联吡啶基共价三嗪框架负载单位点钴用于光催化分解水产氧

氢能是重要的清洁能源,如何低成本获取氢能是其走向实际应用的重要挑战.利用太阳能驱动半导体光催化剂分解水制氢是解决这一挑战的理想途径之一.光催化全解水包括两个半反应,即析氢反应(HER)和析氧反应(OER).其中,光催化OER半反应涉及四个电子的转移(包括O–H键断裂和O–O键形成),其动力学速率远低于两电子转移的HER半反应,因此被认为是光催化全解水的决速步骤.欲实现高效光催化全解水,首先需解决光催化OER半反应动力学缓慢的问题,因此开发高效的OER光催化剂成为当务之急.受单原子催化剂的启发,本文设计并合成了联吡啶基共价三嗪框架(CTF-Bpy),因CTF-Bpy骨架上存在周期性的联吡啶官能团作为金属配位位点,并且有很好的结晶性以及合适的能带结构,是良好的光催化OER反应载体材料.然后通过简单的浸渍配位处理,将单位点的钴作为助催化剂引入到CTF-Bpy中,并用于光催化OER.X射线光电子能谱和X射线近边吸收光谱结果表明,钴是以单位点的Co^(2+)形式存在的.在可见光(λ≥420 nm)照射下,CTF-Bpy-Co在初始1 h内的平均析氧速率为3359μmolg^(–1)h^(–1),5 h内的平均析氧速率为1503μmolg^(–1)h^(–1),光催化性能超过大多数多孔有机聚合物基光催化剂.在420 nm单波长氙灯照射下,CTF-Bpy-Co的光催化析氧表观量子产率(AQY)为0.466%.此外,CTF-Bpy-Co可实现连续析氧40 h,总析氧量可达到180μmol.为明确单位点钴在光催化OER中所起的重要作用,采用相同钴含量的不同形式钴基粒子(游离的Co^(2+),Co,CoO,Co_(2)O_(3)和Co(OH)_(2))作为助催化剂引入CTF-Bpy骨架中进行对比.结果发现,配位的CTF-Bpy-Co表现出最好的光催化析氧效果,表明单位点钴在光催化OER中具有较大的优势.采用密度泛函理论研究了CTF-Bpy-Co的差分电荷密度,并结合上述实验结果提出了CTF-Bpy-Co光催化OER的机理:在可见光激发下,CTF-Bpy-Co光催化剂产生了光生电子和空穴,然后光生电子和空穴被分离并转移到光催化剂与水之间的界面.差分电荷密度证实了电子主要分布于三嗪位点周围,被Ag^(+)迅速捕获生成Ag纳米颗粒;空穴主要分布在Bpy-Co附近,单位点钴可以作为空穴的捕获中心,迅速将Co^(2+)氧化为更高价态的Co^(3+),并与界面上的水分子发生氧化反应产生氧气回到基态,完成整个光催化分解水反应循环.综上所述,为了解决光催化OER的瓶颈问题,本文提出了在催化剂中引入单位点金属助催化剂的策略,显著提升了光催化析氧性能.本研究也为实现更高效的无牺牲剂条件下的光催化全解水提供参考.

氧空位对WO_3光催化析氧活性影响的研究

在500℃下用还原性气体H2O/H2对WO3进行不同时间的处理,得到一系列具有不同氧空位的催化剂。采用XRD、XPS、DRS等技术对催化剂进行了表征,并考察了它们的光催化析氧活性。实验结果表明:适量的氧空位能明显提高催化剂的光催化析氧活性。

日光光催化-好氧生物降解染料废水的研究

[目的]加强印染行业节能减排,提高染料废水处理效率。[方法]采用自制的日光光催化与好氧生物降解在同一反应器同时进行的装置降解印染废水。考察了溶液pH值、催化剂用量、溶液初始浓度、曝气量等单因素以及单一染料和混合染料的影响。[结果]单因素试验条件为:GR进水浓度为20.0 mg/L,曝气量为60.0 ml/min,pH值为3.0,催化剂投加量为0.6 mg/L。此时影响光催化降解去除率的4个因素主次顺序依次为:进水浓度,曝气量,pH值,催化剂投加量。日光光催化-好氧生物降解单一染料B-4BLN、GR废水的染料去除率分别为85.66%、76.93%,COD去除率分别为90.67%、83.33%;此时,日光光催化降解对单一染料B-4BLN、GR废水的染料去除率分别45.78%、36.54%,相应的COD去除率分别为44.18%、28.41%。因此,组合工艺在染料和COD去除方面均比单一的日光光催化要好。虽然二氧化钛对微生物有少量毒性,但不影响好氧菌的活性。[结论]日光光催化-好氧生物降解单一染料和混合染料废水的处理效果都比较好,且此组合工艺具有成本低、投资少、工艺简单等特点,采用日光催化降解与好氧降解在同一反应器同时进行是可行的。

碳酸氧铋光催化剂的研究进展

光催化技术是一种将太阳能转化为化学能的绿色技术,在污染治理和能源生产方面有广阔的应用前景。近几年,碳酸氧铋光催化剂因其优异的光催化性能受到广泛关注,但因其只对紫外光具有响应和回收利用困难等问题限制了在实际生产中的应用。对碳酸氧铋进行形貌控制和改性能有效改善其光催化性能,介绍零维、一维、二维和三维结构的碳酸氧铋光催化剂的研究现状,指出三维结构的碳酸氧铋展现更佳的光催化性能。综述了采用掺杂、金属沉积和构建异质结方式对碳酸氧铋进行改性所取得的进展,提出碳酸氧铋光催化剂在降解机理、降解对象和降解环境等方面需不断努力深入研究。

Experimental studies on photocatalytic oxidation of nitric oxides using titanium dioxide

In order to remove nitric oxides （NO） from flue gas, experimental studies on the photocatalytic oxidation （PCO） of NO are carried out in an efficient laboratory-scale reactor. Nano-sized TiO2 particles loading on quartz sand are prepared and used as the photocatalyst. Effects of several key operating parameters on NO conversion are investigated, including operating temperature, NO inlet concentration, oxygen percentage, relative humidity and residence time. The results illustrate that the NO inlet concentration, the oxygen percentage and the relative humidity play an important role in the oxidation of NO. A lower NO inlet concentration and a higher oxygen percentage result in a higher NO conversion efficiency. When the relative humidity is 8%, the maximum value of NO conversion efficiency is achieved. In addition, the operating temperature and the residence time have a little effect on the conversion efficiency of NO.

Heterostructured BiOI@La(OH)_3 nanorods with enhanced visible light photocatalytic NO removal

Heterostructured BiOI@La（OH）3 nanorod photocatalysts were prepared by a facile chemical impregnation method.The enhanced visible light absorption and charge carrier separation can be simultaneously realized after the introduction of BiOI particles into La（OH）3 nanorods.The BiOI@La（OH）3 composites were applied for visible light photocatalytic oxidization of NO in air and exhibited an enhanced activity compared with BiOI and pure La（OH）3 nanorods.The results show that the energy levels between the La（OH）3 and BiOI phases matched well with each other,thus forming a heterojunctioned BiOI@La（OH）3 structure.This band structure matching could promote the separation and transfer of photoinduced electron-hole pairs at the interface,resulting in enhanced photocatalytic performance under visible light irradiation.The photocatalytic performance of BiOI@La（OH）3 is shown to be dependent on the mass ratio of BiOI to La（OH）3.The highest photocatalytic performance can be achieved when the mass ratio of BiOI to La（OH）3 is controlled at 1.5.A further increase of the mass ratio of BiOI weakened the redox abilities of the photogenerated charge carriers.A new photocatalytic mechanism for BiOI@La（OH）3 heterostructures is proposed,which is directly related to the efficient separation of photogenerated charge carriers by the heterojunction.Importantly,the as-prepared BiOI@La（OH）3 heterostructures exhibited a high photochemical stability after multiple reaction runs.Our findings demonstrate that BiOI is an effective component for the formation of a heterostructure with the properties of a wide bandgap semiconductor,which is of great importance for extending the light absorption and photocatalytic activity of wide bandgap semiconductors into visible light region.

Enhanced photocatalytic performance of cementitious material with TiO_2@Ag modified fly ash micro-aggregates

A TiO2 photocatalyst is coated on the surface of a zeolite fly ash bead（ZFAB） to improve its dispersability and exposure degree in a cement system.The application of Ag particles in TiO2/ZFAB modified cementitious materials is to further enhance the photocatalytic performance.Various Ag@TiO2/ZFAB modified cementitious specimens with different Ag dosages are prepared and the characteristics and photocatalytic performance of the prepared samples are investigated.It is observed that the multi-level pore structure of ZFAB can improve the exposure degree of TiO2 in a cement system and is also useful to enhance the photocatalytic efficiency.With an increment of the amounts of Ag particles in the TiO2/ZFAB modified cementitious samples,the photocatalytic activities increased first and then decreased.The optimal Ag@TiO2/ZFAB modified cementitious sample reveals the maximum reaction rate constant for degrading benzene（9.91×10^-3 min^-1）,which is approximately 3 and 10 times higher than those of TiO2/ZFAB and TiO2 modified samples,respectively.This suggests that suitable Ag particles coupled with a ZFAB carrier could effectively enhance the photocatalytic effects and use of TiO2 in a cement system.Thus,ZFAB as a carrier could provide a potential method for a high efficiency engineering application of TiO2 in the construction field.

Black TiO_2(B)/anatase bicrystalline TiO_(2-x) nanofibers with enhanced photocatalytic performance

Black TiO2（B）/anatase bicrystalline TiO2-x nanofibers were synthesized from a porous titanate derivative by calcination in H2, and were characterized using field-emission scanning electron microscopy, Raman spectroscopy, N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy, thermogravimetric analysis, ultraviolet-visible diffuse reflection spectroscopy and photoluminescence measurements. Characterization results showed that no Ti3＋ was present on the surface of black bicrystalline TiO2-x and oxygen vacancies were distributed in the bulk of both TiO2（B） and anatase phases. The O/Ti atom stoichiometric ratio of black bicrystalline TiO2-x was estimated to be 1.97 from the difference of mass loss between black bicrystalline TiO2-x and white bicrystalline TiO2 without oxygen vacancies. The photocatalytic activity of black bicrystalline TiO2-x was 4.2 times higher than that of white bicrystalline TiO2 and 10.5 times higher than that of anatase TiOz. The high photocatalytic activity of black bicrystalline TiO2-x was attributed to its effective separation of electrons and holes, which may be related to the effects of both bicrystalline structure and oxygen vacancies. Black bicrystalline TiO2-x also exhibited good photocatalytic activity after recycling ten times. The black bicrystalline TiO2-x nanofibers show potential for use in environmental and energy applications.

Solvent-assisted synthesis of porous g-C_3N_4 with efficient visible-light photocatalvtic performance for NO removal

Graphitic carbon nitride（g-C3N4） with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water（CN-W） or ethanol（CN-E） at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.

Facile template-induced synthesis of Ag-modified TiO_2 hollow octahedra with high photocatalytic activity

Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area,low density,good surface permeability,strong light-harvesting capacity,and rapid interfacial charge transfer. However,the present preparation methods usually include complicated and multistep procedures,which can cause damage to the hollow nanostructures. In this paper,a facile template-induced synthesis,based on a template-directed deposition and in situ template-sacrificial dissolution,was employed to prepare Ag-modified TiO 2（Ag/TiO 2） hollow octahedra using Ag2 O octahedra as templates and TiF 4 as the precursor. In the synthetic strategy,the shells of TiO 2 hollow octahedra were formed by coating TiO 2 nanoparticles on the surface of Ag2 O templates based on the template-directed deposition. Simultaneously,the Ag2 O templates can be in situ removed by dissolving the Ag2 O octahedral template in HF solution produced via the hydrolysis reaction of TiF 4 in the reaction system. In addition,Ag nanoparticles were deposited on the inside and outside surfaces of TiO 2 shells by effectively using the photosensitive properties of Ag2 O and Ag＋ ions under light irradiation,along with the formation of TiO 2 hollow octahedra. The Ag/TiO 2 hollow octahedra exhibited high photocatalytic activity because of their（1） short diffusion distances between photogenerated electrons and holes because of the thin shells of Ag/TiO 2 hollow octahedral,（2） deposition of Ag nanoparticles on the inside and outside surfaces of TiO 2 shells,and（3） rapid interfacial charge transfer between TiO 2 shells and Ag nanoparticles. This work may also provide new insights into preparing other Ag-modified and hollow nanostructured photocatalysts.

Strong visible absorption and excellent photocatalytic performance of brown TiO_2 nanoparticles synthesized using one-step low-temperature process

particle size （5.0 nm）, large specific surface area （213.45 m1 2/g）, and efficient response to broadband light over the entire ultraviolet-visible spectrum with a narrow band gap of 1.84 eV. In addition, TiO2 -180℃ exhibited the optimal reaction rate constant for the degradation of methylene blue （0.08287 mg/（Lmin））, which is six times higher than that of the mixed rutile/anatase phase TiO2 photocatalytic standard P25 （0.01342 mg/（L min））. Furthermore, cycling photodegradation ex-periments confirmed the stability and reusability of this catalyst. The unique physicochemical properties resulting from the low-temperature preparation of TiO2 -180℃, including its broadband visible absorption associated with a high concentration of oxygen vacancies, large surface area, and enriched surface -OH/H2O may be responsible for this excellent photocatalytic performance. The use of as-prepared TiO2 -180℃ for practical applications is expected after further optimization.

Preparation of bismuth oxide/titania composite particles and their photocatalytic activity to degradation of 4-chlorophenol

Bismuth oxide/titania, one interfacial composite semiconductor with high photocatalytic activity under solar light, was prepared at low temperature. The structure was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, brunauer-emmett-teller （BET）, X-ray photoelectron spectroscopy （XPS） and diffuse reflection spectra （DRS）. The results indicate that deposited titania nanoparticles on bismuth oxide surface have micro-nano structure, and this composite material exhibits porosity and increased surface hydroxyl groups. Furthermore, the as-prepared photocatalyst shows higher photocatalytic activity to the degradation of 4-chlorophenol than pure titania or P25 under sunlight.

Substrate-dependent photoreactivities of BiOBr nanoplates prepared at different pH values

In this study,we showed that BiO Br nanoplates prepared at different pH values have substratedependent photocatalytic activities under visible-light irradiation. The BiO Br nanoplates synthesized at pH 1（BOB-1） degraded salicylic acid more effectively than did those obtained at pH 3（BOB-3）,but the order of their photocatalytic activities in rhodamine B（RhB） degradation were reversed. Electrochemical Mott–Schottky and zeta-potential measurements showed that BOB-1 had a more positive valence band and lower surface charge,leading to superior photocatalytic activity in salicylic acid degradation under visible light. However,BOB-3 was more powerful in RhB degradation because larger numbers of superoxide radicals were generated via electron injection from the excited RhB to its more negative conduction band under visible-light irradiation; this was confirmed using active oxygen species measurements and electron spin resonance analysis. This study deepens our understanding of the origins of organic-pollutant-dependent photoreactivities of semiconductors,and will help in designing highly active photocatalysts for environmental remediation.

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

Bi_(2)MoO_(6)/WO_(3)复合光催化材料的合成及其可见光催化性能

采用水热法成功制备了不同Bi_(2)MoO_(6)含量的Bi_(2)MoO_(6)/WO_(3)复合光催化剂,利用XRD、SEM、UVVis、EIS和PL对样品进行了微观结构、形貌、光吸收特性、光谱响应和光电流的测试与表征,并考察了Bi_(2)MoO_(6)/WO_(3)复合材料光催化分解水制氧的活性。结果表明,Bi_(2)MoO_(6)/WO_(3)复合样品的光催化活性明显高于纯WO_(3)和Bi_(2)MoO_(6)样品。在模拟太阳光照射下,15%Bi_(2)MoO_(6)/WO_(3)复合催化剂的光催化产氧效率是纯WO_(3)的产氧效率的2.3倍,以Fe(NO_(3))_(3)·9H_(2)O为牺牲剂时,复合催化剂的产氧效率可达到107μmol/(g·h),且具有良好的循环稳定性。分析发现Bi_(2)MoO_(6)/WO_(3)复合样品中Bi_(2)MoO_(6)颗粒与WO_(3)纳米棒的异质结结构提高了光生载流子传输和转移效率,减少了光生电子-空穴对的复合几率,因此有助于增强光催化活性。

Photochemical oxidation mechanism of microcystin-RR by p-n heterojunction Ag/Ag_2O-BiVO_4

Microcystin-RR（MC-RR）,a form of microcystin with two arginine moieties,is a cyanobacterial toxin that has been detected across a wide geographic range.It is a great concern globally because of its potential liver toxicity.Herein,the abilities of BiVO4,Ag-BiVO4,Ag2O-BiVO4 and Ag/Ag2O-BiVO4 to photocatalytically degrade MC-RR under visible-light irradiation（λ≥420 nm） were investigated and compared.The possible degradation pathways were explored through analysis of the reaction intermediates by high-performance liquid chromatography-mass spectrometry.The results showed that the presence of Ag^0 enhanced the photocatalytic efficiency of Ag/Ag2O-BiVO4 via a synergetic effect between Ag2O and Ag^0 at the p-n heterojunction.Moreover,the presence of Ag^0 also greatly promoted the adsorption of MC-RR on the photocatalyst surface.Toxicological experiments on mice showed that the toxicity of MC-RR was significantly reduced after photocatalytic degradation.

Photocatalytic Degradation of Water-Soluble Dyes by LaCoO_3

Pervoskite type oxides LaCoO 3 was prepared by citrate method with the granula of 20 nm-30 nm. With a fluorescent Hg lamp or sunlight as irradiator, the degradation experiments of various water soluble dyes were carried out in the suspension system of LaCoO 3 . The results show that the pervoskite type oxide LaCoO 3 has good photocatalytic activity.Studied by X ray photoelectron spectroscopy and photoacoustic spectra, its photocatalytic activity is found to be related with factors such as the d electron structure of ion Co 3+ ,Co—O binding energy and adsorbed oxygen on the surface etc.

Synthesis and Characterization of Novel N-doped TiO2 Photocatalyst with Visible Light Active

A novel N-doped TiO2 （N1-N2-TiO2） with substitutional and interstitial N impurities simultaneously was successfully synthesized. The catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, photoluminescence, and electron paramagnetic resonance. The results demonstrated that the nitrogen was substituted for the lattice oxygen atoms, and was also interstitially doped into the TiO2 lattice. The photocatalytic tests indicated that the N1-N2-TiO2 showed the highest photocatalytic activities of all the N-doped TiO2 under visible light, attributing to the synergetic effect of substitutional and interstitial nitrogen of N-doped TiO2.

Synthesis and Characterization of TiO2 Doped ZnO Microtubes

The TiO2-doped ZnO microtubes have been successfully fabricated via a wet chemical method, using zinc chloride and titanium sulphate as the starting materials. The assynthesized products were characterized by X-ray diffraction, field emission scanning electron microscopy and room temperature photoluminescence measurement. The photocatalytic activity in degrading methyl orange was measured with a UV-Vis spectrophotometer. The pure ZnO microtubes exhibit an exact hexangular hollow structure with a diameter of about 700 nm, a length of 3 μm and a wall thickness of about 40 nm. The TiO2-doped ZnO microtubes with TiO2/ZnO ratio less than 5% have the same dimension with the pure ZnO microtubes, a smooth column shape, not a hexangular structure. The growth of ZnO may be inhibited by the more Ti^4＋ doped into ZnO structure to achieve a small dimension or a multiphase. The crystallinity of ZnO microtubes decreases with increasing TiO2 content, and then a multiphase containing ZnO, Ti305 and TiO occur when the TiO2/ZnO ratio is more than 5%. The UV emission intensity of the TiO2-doped ZnO obviously increases and then tends to decrease with TiO2/ZnO ratio increasing. The photocatalytic properties of the TiO2-doped ZnO microtubes are very efficient in degrading organic dyes of methyl orange and are well identical with its PL properties and the crystallinity.