Alok Diwakar Bokare

Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes

Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO(•)) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe(2+) or Fe(3+) form), metal oxides (e.g., Fe2O3, Fe3O4), and zero-valent metal (Fe(0)) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H2O2 into HO(•) through conventional Fenton-like pathways. The in situ formation of H2O2 and decomposition into HO(•) can be also achieved using electron transfer mechanism in zero-valent aluminum/O2 system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H2O2 activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications.

Solar production of H2O2 on reduced graphene oxide–TiO2 hybrid photocatalysts consisting of earth-abundant elements only

A superior cocatalytic behavior of reduced graphene oxide (rGO) was observed for the photocatalytic production of H2O2 in the TiO2-based system. The adsorption of phosphate on TiO2 enhanced the production of H2O2 up to a millimolar level. The in situ formation of cobalt phosphate on rGO/TiO2 enabled the photocatalytic production of H2O2 even in the absence of organic electron donors.

Reductive Dechlorination of γ-hexachlorocyclohexane using Fe-Pd Bimetallic Nanoparticles

Nanoscale Fe-Pd bimetallic particles were synthesized and used for degradation of lindane (gamma-hexachlorocyclohexane) in aqueous solution. Batch studies showed that 5mg/L of lindane was completely dechlorinated within 5 min at a catalyst loading of 0.5 g/L and the degradation process followed first-order kinetics. GC-MS analysis in corroboration with GC-ECD results showed the presence of cyclohexane as the final degradation product. The proposed mechanism for the reductive dechlorination of lindane involves Fe corrosion-induced hydrogen atom transfer from the Pd surface. The enhanced degradation efficiency of Fe-Pd nanoparticles is attributed to: (1) high specific surface area of the nanoscale metal particles (60 m(2)/g), manyfold greater that of commercial grade micro- or milli-scale iron particles (approximately 1.6m(2)/g); and, (2) increased catalytic reactivity due to the presence of Pd on the surface. Recycling and column studies showed that these nanoparticles exhibit efficient and sustained catalytic activity.

Chromate-Induced Activation of Hydrogen Peroxide for Oxidative Degradation of Aqueous Organic Pollutants

The oxidation of organic compounds in water was investigated with using chromate as an activator of H(2)O(2). 4-chlorophenol (4-CP) was used as a main model substrate, and its degradation was successfully achieved at circumneutral pH. Unlike the traditional Fenton-based activation of H(2)O(2) that is mainly limited to acidic condition, the oxidative capacity of the proposed Cr(VI)/H(2)O(2) system is active over a wide range of pH 3-11. H(2)O(2) substitutes the oxo ligands of chromate by the peroxo ligands and, subsequently, converts chromate(VI) into a tetraperoxochromate(V) complex. The instantaneous disproportionation between chromium-coordinated peroxo ligands initiates the generation of HO(•) that are responsible for the degradation of organic compounds in the Cr(VI)/H(2)O(2) system. The oxidation rate of 4-CP and the in situ generated concentration of peroxochromate(V) decreased with increasing pH. The generation of HO(•) in the Cr(VI)/H(2)O(2) solution was confirmed by monitoring the production of p-hydroxybenzoic acid from the oxidation of benzoic acid as a probe reaction and by quenching the degradation of 4-CP in the presence of methanol as a radical scavenger. The oxidation of 4-CP investigated at different H(2)O(2) concentrations and pH indicated the pH-dependent competition between peroxo ligand exchange and dissociation reactions. The proposed Cr(VI)/H(2)O(2) process can be ideally suited for the treatment of chromate-contaminated wastewaters with recalcitrant organic compounds. The degradation of 4-CP in actual Cr(VI)-contaminated wastewater was successfully demonstrated in the presence of added H(2)O(2). The Cr(VI)/H(2)O(2) system is proposed as a viable advanced oxidation process.

Advanced Oxidation Process Based on the Cr(III)/Cr(VI) Redox Cycle

Oxidative degradation of aqueous organic pollutants, using 4-chlorophenol (4-CP) as a main model substrate, was achieved with the concurrent H(2)O(2)-mediated transformation of Cr(III) to Cr(VI). The Fenton-like oxidation of 4-CP is initiated by the reaction between the aquo-complex of Cr(III) and H(2)O(2), which generates HO(•) along with the stepwise oxidation of Cr(III) to Cr(VI). The Cr(III)/H(2)O(2) system is inactive in acidic condition, but exhibits maximum oxidative capacity at neutral and near-alkaline pH. Since we previously reported that Cr(VI) can also activate H(2)O(2) to efficiently generate HO(•), the dual role of H(2)O(2) as an oxidant of Cr(III) and a reductant of Cr(VI) can be utilized to establish a redox cycle of Cr(III)-Cr(VI)-Cr(III). As a result, HO(•) can be generated using both Cr(III)/H(2)O(2) and Cr(VI)/H(2)O(2) reactions, either concurrently or sequentially. The formation of HO(•) was confirmed by monitoring the production of p-hydroxybenzoic acid from [benzoic acid + HO(•)] as a probe reaction and by quenching the degradation of 4-CP in the presence of methanol as a HO(•) scavenger. The oxidation rate of 4-CP in the Cr(III)/H(2)O(2) solution was highly influenced by pH, which is ascribed to the hydrolysis of Cr(III)(H(2)O)(n) into Cr(III)(H(2)O)(n-m)(OH)(m) and the subsequent condensation to oligomers. The present study proposes that the Cr(III)/H(2)O(2) combined with Cr(VI)/H(2)O(2) process is a viable advanced oxidation process that operates over a wide pH range using the reusable redox cycle of Cr(III) and Cr(VI).

Sequential Process Combination of Photocatalytic Oxidation and Dark Reduction for the Removal of Organic Pollutants and Cr(VI) using Ag/TiO2

We investigated a sequential photocatalysis-dark reaction, wherein organic pollutants were degraded on Ag/TiO2 under UV irradiation and the dark reduction of hexavalent chromium (Cr(VI)) was subsequently followed. The photocatalytic oxidation of 4-chlorophenol (4-CP), a test organic substrate, induced the generation of degradation intermediates and the storage of electrons in Ag/TiO2 which were then utilized for reducing Cr(VI) in the postirradiation period. The dark reduction efficiency of Cr(VI) was much higher with Ag/TiO2 (87%), compared with bare TiO2 (27%) and Pt/TiO2 (22%). The Cr(VI) removal by Ag/TiO2 (87%) was contributed by adsorption (31%), chemical reduction by intermediates of 4-CP degradation (26%), and reduction by electrons stored in Ag (30%). When formic acid, humic acid or ethanol was used as an alternative organic substrate, the electron storage effect was also observed. The postirradiation removal of Cr(VI) on Ag/TiO2 continued for hours, which is consistent with the observation that a residual potential persisted on the Ag/TiO2 electrode in the dark whereas little residual potential was observed on bare TiO2 and Pt/TiO2 electrodes. The stored electrons in Ag/TiO2 and their transfer to Cr(VI) were also indicated by the UV-visible absorption spectral change. Moreover, the electrons stored in the preirradiated Ag/TiO2 reacted with O2 with showing a sign of low-level OH radical generation in the dark period.

Heterogeneous Catalytic Oxidation of As(III) on Nonferrous Metal Oxides in the Presence of H2O2

The oxidation of As(III) (arsenite) to As(V) (arsenate), a critical pretreatment process for total arsenic removal, is easily achieved using chemical oxidation methods. Hydrogen peroxide (H2O2) is widely used as an environmentally benign oxidant but its practical use for the arsenite oxidation is limited by the strong pH dependence and slow oxidation kinetics. This study demonstrated that H2O2-induced oxidation of As(III) can be markedly enhanced in the presence of nonferrous metal oxides (e.g., WO3, TiO2, ZrO2) as a heterogeneous catalyst working over a wide pH range in ambient reaction conditions. In particular, TiO2 is an ideal catalyst because it is not only active and stable but also easily available and inexpensive. Although the photocatalytic oxidation of As(III) on TiO2 was intensively studied, the thermal catalytic activities of TiO2 and other nonferrous metal oxides for the arsenic oxidation have been little investigated. The heterogeneous oxidation rate increased with increasing the TiO2 surface area and [H2O2] and weakly depended on pH whereas the homogeneous oxidation by H2O2 alone was favored only at alkaline condition. The oxidation rate in the TiO2/H2O2 system was not reduced at all in the absence of dioxygen. It was not retarded at all by OH radical scavengers but markedly inhibited by hydroperoxyl radical scavengers. It is proposed that the surface complexation of H2O2 on TiO2 induces the generation of the surface hydroperoxyl radical through an inner-sphere electron transfer, which subsequently reacts with As(III). The catalytic activity of TiO2 was maintained without showing any sign of deactivation. The heterogeneous catalytic oxidation is proposed as a viable method for the preoxidation treatment of As(III)-contaminated water under ambient conditions.

Bicarbonate-induced activation of H2O2 for metal-free oxidative desulfurization

Efficient oxidative desulfurization (ODS) of model oil containing dibenzothiophene (DBT) and aromatic thiophenic derivatives has been achieved at room temperature using hydrogen peroxide activation by inorganic bicarbonate (HCO3(-)). Using in-situ formation of peroxymonocarbonate as oxidant, the transformation of main model substrate DBT to corresponding DBT-sulfone was easily accomplished in biphasic reaction conditions. In the presence of water-acetonitrile polar phase, increasing the water content upto 50% decreased the extraction capacity more than 3 times, but ∼ 90% DBT oxidation was still achieved. The oxidizing capacity of bicarbonate catalyst was maintained during repeated ODS cycles, but DBT removal efficiency was critically dependent on the extraction capacity of the polar phase. Under heterogeneous reaction conditions, bicarbonate-modified ion-exchange resin achieved similar ODS activity compared to the homogeneous catalytic system. Additionally, the efficient formation of peroxymonocarbonate using gaseous CO2 precursor in alkaline conditions was also utilized for DBT oxidation. The present study proposes the NaHCO3/H2O2 catalytic system as an efficient and cheap metal-free alternative for the oxidative removal of aromatic sulfur compounds from fuel oil.

Inhibition of CO poisoning on Pt catalyst coupled with the reduction of toxic hexavalent chromium in a dual-functional fuel cell

We propose a method to enhance the fuel cell efficiency with the simultaneous removal of toxic heavy metal ions. Carbon monoxide (CO), an intermediate of methanol oxidation that is primarily responsible for Pt catalyst deactivation, can be used as an in-situ reducing agent for hexavalent chromium (Cr (VI)) with reactivating the CO-poisoned Pt catalyst. Using electro-oxidation measurements, the oxidation of adsorbed CO molecules coupled with the concurrent conversion of Cr (VI) to Cr (III) was confirmed. This concept was also successfully applied to a methanol fuel cell to enhance its performance efficiency and to remove toxic Cr (VI) at the same time.

Singlet-Oxygen Generation in Alkaline Periodate Solution.

A nonphotochemical generation of singlet oxygen ((1)O2) using potassium periodate (KIO4) in alkaline condition (pH > 8) was investigated for selective oxidation of aqueous organic pollutants. The generation of (1)O2 was initiated by the spontaneous reaction between IO4(-) and hydroxyl ions, along with a stoichiometric conversion of IO4(-) to iodate (IO3(-)). The reactivity of in-situ-generated (1)O2 was monitored by using furfuryl alcohol (FFA) as a model substrate. The formation of (1)O2 in the KIO4/KOH system was experimentally confirmed using electron spin resonance (ESR) measurements in corroboration with quenching studies using azide as a selective (1)O2 scavenger. The reaction in the KIO4/KOH solution in both oxic and anoxic conditions initiated the generation of superoxide ion as a precursor of the singlet oxygen (confirmed by using superoxide scavengers), and the presence of molecular oxygen was not required as a precursor of (1)O2. Although hydrogen peroxide had no direct influence on the FFA oxidation process, the presence of natural organic matter, such as humic and fulvic acids, enhanced the oxidation efficiency. Using the oxidation of simple organic diols as model compounds, the enhanced (1)O2 formation is attributed to periodate-mediated oxidation of vicinal hydroxyl groups present in humic and fulvic constituent moieties. The efficient and simple generation of (1)O2 using the KIO4/KOH system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral and near-alkaline conditions.