Engineering Copper‐Based Covalent Organic Framework Microenvironments to Enable Efficient CO<sub>2</sub> Electroreduction with Tunable Ethylene/Methane Switch

Chen, Qian; Si, Duan‐Hui; Wu, Qiu‐Jin; Cao, Rong; Huang, Yuan‐Biao

doi:10.1002/adfm.202315368

Cited by 8 publications

(1 citation statement)

References 45 publications

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“…While the ion-exchange process is most effective for sequestering toxic anionic pollutants, conventional ion-exchange resins display poor selectivity, recognition ability, and binding sites. As an alternative, covalent organic frameworks (COFs) with well-defined pores and binding sites are promising for the adsorptive removal of various inorganic and organic pollutants. − In particular, imine-based 2D COFs are used for several applications such as gas adsorption, separation and storage, , molecular separation, , sensing, , heterogeneous catalysis, , organocatalysis, , and electrocatalysis, , for their pore tunability and stability. As a worthwhile choice for sequestering charged pollutants, ionic covalent organic frameworks (iCOFs) have emerged as a superior class of adsorbents.…”

Section: Introductionmentioning

confidence: 99%

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Neem,

Mondal,

Pillai

et al. 2024

ACS Appl. Eng. Mater.

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Water contamination by inorganic and organic pollutants is one of the most contentious global environmental issues. However, conventional scavenging materials often exhibit poor selectivities and limited adsorption capabilities. By contrast, an ionic covalent organic framework (iCOF) with functionalized pores promises effective capture of harmful oxo-anions and carcinogenic dyes and can benefit their removal over a practical platform. We employ facile Schiff base condensation to devise a thermochemically robust guanidinium-based iCOF via the incisive amalgamation of anion exchange, hydrogen bonding, and electrostatic interaction sites. Building on such trifunctionality, the material demonstrates efficient sequestration of dichromate oxoanions and Congo Red (CR) dye in water with rapid kinetics and superior scavenging capacity (Cr 2 O 7 2− : 412 mg/g, CR: 316.3 mg/ g) compared to other porous crystalline materials. Apart from the high selectivity in the presence of interfering anions/dyes, the adsorptive capacities remain unaltered (>90%) for five cycles with postrelease stability. In-depth analysis corroborates that the removal of oxo-anions is driven by the ion-exchange phenomena, while electrostatic, hydrogen bonding, and π−π stacking interactions play a role in dye adsorption, as also supported by density functional theory studies. The real-time potential of iCOF for long-term water purification has been established via the fabrication of a polysulfone (PSF)-based mixed-matrix membrane. The iCOF@PSF ultrafiltration membrane exhibits high water permeance and rejection of both dichromate (87%) and CR (99.9%) with excellent recyclability. Notably, a high permeate flux of the iCOF@PSF membrane for dichromate (88.6 ± 1.8 L/m 2 h bar) and CR dye (86.2 ± 1.5 L/m 2 h bar) validate effective synergism between iCOF functionalities and the PSF matrix in sieving both the anionic pollutants and provide valuable insights into the development of porous charged materials for wastewater remediation over a practical platform.

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Section: Introductionmentioning

confidence: 99%

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Neem,

Mondal,

Pillai

et al. 2024

ACS Appl. Eng. Mater.

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Ionic Liquid‐Induced Product Switching in CO₂ Electroreduction on Copper Reaction Interface

Cai,

Yang,

Feng

et al. 2024

Adv Funct Materials

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The electrochemical reduction of CO2 (CO2RR) mainly occurs at the three‐phase interface, and the properties of an interface can directly affect the CO2RR pathway. Cu‐based materials can produce considerable amounts of alcohols and hydrocarbons, but it is hard to precisely regulate the reaction interface and obtain specific target products. Herein, the properties of the Cu surface through a facile strategy of ionic liquid modification are successfully adjusted. According to theoretical calculations and in situ Raman and FTIR spectra characterizations, it is revealed that the introduction of ionic liquids (e.g., [Bmim][PF6]) can control the energy barriers and distribution density of key intermediates on Cu interface, thus totally change the reaction pathway of CO2 electroreduction. Consequently, the dominant products from the Cu catalyst will be dramatically switched between C2H4 with a 71.1% Faraday efficiency (FE) and CH4 with a 67.2% FE. It is rarely seen in previous reports that the CO2RR products can be fundamentally changed through simple interface modifications. This work offers a straightforward approach to tune the interfacial properties and understand the mechanisms in various electrocatalytic reactions.

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Highly Selective CO₂ Electroreduction to C₂H₄ Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu₂O Nanoparticles via a Synergetic‐Tandem Strategy

He,

Li,

et al. 2024

Angewandte Chemie

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Low *CO coverage on the active sites is a major hurdle in the tandem electrocatalysis, resulting in unsatisfied C2H4 production efficiencies. In this work, we developed a synergetic‐tandem strategy to construct a copper‐based composite catalyst for the electroreduction of CO2 to C2H4, which was constructed via the template‐directed polymerization of ultrathin Cu(II) porphyrin organic framework incorporating atomically isolated Cu(II) porphyrin and Cu(II) bipyridine sites on a carbon nanotube (CNT) scaffold, and then Cu2O nanoparticles were uniformly dispersed on the CNT scaffold. The presence of dual active sites within the Cu(II) porphyrin organic framework create a synergetic effect, leading to an increase in local *CO availability to enhance the C–C coupling step implemented on the adjacent Cu2O nanoparticles for further C2H4 production. Accordingly, the resultant catalyst affords an exceptional CO2‐to‐C2H4 Faradaic efficiency (FEC2H4) of 71.0% at –1.1 V vs reversible hydrogen electrode (RHE), making it one of the most effective copper‐based tandem catalysts reported to date. The superior performance of the catalyst is further confirmed through operando infrared spectroscopy and theoretic calculations.

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Engineering Copper‐Based Covalent Organic Framework Microenvironments to Enable Efficient CO₂ Electroreduction with Tunable Ethylene/Methane Switch

Cited by 8 publications

References 45 publications

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Ionic Liquid‐Induced Product Switching in CO₂ Electroreduction on Copper Reaction Interface

Highly Selective CO₂ Electroreduction to C₂H₄ Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu₂O Nanoparticles via a Synergetic‐Tandem Strategy

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Engineering Copper‐Based Covalent Organic Framework Microenvironments to Enable Efficient CO2 Electroreduction with Tunable Ethylene/Methane Switch

Cited by 8 publications

References 45 publications

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Trifunctionalized Ionic Covalent Organic Framework-Engineered Mixed-Matrix Membranes for Rapid and High-Performance Adsorptive Separation of Charged Aqua Pollutants

Ionic Liquid‐Induced Product Switching in CO2 Electroreduction on Copper Reaction Interface

Highly Selective CO2 Electroreduction to C2H4 Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu2O Nanoparticles via a Synergetic‐Tandem Strategy

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Engineering Copper‐Based Covalent Organic Framework Microenvironments to Enable Efficient CO₂ Electroreduction with Tunable Ethylene/Methane Switch

Ionic Liquid‐Induced Product Switching in CO₂ Electroreduction on Copper Reaction Interface

Highly Selective CO₂ Electroreduction to C₂H₄ Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu₂O Nanoparticles via a Synergetic‐Tandem Strategy