S掺杂的还原态TiO2-x的制备及其可见光催化性能

作为一种稳定、价廉的光催化剂,TiO2被广泛应用于各种污染物的降解;但是,较大的宽禁带(~3.2 eV)和较低的电子迁移率不仅使TiO2很难吸收可见光,而且光生电子和空穴的复合几率高,从而导致TiO2的总体光电效率不高.因此,设计能够被可见光激发、并具有快速光生电子传输的TiO2一直是研究热点.研究表明,Ti3+自掺杂的TiO2(还原态TiO2-x)不仅能够被可见光激发,而且使TiO2具有良好的电子导电性,从而有利于提高TiO2的光电转换效率.另外,非金属元素的掺杂能够减小TiO2的禁带宽度,使TiO2能够响应可见光并具有良好的可见光催化性能,其中S元素的掺杂被广泛研究.目前,S掺杂纳米TiO2的制备通常采用TiS2,单质S,硫脲、二甲亚砜等为S源,但这类原料通常价格昂贵或者具有一定的毒性,因而实际应用受到限制.而制备Ti3+自掺杂TiO2的方法大都是基于"还原法",在真空或强还原性气氛如H2,CO中加热TiO2,或采用高能粒子(电子、氩离子)轰击.在实际应用中,这些方法存在步骤多、条件苛刻、反应时间长和设备昂贵等不足.而且,还原法反应通常发生在颗粒的表面,形成的Ti3+很容易被空气和水中的溶解O2氧化,降低材料的稳定性.虽然在温和的液相中还原Ti4+可用于制备Ti3+掺杂的TiO2,但是由于反应过程中有副产物生成,需要进行后续处理才能得到纯的Ti3+自掺杂TiO2.因此,设计一种简单的制备S掺杂还原态TiO2-x光催化剂仍具有十分重要的意义.前期我们采用H2O2氧化TiH2得到不同状态的前驱体凝胶,然后进行不同方式的后处理得到Ti3+自掺杂的纳米TiO2.本文以TiH2和H2O2反应得到的黄色前驱体凝胶为Ti源,以价格低廉、无毒、稳定的二氧化硫脲为S源和还原剂,采用不同的方法制备了S掺杂的还原态TiO2-x光催化剂.本文初步研究了在凝胶中加入二氧化硫脲后进行水热处理,以及将干燥的凝胶粉末与二氧化硫脲混合热处理对所得产物的影响.并与纯的TiO2、还原态TiO2-x和S掺杂TiO2的光吸收、电化学、光催化性能进行对比研究.采用X射线衍射、透射电子显微镜、高分辨透射电子显微镜、X-射线光电子能谱、紫外-可见漫反射光谱、比表面分析和电化学工作站等技术对产物的结构、形貌和光电性能进行了表征.以罗丹明B(RhB)溶液为模拟废水,考察样品的可见光催化性能.结果表明,不同的后续处理方式不仅影响S掺杂TiO2-x的结晶性和形貌,而且影响产物的光吸收性能和电子传输性能,从而使不同条件下所得产物的可见光催化性能不同.其中,采用热处理方式得到的S掺杂TiO2-x样品在可见光下降解RhB的速率分别是纯的TiO2,TiO2-x和S掺杂TiO2的31,2.5和3.6倍,而且样品具有良好的循环稳定性.     

Visible-light photocatalytic activity of the metastable Bi20TiO32 synthesized by a high-temperature quenching method

Metastable Bi₂₀TiO₃₂ samples were synthesized by a high-temperature quenching method using α-Bi₂O₃ and anatase TiO₂ as raw materials. The photocatalytic activity of the as-prepared samples was measured with the photodegradation of methyl orange at room temperature under visible light irradiation. The Bi₂₀TiO₃₂ samples exhibited good absorption in the visible light region with a band gap of about 2.38 eV and the band structure of Bi₂₀TiO₃₂ was studied. Photodegradation against methyl orange was much better than α-Bi₂O₃ prepared by the same way. The photocatalytic activity of Bi₂₀TiO₃₂ samples is supposed to be associated with the hybridized Bi 6s and O 2p orbitals. In addition, the dispersive characteristic of Bi 6s orbital in the hybridized valence band facilitates the mobility of the photogenerated carriers and hampers their recombination.     

Multiple attribute decision-making method based on projection model for dual hesitant fuzzy set

Fuzzy Optimization and Decision Making - In the decision-making process, retaining the original data information has become a most crucial step. Dual hesitant fuzzy sets (DHFS), which can reflect...     

The synthesis of the near-spherical AgCl crystal for visible light photocatalytic applications

The near-spherical AgCl micro-crystals were prepared by an ionic liquids-assisted hydrothermal method. The influence of ionic liquids (C(x)MimCl x = 4, 8, 12, 16) on (001) facet growth of AgCl was studied systemically. The composition of the as-prepared samples was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and FTIR spectra. The morphological structures were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Based on experimental data and the classical crystal growth theory, a plausible growth mechanism of the near-spherical AgCl was proposed. The plasmonic photocatalyst Ag@AgCl prepared from the near-spherical AgCl showed higher activity than that of cubic morphologies.     

Highly Efficient Visible‐Light Plasmonic Photocatalyst Ag@AgBr

Visible improvements : Owing to the plasmon resonance of silver nanoparticles deposited on the surface of AgBr, the newly‐prepared plasmonic photocatalyst Ag§AgBr has a strong absorption in the visible region (see picture) and shows high efficiency in the photodegradation of organic pollutants under visible light.

     

α-Fe2O3 hollow structures: formation of single crystalline thin shells

Novel α-Fe(2)O(3) hollow polyhedra structures with single crystalline thin shells were synthesized by a facile one-pot template-free hydrothermal method, which exhibit high efficiency on the decoloration of RhB aqueous solution in the presence of H(2)O(2). Based on experimental analysis, a plausible growth process is proposed.     

Hydrogenated titania: synergy of surface modification and morphology improvement for enhanced photocatalytic activity

Surface-hydrogenated anatase TiO(2) (TiO(2)-H) nanowire-microspheres were prepared by converting protonated titanate nanotube to TiO(2)-H under a hydrogen atmosphere. We show that TiO(2)-H nanowire-microspheres have Ti-H and O-H bonds on their surface and exhibit improved visible-light absorption and highly enhanced photocatalytic activity.     

In Situ Preparation of CsPbBr3@CsPb2Br5 Composite Assisted with Water as a Highly Efficient and Stable Catalyst for Photothermal CO2 Hydrogenation

Lead halide perovskite has triggered a lot of research due to its superior optical properties. However, halide perovskite materials have poor environmental stabilities and are easily affected by external factors such as water and heat, resulting in structural decomposition and performance failure. Contrary to this commonplace concept, it is found that CsPbBr₃ (CPB) can convert to CsPb₂Br₅ (CP2B5) partially when meeting a small amount of water, and the CsPbBr₃@CsPb₂Br₅ (CPB@CP2B5) composite is synthesized by an in situ method accordingly. The CPB@CP2B5 composite shows an enhanced catalytic performance compared with pure CPB, as well as a dramatically synergistic effect of photo and thermal for catalytic CO₂ hydrogenation. The CO production rate of CPB@CP2B5 is determined as 69 μmol g⁻¹ h⁻¹ under light irradiation at 200 °C, which is 156.8 and 43.4 times higher than that under pure photo (0.44 μmol g⁻¹ h ⁻¹) and pure thermal (1.59 μmol g⁻¹ h ⁻¹) condition, respectively. Meanwhile, the CPB@CP2B5 sample is also stable, which shows no significant decline in the catalytic activity during 8 cycles of repeated experiments. The probable mechanism is explored by utilizing a series of in situ characterizations.     

On Structural Features Necessary for Near‐IR‐Light Photocatalysts

In the search for photocatalysts that can directly utilize near‐IR (NIR) light, we investigated three oxides Cu₃(OH)₄SO₄ (antlerite), Cu₄(OH)₆SO₄, and Cu₂(OH)₃Cl by photodecomposing 2,4‐dichlorophenol over them under NIR irradiation and by comparing their electronic structures with that of the known NIR photocatalyst Cu₂(OH)PO₄. Both Cu₃(OH)₄SO₄ and Cu₄(OH)₆SO₄ are NIR photocatalysts, but Cu₂(OH)₃Cl is not. Thus, in addition to the presence of two different CuO_m and Cu′O_n polyhedra linked with Cu?O?Cu′ bridges, the presence of acceptor groups (e.g., SO₄, PO₄) linked to the metal oxygen polyhedra is necessary for NIR photocatalysts.