TiO2光催化空气净化及抗菌材料的研究与应用

介绍了TiO2光催化氧化原理和抗菌杀菌原理，对其在空气净化和抗菌材料方面的应用进行了评述。     

Synthesis of LaVO4/TiO2 heterojunction nanotubes by sol-gel coupled with hydrothermal method for photocatalytic air purification

With the aim of improving the effective utilization of visible light, the LaVO(4)/TiO(2) heterojunction nanotubes were fabricated by sol-gel coupled with hydrothermal method. The photocatalytic ability was demonstrated through catalytic removal of gaseous toluene species. The nanotube samples were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), surface photovoltage (SPV), Raman spectra and N(2) adsorption-desorption measurements. The characterization results showed that the samples with high specific surface areas were of typical nanotubular morphology, which would lead to the high separation and transfer efficiency of photo induced electron-hole pairs. The as-prepared nanotubes exhibited high photocatalytic activity in decomposing toluene species under visible light irradiation with fine photochemical stability. The enhanced photocatalytic performance of LaVO(4)/TiO(2) nanotubes might be attributed to the matching band potentials, the interconnected heterojunction of LaVO(4) versus TiO(2), and the large specific surface areas of nanotubes.     

Nanocatalysts for Suzuki cross-coupling reactions

This critical review deals with the applications of nanocatalysts in Suzuki coupling reactions, a field that has attracted immense interest in the chemical, materials and industrial communities. We intend to present a broad overview of nanocatalysts for Suzuki coupling reactions with an emphasis on their performance, stability and reusability. We begin the review with a discussion on the importance of Suzuki cross-coupling reactions, and we then discuss fundamental aspects of nanocatalysis, such as the effects of catalyst size and shape. Next, we turn to the core focus of this review: the synthesis, advantages and disadvantages of nanocatalysts for Suzuki coupling reactions. We begin with various nanocatalysts that are based on conventional supports, such as high surface silica, carbon nanotubes, polymers, metal oxides and double hydroxides. Thereafter, we reviewed nanocatalysts based on non-conventional supports, such as dendrimers, cyclodextrin and magnetic nanomaterials. Finally, we discuss nanocatalyst systems that are based on non-conventional media, i.e., fluorous media and ionic liquids, for use in Suzuki reactions. At the end of this review, we summarise the significance of nanocatalysts, their impacts on conventional catalysis and perspectives for further developments of Suzuki cross-coupling reactions (131 references).     

Nanocatalysts for biodiesel production

Biofuels are a class of clean fuels and promising for energy demand. Biodiesel is relatively costly, which limits the commercialization of the product. The waste edible oil and animal fats are raw materials for biodiesel production. This paper focuses on the catalytic production of biofuels and reviews the application of different catalysts to produce biodiesel from waste oils by using esterification and transesterification reactions. The reaction in the presence of nanocatalysts is carried out under mild operating conditions. Nowadays, magnetic nanocatalysts are preferred to bulk catalysts due to the absence of mass transfer resistance and fast deactivation as well as high recovery rate during the separation. Functionalized magnetic nanocatalysts are more attractive for biodiesel production. Further studies should do to develop highly active and selective nanocatalysts for industrial scale.     

高熵纳米合金在电化学催化中的应用

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO₂ reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.     

“Hybrid” photocatalytic systems for production of molecular hydrogen

It has been shown on the example of semiconductor (CdS, TiO₂) and metal complex (solvate complexes (V(III), Eu(III), Zr(IV)) photocatalysts that they can form a single photocatalytic system that is characterized by higher efficiency in the direction of the formation of hydrogen from alcohol-water solutions than the individual substances. Successful functioning of such a hybrid photocatalytic system is possible if the principle of energy correspondence is satisfied: the potential of the conduction zone of the semiconductor must be more negative than the redox potential of the Meⁿ⁺/Me^(n–1)+ pair. In this case a photogenerated electron of the conduction zone is accepted by a metal ion Meⁿ⁺ and, thus, the electron-hole recombination process is suppressed. The resulting reduced form of the metal Me^(n–1)+ in the presence of metallic palladium decomposes the protonated molecules of water with the formation of H₂.Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 25, No. 4, pp. 452–459, July–August, 1989.     

Adsorption and photocatalytic decomposition of amino acids in TiO2 photocatalytic systems

The adsorption and photodecomposition of seven kinds of amino acids on a TiO2 surface were investigated by zeta potential measurements and 1H NMR spectroscopy in TiO2 aqueous suspension systems. The decomposition rates increased in the order of Phe < Ala < Asp < Trp < Asn < His < Ser. For Phe, Trp, Asn, His, and Ser, the isoelectric point (IEP) of TiO2 shifted to a lower pH with increasing decomposition rates upon adsorption on TiO2, suggesting that the effective adsorption and photocatalytic sites for these amino acids should be the basic terminal OH on the solid surface. Since the amino acids that decomposed faster than the others contain -OH (Ser), -NH (Trp, His), or -NH2 (Asn) in their side chain, they are considered to interact with the basic terminal OH groups more preferably by the side chain and are vulnerable to photocatalytic oxidation. On the other hand, Ala interacts with the acidic bridged OH on TiO2 to cause an IEP shift to a higher pH. The correlation of the surface hydroxyl groups with the photocatalysis of amino acids was verified by the use of calcined TiO2 without surface hydroxyl groups.     

Hollow Heterostructured Nanocatalysts for Boosting Electrocatalytic Water Splitting

The implementation of electrochemical water splitting demands the development and application of electrocatalysts to overcome sluggish reaction kinetics of hydrogen/oxygen evolution reaction (HER/OER). Hollow nanostructures, particularly for hollow heterostructured nanomaterials can provide multiple solutions to accelerate the HER/OER kinetics owing to their advantageous merit. Herein, the recent advances of hollow heterostructured nanocatalysts and their excellent performance for water splitting are systematically summarized. Starting by illustrating the intrinsically advantageous features of hollow heterostructures, achievements in engineering hollow heterostructured electrocatalysts are also highlighted with the focus on structural design, interfacial engineering, composition regulation, and catalytic evaluation. Finally, some perspective insights and future challenges of hollow heterostructured nanocatalysts for electrocatalytic water splitting are also discussed.     

Carbon dots and carbon nitride composite for photocatalytic removal of uranium under air atmosphere

Photocatalytic removal of uranium has attracted much attention in nuclear wastewater treatment and it is highly needed to develop functional photocatalyst with excellent removal performance. In this work, seven kinds of carbon dots/carbon nitride (CDs/CN) composites were synthesized and SerCDs/CN with the best photo-assisted uranium removal performance was screened out. It was found that the introduction of CDs could bring in higher photocurrent density, lower interfacial charge transfer impedance and narrower band gap, resulting in a much-improved removal performance. SerCDs/CN had shown a removal capacity as high as 1690 mg/g and the reaction could be operated under air atmosphere which is promising in real application.     

Efficient Co@Co3O4 core-shell catalysts for photocatalytic water oxidation and its behaviors in two different photocatalytic systems

The photocatalytic performances of water oxidation were usually carried out in two different systems,photosensitizer and non-photosensitizer systems.There is fe...     

Energetics of electron processes in semiconductor photocatalytic systems

The energetics of electron processes in photocatalytic systems based on dispersed semiconductors, their nanocomposites and heterostructures are examined. Methods for the approximate estimation and quantitative determination of their energetic characteristics are evaluated and energy diagrams of photocatalytic systems based on semiconductor nanocomposites and their heterostructures are plotted. Analysis of the diagrams permits the elucidation of the nature of their photocatalytic effects in redox reactions. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 03039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 2, pp. 69–89, March–April, 2000.     

Selective fabrication of porous iron oxides hollow spheres and nanofibers by electrospinning for photocatalytic water purification

Porous hematite (α-Fe₂O₃) hollow spheres and nanofibers could be obtained via electrospinning and subsequent thermal decomposition in air. The precursor could be fabricated by electrospinning using Fe(NO₃)₃ as the iron source and Polyvinylpyrrolidone (PVP) as a complexing reagent. Upon calcination, pure porous α-Fe₂O₃ hollow spheres and nanofibers could be obtained at 650 °C for 3 h. The novel hollow spheres have an abundantly porous structure as well as large surface areas. Benefitting from the special porous structure, narrow bandgap, and higher surface area, porous α-Fe₂O₃ hollow materials are used as visible-light-responsive photocatalysts. So we have investigated the visible light photodegradation behavior of porous hematite (α-Fe₂O₃) hollow spheres and nanofibers towards organic dyes, as Rhodamine B (RhB). The synergetic effects of higher surface area, pore structures promoted the photocatalytic efficiency for RhB degradation under visible light and contributed to achieving the enhanced and stable photocatalytic activity.     

聚苯并噁嗪固载钯基纳米催化剂在芳香醇氧化反应中的应用

以球状聚苯并噁嗪为载体,采用浸渍热解法合成了钯炭纳米催化剂.通过透射电子显微镜观察发现,钯纳米粒子几乎全部均匀分布在载体上,且尺寸均一,平均直径约为3. 5 nm.结果表明,载体表面含有丰富的含氮含氧官能团,氮和氧原子与钯之间存在相互作用,从而使聚苯并噁嗪能够有效固载钯纳米粒子.采用相同的方法进一步合成Pd-Au/C和Pd-Pt/C双金属催化剂,Pd-Au和Pd-Pt纳米粒子也展现出良好的分散性,无明显团聚现象,平均直径分别为4. 3和4. 2 nm,进一步说明聚苯并噁嗪对金属活性组分的有效固载.将催化剂应用于苯甲醇氧化反应,其中Pd₁-Au₁/C在2 h的转化率为98%,对产物苯甲醛的选择性大于99%,该催化剂经过焙烧可恢复催化活性,表现出良好的循环稳定性,并能将不同取代基的芳香醇氧化为相应的醛,是一种良好的醇氧化催化剂.     

Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media

This review focuses on the heterogeneous photocatalytic treatment of organic dyes in air and water. Representative studies spanning approximately three decades are included in this review. These studies have mostly used titanium dioxide (TiO₂) as the inorganic semiconductor photocatalyst of choice for decolorizing and decomposing the organic dye to mineralized products. Other semiconductors such as ZnO, CdS, WO₃, and Fe₂O₃ have also been used, albeit to a much smaller extent. The topics covered include historical aspects, dark adsorption of the dye on the semiconductor surface and its role in the subsequent photoreaction, semiconductor preparation details, photoreactor configurations, photooxidation kinetics/mechanisms and comparison with other Advanced Oxidation Processes (e.g., UV/H₂O₂, ozonation, UV/O₃, Fenton and photo-Fenton reactions), visible light-induced dye decomposition by sensitization mechanism, reaction intermediates and toxicity issues, and real-world process scenarios.     

Regularities of decomposition of organic vapors using a photocatalytic air cleaner

The kinetics of oxidation of vapors of model air contaminators, viz., acetone, ethanol, and heptane, was studied using a photocatalytic air cleaner. The composition of the oxidation products was determined, and the rates of oxidation of the starting substances were measured. The deep oxidation of the starting substrates to CO₂ and H₂O occurs until their concentration achieves a limiting value. At higher concentrations a “breakthrough” of the starting substrate is observed. Ethanol is oxidized with the formation of intermediate products. The experimental data obtained were approximated by a kinetic model, which includes stages of formation of intermediates and their competitive adsorption. The results of the approximation agree well with the experimental data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1812–1818, August, 2005.     

Dual affinity method for plasmid DNA purification in aqueous two-phase systems

The DNA binding fusion protein, LacI–His₆–GFP, together with the conjugate PEG–IDA–Cu(II) (10 kDa) was evaluated as a dual affinity system for the pUC19 plasmid extraction from an alkaline bacterial cell lysate in poly(ethylene glycol) (PEG)/dextran (DEX) aqueous two-phase systems (ATPS). In a PEG 600–DEX 40 ATPS containing 0.273 nmol of LacI fusion protein and 0.14% (w/w) of the functionalised PEG–IDA–Cu(II), more than 72% of the plasmid DNA partitioned to the PEG phase, without RNA or genomic DNA contamination as evaluated by agarose gel electrophoresis. In a second extraction stage, the elution of pDNA from the LacI binding complex proved difficult using either dextran or phosphate buffer as second phase, though more than 75% of the overall protein was removed in both systems. A maximum recovery of approximately 27% of the pCU19 plasmid was achieved using the PEG–dextran system as a second extraction system, with 80–90% of pDNA partitioning to the bottom phase. This represents about 7.4 μg of pDNA extracted per 1 mL of pUC19 desalted lysate.     

Molecular design in photocatalysis: Physicochemical principles for designing high-efficiency photocatalytic oxidation-reduction systems

We generalize the results of our research and develop the concept of molecular design as a strategy for controlling photocatalytic processes by designing organized systems in which all the conversions connected with electron transfer are coordinated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 4, pp. 175–191, July–August, 1994.We would like to express our deep appreciation to our colleagues A. V. Korzhak, N. F. Guba, and S. V. Kulik, the coauthors of our original papers which were the basis for this generalization.