Green synthesis of a redox-active riboflavin-integrated Ni-MOF and its versatile electrocatalytic applications towards oxygen evolution and reduction, and HMF oxidation reactions

Sekar, Pandiaraj; Vasanthakumar, P.; Shanmugam, Ramasamy; Kumar, Sunil; Agnoli, Stefano; Deepak, Rajasekharan Jayakumari; Murugan, Karthik; Bhuvanesh, Nattamai; Karvembu, Ramasamy

doi:10.1039/d2gc02939a

Cited by 14 publications

(6 citation statements)

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“…Similarly, the stretching vibration of the ‐COOH (located at 1787.5 cm −1 ) in the protein center of Fpo and HdrABC was tracked to investigate the potential dependence of mediated electron transfer. [ 49 ] Particularly, the peak intensity of ‐COOH first increases progressively between 0 and −0.4 V, and then remains relatively unchanged with further decreased potential (Figure 3l), implying that the efficiency of mediated electron transfer is quite stable after it gets over the corresponding charge transfer barrier. This well explains that the FE of CH 4 obtained with M. barkeri ‐CF holds relatively steady at the tested potentials, while that obtained with M. barkeri ‐Co‐N 4 @Co‐NP exhibits a slightly decreased FE of CH 4 at large potentials (Figure 2c).…”

Section: Resultsmentioning

confidence: 98%

Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri

Xia,

Cheng,

Chen

et al. 2023

Advanced Materials

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Unfavorable electron transfer at the biotic‐abiotic interface and slow electron utilization by metabolism hinder the fast conversion of CO2 in bio‐electrochemical systems. To significantly advance the bio‐electrochemical CO2‐conversion rate and unfold the correlation between the abiotic electrode and the attached microorganisms, an atomic‐nanoparticle bridge of Co‐N4@Co‐NP crafted in metal‐organic frameworks‐derived nanosheets is integrated with a model methanogen of Methanosarcina barkeri (M.barkeri). The direct bonding of N in Co‐N4 and Fe in member protein of Cytb activates a fast direct electron transfer path while the Co nanoparticles further strengthen this bonding via decreasing the energy gap between the p‐band center of N and the d‐band center of Fe. This multi‐orbital tuning operation of Co nanoparticles also enhances the coenzyme F420‐mediated electron transfer by enabling the electron flow direct to the hydrogenation sites. Particularly, the increased surface electric field of the Co‐N4@Co‐NP bridge‐based nanosheet electrode facilitates the interfacial Na+ accumulation to expedite ATPase transport for powering intracellular CO2 conversion. Remarkably, the self‐assembled M.barkeri‐Co‐N4@Co‐NP biohybrid achieves a high methane production rate of 3860 mmol/m2/day, which greatly outperforms other reported biohybrid systems. This work demonstrates a comprehensive scrutinization of biotic‐abiotic energy transfer, which may serve as a guiding principle for efficient bio‐electrochemical system design.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 98%

Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri

Xia,

Cheng,

Chen

et al. 2023

Advanced Materials

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“…In 2022, Karvembu and co-workers incorporated redox-active riboflavin (Rbf) into an Ni-MOF by using a green and convenient mechanochemical method [111]. The conductivity of the Rbf-doped Ni-MOF (Rbf-Ni-MOF) was four-fold higher than the original Ni-MOF.…”

Section: Mofsmentioning

confidence: 99%

Recent Advances in Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid by Heterogeneous Catalysts

Ma,

Wang,

et al. 2024

Catalysts

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The utilization and development of biomass resources is an efficient solution to mitigate the fossil energy crisis. Based on the advantages of mild reaction conditions, rapid reaction, and high conversion, the synthesis of 2,5-furandicarboxylic acid (FDCA) by the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMFOR) has attracted considerable attention. This review will summarize the recent advances of HMFOR to FDCA, including the reaction pathway and mechanism, as well as the catalytic performance of various heterogeneous electrocatalysts. The challenges and prospects for HMFOR are also focused on. Finally, it is expected that this work may provide guidance for the design of high-efficiency electrocatalysts and thereby accelerate the industrialization process of biomass utilization.

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“…Nevertheless, compared to the classical ligand, H 2 FDC-related MOFs are still relatively few, with only about 100 associated reports. Also, the applications of such MOFs are mainly focused on luminescence, − gas adsorption, − and catalysis, − and only one MOF related to proton conductivity has been involved …”

Section: Introductionmentioning

confidence: 99%

Syntheses and High Proton Conductivities of Two 3D Zr(IV)/Hf(IV)-MOFs from Furandicarboxylic Acid

Chen

et al. 2023

Inorg. Chem.

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With the gradual progress of research on proton-conducting metal–organic framework (MOFs), it has become a challenging task to find MOF materials that are easy to prepare and have low toxicity, high stability, and splendid proton conductivity. With the abovementioned objectives in mind, we selected the non-toxic organic ligand 2,5-furandicarboxylic acid and the low toxic quadrivalent metals zirconium(IV) or hafnium(IV) as starting materials and successfully obtained 2 three-dimensional porous MOFs, [M6O4(OH)4(FDC)4(OH)4(H2O)4] [M = ZrIV (1) and HfIV (2)], with ultrahigh water stability using a rapid and green synthesis approach. Their proton conductive ability is remarkable, thanks to the large number of Lewis acidic sites contained in their porous frameworks and the abundant H-bonding network, hydroxyl groups, as well as coordination and crystalline water molecules. The positive correlation of their proton conductivity with relative humidity (RH) and the temperature was observed. Notably, their optimized proton conductivities are 2.80 × 10–3 S·cm–1 of 1 and 3.38 × 10–3 S·cm–1 of 2 under 100 °C/98% RH, which are at the forefront of Zr(IV)/Hf(IV) MOFs with prominent proton conductivity. Logically, their framework features, nitrogen/water adsorption/desorption data, and activation energy values are integrated to deduce their proton conductivity and conducting mechanism differences.

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Green synthesis of a redox-active riboflavin-integrated Ni-MOF and its versatile electrocatalytic applications towards oxygen evolution and reduction, and HMF oxidation reactions

Abstract: The post-synthetic modification (PSM) of metal-organic frameworks (MOFs) with redox-active molecules under mild conditions is a highly challenging tool to modify the inherent properties of MOFs without altering their crystallinity...

Cited by 14 publications

References 51 publications

Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri

Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri

Recent Advances in Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid by Heterogeneous Catalysts

Syntheses and High Proton Conductivities of Two 3D Zr(IV)/Hf(IV)-MOFs from Furandicarboxylic Acid

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Green synthesis of a redox-active riboflavin-integrated Ni-MOF and its versatile electrocatalytic applications towards oxygen evolution and reduction, and HMF oxidation reactions

Abstract: The post-synthetic modification (PSM) of metal-organic frameworks (MOFs) with redox-active molecules under mild conditions is a highly challenging tool to modify the inherent properties of MOFs without altering their crystallinity...

Cited by 14 publications

References 51 publications

Revealing Co‐N4@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO2‐Conversion with Methanosarcina Barkeri

Revealing Co‐N4@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO2‐Conversion with Methanosarcina Barkeri

Recent Advances in Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid by Heterogeneous Catalysts

Syntheses and High Proton Conductivities of Two 3D Zr(IV)/Hf(IV)-MOFs from Furandicarboxylic Acid

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Product

Resources

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Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri

Revealing Co‐N₄@Co‐NP Bridge‐Enabled Fast Charge Transfer and Active Intracellular Methanogenesis in Bio‐Electrochemical CO₂‐Conversion with Methanosarcina Barkeri