Photocatalytic reduction of Cr(VI) over cinder-based nanoneedle in presence of tartaric acid: Synergistic performance and mechanism

Cr(VI) is a common heavy metal ion, which will seriously harm human body and environment. Therefore, the removal of Cr(VI) has become an attractive topic. In this work, cinder was used as a raw material to synthesize a nanoneedle material: γ-([email protected]) (γ[email protected]). The physicochemical properties of γ[email protected] were thoroughly characterized, and its effectiveness as a catalyst for photocatalytic reduction of Cr(VI) was evaluated. The results showed that Cr(VI) could be efficiently reduced by γ[email protected] in the presence of tartaric acid (TA) under visible light. The variable factors on the reaction were investigated in detail, and the results showed that under optimal conditions (γ[email protected] 0.4 g/L, TA 0.6 g/L, pH 2), Cr(VI) was completely reduced within 7 min. Besides, scavenger experiments and EPR proved that O₂^{? —} and CO₂^{? —} played a significant role in the photocatalytic reduction of Cr(VI). TA acts as a sacrificial agent to trap the holes and generate strong reducing free radicals: CO₂^{? —}. Dissolving O₂ could react with electrons to generate O₂^{? —}. This work discussed the performance and mechanism of photocatalytic reduction of Cr(VI) in detail, which provided a new idea for the resource utilization of solid waste and the treatment of heavy metal sewage.     

Optimization, equilibrium, adsorption behavior and role of surface functional groups on graphene oxide-based nanocomposite towards diclofenac drug

Aquatic contamination of diclofenac (DCF), an emergent non-steroidal anti-inflammatory drug (NSAIDs), can result in adverse effects to many ecosystems through biomagnification. Hence, introducing effective remediation techniques to sequester the pharmaceutical wastes is highly fundamental to prevent their accumulation in the environment. Generally, adsorption has been presented as a green and efficient approach. Herein, we report the characterization and application of the novel magnetic nanocomposite ([email protected]₂O₄) derived from cobalt-based ferrite (CoFe₂O₄) and graphene oxide (GO) for DCF adsorption. For the optimization procedure, the response surface methodology (RSM) was adopted to investigate the impacts of DCF concentration (1.6–18.4 mg/L), DCF dosage (0.08–0.92 g/L), and solution pH (2.6–9.4) to find the optimum conditions for DCF removal, at 10.5 mg/L, 0.74 g/L, and pH 4, respectively. For the adsorption experiments, the kinetic, isotherm, thermodynamic, and intraparticle diffusion models were systematically studied. Moreover, we have elucidated the role of functional groups on the surface of [email protected]₂O₄ in enhancing the adsorption of DCF drug. With good removal efficiency (up to 86.1%), high maximum adsorption capacity (32.4 mg/g), [email protected]₂O₄ can be a potential candidate to eliminate DCF drug from water.     

Initial carbon release characteristics, mechanisms and denitrification performance of a novel slow release carbon source

External carbon source addition is one of the effective methods for the treatment of wastewater with low carbon to nitrogen ratio (C/N). Compared with fast-release liquid carbon sources, slow-release solid carbon sources are more suitable for the denitrification process. A novel slow-release solid carbon source (corncob-polyvinyl alcohol sodium alginate- poly-caprolactone, i.e. CPSP) was prepared using corn cob (CC) and poly-caprolactone with polyvinyl alcohol sodium alginate as hybrid scaffold. The physical properties and carbon release characteristics of CPSP and three other carbon sources were compared. CPSP had stable framework and good carbon release performance, which followed the second order release equation. The formic acid, acetic acid, propionic acid and butyric acid released from CPSP accounted for 8.27% ± 1.66 %, 56.48% ± 3.71 %, 18.46% ± 2.69% and 16.79% ± 3.02% of the total released acids respectively. The start-up period of CPSP was shorter than that of the other carbon sources in denitrification experiment, and no COD pollution was observed in the start-up phase (25–72 h) and stable phase (73–240 hr). The composition and structure of the dissolved organic compounds released by CPSP and other carbon sources were analyzed by UV-Vis absorption spectroscopy and three-dimensional fluorescence spectroscopy, which indicated that CPSP was more suitable for denitrification than the other studied carbon sources.

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Use of catalytic wet air oxidation (CWAO) for pretreatment of high-salinity high-organic wastewater

Catalytic wet air oxidation (CWAO) coupled desalination technology provides a possibility for the effective and economic degradation of high salinity and high organic wastewater. Chloride widely occurs in natural and wastewaters, and its high content jeopardizes the efficacy of Advanced oxidation process (AOPs). Thus, a novel chlorine ion resistant catalyst B-site Ru doped LaFe_1-xRu_xO_3-δ in CWAO treatment of chlorine ion wastewater was examined. Especially, LaFe_0.85Ru_0.15O_3-δ was 45.5% better than that of the 6%RuO₂@TiO₂ (commercial carrier) on total organic carbon (TOC) removal. Also, doped catalysts LaFe_1-xRu_xO_3-δ showed better activity than supported catalysts RuO₂@LaFeO₃ and RuO₂@TiO₂ with the same Ru content. Moreover, LaFe_0.85Ru_0.15O_3-δ has novel chlorine ion resistance no matter the concentration of Cl⁻ and no Ru dissolves after the reaction. X-ray diffraction (XRD) refinement, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and X-ray absorption fine structure (XAFS) measurements verified the structure of LaFe_0.85Ru_0.15O_3-δ. Kinetic data and density functional theory (DFT) proved that Fe is the site of acetic acid oxidation and adsorption of chloride ions. The existence of Fe in LaFe_0.85Ru_0.15O_3-δ could adsorb chlorine ion (catalytic activity inhibitor), which can protect the Ru site and other active oxygen species to exert catalytic activity. This work is essential for the development of chloride-resistant catalyst in CWAO.

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Efficient capture of aqueous humic acid using a functionalized stereoscopic porous activated carbon based on poly(acrylic acid)/food-waste hydrogel

Stereoscopic porous carbons have shown good potential in humic acid (HA) removal. In this work, a novel stereoscopic porous activated carbon (SPAC) was designed and synthesized via the self-assembly of a hydrogel based on food waste during in-situ polymerization, vacuum drying, carbonization, and activation. Then, the SPAC was functionalized with 3-aminopropyltriethoxysilane (APTES) and the adsorption behavior of the modified SPAC (SPAC-NH₂) was studied systematically. The effects of pH, contact time, initial concentration of HA, and adsorbent dose were investigated, showing that optimal HA removal efficiency (> 98.0%) could be achieved at an initial HA concentration of 100?mg/L. The experimental adsorption isotherm data was fitted to the Langmuir model with a maximum adsorption capacity of 156.0?mg?HA/g SPAC-NH₂. Analysis of the mechanism indicated that the removal of HA was mainly realized through the amidization reaction between the COOH groups of HA and the NH₂ groups of APTES. All of the above results showed that SPAC-NH₂ powder is an efficient, eco-friendly, and reusable adsorbent which is suitable for the removal of HA from wastewater.     

Catalytic performance and reaction mechanisms of NO removal with NH3 at low and medium temperatures on Mn-W-Sb modified siderite catalysts

Iron-based catalysts have been explored for selective catalytic reduction (SCR) of NO due to environmentally benign characters and good SCR activity. Mn-W-Sb modified siderite catalysts were prepared by impregnation method based on siderite ore, and SCR performance of the catalysts was investigated. The catalysts were analyzed by X-ray diffraction, H₂-temperature-programmed reduction, Brunauer-Emmett-Teller, Thermogravimetry-derivative thermogravimetry and in-situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified siderite catalysts calcined at 450°C mainly consist of Fe₂O₃, and added Mn, W and Sb species are amorphous. 3Mn-5W-1.5Sb-siderite catalyst has a wide temperature window of 180-360°C and good N₂ selectivity at low temperatures. In-situ DRIFTS results show NH₄⁺, coordinated NH₃, NH₂, NO₃⁻ species (bidentate), NO₂⁻ species (nitro, nitro-nitrito, monodentate), and adsorbed NO₂ can be discovered on the surface of Mn-W-Sb modified siderite catalysts, and doping of Mn will enhance adsorbed NO₂ formation by synergistic catalysis with Fe³⁺. In addition, the addition of Sb can inhibit sulfates formation on the surface of the catalyst in the presence of SO₂ and H₂O. Time-dependent in-situ DRIFTS studies also indicate that both of Lewis and Brønsted acid sites play a role in SCR of NO by ammonia at low temperatures. The mechanism of NO removal on the 3Mn-5W-1.5Sb-siderite catalyst can be discovered as a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms with three reaction pathways. The mechanism of NO, oxidized by synergistic catalysis of Fe³⁺ and Mn^4+/3+ to form NO₂ among three pathways, reveals the reason of high NO_x conversion of the catalyst at medium and low temperatures.

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Performance and mechanism of Cr(VI) removal by zero-valent iron loaded onto expanded graphite

Zero-valent iron (ZVI) was loaded on expanded graphite (EG) to produce a composite material (EG-ZVI) for efficient removal of hexavalent chromium (Cr(VI)). EG and EG-ZVI were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and Brunauer–Emmett–Teller (BET) analysis. EG-ZVI had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(VI) removal performance. The results showed that the Cr(VI) removal rate was 98.80% for EG-ZVI, which was higher than that for both EG (10.00%) and ZVI (29.80%). Furthermore, the removal rate of Cr(VI) by EG-ZVI showed little dependence on solution pH within a pH range of 1–9. Even at pH 11, a Cr(VI) removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZVI could enhance the removal of Cr(VI) via chemical reduction and physical adsorption, respectively. X-ray photoelectron spectroscopy (XPS) was used to analyze the mechanisms of Cr(VI) removal, which indicated that the ZVI loaded on the surface was oxidized, and the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III) hydroxide/oxyhydroxide on the surface of EG-ZVI.     

Performance and mechanism of Cr(Ⅵ) removal by zero-valent iron loaded onto expanded graphite

Zero-valent iron(ZⅥ) was loaded on expanded graphite(EG) to produce a composite material(EG-ZⅥ) for efficient removal of hexavalent chromium(Cr(Ⅵ)). EG and EG-ZⅥ were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM),Fourier-transform infrared(FTIR) spectroscopy and Brunauer–Emmett–Teller(BET) analysis. EG-ZⅥ had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(Ⅵ) removal performance. The results showed that the Cr(Ⅵ) removal rate was 98.80% for EG-ZⅥ,which was higher than that for both EG(10.00%) and ZⅥ(29.80%). Furthermore, the removal rate of Cr(Ⅵ) by EG-ZⅥ showed little dependence on solution p H within a p H range of 1–9.Even at pH 11, a Cr(Ⅵ) removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZⅥ could enhance the removal of Cr(Ⅵ) via chemical reduction and physical adsorption,respectively. X-ray photoelectron spectroscopy(XPS) was used to analyze the mechanisms of Cr(Ⅵ) removal, which indicated that the ZⅥ loaded on the surface was oxidized, and the removed Cr(Ⅵ) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III)hydroxide/oxyhydroxide on the surface of EG-ZⅥ.     

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

Removal and desorption of chromium in synthetic effluent by a mixed culture in a bioreactor with a magnetic field

Two chromium removal experiments were performed in bioreactors with and without a magnetic field under the same conditions.The release of the chromium present in the biomass was tested in two experiments one with the initial pH of the medium and one with pH 4.0.The objective was to remove Cr(Ⅵ) and total Cr from the effluent,this was carried out by placing biological treatments of synthetic effluent contaminated with 100 mg/L of Cr(Ⅵ) in a bioreactor with neodymium magnets that applied a magnetic field(intensity85.4 mT) to the mixed culture.The removal of Cr(Ⅵ) was approximately 100.0% for the bioreactor with a magnetic field and 93,3% for the bioreactor without a magnetic field for9 hr of recirculation of the synthetic effluent by the bioreactor.The removal of total Cr was61.6% and 48.4%,with and without a magnetic field,respectively;for 24 hr.The desorption of Cr(VI) in the synthetic effluent was 0.05 mg/L,which is below the limit established by Brazilian legislation(0.1 mg/L) for the discharge of effluent containing Cr(Ⅵ) into bodies of water.The results obtained for the removal of chromium in synthetic effluent suggested that there was no significant influence on the viable cell count of the mixed culture.The desorption of Cr(Ⅵ) in synthetic effluent after bioadsorption of chromium by the mixed culture in the process of removal of chromium in bioreactors with and without a magnetic field was not significant in either of the experiments with different initial pHs.