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.     

MOF assisted synthesis of a Ho2O3/CNT nanocomposite photocatalyst for organic pollutants degradation

In this work, a holmium oxide (Ho₂O₃/CNT) photocatalysts were successfully synthesized through a MOF assisted route for the first time. The effects of the morphology and purity on the photocatalytic behavior of the products, were investigated by determining various physicochemical properties. The Ho₂O₃/CNT nanocomposite was systematically analyzed by powder X-ray diffraction (P-XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy studies. The Ho₂O₃ derived from a MOF assisted synthetic route using Ho(NO₃)₃·5H₂O and terephthalic acid with a 1:1 M ratio at a temperature of 750 °C for 3 h prove the most advantageous, 98% degradation of 20 mg/L aqueous tetracycline pollutant was observed within 60 min. The elevated photocatalytic activity was mainly attributable to the unique synthetic route, improved crystallinity, wide UV-light absorption rate and excellent adsorption capabilities of CNT, as well as enhanced oxygen deficiency. The photocatalytic results confirm that the Ho₂O₃/CNT nanocomposite is an efficient photocatalyst for the degradation of toxic tetracycline pollutant and is thus suitable for use in environmental remediation.     

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.     

浮石光催化剂的制备及其在印染废水处理中的应用

以天然浮石为载体,用溶胶-凝胶法制备含pb2 的TiO2光催化剂,并用制备的光催化剂处理活性艳红X-3B染料废水.研究了催化剂制备时溶胶的涂覆次数、掺杂Pb2 浓度、染液pH值、处理温度对染料废水处理效果的影响.结果表明,当涂覆4次、Pb(NO3)2浓度为2.0g/L,处理温度70℃条件下处理75min,脱色率可达89%.     

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。