Photocatalytic degradation of para-hydroxybenzoic acid: Relationship between substrate adsorption and photocatalytic degradation

 Dark adsorption and photocatalytic degradation of para-hydroxybenzoic acid (PHBA) was studied in the presence of Degussa P-25 titanium dioxide photocatalyst under concentrated solar radiation. This work includes the study of the effect of pH, and of the presence of different anions and cations on dark adsorption and photocatalytic degradation (PCD) of PHBA on titanium dioxide. The results obtained clearly indicate that there is a link between the extent of adsorption of PHBA and its PCD. Conditions that favor greater adsorption of PHBA also favor a greater PCD. This points to the possibility that the mechanism of PCD involves a surface reaction between adsorbed PHBA and OH ° radical. Anions were generally found to have a detrimental effect on the photocatalytic degradation of PHBA. Cl^– caused the greatest decrease in the PCD followed by NO₃ ^–, HCO₃ ^– and SO₄ ^2–. Cations Cu²⁺ and Fe²⁺ were not found to assist the degradation of PHBA, possibly due to the anions associated with them. Received: 15 May 2000 / Accepted: 15 July 2000     

Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2

Mg-Al hydrotalcites intercalated with five different interlayer anions—CO₃²⁻, SO₄²⁻, Cl⁻, HPO₄²⁻ or terephthalate—were synthesized by either the coprecipitation or ion-exchange method. The structure of the as-synthesized samples and the presence of intended anions in the interlayer gallery of hydrotalcites were determined by X-ray diffraction and FTIR spectroscopy. On calcination at 600 °C the materials were transformed into mixed metal oxides. The kind of the counterbalancing anions present in the parent hydrotalcite influences strongly textural parameters of the obtained Mg-Al oxides. Both temperature-programmed desorption of NH₃ and CO₂, and test reaction of 2-methyl-3-butyn-2-ol (MBOH) conversion were used to determine the acidity and basicity of the samples. The hydrotalcite derived mixed Mg-Al oxides showed the presence of Brønsted and Lewis acid and base sites. However, the strong basic character of the solids caused that acetone and acetylene were observed as the major products of MBOH conversion.     

Photocatalytic treatment of 4-chlorophenol in aqueous ZnO suspensions: Intermediates,influence of dosage and inorganic anions

The photocatalytically driven removal of eco-persistent 4-chlorophenol from water using ZnO is reported here. Kinetic dependence of transformation rate on operating variables such as initial 4-chlorophenol concentration and photocatalyst doses was investigated. A complete degradation of 4-chlorophenol at 50 mg L⁻¹ levels was realised in 3 h. Analytical profiles on 4-chlorophenol transformation were consistent with the best-line fit of the pseudo zero-order kinetics. The addition of small amounts of inorganic anions as SO₄²⁻, HPO₄⁻, S₂O₈²⁻ and Cl⁻ revealed two anion types: active site blockers and rate enhancers. Fortunately, Cl⁻ and SO₄²⁻ commonly encountered in contaminated waters enhanced the rate of 4-chlorophenol degradation. The reaction intermediates and route to 4-chlorophenol mineralisation were elucidated by combined RP-HPLC and GC–MS methods. In addition to previously reported pathway products of 4-chlorophenol photo-oxidation catechol was detected. A radical mechanism involving o-hydroxylation is proposed to account for the formation of catechol.     

Synthesis and characterization of layered double hydroxides (LDHs) with intercalated chromate ions

Chromate intercalated layered double hydroxides (LDHs) having the formula M^II₆M′^III₂(OH)₁₆CrO₄·4H₂O (M^II = Ca, Mg, Co, Ni, Zn with M′^III = Al and M^II = Mg, Co, Ni with M′^III = Fe) have been prepared by coprecipitation. The products obtained are replete with stacking disorders. DIFFaX simulations show that the stacking disorders are of three kinds: (i) turbostratic disorder of an originally single layered hexagonal (1H) crystal, (ii) random intergrowth of polytypes with hexagonal (2H) and rhombohedral (3R) symmetries and (iii) translation of randomly chosen layers by (2/3, 1/3, z) and (1/3, 2/3, z) leading to stacking faults having a local structure of rhombohedral symmetry. IR spectra show that the CrO₄²⁻ ion is incorporated either in the T_d or in the C_3v symmetry. The interlayer spacing in the latter case is 7.3 Å characteristic of a single atom thick interlayer showing that the CrO₄²⁻ ion is grafted to the metal hydroxide slab. On thermal treatment, the CrO₄²⁻ ion transforms into Cr(III) and is incorporated into the spinel oxide or phase separates as Cr₂O₃. In the LDH of Mg with Al, Cr(III) remains in the MgO lattice as a defect and promotes the reconstruction of the LDH on soaking in water. In different LDHs, 18-50% of the CrO₄²⁻ ion is replaceable with carbonate anions showing only partial mineralization of the water-soluble chromate. The extent of replaceable chromates depends upon the solubility of the corresponding LDH, which in turn is determined by the solubility of the MCrO₄. These studies have profound implications for the possible use of LDHs for chromate amelioration in green chemistry.     

Eu-modification of luminescent hybrid bimodal mesoporous silicas with various anions (NO3, CH3COO,and Cl)

In order to enhance the intensity of luminescent hybrid bimodal mesoporous silica (LHMS), the rare earth Eu³⁺ ion was employed as an enhancer to modify 1,8-naphthalic anhydride (NA) molecules. The modified LHMS were prepared with various anions of europium salts including Cl⁻, NO₃⁻, and CH₃COO⁻. The structure and photoluminescence properties of the obtained samples were characterized by XRD, TEM, N₂-adsorption/desorption, FT-IR, TGA, ICP-OES, and PL measurements. The results showed that the bimodal mesoporous system of BMMs could be preserved after functionalization via grafted Eu³⁺-modified NA molecules onto mesoporous matrix. However, the structure parameters and textural properties of resultant LHMS series were obviously influenced by the anions volume. Meanwhile, the luminescent performances of LHMS series were seriously impacted by both of the binding force between Eu³⁺ and various anions and steric hindrance of the anions, resulting in the intensity of emission peak of obtained LHMS series declining as following order: LHMS-EN (NO₃⁻) > LHMS-EA (CH₃COO⁻) > LHMS-EC (Cl⁻). Finally, the related mechanism was discussed in-depth.     

Structural characterization and photocatalytic properties of novel Bi2YVO8

Bi₂YVO₈ was prepared by solid-state reaction for the first time. The structural and photocatalytic properties of Bi₂YVO₈ were studied. The results showed that this compound has the tetragonal crystal system with space group I4/mmm. The band gap of Bi₂YVO₈ was estimated to be about 2.09 eV by plotting (αhν)² versus hν and obtaining the hν axis intercept value according to Tauc's equation. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water with Bi₂YVO₈ as the photocatalyst under ultraviolet light irradiation (wavelength = 390 nm). Degradation of aqueous methylene blue photocatalyzed by this compound was investigated under visible light irradiation. Bi₂YVO₈ showed higher photocatalytic activity compared to Bi₂YTaO₇, Bi₂InTaO₇ or TiO₂ (P-25). Complete removal of aqueous methylene blue was achieved after visible light irradiation for 170 min. The decrease of the total organic carbon and the formation of inorganic products such as SO₄²⁻ and NO₃⁻ revealed the continuous mineralization of aqueous methylene blue during photocatalytic reaction.     

Specific ion effects on the properties of cationic Gemini surfactant monolayers

The effects of some anions of the Hofmeister series and different divalent cations of alkaline earth metals on the properties of Langmuir monolayers of the cationic Gemini surfactant ethyl-bis (dimethyl octadecylammonium bromide) have been investigated. Surface pressure and potential isotherms at the air-water interface were obtained on aqueous subphases containing sodium salts with several anions of the Hofmeister series (Cl⁻, NO₃⁻, Br⁻, I⁻, ClO₄⁻, and SCN⁻). The influence of the investigated anions on the monolayer properties can be ordered according to the Hofmeister series with a change in the order between bromide and nitrate anions. On the other hand, for a given anion, the cation of the salt also influences the surface properties of the Langmuir films. The monolayers can be transferred onto mica by the Langmuir-Blodgett technique and then the Langmuir-Blodgett films were characterized by atomic force microscopy (AFM). The AFM images show that the molecules become more closely packed and nearly vertical to the surface when anions screen the electric charge of the surfactant molecules.     

Microwave hydrothermal synthesis of AgInS2 with visible light photocatalytic activity

AgInS₂ nanoparticles with superior visible light photocatalytic activity were successfully synthesized by a microwave hydrothermal method. This method is a highly efficient and rapid route that involves no organic solvents, catalysts, or surfactants. The photocatalytic activity of AgInS₂ nanoparticles was investigated through the degradation of dyes under visible light irradiation. Compared with TiO_2−xN_x, AgInS₂ has exhibited a superior activity for photocatalytic degradation MO under the same condition. The experiment results showed that superoxide radicals (O₂⁻), hydrogen peroxides (H₂O₂) and holes (h⁺) were the mainly active species for the degradation of organic pollutants over AgInS₂. Through the determination of flat band potential, the energy band structure of the sample was obtained. A possible mechanism for the degradation of organic pollutant over AgInS₂ was proposed.     

Microwave-assisted synthesis of palladium nanocubes and nanobars

Microwave was employed in the shape-controlled synthesis of palladium nanoparticles. Palladium nanocubes and nanobars with a mean size of about 23.8 nm were readily synthesized with H₂PdCl₄ as a precursor, tetraethylene glycol (TEG) as both a solvent and a reducing agent in the presence of PVP and CTAB in 80 s under microwave irradiation. The structures of the as-prepared palladium nanoparticles were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and ultraviolet-visible (UV-vis) absorption spectroscopy. The formation of PdBr₄²⁻due to the coordination replacement of the ligand Cl⁻ ions in PdCl₄²⁻ ions by Br⁻ ions in the presence of bromide was responsible for the synthesis of Pd nanocubes and nanobars. In addition, a milder reducing power, a higher viscosity and a stronger affinity of TEG were beneficial to the larger sizes of Pd nanocubes and nanobars.     

Anion-exchange properties of nickel–aluminum layered double hydroxide prepared by liquid phase deposition

The optimum coordination structure of Ni–fluoro complexes for the preparation of Ni–Al LDH by LPD process and the diverse anion-exchange properties of as-deposited Ni–Al on α-alumina powder were quantitatively evaluated for the industrial application of new positive material for alkali secondary batteries. The [NiF_6−x−y(NH₃)_x(OH⁻)_y]ⁿ⁺ was more suitable than [NiF₆]⁴⁻ as the precursor of the deposition of Ni–Al LDH in the LPD reaction, and the improved LPD reaction achieved the synthesis of high purity and high crystallinity Ni–Al LDH. All anion-exchanged Ni–Al LDHs for OH⁻–, Cl⁻–, SO₄²⁻–, and CH₃COO⁻–forms kept the high crystallinity and showed the enlargement of interlayer distances. The tilting angle of the intercalated CH₃COO⁻ anions was about 15°. Anion-exchange capacity remained constant at a minimum of 0.8 meq g⁻¹ in pH >10, increased as pH decreased, and reached a maximum of 8 meq g⁻¹ at pH 2. Anion-exchange of OH⁻–form of Ni–Al LDH was accelerated by the neutralization of hydroxide ions in interlayers, in addition, the anion-exchange capacity and the crystallinity of Ni–Al LDH could be controlled by the amount of doped aluminum ions.     

Hybrid inorganic/organic composites of Mg-Al layered double hydroxides intercalated with citrate, malate, and tartrate prepared by co-precipitation

Inorganic/organic composite materials composed of Mg-Al layered double hydroxides (Mg-Al LDHs) intercalated with citrate (C₆H₅O₇³⁻), malate (C₄H₄O₅²⁻), or tartrate (C₄H₄O₆²⁻) anions were prepared by a co-precipitation technique and characterized by X-ray diffraction and compositional analyses. The molecular orientation of the organic component in the interlayer space was determined. At low intercalation levels, citrate ion was inclined at an angle of 26° relative to the brucite-like layers of Mg-Al LDH. At higher solution concentrations, both the Mg(C₆H₅O₇)⁻ complex and free C₆H₅O₇³⁻ were isotropically oriented in the interlayer space. For both malate·Mg-Al LDH and tartrate·Mg-Al LDH, the organic anions were inclined at 26° relative to the Mg-Al LDH layers regardless of anion concentration.     

La-doped ZnO nanoparticles: Simple solution-combusting preparation and applications in the wastewater treatment

La-doped ZnO nanoparticles have been successfully synthesized by a simple solution combustion method via employing a mixture of ethanol and ethyleneglycol (v/v = 60/40) as the solvent. Zinc acetate and oxygen gas in the atmosphere were used as zinc and oxygen sources, and La(NO₃)₃ as the doping reagent. The as-obtained product was characterized by means of powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy. Experiments showed that La-doped ZnO nanoparticles exhibited the higher capacities for the removal of Pb²⁺ and Cu²⁺ ions in water resource than undoped ZnO nanoparticles.     

Geochemistry of the upper Han River basin, China: 2: Seasonal variations in major ion compositions and contribution of precipitation chemistry to the dissolved load

A total of 252 water samples were collected from 42 sites across the upper Han River basin during the time period from 2005–2006. Major ions (Cl⁻, NO₃⁻, SO₄²⁻, HCO₃⁻, Na⁺, K⁺, Ca²⁺ and Mg²⁺), Si, water temperature, pH, EC and TDS were determined and consequently correlation matrix, analysis of variance, factor analysis and principal component analysis were performed in order to identify their seasonal variations and atmospheric inputs into river solutes. The results reveal that pH, EC, TDS, Cl⁻, SO₄²⁻, HCO₃⁻, Ca²⁺ and Mg²⁺, K⁺ and Si generally tend to show the minimum compositions in months belong to the rainy season, while the dry season for NO₃⁻ and Na⁺. NO₃⁻, Mg²⁺ and Si have the maximum concentrations in months belong to the rainy season. By comparing the major ions relating to hydrological regime, NO₃⁻, contrary to other elements, has higher concentration in the rainy season. The overall water quality is non-polluted, while there are indications of enrichment of inorganic anions including NO₃⁻ causing water entrophication in the near future. The atmospheric inputs contribute to river solutes is limited with a mean inputs of approximate 1% in the basin. The understanding of the major ion dynamics would help water quality conservation in the basin for China's interbasin water transfer project.     

Preparation and intercalation chemistry of magnesium-iron(III) layered double hydroxides containing exchangeable interlayer chloride and nitrate ions

Layered double hydroxides (LDHs) with Mg²⁺ and Fe³⁺ cations in the brucite-like layers and having chloride or nitrate ions in the interlayer region have been prepared and characterized by powder X-ray diffraction (PXRD), elemental analysis and thermal analysis. Thermal decomposition of the LDH-nitrate occurs in two steps, with loss of water followed by simultaneous dehydroxylation of the layers and loss of NO_x/O₂ arising from the nitrate anions. Thermal decomposition of the LDH-chloride involves an additional step, with chloride ions becoming grafted to the layers, prior to loss of HCl. The interlayer anions may be readily replaced by sulfate, thiosulfate, tartrate and vinylbenzenesulfonate ions suggesting that these materials may be useful precursors to Mg-Fe(III) LDHs intercalated with a variety of inorganic and organic anions.     

An aqueous sol-gel synthesis of chromium(III) doped mesoporous titanium dioxide for visible light photocatalysis

Nanoparticles of titanium dioxide doped with Cr³⁺ ions have been prepared through an aqueous sol-gel method. The mesoporous nature of both pure and Cr³⁺ doped TiO₂ powders, with specific surface area of 7.4 and 6.6 m² g⁻¹, respectively, is maintained even at calcination temperature of 800 °C. The transformation of TiO₂ from the anatase to rutile phase is suppressed up to 800 °C by Cr³⁺ ion doping. Even though surface area values are decreased, the doped materials show improved photocatalytic activity, which may be due to increased crystallinity of the anatase phase without the formation of rutile. Doped materials have a red-shift in the band gap energy and hence, photoactivity under visible light. The rate of photodegradation of methylene blue dye for both pure and doped TiO₂ under visible light has been monitored in this study. The 0.25 mol% Cr(III) doped photocatalyst, calcined at 800 °C, shows the highest photocatalytic activity under visible light with a rate constant of ∼15.8 × 10⁻³ min⁻¹, which is nearly three times higher than that of commercially available Degussa P25 titania (5.8 × 10⁻³ min⁻¹).     

New solid acids in the triple-layer Dion-Jacobson layered perovskite family

Dion-Jacobson type layered perovskites such as A′Ca₂Nb₃O₁₀ (A′ = K, Rb, H) have continued to be of great interest due to their compositional variability, rich interlayer chemistry, and wide range of physical properties. In this study, we investigated the range and effects of substitutional doping of Ta⁵⁺ for Nb⁵⁺ and of Sr²⁺ for Ca²⁺ in A′Ca₂Nb₃O₁₀. We have prepared and characterized three new solid solutions: KCa₂Nb_3−xTa_xO₁₀, RbCa₂Nb_3−xTa_xO₁₀, and RbCa_2−xSr_xNb₃O₁₀. These materials all readily undergo proton exchange to form two new series of hydrated solid acid phases, which in most cases can be dehydrated to form stable HCa₂Nb_3−xTa_xO₁₀ and HCa_2−xSr_xNb₃O₁₀ compounds. Intercalation studies with n-hexylamine and pyridine were carried out to gauge the relative Brønsted acidities across the HCa₂Nb_3−xTa_xO₁₀ series, and we determined that materials with the highest tantalum contents are weaker acids than the parent compound HCa₂Nb₃O₁₀. Preliminary intercalation studies with pyridine for the HCa_2−xSr_xNb₃O₁₀·yH₂O solid acids, however, showed no significant difference in acidity with varying strontium content.     

Preparation and chemical transformation of surfactant-templated hybrid phase containing [MoS4] anions

Exchange reaction between (NH₄)₂MoS₄ and CTABr in aqueous solution produces lamellar compound (CTA)₂MoS₄, which after a treatment with aqueous N₂H₄ under the mild conditions transforms to a lamellar mesophase containing [Mo₂O₂S₂(S₂)₂]²⁻ anions.     

Nickel titanate microtubes constructed by nearly spherical nanoparticles: Preparation, characterization and properties

In this paper, we report the successful synthesis of NiTiO₃ microtubes constructed by nearly spherical nanoparticles via a simple solution-combusting method employing a mixture of ethanol and ethyleneglycol (V/V = 60/40) as the solvent, nickel acetate as the nickel source, tetra-n-butyl titanate as the titanium source and oxygen gas in the atmosphere as the oxygen source. The as-obtained product was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray spectrometry (EDS). The UV-vis absorption spectrum of the product showed two absorption peaks centered at 258.6 and 350.1 nm, respectively. The Brunauer-Emmett-Teller (BET) surface area of the product was 14.06 m²/g and the pore size distribution mainly located from 20 to 30 nm. The photocatalytic degradation property of the product for organic dyes showed that the as-obtained porous NiTiO₃ microtubes could strongly promote the degradation of organic dyes including Pyronine B, Safranine T and Fluorescein.     

Cu magic angle spinning (MAS) nuclear magnetic resonance (NMR) study of CuX crystals (X=Cl, Br, and I) and CuX-based glasses (X=Cl, Br, and I)

⁶³Cu MAS NMR spectra of CuX crystals (X=Cl, Br, and I) and CuX-based glasses (X=Cl, Br, and I) have been measured. The CuCl and CuI crystals gave the isotropic chemical shift values around 0 ppm, and the CuBr crystal, around −55 ppm. The peak positions of the chlorocuprate(I), bromocuprate(I), and iodocuprate(I) glasses were very close to those of the CuX crystals, respectively. This result indicates that these glasses mainly consist of CuX₄ tetrahedra (X=Cl, Br, and I). The halogen coordination environments around Cu⁺ in bromochlorocuprate(I) glasses were dependent on the kind of modifying cation and the Br⁻/(Cl⁻+Br⁻) ratio. The bromochlorocuprate(I) glasses were mainly composed of CuCl_mBr_4−m or CuCl_nBr_4−n tetrahedra (m=0, 1, 2, and 4; n=0, 1, and 4).     

Diclofenac photodegradation under simulated sunlight: Effect of different forms of nitrogen and kinetics

A synthetic non-steroidal anti-inflammatory drug diclofenac is one of the most frequently detected pharmaceuticals in various water samples. One of the most important degradation processes relating to diclofenac is its photodegradation in the aquatic environment. This paper studies the kinetic model for diclofenac degradation in water and the variation of the photodegradation of diclofenac in the presence of different forms of nitrogen changes with different pE values in the aquatic environment under simulated sunlight. The results demonstrate that degradation pathways proceed via pseudo first-order kinetics in all cases and the photodegradation of diclofenac is the sum of the degradation by direct photolysis and self-sensitization. NO₃⁻ and NO₂⁻ have inhibiting effects on the photodegradation of diclofenac. The different forms of nitrogen changes with different pE values and this has a significant influence on the photodegradation of diclofenac. The results show that when NH₄⁺ and NO₂⁻ coexist in the aquatic environment, the inhibiting effect on the photodegradation diclofenac is less than the sum of the partial inhibiting effects. The results indicated that NO₂⁻ had an obvious antagonistic action for NH₄⁺. When NO₃⁻ and NO₂⁻ coexisted in the aquatic environment, a similar antagonistic action between NO₃⁻ and NO₂⁻ was observed.