Sustainable wood-based nanotechnologies for photocatalytic degradation of organic contaminants in aquatic environment

•Wood and its reassemblies are ideal substrates to develop novel photocatalysts. •Synthetic methods and mechanisms of wood-derived photocatalysts are summarized. •Advances in wood-derived photocatalysts for organic pollutant removal are summed up. •Metal doping, morphology control and semiconductor coupling methods are highlighted. •Structure-activity relationship and catalytic mechanism of photocatalysts are given. Wood-based nanotechnologies have received much attention in the area of photocatalytic degradation of organic contaminants in aquatic environment in recent years, because of the high abundance and renewability of wood as well as the high reaction activity and unique structural features of these materials. Herein, we present a comprehensive review of the current research activities centering on the development of wood-based nanocatalysts for photodegradation of organic pollutants. This review begins with a brief introduction of the development of photocatalysts and hierarchical structure of wood. The review then focuses on strategies of designing novel photocatalysts based on wood or its recombinants (such as 1D fiber, 2D films and 3D porous gels) using advanced nanotechnology including sol-gel method, hydrothermal method, magnetron sputtering method, dipping method and so on. Next, we highlight typical approaches that improve the photocatalytic property, including metal element doping, morphology control and semiconductor coupling. Also, the structure-activity relationship of photocatalysts is emphasized. Finally, a brief summary and prospect of wood-derived photocatalysts is provided.     

油酸铵改性的高活性TiO2/V-TiO2复合光催化剂的制备及光催化降解甲基橙的研究

采用溶胶-凝胶法,将经过油酸铵改性的掺钒二氧化钛粉末投入到纯TiO2溶胶中,烘干、煅烧,制得带有n-n异质结半导体结构的复合型高活性掺钒二氧化钛光催化剂,并通过XRD、TEM、XPS等技术对样品进行了表征。通过对甲基橙溶液的光催化降解实验来考察TiO2/V-TiO2催化剂的光催化活性。结果表明：TiO2/V-TiO2复合催化剂拥有比纯TiO2更高的光催化活性。其中,V的掺杂摩尔分数为0.5%、TiO2：V-TiO2的质量比为10∶1的最佳复合催化剂,其光催化活性是纯TiO2的5.1倍。     

Preparation and characterization of ZnO/ZnS hybrid photocatalysts via microwave-hydrothermal method

The photocatalytic performance of ZnO/ZnS hybrid nanocomposite was largely higher than that of the mere ZnO or ZnS nanoparticles, but the complicated procedure and misdistribution of final products limited its large-scale productions. The exploration of a novel synthesis route of ZnO/ZnS hybrid photocatalysts with high catalytic performance is becoming a crucial step for the large-scale application of ZnO/ZnS hybrid photocatalytic technique. Preparation and characterization of nanosized ZnO/ZnS hybrid photocatalysts were studied in this paper. The photocatalysts were obtained via microwave-hydrothermal crystallization with the help of sodium citrate. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), particle size distribution (PSD), and Fourier transformed infrared spectroscopy (FT-IR). The results indicated that so-synthesized ZnO/ZnS samples consisted of the high pure cubic (sphalerite) ZnS and hexagonal ZnO nanocrystallines with a narrow particle size distribution. The possible formation mechanisms of ZnO/ZnS nanocrystallines were mainly attributed to the superficially protective effect of citrate. The photocatalytic experiments demonstrated that the ZnO/ZnS photocatalysts exhibited a higher catalytic activity for the degradation of acid fuchsine than other monocomponents.     

大气污染控制中高梯度磁分离技术的研究与应用

本文概述了高梯度磁分离技术在燃煤脱硫除灰、烟气除尘方面的应用与研究进展以及超导磁分离技术在燃煤脱硫方面的研究，并展望了超导磁分离技术在环境保护中的应用前景。     

Recent advances in special morphologic photocatalysts for NOx removal

● Systematic information of recent progress in photocatalytic NO _x removal is provided. ● The photocatalysts with special morphologies are reviewed and discussed. ● The morphology and photocatalytic NO _x removal performance is related. The significant increase of NO_x concentration causes severe damages to environment and human health. Light-driven photocatalytic technique affords an ideal solution for the removal of NO_x at ambient conditions. To enhance the performance of NO_x removal, 1D, 2D and 3D photocatalysts have been constructed as the light absorption and the separation of charge carriers can be manipulated through controlling the morphology of the photocatalyst. Related works mainly focused on the construction and modification of special morphologic photocatalyst, including element doping, heterostructure constructing, crystal facet exposing, defect sites introducing and so on. Moreover, the excellent performance of the photocatalytic NO_x removal creates great awareness of the application, which has promising practical applications in NO_x removal by paint (removing NO_x indoor and outdoor) and pavement (degrading vehicle exhausts). For these considerations, recent advances in special morphologic photocatalysts for NO_x removal was summarized and commented in this review. The purpose is to provide insights into understanding the relationship between morphology and photocatalytic performance, meanwhile, to promote the application of photocatalytic technology in NO_x degradation.     

磁性介孔硅胶萃取剂的制备及萃取性能研究

合成了C18基团修饰的磁性介孔硅胶材料,并利用该材料建立了磁性固相萃取-色谱分析方法,测定了几种环境水样中酞酸酯类(PAEs)污染物的含量.结果表明,该材料具有较大的比表面积(273 m.2g-1)和饱和磁通量(29 emu.g-1),对水样中痕量的PAEs有较强的萃取能力,而且萃取剂的磁分离特性使得萃取操作更为方便、快捷.在优化条件下,30 mg萃取剂在40 min内即可从500 mL水样中萃取痕量PAEs,回收率可达80%以上.此外,该萃取剂在处理复杂环境样品时仍能保持较强的萃取能力,环境水样中4种PAEs的检测限可达15.6—32.5 ng.L-1,加标回收率为62%—109%,相对标准偏差为2%—8%.     

TiO2/粉煤灰的制备及光催化性能研究

以钛酸丁酯为原料,以粉煤灰微珠为载体,采用溶胶-凝胶法制备了TiO2/粉煤灰光催化剂.负载于粉煤灰表面的TiO2平均粒径约为7nm,晶型为锐钛矿型,该催化剂在太阳光下降解初始浓度为10mg·l-1的甲基橙,经6h,甲基橙的降解率可达98.9%,将其应用于实际样品的测定,经3h降解率可达96.1%,显示出优越的光催化降解性能.     

Low-temperature preparation of a N-TiO2/macroporous resin photocatalyst to degrade organic pollutants

Environmental Chemistry Letters - Highly active TiO2 photocatalysts prepared at a low temperature are promising reagents to degrade organic pollutants.  Moreover, the addition of...     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

佛山农业表层土壤磁化率特征及其与重金属含量的关系

环境磁学方法针对城市、矿区、工业区等特定区域土壤的研究现已比较普遍,但在农业土壤重金属研究中的应用还比较少。本文对采自佛山市的532件农业表层土壤样品进行低频（976 Hz）和高频（15616 Hz）磁化率测试,在分析其空间分布特征的基础上选取175件（其中,旱地土样149件,水田土样26件）代表性样品进行重金属（Cd、Pb、Cr、Cu、Ni、Zn、Hg、As）含量的分析测试。在分析不同土壤样品磁化率与重金属含量之间相关关系的基础上,从旱地和水田土壤中分别挑选出6种与低频磁化率高度相关的重金属元素（旱地Ni、Cu、Cr、Zn、Cd、Pb,相关系数分别为0.599、0.492、0.279、0.510、0.445、0.225;水田Ni、Cu、Cr、Zn、Cd、Hg,相关系数分别为0.728、0.699、0.606、0.602、0.764、0.450）进行回归分析,列出回归方程,并得到一些初步认识。主要有（1）低频磁化率与频率磁化率在空间分布上总体呈现相反趋势;（2）重金属含量与低频磁化率总体呈正相关,但正相关的元素种类在旱地和水田土壤中有所差异;（3）所研究的旱地土壤重金属含量与频率磁化率呈负相关关系,但这种相关关系在水田土壤中没有明显表现;（4）Pb 元素在旱地土壤中与低频磁化率表现出显著正相关（P〈0.01）,在水田土壤中却与低频磁化率和频率磁化率表现出一定的负相关性。（5）通过测定农业土壤的磁化率即可初步推算出相应的重金属含量,为磁学方法在农业表层土壤重金属快速监测领域的进一步应用提供了数据支持和科学依据。     

Occurrence of bisphenol A in surface and drinking waters and its physicochemical removal technologies

Bisphenol A (BPA), an endocrine disrupting compound, has caused wide public concerns due to its wide occurrence in environment and harmful effects. BPA has been detected in many surface waters and drinking water with the maximum concentrations up to tens of μg·L^-1. The physicochemical technology options in eliminating BPA can be divided into four categories: oxidation, advanced oxidation, adsorption and membrane filtration. Each removal option has its own limitation and merits in removing BPA. Oxidation and advanced oxidation generally can remove BPA efficiently while they also have some drawbacks, such as high cost, the generation of a variety of transformation products that are even more toxic than the parent compound and difficult to be mineralized. Only few advanced oxidation methods have been reported to be able to mineralize BPA completely. Therefore, it is important not only to identify the major initial transformation products but also to assess their estrogenic activity relative to the parent compounds when oxidation methods are employed to remove BPA. Without formation of harmful by-products, physical separation methods such as activated carbon adsorption and membrane processes are able to remove BPA in water effluents and thus have potential as BPA removal technologies. However, the necessary regeneration of activated carbon and the low BPA removal efficiency when the membrane became saturated may limit the application of activated carbon adsorption and membrane processes for BPA removal. Hybrid processes, e.g. combining adsorption and biologic process or combining membrane and oxidation process, which can achieve simultaneous physical separation and degradation of BPA, will be highly preferred in future.     

Nanostructured semiconducting materials for efficient hydrogen generation

Massive production of hydrogen by water decomposition triggered by a solar light active photocatalyst is a major objective in chemistry and a promising avenue to overcome the global energy crisis. The development of efficient, stable, economically viable and eco-friendly photocatalysts for hydrogen production is a challenging task. This article reviews the use of nanocomposite in three combinations: metal oxide–metal oxide semiconductor, metal–metal oxide semiconductor and metal chalcogenide–metal oxide core–shell nanostructures. These core–shell structures occur in two forms: a simple form where the photocatalyst is either in the core or the shell or in a more complex system where the core–shell structure comprises a co-catalyst deposited on a semiconducting material. We discuss the design, synthesis and development of semiconductor-based nanocomposite photocatalysts for hydrogen production. The major points are the role of catalytic active sites, the chemical nature of sacrificial agents, the effect of light sources, the variable light intensity and the energy efficiency calculation. For TiO₂-based nanocomposites, the metal oxide or metal co-catalyst loading of 1.0–3.0 wt% was optimal. TiO₂ nanotube–CuO hybrid nanocomposites produce 1,14,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\), whereas TiO₂/Au nanocomposites display 1,60,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\). For core–shell catalysts, a shell thickness of 2–20 nm was found for the best activity, and its performance is as follows: (a) CdS–NiO system produces around 19,949 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\) and (b) CuO–Cr₂O₃ as co-catalyst immobilized on TiO₂ system produces around 82,390 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\).     

Visible light-assisted photocatalytic oxidation of organic pollutants using nitrogen-doped titania

An experimental research into the aqueous photocatalytic oxidation (PCO) of organic groundwater pollutants, methyl-tert-butyl ether (MTBE), tert-butyl alcohol, phenol, humic substances, 2-ethoxy ethanol and ethylene glycol was undertaken using visible light-sensitive nitrogen-doped titanium dioxide photocatalysts. Nitrogen-doped titania proved to be an effective photocatalyst for MTBE with its action comparable to and even surpassing that of Degussa P25. In contrast, with the other substances the photocatalysts showed negligible activity. This difference was explained by the poor adsorption properties of N-doped catalysts. The predominance of different PCO mechanisms dependent of the surface properties of N-TiO₂ catalysts was elucidated.     

Nonpolar cross-stacked super-aligned carbon nanotube membrane for efficient wastewater treatment

● A novel nonpolar super-aligned carbon nanotube (SACNT) membrane was prepared. ● SACNT membranes achieved smoother and more uniform structures. ● SACNT membranes have inert chemistry and unique nonpolar wetting feature. ● SACNT membranes exhibit superior separation and antifouling capabilities. ● SACNT membranes achieved superior oil/water separation efficiency. Membrane separation technology has made great progress in various practical applications, but the unsatisfactory separation performance of prevailing membrane materials hampers its further sustainable growth. This study proposed a novel nonpolar super-aligned carbon nanotube (SACNT) membrane, which was prepared with a layer-by-layer cross-stacking method. Through controlling the number of stacked SACNT layers, three kinds of SACNT membranes (SACNT_200, SACNT_300, and SACNT_400) were prepared. Systematic characterizations and filtration tests were performed to investigate their physico-chemical properties, surface wetting behavior, and filtration performance. Compared with two commercial membranes (Com_0.22 and Com_0.45), all the SACNT membranes achieved smoother and more uniform structures. Due to the hexagonal graphene structure of CNTs, the surface chemistry of the SACNT membranes is simple and inert, thereby potentially eliminating the covalent-bonding-induced membrane fouling. Besides, the SACNT membranes exhibited a typical nonpolar wetting behavior, with high contact angles for polar liquids (water: ~124.9°–126.5°; formamide: ~80.0°–83.9°) but low contact angles for nonpolar diiodomethane (~18.8°–20.9°). This unique nonpolar feature potentially leads to weak interactions with polar substances. Furthermore, compared with the commercial membranes, the SACNT membranes obtained a significantly higher selectivity while achieving a comparable or higher permeability (depending on the number of stacked layers). Moreover, the SACNT membranes exhibited superior separation performance in various application scenarios, including municipal wastewater treatment (> 2.3 times higher cleaning efficiency), electro-assistant fouling inhibition (or even self-cleaning), and oil/water separation (> 99.2 % of separation efficiency), suggesting promising application prospects in various fields.     

Application of proteomics in environmental science

Proteomics involves the separation of proteins, identification of the amino acid sequence of the interested or target proteins, study of the function of the proteins, modification, structure and ultimate assignments to functional pathways in the cell. The proteomic investigations have contributed greatly to human diseases studies, new drugs discovery researches, and environmental science in recent years. This article provides a review on the development of the main proteomic technologies, including both the gel based and non-gel based technologies, and their applications in environmental science. Proteomic technologies have been utilized in the environmental stresses studies to analyze the induction or reduction of proteins at expression level and identify the target proteins to investigate their function in response to environmental stresses, such as high or low pH, oxidation stress, and toxic chemicals. Such protein responses are also helpful to understand the mechanisms of some cellular activities and the functions of some proteins.     

静态光催化去除甲醛及其分解产物的研究

以静态光催化去除甲醛,研究光催化过程中温度、相对湿度、一氧化碳和二氧化碳浓度的变化情况．结果表明,光催化降解相对于光催化剂吸附去除来说可以更有效地去除空气中的甲醛,但是温度、相对湿度、一氧化碳和二氧化化碳浓度都会随之升高,尤其是产物中存在一氧化碳,使得光催化的副产物造成更严重的二次污染并降低催化的活性．     

Photocatalytic degradation of the acetaminophen by nanocrystal-engineered TiO2 thin film in batch and continuous system

• Photocatalytic activity was improved in TiO₂ thin film by rapid thermal annealing. • Photoreactor was designed for TiO₂ thin film. • Considerable reusability and durability of prepared photocatalysts were studied. Un-biodegradable pharmaceuticals are one of the major growing threats in the wastewaters. In the current study, TiO₂ thin film photocatalysts were designed by nanocrystal engineering and fabricated for degradation of the acetaminophen (ACE) in a photocatalytic reaction under UV light irradiation in batch and continuous systems. The photocatalyst was prepared by sputtering and then engineered by thermal treatment (annealing at 300℃ (T300) and 650℃ (T650)). The annealing effects on the crystallinity and photocatalytic activity of the TiO₂ film were completely studied; it was found that annealing at higher temperatures increases the surface roughness and grain size which are favorable for photocatalytic activity due to the reduction in the recombination rate of photo-generated electron-hole pairs. For the continuous system, a flat plate reactor (FPR) was designed and manufactured. The photocatalytic performance was decreased with the increase of flow rate because the higher flow rate caused to form the thicker film of the liquid in the reactor and reduced the UV light received by photocatalyst. The reusability and durability of the samples after 6 h of photocatalytic reaction showed promising performance for the T650 sample (annealed samples in higher temperatures).     

The interethnic differences of the human serum paraoxonase polymorphism analysed by a quantitative and a qualitative method †

The polymorphism of the human serum paraoxonase¹ was analyzed by two distinguished methods in six different ethnic groups (Caucasians, Mongoloids, Negroids), using (1) the Computer Method² and (2) the Carro‐Ciampi Method³‘⁴. Analysis of the response of the enzyme activities to salts resulting in low and high activity ratios.

Comparison of the results:

In Caucasians we distinguished three phenotypes by the Computer method. The polymorphism was governed by two alleles. The Hardy‐Weinberg rule for a two‐allele model was valid. Individuals belonging to the homozygotic group with low activity had a low activity ratio (Carro‐Ciampi method). With both methods a frequency between 57% and 61% was observed for this group. Individuals with medium and high activity had a high activity ratio.

In Negroids and Mongoloids samples we found (by the Computer method) a low activity group (Ghanaians 9.6%, Jamaicans 13.6%, Indonesians 6.7%, Koreans 19.6%). The Hardy‐Weinberg rule for a two‐ or three‐allele model was not valid. Individuals belonging to the low activity group had a low activity ratio, all individuals with higher activity a high activity ratio (Carro‐Ciampi method).

Our results suggest that the members of the low activity group in the three races are homozygote for an identical allele.     

Enhancement on the ammonia oxidation capacity of ammonia-oxidizing archaeon originated from wastewater: Utilizing low-density static magnetic field

• AOA’s ammonia oxidizing capacity was enhanced under moderate magnetic field. • AOA possessed a certain magnetotaxis under uneven magnetic field. • Enhanced ammonia oxidizing capacity was lost once magnetic field was removed. Ammonia-oxidizing archaeon (AOA) could play important roles for nitrogen removal in the bioreactors under conditions such as low pH and low dissolved oxygen. Therefore, enhancing ammonia oxidation capability of AOA has great significance for water and wastewater treatment, especially under conditions like low dissolved oxygen concentration. Utilizing a novel AOA strain SAT1, which was enriched from a wastewater treatment plant by our group, the effect of magnetic field on AOA’s ammonia oxidation capability, its magnetotaxis and heredity were investigated in this study. Compared with control experiment, AOA’s maximum nitrite-N formation rate during the cultivation increased by 56.8% (0.65 mgN/(L·d)) with 20 mT magnetic field. Also, it was testified that AOA possessed a certain magnetotaxis. However, results manifested that the enhancement of AOA’s ammonia oxidation capability was not heritable, that is, lost once the magnetic field was removed. Additionally, the possible mechanism of improving AOA’s ammonia oxidation capability by magnetic field was owing to the promotion of AOA single cells’ growth and fission, rather than the enhancement of their ammonia oxidation rates. The results shed light on the application of AOA and methods to enhance AOA’s ammonia oxidation capability, especially in wastewater treatment processes under certain conditions.     

(Super)paramagnetic nanoparticles as platform materials for environmental applications: From synthesis to demonstration

• The fabrication of monodisperse, (super)paramagnetic nanoparticles is summarized. • Monolayer and bilayer surface coating structures are described. • Mono/bilayer coated nanoparticles showed high sorption capacities for U, As, and Cr. Over the past few decades, engineered, (super)paramagnetic nanoparticles have drawn extensive research attention for a broad range of applications based on their tunable size and shape, surface chemistries, and magnetic properties. This review summaries our recent work on the synthesis, surface modification, and environmental application of (super)paramagnetic nanoparticles. By utilizing high-temperature thermo-decomposition methods, first, we have broadly demonstrated the synthesis of highly monodispersed, (super)paramagnetic nanoparticles, via the pyrolysis of metal carboxylate salts in an organic phase. Highly uniform magnetic nanoparticles with various size, composition, and shape can be precisely tuned by controlled reaction parameters, such as the initial precursors, heating rate, final reaction temperature, reaction time, and the additives. These materials can be further rendered water stable via functionalization with surface mono/bi-layer coating structure using a series of tunable ionic/non-ionic surfactants. Finally, we have demonstrated platform potential of these materials for heavy metal ions sensing, sorption, and separation from the aqueous phase.