An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

Enhanced properties for visible-light-driven photocatalysis of Ag nanoparticle modified Bi2MoO6 nanoplates

The visible light driven Bi₂MoO₆ photocatalyst doped with different contents of Ag nanoparticles was successfully synthesized by a combination of hydrothermal and sonochemical methods. The as-synthesized samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning and transmission electron microscopy (SEM and TEM) and UV–visible spectroscopy to investigate crystalline structure, morphology, composition and photocatalytic properties. XRD patterns and TEM images of the samples revealed pure phase orthorhombic Bi₂MoO₆ nanoplates without any detection of Ag dopant due to its low concentration and very tiny particle size. TEM images showed that Ag nanoparticles with the size of 10–15 nm were dispersed randomly on the surface of Bi₂MoO₆. The XPS analysis of Ag/Bi₂MoO₆ nanocomposites revealed the presence of additional metallic Ag. Photocatalytic activities of the Ag/Bi₂MoO₆ nanocomposites were evaluated by determining the degradation of rhodamine B (RhB) under visible light radiation. In this research, the 10 wt% Ag/Bi₂MoO₆ nanocomposites showed the best photocatalytic activity. The results suggest that the dispersion of Ag nanoparticles on the surface of Bi₂MoO₆ significantly enhances its photocatalytic activity.     

Carbon-based TiO2-x heterostructure nanocomposites for enhanced photocatalytic degradation of dye molecules

Application of brown titanium dioxide (TiO_2-x) and its modified composite forms in the photocatalytic decomposition of organic pollutants in the environment is a promising way to provide solutions for environmental redemption. Herein, we report the synthesis of effective and stable TiO_2-x nanoparticles with g-C₃N₄, RGO, and multiwalled carbon nanotubes (CNTs) using a simple hydrothermal method. Among all the as-synthesized samples, excellent photocatalytic degradation activity was observed for RGO-TiO_2-x nanocomposite with high rate constants of 0.075 min^?1_, 0.083 min^?1 and 0.093 min^?1 for methylene blue, rhodamine-B, and rosebengal dyes under UV–Visible light irradiation, respectively. The altered bandgap (1.8 eV) and the large surface area of RGO-TiO_2-x nanocomposite impacts on both absorption of visible light and efficiency of photogenerated charge electron (e^?)/hole (h⁺) pair separation. This resulted in enhanced photocatalytic property of carbon-based TiO_2-x nanocomposites. A systematic study on the influence of different carbon nanostructures on the photocatalytic activity of brown TiO_2-x is carried out.     

Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

PHOTOCATALYTIC OXIDATION OF ALDEHYDES/PCE USING POROUS ANATASE TITANIA AND VISIBLE-LIGHT-RESPONSIVE BROOKITE TITANIA

We have synthesized an annealed porous aerogel titania (LUAG2), which demonstrates a very high photocatalytic activity for aldehydes and perchloroethylene (PCE) photocatalytic oxidation (PCO) in gas phase under blacklight and fluorescent light irradiation. LUAG2 has a BET surface area of 237 m²/g and a porosity of 0.31 (volume fraction). X-ray diffraction (XRD) analysis shows LUAG2 is nearly pure anatase. It has improved the destruction of PCE and aldehydes as a group by 10-34% with black light compared to Degussa P-25. The optimum water vapor to butyraldehyde molar ratio is around 1/3. LUAG2 also shows better mineralization to CO₂ than Degussa P-25 TiO₂ does. Under irradiation of a 4 W fluorescent lamp LUAG2 gives a consistently higher conversion than that of Degussa P-25. The highly active photocatalyst indicates potential applications in indoor and outdoor environmental pollution control. A visible-light-responsive TiO₂, NTB 200, is also investigated for comparison purposes.     

Effect of applying voltage on photocatalytic destruction of 1,4-dioxane in aqueous system

In the current work, we prepared a TiO₂ coating on stainless mesh using electrophoretic deposition (EPD), and applied voltage to a stainless mesh to examine the synergy effect on photocatalysis of both 1,4-dioxane and ethylene glycol diformate (EGDF), a main intermediate of the photocatalysis of 1,4-dioxane. The photocatalytic decomposition rate of 1,4-dioxane depends on applying voltage under diffusion-limited reaction conditions. Ethylene glycol diformate and 1,4-dioxane exhibited inverse voltage dependence. Voltage swing provides high-efficiency photocatalysis of 1,4-dioxane while suppressing EGDF formation. This method will be effective for a photocatalysis system containing several chemicals, each with different voltage dependence.     

Hydrothermal synthesis, characterization, and photocatalytic performances of Cr incorporated, and Cr and Ti co-incorporated MCM-41 as visible light photocatalysts for water splitting

A series of Cr incorporated, and Cr and Ti co-incorporated MCM-41 photocatalysts were synthesized by hydrothermal method. X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence analysis (XRF), N₂ adsorption–desorption isotherms and Raman spectra were used to investigate the effects of the incorporated elements on the structure of MCM-41. The experimental results for photocatalytic water splitting under visible light irradiation (λ > 430 nm) demonstrated that the photocatalytic activities of Cr-MCM-41 and Cr-Ti-MCM-41 catalysts for hydrogen production decreased with an increase in the amount of Cr incorporated. Compared with the Cr-MCM-41 which had the same amount of incorporated Cr, the Cr-Ti-MCM-41 exhibited much higher hydrogen evolution activities.     

光催化剂在瓷砖表面的低温固定技术及高效降解甲醛大理石瓷砖的研制

笔者研制了一种高效广谱光催化剂,并研究了在低温条件下,使光催化剂粒子能够牢固地附着在瓷砖的表面,实现了瓷砖降解甲醛功能的持久性。     

Removal of paraquat in aqueous suspension of TiO<Subscript>2</Subscript> in an immersed UV photoreactor

Experiments were performed to investigate the effect of operating parameters on the photodegradation efficiency of paraquat in a TiO₂-suspended photoreactor with immersed UV lamps. TiO₂ particles were prepared by a hydrothermal method. The removal rate of paraquat in the reactor was 0.54 mg/l/h with only air-sparging. The removal rate in 24 h with both the UV radiation and air-sparging was 50% higher than that with only the UV radiation. Variations of the paraquat concentration at the UV intensities of 4 and 8 W/m₂ decreased slowly with time, but that at 12 W/m₂ decreased more rapidly. The removal efficiency at the air-sparging flow rate of 1 //min increased as a UV light intensity increased. pH value in the reactor at the UV intensity of 12 W/m₂ decreased with time until 12 h and then increased with time over 12 h.     

Photocatalytic effect of carbon-modified n-TiO2 nanoparticles under visible light illumination

The present research focused on wet process synthesis of visible light active carbon-modified (CM)-n-TiO₂ nanoparticles and their photocatalytic activity. The CM-n-TiO₂ was synthesized by hydrolysis of TiCl₄ in the presence of tetrabutylammonium hydroxide and also in the presence of glucose and sodium hydroxide. UV–vis spectra, X-ray diffraction (XRD), and FT-IR were used to characterize these photocatalysts. It was found that the CM-n-TiO₂ nanoparticles synthesized by hydrolysis with tetrabutylammonium hydroxide or with sodium hydroxide and glucose when subjected to extended aging and subsequent calcinations absorb well into the visible to near infrared region up to 800 nm and exhibit enhanced visible light photocatalytic activity on degradation of 4-chlorophenol. CM-n-TiO₂ synthesized using glucose as the carbon source generated 13-fold increase in the initial rate of photodegradation of 4-chlorophenol compared to those by regular n-TiO₂, whereas, it increased only eight-fold when tetrabutylammonium hydroxide was used as the carbon source.