Co-ZFO@Mn-CN with 1 O 2 and O 2 •− as main reactive oxygen species was synthesized for catalytic ozonation , which could efficiently degrade organic pollutants . EPR and XPS analysis indicated that lattice doping of Co induced formation of abundant of OVs, which could provide localized electrons for O 3 activation with the generation of HO 2 • /O 2 •− . 1 O 2 and H 2 O 2 were produced by the recombination of HO 2 • /O 2 •− . DFT calculation demonstrated that H 2 O 2 was deprotonated to generate HOO − , which preferred to form HOO-Mn-N X bonds with Co-ZFO@Mn-CN. Under the attack of O 3 , HOO-Mn-N X bonds were broken with the generation of HO 2 • and HO 3 • /O 3 •− , not only accelerating 1 O 2 production for organics degradation but also avoiding Mn(Ⅱ) sites oxidation . Combining advantages of OVs and HOO-Mn-N X , Co-ZFO@Mn-CN achieved 70–100% mineralization for different organic pollutants . Thus, this work provided a simple and efficient way for enhancing the utilization of O 3 by the synergistic effect of OVs and HOO-Mn-N X bonds, also improving ROS transformation.
The hydrogen peroxide oxidation reaction (HPOR) plays a vital role in the emerging H2-H2O2 cycle energy storage system, in which the rational design of HPOR electrocatalyst is essential for achieving high system efficiency. Herein, we establish the HPOR activity trends using structurally well-defined metal phthalocyanines (MPc) as model catalysts via a combined experimental and computational approach. The measured activity sequence follows the order of CoPc > FePc > MnPc > ZnPc > H2Pc > NiPc > CuPc based on their site-normalized exchange current (i0-s). Theoretical calculations indicate that the binding free energy of hydroperoxyl intermediate, HOO*, on MPc (ΔGHOO*) is the activity descriptor for HPOR. A volcano-type activity trend is observed by correlating the logarithm of i0-s (logi0-s) with the ΔGHOO* values and agrees with the theoretical predictions. This HPOR activity trend provides insights into the design of highly active electrocatalysts for HPOR and related energy applications.
Uddin W.,Nawabi M. Y.,Rehman S. Ur.,Hu G.,Khan J.,Shen X.
Abstract We introduced a novel technique for monitoring the activity of analytes for the first time. The technique is built upon the inhibitory effect caused by the free-radical-scavengers on the pattern of novel Briggs–Rauscher (BR) electrochemical oscillator catalyzed by tetra-aza-macrocyclic complex catalyst ([NiL](ClO 4 ) 2 . The ligand “L” in the complex is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The effect involves a sudden ceasing of oscillation, an inhibition time ( t in ) that directly proportional to the amount of additive ( p -Dimethylaminobenzaldehyde ( p -DMAB)) added, and subsequent restoration of oscillations. Thus, a linear regression curve between concentrations range of 2.7 × 10 –7 mol L –1 to 4.5 × 10 –6 mol L –1 p -DMAB Vs t in was achieved with a correlation coefficient of 0.98. The observed limit of detection (LOD) is 2.7 × 10 –7 mol L –1 while the RSD calculated from 7 measurements of 2.5 × 10 –6 mol L –1 p -DMAB is 1.5%. Factors that influence the determination of p -DMAB were also studied. The mechanistic interpretation of the perturbed oscillation was anticipated from both NF and FCA models. A fleeting elucidation is that the intermediate species (HOO • ) produced during oscillatory reactions and reacted with p ‑DMAB. As a result, the oscillation was temporarily ceased.
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