Jiadong Xiao

Organic pollutants removal in wastewater by heterogeneous photocatalytic ozonation

Heterogeneous photocatalysis and ozonation are robust advanced oxidation processes for eliminating organic contaminants in wastewater. The combination of these two methods is carried out in order to enhance the overall mineralization of refractory organics. An apparent synergism between heterogeneous photocatalysis and ozonation has been demonstrated in many literatures, which gives rise to an improvement of total organic carbon removal. The present overview dissects the heterogeneous catalysts and the influences of different operational parameters, followed by the discussion on the kinetics, mechanism, economic feasibility and future trends of this integrated technology. The enhanced oxidation rate mainly results from a large amount of hydroxyl radicals generated from a synergistically induced decomposition of dissolved ozone, besides superoxide ion radicals and the photo-induced holes. Six reaction pathways possibly exist for the generation of hydroxyl radicals in the reaction mechanism of heterogeneous photocatalytic ozonation.

2D/2D nano-hybrids of γ-MnO2 on reduced graphene oxide for catalytic ozonation and coupling peroxymonosulfate activation

Two-dimensional reduced graphene oxide (2D rGO) was employed as both a shape-directing medium and support to fabricate 2D γ-MnO2/2D rGO nano-hybrids (MnO2/rGO) via a facile hydrothermal route. For the first time, the 2D/2D hybrid materials were used for catalytic ozonation of 4-nitrophenol. The catalytic efficiency of MnO2/rGO was much higher than either MnO2 or rGO only, and rGO was suggested to play the role for promoting electron transfers. Quenching tests using tert-butanol, p-benzoquinone, and sodium azide suggested that the major radicals responsible for 4-nitrophenol degradation and mineralization are O2(-) and (1)O2, but not ·OH. Reusability tests demonstrated a high stability of the materials in catalytic ozonation with minor Mn leaching below 0.5 ppm. Degradation mechanism, reaction kinetics, reusability and a synergistic effect between catalytic ozonation and coupling peroxymonosulfate (PMS) activation were also discussed.

Efficient Catalytic Ozonation over Reduced Graphene Oxide for p-Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and Mechanism

Nanocarbons have been demonstrated as promising environmentally benign catalysts for advanced oxidation processes (AOPs) upgrading metal-based materials. In this study, reduced graphene oxide (rGO) with a low level of structural defects was synthesized via a scalable method for catalytic ozonation of p-hydroxylbenzoic acid (PHBA). Metal-free rGO materials were found to exhibit a superior activity in activating ozone for catalytic oxidation of organic phenolics. The electron-rich carbonyl groups were identified as the active sites for the catalytic reaction. Electron spin resonance (ESR) and radical competition tests revealed that superoxide radical ((•)O2(-)) and singlet oxygen ((1)O2) were the reactive oxygen species (ROS) for PHBA degradation. The intermediates and the degradation pathways were illustrated from mass spectroscopy. It was interesting to observe that addition of NaCl could enhance both ozonation and catalytic ozonation efficiencies and make ·O2(-) as the dominant ROS. Stability of the catalysts was also evaluated by the successive tests. Loss of specific surface area and changes in the surface chemistry were suggested to be responsible for catalyst deactivation.

Excitatory and inhibitory receptive fields of tectal cells are differentially modified by magnocellular and parvocellular divisions of the pigeon nucleus isthmi.

Abstract It has been known that magnocellular and parvocellular divisions of the pigeon nucleus isthmi exert excitatory and inhibitory actions on tectal cells, respectively. The present study shows that injection of N-methyl-D-aspartate into the parvocellular division results in an increase in responsive strength and extent of the inhibitory receptive fields, which expand into the excitatory receptive fields of tectal cells. This injection concurrently leads to a decrease in responsiveness and extent of the excitatory fields. On the other hand, injection of acetylcholine into the magnocellular division enhances visual responsiveness, although the excitatory field is not obviously changed in extent. Meanwhile, strength and extent of the inhibitory fields are decreased by acetylcholine. The excitatory and inhibitory fields are reduced in both strength and extent by magnocellular and parvocellular injection of lidocaine, respectively. It suggests that isthmic inputs from both parvocellular and magnocellular divisions converge onto the same tectal cells, and the magnocellular and parvocellular subnuclei can modulate excitatory and inhibitory receptive fields of tectal cells, respectively, with some interactions between both fields.

Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag+/TiO2: Influence of electron donating and withdrawing substituents

A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag(+)/TiO2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (O2(-)) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between O2(-) and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of O2(-) and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by O2(-), while O2(-) preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by O2(-) could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered.

Effects of glutamatergic, cholinergic and GABAergic antagonists on tectal cells in toads

The present paper using microiontophoresis analysis describes transmitters and their receptor subtypes used in retinotectal and isthmotectal transmission, and suggests several modes converging retinotectal and isthmotectal afferents on tectal neurons in toads (Bufo bufo gargarizans). Neuronal responses of tectal cells were extracellularly recorded to both visual stimulation and electrical stimulation of the nucleus isthmi, and effects of glutamatergic, cholinergic, GABAergic and glycinergic antagonists on these responses examined. Visual responses in 80% of tectal cells were reversibly blocked by the N-methyl-D-aspartate antagonist 3-Rs-2-carboxypiperazin-4-yl-propyl-1-phosphonic acid, and those of the remaining 20% of cells by the muscarinic antagonist atropine, suggesting that there may be at least two kinds of retinotectal synapse that use glutamate and N-methyl-D-aspartate receptors, and acetylcholine and muscarinic receptors, respectively. Electrical stimulation of the nucleus isthmi elicited excitatory responses in 67% of tectal cells, excitatory-inhibitory responses in 16% of cells, and inhibitory responses in 17% of cells examined. The excitatory responses were reversibly abolished by atropine, but not affected by either 3-Rs-2-carboxypiperazin-4-yl-propyl-1-phosphonic acid or the alpha-amino-3-hydroxy-5-methyl-4-isoxazole-propionate antagonist 6-cyano-7-nitroquinoxaline-2,3-dione, whereas the inhibitory responses were released by the GABA receptor A antagonist bicuculline, but not influenced by the GABA receptor B antagonist 2-hydroxysaclofen and glycinergic antagonist strychnine. Excitatory and inhibitory components in the excitatory-inhibitory responses were blocked by atropine and bicuculline, respectively. It appears that glutamatergic and cholinergic afferents from the retina, and cholinergic and GABAergic afferents from the nucleus isthmi may converge on tectal neurons in at least five modes of synaptic connections, in agreement with the heterogeneous populations of tectal cells in amphibians.

Selection of active phase of MnO2 for catalytic ozonation of 4-nitrophenol

Catalytic ozonation is a highly effective method in wastewater treatment, and MnO2 materials are widely recognized as active heterogeneous catalysts in this process. Many works reported the progress in active MnO2 synthesis, but the active phase is rarely systematically studied. In this paper, all six phases of MnO2 (α-, β-, δ-, γ-, λ- and ε-) were synthesized by facile methods. Their catalytic activities in ozonation of 4-nitrophenol (4-NP) were evaluated and correlated with the physicochemical properties obtained from X-ray Diffraction (XRD), transmission electron microscopy (TEM), physical adsorption and cyclic voltammetry (CV) analysis. α- MnO2 was found to be the most active catalyst in 4-NP degradation at neutral pH. MnO2 with low average oxidation state (AOS) showed stronger oxidation/reduction peaks in CV characterization, which benefited catalytic decomposition of ozone to generate active species. Superoxide radical was confirmed as the main oxidizing species, along with singlet oxygen and ozone molecule oxidation in bulk solution and little contribution of oxidation on the MnO2 surface. Mn2+ leaching happened during catalytic ozonation, but its catalytic role is negligible. This result may give rise to the preparation of new active MnO2 catalysts.

Activated carbon enhanced ozonation of oxalate attributed to HO oxidation in bulk solution and surface oxidation: Effect of activated carbon dosage and pH

Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon (AC) in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals (HO) in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol (tBA) with low dosages of AC, while it was hardly affected by tBA when the AC dosage was greater than 0.3g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05g/L, but it did not work when the AC dosage was no less than 0.1g/L. These observations indicate that HO in bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HO oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HO oxidation in basic bulk solution. A mechanism involving both HO oxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.

Is C3N4 Chemically Stable toward Reactive Oxygen Species in Sunlight-Driven Water Treatment?

Reactive oxygen species (ROS) are key oxidants for the degradation of organic pollutants in sunlight-driven photocatalytic water treatment, but their interaction with the photocatalyst is easily ignored and, hence, is comparatively poorly understood. Here we show that graphitic carbon nitride (C3N4, a famous visible-light-responsive photocatalyst) is chemically stable toward ozone and superoxide radical; in contrast, hydroxyl radical (•OH) can tear the heptazine unit directly from C3N4 to form cyameluric acid and further release nitrates into the aqueous environment. The ratios of released nitrogen from nanosheet-structured C3N4 and bulk C3N4 that finally exists in the form of NO3- reach 9.5 and 6.8 mol % in initially ultrapure water, respectively, after 10 h treatment by solar photocatalytic ozonation, which can rapidly generate abundant •OH to attack C3N4. On a positive note, in the presence of organic pollutants which compete against C3N4 for •OH, the C3N4 decomposition has been completely or partially blocked; therefore, the stability of C3N4 under practical working conditions has been obviously preserved. This work supplements the missing knowledge of the chemical instability of C3N4 toward •OH and calls for attention to the potential deactivation and secondary pollution of catalysts in •OH-involved water treatment processes.

Insights into the mechanism of phenolic mixture degradation by catalytic ozonation with a mesoporous Fe3O4/MnO2 composite

A mesoporous Fe3/MnO2 composite was fabricated by a co-precipitation method in this paper, and it showed a much higher activity than Fe3O4 and MnO2 in the catalytic ozonation of a p-cresol and p-chlorophenol mixture. The physicochemical properties of Fe3O4 and MnO2 and Fe3O4/MnO2 were compared using XRD, SEM, TEM and N2 physical adsorption/desorption. pH had a significant effect on the degradation rate of the phenols and catalyst stability, and the degradation order of p-cresol and p-chlorophenol also varied in different mediums. pH 9 was found to be the optimal condition both for catalytic activity and metal leaching. Attenuated total reflection Fourier transform infrared spectra confirmed that ozone replaced chemically adsorbed water on the Fe3O4/MnO2 surface and evolved into reactive radicals. Electron spin resonance and quenching experiments with different scavengers were conducted to reveal that the hydroxyl radicals were mainly responsible for the phenolic mixture degradation at pH 9, along with a little contribution of singlet oxygen and molecular ozone. A detailed mineralization pathway of the phenolic mixture was also proposed according to the gas chromatography-mass spectrometry results.