Yongbing Xie

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.

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15vol.% TFA solution, L/S ratio of 8.0 mL g(-1), reacting at 40°C for 180 min along with appropriate agitation. LiNi1/3Co1/3Mn1/3O2 is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi1/3Co1/3Mn1/3O2 powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi1/3Co1/3Mn1/3O2 are 201 mAh g(-)(1) and 155.4 mAh g(-1) (2.8-4.5 V, 0.1C), respectively. The discharge capacity remains at 129 mAh g(-1) even after 30 cycles with a capacity retention ratio of 83.01%.

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.

Highly selective PdCu/amorphous silica-alumina (ASA) catalysts for groundwater denitration.

Catalytic nitrate reduction is a promising technology in groundwater purification. In this study, PdCu bimetallic catalysts supported on an industrial amorphous silica-alumina (ASA) were synthesized and used to simulate catalytic removal of nitrate in groundwater. The catalysts exhibited very high activity and the highest catalytic selectivity toward N₂O and N₂ was 90.2%. The optimal Pd/Cu weight ratio was four. Relatively low reduction temperature was found benefit the catalytic stability and 300 °C was the appropriate reduction temperature during catalyst preparation. With an average particle size 5.4 nm, the metal particles were very uniformly distributed on the catalyst surface prepared with the codeposition method. This kept the catalyst more stable than the PdCu/Al₂O₂ catalyst with larger metal particles. According to XRD, TEM, and XPS results, the metals maintained zero-valence but aggregated by about 2 nm during the denitration reaction, which caused gradual deactivation of the catalysts. Little leaching of Cu and Pd from the catalyst might also have a slightly negative impact to the stability of the catalysts. A simple treatment was found to redistribute the particles on the deactivated catalysts, and high catalytic activity was recovered after this process.

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.

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag + /TiO2

Photocatalytic ozonation of phenol and oxalic acid (OA) was conducted with a Ag(+)/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag(+) greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag(+) was easily reduced and deposited on the surface of TiO2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag(+) can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.

Capacitive deionization by ordered mesoporous carbon: electrosorption isotherm, kinetics, and the effect of modification

AbstractIn this study, an ordered mesoporous carbon (OMC) was synthesized and investigated as electrodes for capacitive deionization (CDI). The influence of working parameters on salt removal was studied and the electrosorption isotherm and kinetics were investigated. It was found that the electrosorption process fitted both Langmuir isotherm and Freundlich isotherm, and followed pseudo-first-order kinetics. The maximum electrosorptive capacity was 10.1 mg/g at the optimized applied voltage of 1.2 V and flow rate of 40 ml/min. In order to investigate the effect of surface groups on CDI efficiency, OMC was modified by H2O2 solution or thermal treatment under N2 atmosphere, without significantly changing its textural properties. X-ray photoelectron spectroscopy measurements showed that the amount of surface oxygen-containing groups was decreased and increased by the thermal and chemical treatments, respectively. CDI experiments revealed that OMC modified by H2O2 solution performed better than original OMC, ...

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.