Penghui Du

A combination of electro-enzymatic catalysis and electrocoagulation for the removal of endocrine disrupting chemicals from water.

We in this study investigated a novel electrochemical approach combining electro-enzyme and electrocoagulation to precipitate bisphenol A (BPA) from water containing humic acid (HA). Horseradish peroxidase was immobilized on the graphite felt of Ti electrode as HRP-GF/Ti cathode, with aluminum plate anode establishing a pair of working electrodes. BPA was 100% removed and the reduction of total organic carbon (TOC) reached 95.1% after 20-min sequencing treatment with the current density of 2.3 mA/cm(2). Real wastewater (TOC=28.76 mg/L, BPA=4.1 μg/L) also can achieve 94% BPA removal and 52% TOC reduction after sequencing treatment. Additionally, coupled electro-system with continuous flow only required energy of 0.016 kWh/m(3) to achieve simultaneous 90% BPA and 85% TOC removal. As indicated in the time-of-flight mass spectrometry and FTIR spectra, the electro-enzymatic process not only oxidized BPA into dimer and BPA-3,4-quinone, but also greatly altered the chemical and structural features of HA, where hydrophilic moieties (phenolic and alcohols) transformed into hydrophobic forms (ethers, quinone and aliphatic). These polymerized products were effectively separated from aquous solution during anodic electrocoagulation, leading to significant removal of BPA and TOC. Thus, the coupled process may provide a faster and less energy strategy to control certain emerging contaminants in water/wastewater treatment.

A Highly Sensitive and Selective Hydrogen Peroxide Biosensor Based on Gold Nanoparticles and Three-Dimensional Porous Carbonized Chicken Eggshell Membrane

A sensitive and noble amperometric horseradish peroxidase (HRP) biosensor is fabricated via the deposition of gold nanoparticles (AuNPs) onto a three-dimensional (3D) porous carbonized chicken eggshell membrane (CESM). Due to the synergistic effects of the unique porous carbon architecture and well-distributed AuNPs, the enzyme-modified electrode shows an excellent electrochemical redox behavior. Compared with bare glass carbon electrode (GCE), the cathodic peak current of the enzymatic electrode increases 12.6 times at a formal potential of −100mV (vs. SCE) and charge-transfer resistance decreases 62.8%. Additionally, the AuNPs-CESM electrode exhibits a good biocompatibility, which effectively retains its bioactivity with a surface coverage of HRP 6.39×10−9 mol cm−2 (752 times higher than the theoretical monolayer coverage of HRP). Furthermore, the HRP-AuNPs-CESM-GCE electrode, as a biosensor for H2O2 detection, has a good accuracy and high sensitivity with the linear range of 0.01–2.7 mM H2O2 and the detection limit of 3μM H2O2 (S/N = 3).

Photocatalysis of bisphenol A by an easy-settling titania/titanate composite: Effects of water chemistry factors, degradation pathway and theoretical calculation

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min-1, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f0) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

Transformation, products, and pathways of chlorophenols via electro-enzymatic catalysis: How to control toxic intermediate products

Chlorophenols can be easily oxidized into chlorobenzoquinones (CBQs), which are highly toxic and have been linked to bladder cancer risk. Herein, we report the transformation, products, and pathways of 2,4-dichlorophenol (DCP) by horseradish peroxidase (HRP) and electro-generated hydrogen peroxide (H2O2) and suggest methods to control the formation of toxic intermediate products. After a 10-min electroenzymatic process, 99.7% DCP removal may be achieved under optimal conditions. A total of 16 reaction products, most of which are subsequently verified as DCP polymers and related quinone derivatives, are identified by using ultra-performance liquid chromatography-time-of-flight mass spectrometry (UPLC-TOF-MS). A five-step reaction pathway for DCP transformation, including HRP-driven substrate oxidation, substitution and radical coupling, quick redox equilibrium, nucleophilic reaction and precipitation from aqueous solution, is proposed. Current variations and the presence of CO2 could significantly affect these reaction pathways. In particular, higher currents enhance the hydroxylation process by promoting alkaline conditions and abundant H2O2 formation. As both OH(-) and H2O2 are strong nucleophiles, they easily react with CBQ products to form hydroxylated products, which can significantly reduce solution toxicity. An adequate supply of CO2 can provide favorable pH conditions and facilitate enzymatic steps, such as substrate oxidation and radical coupling, to generate precipitable polymerized products. All of the results suggest that toxic intermediate products can be effectively reduced and controlled during the electro-enzymatic process to remove DCP and other phenolic pollutants from wastewaters.

Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

Biosynthesis of Palladium Nanoparticles Using Shewanella loihica PV-4 for Excellent Catalytic Reduction of Chromium (VI)

Chromium contamination can be remediated by catalytic reduction with precious metal palladium (Pd). Thus, enhancing the catalytic performance of Pd is of strong interest. An environmentally friendly and nontoxic approach for the production of palladium nanoparticles (Pd-NPs) is to use microorganisms. Herein, the biosynthesis of Pd-NPs by Shewanella loihica PV-4 is reported for the first time. Both extracellular and intracellular bioreduction of Pd(II) has contributed to this bio-fabrication, with the production of Pd0 particles in the size range of 4–10 nm. It was found that several factors including a higher initial Pd(II) concentration, weak acid medium conditions, and a larger dosage of sodium formate and biomass amount could facilitate this synthesis process. The biosynthesized Pd-NPs exhibited excellent catalytic activities for chromium(VI) reduction, with complete removal of Cr(VI) after 3 h of operation with a catalyst amount of 0.5 mg mL−1, an initial Cr(VI) concentration of 0.5 mM, and formic acid as the electron donor; these are significant advantages compared to chemically prepared Pd0. Cr(VI) reduction catalyzed by biosynthesized Pd-NPs was promoted with factors such as a higher dosage of formic acid, lower pH, and a lower initial Cr(VI) concentration. Density functional theory calculations of formic acid decomposition on Pd-NPs revealed that Pd-NPs facilitated formic acid decomposition into CO2 and H2. These results have collectively demonstrated the feasibility of the biosynthesis of Pd-NPs by Shewanella loihica PV-4 and their potential application as promising catalysts for the remediation of chromium contamination.

Oxidation of Amino Acids by Peracetic Acid: Reaction Kinetics, Pathways and Theoretical Calculations

Peracetic acid (PAA) is a sanitizer with increasing use in food, medical and water treatment industries. Amino acids are important components in targeted foods for PAA treatment and ubiquitous in natural waterbodies and wastewater effluents as the primary form of dissolved organic nitrogen. To better understand the possible reactions, this work investigated the reaction kinetics and transformation pathways of selected amino acids towards PAA. Experimental results demonstrated that most amino acids showed sluggish reactivity to PAA except cysteine (CYS), methionine (MET), and histidine (HIS). CYS showed the highest reactivity with a very rapid reaction rate. Reactions of MET and HIS with PAA followed second-order kinetics with rate constants of 4.6 ± 0.2, and 1.8 ± 0.1 M−1⋅s−1 at pH 7, respectively. The reactions were faster at pH 5 and 7 than at pH 9 due to PAA speciation. Low concentrations of H2O2 coexistent with PAA contributed little to the oxidation of amino acids. The primary oxidation products of amino acids with PAA were [O] addition compounds on the reactive sites at thiol, thioether and imidazole groups. Theoretical calculations were applied to predict the reactivity and regioselectivity of PAA electrophilic attacks on amino acids and improved mechanistic understanding. As an oxidative disinfectant, the reaction of PAA with organics to form byproducts is inevitable; however, this study shows that PAA exhibits lower and more selective reactivity towards biomolecules such as amino acids than other common disinfectants, causing less concern of toxic disinfection byproducts. This attribute may allow greater stability and more targeted actions of PAA in various applications.

In Situ Nanoreactors: Controllable Photoluminescent Carbon-Rich Polymer Nanodots Derived from Fatty Acid under Photoirradiation

Amphiphilic nanoreactors have been recently used to fabricate photoluminescent carbon-rich polymer nanodots (PCPNs). However, the applications of PCPNs have been limited by their requirements for high temperature and toxic organic solvents or catalysts and the difficult control of their luminescent properties. Herein, a novel and facile strategy is reported for the synthesis of controllable PCPNs. This strategy involves the use of in situ vesicular nanoreactors under mild photoirradiation with fatty acid as the precursor. The conjugation degree of the uniformly sized PCPNs can be increased by extending photoreaction time, thus enabling the tuning of the optical properties of PCPNs. The PCPNs, which feature controllable and outstanding luminescent properties, low cytotoxicity, and biocompatibility, are successfully applied in bioimaging and as fluorescent ink. The present strategy is an attractive and facile platform for the preparation of carbon-rich nanomaterials with controllable photoluminescence.