Electrochemical reduction of nitrobenzene via redox-mediated chronoamperometry

Stergiou, Athanasios D.; Broadhurst, Daniel H.; Symes, Mark D.

doi:10.1016/j.xpro.2022.101817

Cited by 9 publications

(4 citation statements)

References 18 publications

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“…To achieve the best electrochemical response, the effects of different electrolyte solutions, electrolyte concentration, and pH of the solution on the electrocatalysis of the sensor toward NB were investigated ( Sang et al, 2014 ; Stergiou et al, 2022 ). In different electrolyte and buffer solutions, the best response of the Mn-CPM-99/ITO electrode toward NB was obtained in NaCl solution ( Figure 6A and inset).…”

Section: Resultsmentioning

confidence: 99%

Construction of porphyrinic manganese-organic frameworks based on structural regulation for electrochemical determination of nitrobenzene in water and vegetable samples

Wang,

Zhang,

et al. 2024

Front. Chem.

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Nitrobenzene (NB) is one of the major organic pollutants that has seriously endangered human health and the environment even in trace amounts. Therefore, it is of great significance to detect trace NB efficiently and sensitively. Herein, a porphyrinic metal-organic framework (MOF) of Mn-PCN-222 (PCN, porous coordination network) was first synthesized by the coordination between Zr6 cluster and tetrakis (4-carboxyphenyl)-porphyrin-Mn (Ⅲ) (MnTCPPCl) ligand. To regulate its structure and the electrochemical properties, a phenyl group was inserted in each branched chain of TCPP to form the TCBPP organic ligand. Then, we used Zr6 clusters and manganese metalloporphyrin (MnTCBPPCl) to synthesize a new porphyrin-based MOF (Mn-CPM-99, CPM, crystalline porous material). Due to the extended chains of TCPP, the rod-shaped structure of Mn-PCN-222 was switched to concave quadrangular bipyramid of Mn-CPM-99. Mn-CPM-99 exhibited higher porosity, larger specific surface area, better electrochemical performances than those of Mn-PCN-222. By using modular assembly technique, Mn-CPM-99 film was sequentially assembled on the surface of indium-tin-oxide (ITO) to prepare an electrochemical sensor (Mn-CPM-99/ITO). The proposed sensor showed excellent electrochemical reduction of NB and displayed three linear response ranges in the wide concentration ranges. The obtained low limit of detection (LOD, 1.3 nM), high sensitivity and selectivity, and good reproducibility of the sensor for NB detection fully illustrate that Mn-CPM-99 is an excellent candidate for electrochemical sensor interface material. Moreover, the sensor was successfully applied to the detection of NB in lake water and vegetable samples showing satisfactory recovery of 98.9%–101.8%.

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Section: Resultsmentioning

confidence: 99%

Construction of porphyrinic manganese-organic frameworks based on structural regulation for electrochemical determination of nitrobenzene in water and vegetable samples

Wang,

Zhang,

et al. 2024

Front. Chem.

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“…Regarding non‐aromatic substrates, the oxidation of light alcohols mediated by [{Ru 4 O 4 (OH) 2 (H 2 O) 4 }(γ‐SiW 10 O 36 ) 2 ] 10− (1[(γ‐SiW 10 O 36 ) 2 ] 10− ) was reported by Liu et al ., [46] as well as the oxidation of light hydrocarbons using{Fe 30 W 72 } by Neumann [47] . Recently, Stergiou and Symes published their studies on selective electrocatalytic reduction of substituted nitrobenzenes to their aniline derivates using H 3 [PW 12 O 40 ] as a redox mediator [48–50] . Although POMs represent an important catalyst class for biomass conversion, [4] electrochemical applications in this field are rare [51,52] .…”

Section: Introductionmentioning

confidence: 99%

“…[47] Recently, Stergiou and Symes published their studies on selective electrocatalytic reduction of substituted nitrobenzenes to their aniline derivates using H 3 [PW 12 O 40 ] as a redox mediator. [48][49][50] Although POMs represent an important catalyst class for biomass conversion, [4] electrochemical applications in this field are rare. [51,52] Electrochemical biomass conversion is considered an important 21 st century technique because it combines renewable carbon feedstocks and decarbonized electrical energy.…”

Section: Introductionmentioning

confidence: 99%

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Mürtz,

Raabe,

Poller

et al. 2024

ChemCatChem

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Polyoxometalates (POMs) are known for their unique redox properties, making them interesting candidates as redox mediators in electro‐organic transformations. We investigated derivatives of H3[PMo12O40], a classical Keggin‐type POM, as a potential redox mediator in the indirect electrolysis of biobased glyceraldehyde (GLAD), focusing on the effects of double substitution of the Mo framework metal by redox active transition metals (Mo replaced by V, Ni, Co, Mn). By combining electrochemical techniques with HPLC, UV‐Vis spectroscopy, and 31P‐NMR spectroscopy, a comprehensive overview of the reaction pathways, as well as the electronic and structural changes of the POM during the reaction were revealed. This work not only contributes to the fundamental understanding of POMs as redox mediators, but also paves the way for innovative development of sustainable and environmentally friendly electro‐organic transformations.

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“…Against this backdrop, the use of polyoxometalates as electro-generated reducing agents for the more selective reduction of nitrobenzene and allied substituted nitroarenes to their corresponding anilines has gained traction, both when used as reagents in excess and when used in catalytic amounts as part of an electrocatalytic cycle. , In the latter case, the polyoxometalate mediator was shown to shut down the direct electrochemical reduction of the nitroarenes at the cathode that would otherwise lead to undesirable side reactions. However, the scope of the reactions reported in this previous study was limited, as our aim was primarily to elucidate the mechanism of reaction for the electrochemical reduction of nitrobenzene to aniline.…”

Section: Introductionmentioning

confidence: 99%

Highly Selective Electrocatalytic Reduction of Substituted Nitrobenzenes to Their Aniline Derivatives Using a Polyoxometalate Redox Mediator

2022

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Anilines and substituted anilines are used on the multi-ton scale for producing polymers, pharmaceuticals, dyes, and other important compounds. Typically, these anilines are produced from their corresponding nitrobenzene precursors by reaction with hydrogen at high temperatures. However, this route suffers from a number of drawbacks, including the requirement to handle hydrogen gas, rather harsh reaction conditions that lead to a lack of selectivity and/or toleration of certain functional groups, and questionable environmental sustainability. In light of this, routes to the reduction of nitrobenzenes to their aniline derivatives that operate at room temperature, in aqueous solvent, and without the requirement to use harsh process conditions, hydrogen gas, or sacrificial reagents could be of tremendous benefit. Herein, we report on a highly selective electrocatalytic route for the reduction of nitrobenzenes to their corresponding anilines that works in aqueous solution at room temperature and which does not require the use of hydrogen gas or sacrificial reagents. The method uses a polyoxometalate redox mediator, which reversibly accepts electrons from the cathode and reacts with the nitrobenzenes in solution to reduce them to the corresponding anilines. A variety of substituted nitroarenes are explored as substrates, including those with potentially competing reducible groups and substrates that are difficult to reduce selectively by other means. In all cases, the selectivity for the redox-mediated route is higher than that for the direct reduction of the nitroarene substrates at the electrode, suggesting that redox-mediated electrochemical nitroarene reduction is a promising avenue for the more sustainable synthesis of substituted anilines.

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Electrochemical reduction of nitrobenzene via redox-mediated chronoamperometry

Cited by 9 publications

References 18 publications

Construction of porphyrinic manganese-organic frameworks based on structural regulation for electrochemical determination of nitrobenzene in water and vegetable samples

Construction of porphyrinic manganese-organic frameworks based on structural regulation for electrochemical determination of nitrobenzene in water and vegetable samples

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Highly Selective Electrocatalytic Reduction of Substituted Nitrobenzenes to Their Aniline Derivatives Using a Polyoxometalate Redox Mediator

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