Yueping Bao

Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on superoxide radicals.

The micron grade multi-metal oxide bismuth silicate (Bi12SiO20, BSO) was prepared by the chemical solution decomposition technique. Photocatalytic degradation of pentachlorophenol (PCP) was investigated in the presence of BSO under xenon lamp irradiation. The reaction kinetics followed pseudo first-order and the degradation ratio achieved 99.1% after 120 min at an initial PCP concentration of 2.0 mg/L. The pH decreased from 6.2 to 4.6 and the dechlorination ratio was 68.4% after 120 min at an initial PCP concentration of 8.0 mg/L. The results of electron spin resonance showed that superoxide radical (O2*-) was largely responsible for the photocatalytic degradation of PCP. Interestingly, this result was different from that of previous photocatalytic reactions where valence band holes or hydroxyl radicals played the role of major oxidants. Some aromatic compounds and aliphatic carboxylic acids were determined by GC/MS as the reaction intermediates, which indicated that O2*- can attack the bond between the carbon and chlorine atoms to form less chlorinated aromatic compounds. The aromatic compounds were further oxidized by O2*- to generate aliphatic carboxylic acids which can be finally mineralized to CO2 and H2O.

Electrochemical mineralization of pentachlorophenol (PCP) by Ti/SnO2-Sb electrodes.

Electrochemical degradation of pentachlorophenol (PCP) in aqueous solution was investigated over Ti/SnO2-Sb electrodes prepared by sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements were used to characterize the physicochemical properties of the electrodes. The electrochemical degradation of PCP followed pseudo-first-order kinetics. The main influencing factors, including the types of supporting electrolyte (i.e., NaClO4, Na2SO4, Na2SO3, NaNO3, and NaNO2), initial concentrations of PCP (5-1000mgL(-1)), pH values (3.0-11.0), and current densities (5-40mAcm(-2)) were evaluated. The degradation and mineralization ratios of 100mgL(-1) of PCP achieved >99.8% and 83.0% after 30min electrolysis with a 10mmolL(-1) Na2SO4 at a current density of 10mAcm(-2), respectively. The corresponding half-life time (t1/2) was 3.94min. The degradation pathways that were involved in dechlorination, protons generation, and mineralization processes were proposed based on the determination of total organic carbon, chloride, and intermediate products (i.e., low chlorinated phenol and some organic acids). The toxicity of PCP and its intermediates could be reduced effectively by electrolysis. These results showed that electrochemical technique could achieve a significant mineralization rate in a short time (<30min), which provided an efficient way for PCP elimination from wastewater.

Evidence of superoxide radical contribution to demineralization of sulfamethoxazole by visible-light-driven Bi2O3/Bi2O2CO3/Sr6Bi2O9 photocatalyst

Photocatalytic degradation of sulfamethoxazole (SMX) was investigated using Bi2O3/Bi2O2CO3/Sr6Bi2O9 (BSO) photocatalyst under visible light (>420 nm) irradiation. The photochemical degradation of SMX followed pseudo-first-order kinetics. The reaction kinetics was determined as a function of initial SMX concentrations (5-20 mg L(-1)), initial pH (3-11) and BSO concentrations (6-600 mg L(-1)). Approximately, 90% of SMX (10 mg L(-1)) degradation and 36% of TOC reduction were achieved at pH 7.0 after 120 min irradiation. The main mineralization products, including NH4(+), NO3(-), SO4(2-) and CO2, as well as intermediates 3-amino-5-methylisoxazole (AMI), p-benzoquinone (BZQ), and sulfanilic acid (SNA) were detected in aqueous solution. The formation of O2(*-) radical was evidenced by using electron spin resonance and a chemiluminescent probe, luminal. A possible degradation mechanism involving excitation of BSO, followed by charge injection into the BSO conduction band and formation of reactive superoxide radical (O2(*-)) was proposed for the mineralization of SMX. During the reaction, the O2(*-) radical attacks the sulfone moiety and causes the cleavage of the SN bond, which leads to the formation of two sub-structure analogs, AMI and SNA.

A high activity of Ti/SnO2-Sb electrode in the electrochemical degradation of 2,4-dichlorophenol in aqueous solution

Electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was investigated over Ti/SnO2-Sb anode. The factors influencing the degradation rate, such as applied current density (2-40 mA/cm2), pH (3-11) and initial concentration (5-200 mg/L) were evaluated. The degradation of 2,4-DCP followed apparent pseudo first-order kinetics. The degradation ratio on Ti/SnO2-Sb anode attained > 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant current density of 30 mA/cm2 with a 10 mmol/L sodium sulphate (Na2SO4) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L) degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, the degradation rate constant (k) and the degradation half-life (t1/2) were 0.21 min- and (2.8 +/- 0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) were detected as intermediates. The energy efficiencies for 2,4-DCP degradation (5-200 mg/L) with Ti/SnO2-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO2-Sb anode with a high activity to rapid organic oxidation could be employed to degrade chlorophenols, particularly 2,4-DCP in wastewater.

Rapid dechlorination of chlorophenols in aqueous solution by [Ni|Cu] microcell

The [Ni|Cu] microcell was prepared by mixing the Ni(0) and Cu(0) particles. The composition and crystal form were characterized by X-ray diffraction (XRD) and scanning electron microscope. The results evidenced the zero-valence metals Ni and Cu were exposed on the surface of particles mixture. The [Ni|Cu] microcell was employed to decompose chlorophenols in aqueous solution by reductive dechlorination. The dechlorination rates of chlorophenols by [Ni|Cu] were >10 times faster than those by [Fe|Cu], [Zn|Cu], [Sn|Cu], and [Fe|Ni] mixtures under the same conditions. [Ni|Cu] is different from other zero valent metals (ZVMs) in that it performed the best at neutral pH. The main products of chlorophenol dechlorination were cyclohexanol and cyclohexanone. The reduction kinetics was between pseudo zero-order and first-order, depending on the pH, concentration, and temperature. These results, combined with electrochemical analysis, suggested that Ni(0) acted as a reductant and catalyst in dechlorination reaction. The H* corridor mechanism from Ni(0) to Cu(0) was also proposed based on hydrogen spillover. The inhibition on the release of Ni(2+) by adding natural organic matters and adjusting pH was investigated.

Photocatalytic degradation of fipronil in water by silver-modified lithium vanadium phosphate spheres under visible light irradiation

A novel visible light-driven photocatalyst, lithium vanadium phosphate sphere (LVPS), was prepared by a ball-milling method. For enhancing the photocatalytic performance, LVPS was further modified with silver (ALVPS) by a UV-light photoreduction method. After modification, the crystalline phase of LVPS did not change, however, the UV-Vis diffuse reflectance spectrum of ALVPS was extended to 656 nm, which greatly improved its photoabsorptivity for visible light and enhanced its electron donating capacity. Under the irradiation of sunlight or visible light (>400 nm), ALVPS can rapidly remove fipronil (a persistent organic pollutant, 5 mg L−1) from aqueous solution. More than 99.7% of fipronil was removed by ALVPS after 0.5 h of irradiation, yielding a much higher removal rate than those achieved by nano-TiO2 and Bi2O3. Photo-generated carrier trapping experiments were conducted to elucidate the photocatalytic degradation mechanism further. Hydrogen peroxide and potassium bromate suppressed the photocatalytic activity of ALVPS, while superoxide dismutase and sodium azide reinforced it, verifying that photo-generated electrons played a key role in the photochemical reaction.