great potential as electrode materials that determine the performance of a range of electrochemical energy technologies. Among these, 2D copper-based materials, such as Cu-O, Cu-S, Cu-Se, Cu-N, and Cu-P, have attracted tremendous research interest, because of the combination of remarkable properties, such as low cost, excellent chemical stability, facile fabrication, and significant electrochemical properties. Herein, the recent advances in the emerging 2D copper-based materials are summarized. A brief summary of the crystal structures and synthetic methods is started, and innovative strategies for improving electro...

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Br-Doped CuO Multilamellar Mesoporous Nanosheets with Oxygen Vacancies and Cetyltrimethyl Ammonium Cations Adsorption for Optimizing Intermediate Species and Their Adsorption Behaviors toward CO₂ Electroreduction to Ethanol with a High Faradaic Efficiency

Cited by 16 publications

References 52 publications

Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

Metal–Organic Framework-Derived BiIn Bimetallic Oxide Nanoparticles Embedded in Carbon Networks for Efficient Electrochemical Reduction of CO₂ to Formate

Emerging 2D Copper‐Based Materials for Energy Storage and Conversion: A Review and Perspective

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Br-Doped CuO Multilamellar Mesoporous Nanosheets with Oxygen Vacancies and Cetyltrimethyl Ammonium Cations Adsorption for Optimizing Intermediate Species and Their Adsorption Behaviors toward CO2 Electroreduction to Ethanol with a High Faradaic Efficiency

Cited by 16 publications

References 52 publications

Efficacious CO2 Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO2 Electroreduction to CO

Efficacious CO2 Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO2 Electroreduction to CO

Metal–Organic Framework-Derived BiIn Bimetallic Oxide Nanoparticles Embedded in Carbon Networks for Efficient Electrochemical Reduction of CO2 to Formate

Emerging 2D Copper‐Based Materials for Energy Storage and Conversion: A Review and Perspective

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Br-Doped CuO Multilamellar Mesoporous Nanosheets with Oxygen Vacancies and Cetyltrimethyl Ammonium Cations Adsorption for Optimizing Intermediate Species and Their Adsorption Behaviors toward CO₂ Electroreduction to Ethanol with a High Faradaic Efficiency

Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

Efficacious CO₂ Adsorption and Activation on Ag Nanoparticles/CuO Mesoporous Nanosheets Heterostructure for CO₂ Electroreduction to CO

Metal–Organic Framework-Derived BiIn Bimetallic Oxide Nanoparticles Embedded in Carbon Networks for Efficient Electrochemical Reduction of CO₂ to Formate