scholarly journals Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte

Water ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1322 ◽  
Author(s):  
Ambauen ◽  
Muff ◽  
Mai ◽  
Hallé ◽  
Trinh ◽  
...  

The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na2SO4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.

Author(s):  
Christian E. Alvarez-Pugliese ◽  
Paola Moreno-Wiedman ◽  
Fiderman Machuca-Martínez ◽  
Nilson Marriaga-Cabrales

AbstractElectrochemical oxidation of pretreated distillery wastewater was performed using a boron doped diamond anode (BDD). The role of direct oxidation of organic matter was assessed with experiments of linear sweep voltammetry, noting that the deactivation of the electrode surface occurs in the region of potentials below oxygen evolution. Then, galvanostatic bulk electrolyses were conducted during 4 hours at current densities (20 mAcm


Water ◽  
2020 ◽  
Vol 12 (12) ◽  
pp. 3546
Author(s):  
Alfredo Martínez-Cruz ◽  
Annabel Fernandes ◽  
Lurdes Ciríaco ◽  
Maria José Pacheco ◽  
Fátima Carvalho ◽  
...  

A short review on the treatment of effluents from food processing industries by electrochemical oxidation (EO) was performed. Olive mill wastewater (OMW) and boron-doped diamond (BDD) are the most reported effluent and anode material, respectively. The addition of NaCl or Na2SO4 as supporting electrolytes is common in these studies, and their influence on the EO performance depends, among other things, on the anode material, since the electrolyte oxidation mechanism is different when active and non-active anode materials are utilized. A case-study on the application of a pilot plant, working in batch mode with recirculation, equipped with a BDD anode, to treat 4 L of OMW, slaughterhouse (SW) and winery (WW) wastewaters, with initial chemical oxygen demands (COD) of 20.5, 3.6 and 0.26 g L−1, respectively, is presented and discussed. In 16 h assays, 94% COD removal was achieved for OMW, and for SW and WW the Portuguese COD legal discharge limit of 150 mg L−1 was accomplished. Process efficiency decreased for lower organic load. NaCl addition increased COD removal in SW and WW, but presented an adverse effect for OMW COD removal, when compared to Na2SO4 addition. Nevertheless, lower specific energy consumptions were attained in chloride medium (48 Wh (g COD)−1).


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Rengan Luo ◽  
Haifeng Lv ◽  
Qiaobo Liao ◽  
Ningning Wang ◽  
Jiarui Yang ◽  
...  

AbstractThe control of charge transfer between radical anions and cations is a promising way for decoding the emission mechanism in electrochemiluminescence (ECL) systems. Herein, a type of donor-acceptor (D-A) covalent organic framework (COF) with triphenylamine and triazine units is designed as a highly efficient ECL emitter with tunable intrareticular charge transfer (IRCT). The D-A COF demonstrates 123 folds enhancement in ECL intensity compared with its benzene-based COF with small D-A contrast. Further, the COF’s crystallinity- and protonation-modulated ECL behaviors confirm ECL dependence on intrareticular charge transfer between donor and acceptor units, which is rationalized by density functional theory. Significantly, dual-peaked ECL patterns of COFs are achieved through an IRCT mediated competitive oxidation mechanism: the coreactant-mediated oxidation at lower potential and the direct oxidation at higher potential. This work provides a new fundamental and approach to improve the ECL efficiency for designing next-generation ECL devices.


2015 ◽  
Vol 14 (03) ◽  
pp. 1550020 ◽  
Author(s):  
Yuan Yuan ◽  
Wei Hu ◽  
Xuhui Chi ◽  
Cuihua Li ◽  
Dayong Gui ◽  
...  

The oxidation mechanism of diethyl ethers by NO2was carried out using density functional theory (DFT) at the B3LYP/6-31+G (d, p) level. The oxidation process of ether follows four steps. First, the diethyl ether reacts with NO2to produce HNO2and diethyl ether radical with an energy barrier of 20.62 kcal ⋅ mol-1. Then, the diethyl ether radical formed in the first step directly combines with NO2to form CH3CH ( ONO ) OCH2CH3. In the third step, the CH3CH ( ONO ) OCH2CH3was further decomposed into the CH3CH2ONO and CH3CHO with a moderately high energy barrier of 32.87 kcal ⋅ mol-1. Finally, the CH3CH2ONO continues to react with NO2to yield CH3CHO , HNO2and NO with an energy barrier of 28.13 kcal ⋅ mol-1. The calculated oxidation mechanism agrees well with Nishiguchi and Okamoto's experiment and proposal.


2010 ◽  
Vol 132 ◽  
pp. 271-278 ◽  
Author(s):  
Dan Mei Yu ◽  
Chang Guo Chen ◽  
Shu Lei ◽  
Xiao Yuan Zhou ◽  
Guo Zhong Cao

The electrochemical oxidation of sodium borohydride (NaBH4) on Pt electrode in alkaline electrolyte with the addition of thiourea has been studied by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry (CP). NaBH4 is readily to react with hydroxyl groups to release hydrogen through either direct oxidation or catalytic hydrolysis. The experimental results demonstrated that the addition of an appropriate amount of thiourea to the alkaline electrolyte resulted in the suppression of catalytic hydrolysis and diffusion of borohydride ions through the separation membrane.


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