Photocatalytic H2 Evolution on TiO2 Assembled with Ti3C2 MXene and Metallic 1T-WS2 as Co-catalysts

The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.     

P(MMA-AN)/TiO2复合粒子的制备及光催化性能

采用原位乳液聚合方法制备了基于共价键结合的P(MMA-AN)/TiO2复合粒子,红外光谱和热失重分析结果表明P(MMA-AN)在TiO2表面接枝率为15.9%。以甲基橙溶液为目标污染物,研究了P(MMA-AN)/TiO2复合粒子和TiO2对甲基橙的吸附和光催化降解甲基橙溶液的性能,结果表明:两种粒子对甲基橙的吸附都很少;在相同时间内,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解性能优于TiO2,紫外光照180 min后,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解率达到了88%,而TiO2仅为74%。     

Photocatalytic degradation of methyl orange using a TiO2/Ti mesh electrode with 3D nanotube arrays

To further improve the photocatalytic techniques for water purification and wastewater treatment, we successfully prepared a new type of TiO(2)/Ti mesh photoelectrode, by anodization in ethylene glycol solution. The three-dimensional arrays of nanotubes formed on Ti mesh show a significant improvement in photocatalytic activity, compared to the nanotube arrays formed on foil. This can be demonstrated by about 22 and 38% enhancement in the degradation efficiency per mass and per area, respectively, when TiO(2)/Ti mesh electrode was used to photocatalyze methyl orange (MO). Furthermore, the effects of different parameters on MO photodegradation were investigated, such as different photoelectrode calcination temperature, the initial pH value of MO solution, and the present of hydrogen peroxide. The superior photocatalytic activity could be achieved by the TiO(2)/Ti mesh photoelectrode calcinated at 550 °C, due to the appearance of mixed crystal phases of anatase and rutile. In strong acidic or caustic conditions, such as pH 1 or 13, a high degradation efficiency can be both obtained. The presence of H(2)O(2) in photocatalytic reactions can promote photocatalytic degradation efficiencies. Moreover, the experimental results demonstrated the excellent stability and reliability of the TiO(2)/Ti mesh electrode.     

Degradation of bisphenol A in aqueous solution by H2O2-assisted photoelectrocatalytic oxidation

A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.     

Ultrathin Co(Ni)-doped MoS<Subscript>2</Subscript> nanosheets as catalytic promoters enabling efficient solar hydrogen production

The design of efficient artificial photosynthetic systems that harvest solar energy to drive the hydrogen evolution reaction via water reduction is of great importance from both the theoretical and practical viewpoints.Integrating appropriate co-catalyst promoters with strong light absorbing materials represents an ideal strategy to enhance the conversion efficiency of solar energy in hydrogen production.Herein,we report,for the first time,the synthesis of a class of unique hybrid structures consisting of ultrathin Co(Ni)-doped MoS2 nanosheets (co-catalyst promoter) intimately grown on semiconductor CdS nanorods (light absorber).The as-synthesized one-dimensional CdS@doped-MoS2 heterostructures exhibited very high photocatalytic activity (with a quantum yield of 17.3％) and stability towards H2 evolution from the photoreduction of water.Theoretical calculations revealed that Ni doping can increase the number of uncoordinated atoms at the edge sites of MoS2 nanosheets to promote electron transfer across the CdS/MoS2 interfaces as well as hydrogen reduction,leading to an efficient H2 evolution reaction.     

S、RE共掺杂TiO2的制备及其可见光分解水制氢性能

采用溶胶-凝胶法制备了系列稀土(La、Eu、Nd、Tb、Er)和硫共掺杂TiO2光催化剂RE/S/TiO2。通过紫外-可见(UV-Vis)漫反射、X射线衍射(XRD)对催化剂进行了表征。以EDTA为电子给体,考察了光催化剂在可见光照射下的制氢活性。研究结果表明,S/TiO2具有可见光活性,稀土掺杂进一步提高了S/TiO2可见光活性,其活性顺序依次为Eu/S/TiO2>La/S/TiO2>Nd/S/TiO2>Tb/S/TiO2>Er/S/TiO2。与纯TiO2和S/TiO2光催化剂相比,稀土掺杂使催化剂的粒径减小,晶格畸变应力增大,从而提高了催化剂可见光制氢活性。     

3D Bi12TiO20/TiO2 hierarchical heterostructure: synthesis and enhanced visible-light photocatalytic activities

A three-dimensional (3D) multicomponent oxide, Bi(12)TiO(20)/TiO(2) hierarchical heterostructure was successfully synthesized via a one-step and template-free hydrothermal route. X-ray diffraction and X-ray photoelectron spectroscopy measurements confirm that the composition of the as-fabricated sample is Bi(12)TiO(20)/TiO(2) composite. Scanning and transmission electron microscopy observation reveals that the as-synthesized sample is microsized flower-like hierarchical networks consisted of Bi(12)TiO(20) nanorods decorated with the primary TiO(2) nanoparticles. Extension of the light absorption from the ultraviolet region to the visible-light region was confirmed by UV-vis absorption spectra. Due to the structure-property relationships, the 3D Bi(12)TiO(20)/TiO(2) heterostructure exhibited enhanced visible photocatalytic activity over that of Bi(12)TiO(20) and TiO(2) samples in the decomposition of Rhodamine B in water which is a typical model pollutant. The enhanced photocatalytic activity can be attributed to the extended absorption in the visible light region resulting from the 3D Bi(12)TiO(20)/TiO(2) heterostructures, and the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the Bi(12)TiO(20)/TiO(2) junction interface, demonstrating that the Bi(12)TiO(20)/TiO(2) heterostructure is a promising candidate as a visible light photocatalyst.     

Enhanced photocatalytic activity by the construction of a TiO<Subscript>2</Subscript>/carbon nitride nanosheets heterostructure with high surface area via direct interfacial assembly

A TiO2 heterostructure modified with carbon nitride nanosheets (CN-NSs) has been synthesized via a direct interfacial assembly strategy.The CN-NSs,which have a unique two-dimensional structure,were favorable for supporting TiO2 nanoparticles (NPs).The uniform dispersion of TiO2 NPs on the surface of the CN-NSs creates sufficient interfacial contact at their nanojunctions,as was confirmed by electron microscopy analyses.In comparison with other reported metal oxide/CN composites,the strong interactions of the ultrathin CN-NSs layers with the TiO2 nanoparticles restrain their re-stacking,which results in a large specific surface area of 234.0 m2·g-1.The results indicate that the optimized TiO2/CN-NSs hybrid exhibits remarkably enhanced photocatalytic efficiency for dye degradation (with k of 0.167 min-1 under full spectrum) and H2 production (with apparent quantum yield =38.4％ for,λ =400 ± 15 nm monochromatic light).This can be ascribed to the improved surface area and quantum efficiency of the hybrid,with a controlled ratio that reaches the appropriate balance between producing sufficient nanojunctions and absorbing enough photons.Furthermore,based on the identification of the main active species for photodegradation,and the confirmation of active sites for H2 evolution,the charge transfer pathway across the TiO2/CN-NSs interface under simulated solar light is proposed.     

H(2)O(2)-sensitized TiO(2)/SiO(2) composites with high photocatalytic activity under visible irradiation

TiO(2)/SiO(2) composite photocatalysts were prepared by depositing of TiO(2) onto nano-SiO(2) particles. X-ray diffraction (XRD), transmission electron micrograph (TEM), Raman spectrometer, UV-Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy (FT-IR) were employed to characterize the properties of the synthesized TiO(2)/SiO(2) composites. These results indicated that the products without calcination were amorphous, and calcination could enhance the crystallinity of TiO(2). Increases in the amount of TiO(2) would decrease the dispersion in the composites. H(2)O(2)-sensitized TiO(2)/SiO(2) composite photocatalysts could absorb visible light at wavelength below 550 nm. The photocatalytic activity of as-prepared catalysts was characterized by methyl-orange degradation. The results showed the uncalcined composite photocatalysts with amorphous TiO(2) exhibited higher photocatalytic activity under visible light, and the activity of catalysts with TiO(2) content over 30% decreased with increasing of TiO(2) content. Increases in the calcination temperature and TiO(2) content promote the formation of bulk TiO(2) and result in a decrease in activity.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: preparation and photocatalytic behavior of TiO2/Sr2CeO4

The paper demonstrates that the photocatalytic activity of TiO(2) towards the decomposition of gaseous benzene in a batch reactor can be greatly improved by loading TiO(2) on the surface of Sr(2)CeO(4). The research investigates the optimum loading amount of TiO(2) on Sr(2)CeO(4) in enhancing the photocatalytic activity of TiO(2). The prepared photocatalyst was characterized by XRD, UV-vis diffuse reflectance and XPS analyses. TiO(2) is loaded on Sr(2)CeO(4) at 773K. TiO(2)/Sr(2)CeO(4) absorbs much more visible light than TiO(2). The XPS spectrum shows that there are Ti, O, C, Sr elements on the surface of the TiO(2)/Sr(2)CeO(4), and that the binding energy value of Ti2p transfers to a lower value. TiO(2)/Sr(2)CeO(4) demonstrates 2.0 times the photocatalytic activity of pure TiO(2). Based upon these observations, the mechanistic role of Sr(2)CeO(4) in the photocatalytic oxidation reaction has been suggested.     

新型二维TiSe2纳米片的可控合成及其生长机理

溶液法是一种反应温和、易控制且常用的合成方法。目前已报道的溶液法制备TiSe₂时通常采用三辛基膦(TOP)为溶剂, 但这种试剂有毒, 对人体和环境都有潜在的危害。本研究通过简单的、无TOP的溶液法成功地制备了单分散的六边形TiSe₂纳米片, 并通过调整反应时间研究TiSe₂纳米片的形貌演变规律。利用XRD、SEM、EDS和紫外-可见漫反射对其物相、形貌、元素以及光学性能进行了系统的表征; 根据SEM结果对其生长过程及形貌演变规律进行了研究, 并提出一种螺旋状逐层生长的机理; 分析考察了TiSe₂纳米片对罗丹明B(RhB)的光催化活性, 发现其具有高于P25的降解能力, 这表明TiSe₂纳米片作为光催化材料具有广阔的应用前景。     

γ-Bi2O3/TiO2复合纤维的制备及光催化性能

采用静电纺丝技术与溶剂热法相结合制备了γ-Bi2O3/TiO2复合纤维光催化材料.利用X射线衍射(XRD)、扫描电镜(SEM)、电子能谱(EDS)、透射电镜(TEM)、高分辨透射电镜(HRTEM)和紫外–可见吸收光谱(UV-Vis)等分析测试手段对材料进行了表征,并以罗丹明B(RB)的脱色降解为模式反应,考察了材料的可见光催化性能.结果表明:γ-Bi2O3纳米片均匀地生长在TiO2纤维上,形成了具有异质结构的γ-Bi2O3/TiO2复合纤维光催化材料,其光谱响应范围拓宽至可见光区,有利于TiO2光生电子和空穴的分离,增强了体系的量子效率.与纯TiO2纤维相比可见光催化活性明显提高,对RB的脱色率达87.8%.     

Oxygen vacancies facilitated photocatalytic detoxification of three typical contaminants over graphene oxide surface embellished BiOCl photocatalysts

A conventional solvothermal way was used to synthesize graphene oxide (GO)/BiOCl photocatalytic nanomaterials with enhanced photocatalytic performance. Due to the introduction of GO, there are intuitive changes in morphology, indicating that GO can guide the growth of GO/BiOCl catalysts. The results of X-ray photoelectron spectroscopy (XPS) and Raman show that a strong chemical interaction occurs around GO and BiOCl. The results of trapping experiments show that O₂^– is the major active species. XPS analysis confirms that the 0.75% GO/BiOCl produces the highest level of oxygen vacancies (OVs). All the GO/BiOCl photocatalysts possess better photocatalytic properties than the neat BiOCl, and 0.5% GO/BiOCl exhibits the highest photoactivity. The photocatalytic activity of 0.5% GO/BiOCl composite for detoxification of rhodamine B (RhB) and tetracycline (TC) under visible light illumination is 4.6 and 6.3 times of that on the reference BiOCl, separately, the photocatalytic activity of 0.5% GO/BiOCl for detoxication of perfluorooctanoic acid (PFOA) is 1.25 times of that of the single BiOCl under UV light illumination, which can be credited to the high separation rate of carriers and the strong interaction between GO and BiOCl. Combining with the results, a separation and transfer mechanism of carriers was revealed.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Synthesis and performance of novel magnetically separable nanospheres of titanium dioxide photocatalyst with egg-like structure

A magnetically separable photocatalyst TiO(2)/SiO(2)/NiFe(2)O(4) (TSN) nanosphere with egg-like structure was prepared by a unique process that combined a liquid catalytic phase transformation method, reverse micelle technique and chemical precipitation means. The prepared photocatalyst shows high photocatalytic activity for the degradation of methyl orange in water. The magnetic property measurements indicate that the photocatalyst possesses a superparamagnetic nature. It can be separated from water when an external magnetic field is added and redispersed into water solution after the external magnetic field is eliminated. It is one of the promising photocatalysts for wastewater treatment. A transmission electron microscope (TEM) and an x-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that nickel ferrite core nanoparticles were completely encapsulated into monodisperse silica nanospheres as carrier, and titania nanoparticle aggregates were coated onto the surface of SN nanospheres, forming an imperfect TiO(2) shell for photocatalysis. The SiO(2) layer between the NiFe(2)O(4) core and the TiO(2) shell effectively prevents the injection of charges from TiO(2) particles to NiFe(2)O(4), which gives rise to an increase in photocatalytic activity. Moreover, the recycled TSN exhibits good repeatability of the photocatalytic activity.     

Synthesis of one-dimensional TiO2/V2O5 branched heterostructures and their visible light photocatalytic activity towards Rhodamine B

We present the synthesis and visible-light-induced catalytic activity of one-dimensional (1D) TiO(2)/V(2)O(5) branched heterostructures. The 1D TiO(2)/V(2)O(5) heterostructures were prepared by RF reactive magnetron sputtering of V(2)O(5) onto electrospun TiO(2) nanofibers. Then, the samples were annealed at 300?°C for 2 h in air ambient to form the 1D TiO(2)/V(2)O(5) branched heterostructures. The photodecomposition rate of Rhodamine B (RhB) by the 1D TiO(2)/V(2)O(5) branched heterostructures under visible light was much faster than that of pure TiO(2) nanofibers, revealing that the visible-light-induced catalytic activity of the 1D TiO(2)/V(2)O(5) branched heterostructures was greatly improved. The enhancement of the photocatalytic activity of the 1D TiO(2)/V(2)O(5) branched heterostructures can be ascribed to the coupling with a small bandgap semiconductor material V(2)O(5), where the absorption range is extended, the photogenerated electrons and holes are highly separated and the surface charge carrier transfer rate is promoted.     

Visible light photocatalytic H₂-production activity of CuS/ZnS porous nanosheets based on photoinduced interfacial charge transfer

Visible light photocatalytic H(2) production through water splitting is of great importance for its potential application in converting solar energy into chemical energy. In this study, a novel visible-light-driven photocatalyst was designed based on photoinduced interfacial charge transfer (IFCT) through surface modification of ZnS porous nanosheets by CuS. CuS/ZnS porous nanosheet photocatalysts were prepared by a simple hydrothermal and cation exchange reaction between preformed ZnS(en)(0.5) nanosheets and Cu(NO(3))(2). Even without a Pt cocatalyst, the as-prepared CuS/ZnS porous nanosheets reach a high H(2)-production rate of 4147 μmol h(-1) g(-1) at CuS loading content of 2 mol % and an apparent quantum efficiency of 20% at 420 nm. This high visible light photocatalytic H(2)-production activity is due to the IFCT from the valence band of ZnS to CuS, which causes the reduction of partial CuS to Cu(2)S and thus enhances H(2)-production activity. This work not only shows a possibility for substituting low-cost CuS for noble metals in the photocatalytic H(2) production but also for the first time exhibits a facile method for enhancing H(2)-production activity by photoinduced IFCT.     

氩等离子体处理增强TiO_2∶Er/p~+-Si异质结器件的电致发光

在我们以前的工作[1]中,报道了基于重掺硼硅片(p~+-Si)上掺Er的TiO_2(TiO_2∶Er)薄膜的TiO_2∶Er/p~+-Si异质结器件的电致发光。本文研究了TiO_2∶Er薄膜的氩(Ar)等离子体处理对TiO_2∶Er/p~+-Si异质结器件电致发光的影响。研究发现:Ar等离子体处理使TiO_2∶Er/p~+-Si异质结器件与Er3+离子相关的可见和近红外电致发光都得到了显著的增强,同时也增强了与TiO_2基体中氧空位相关的电致发光。这是由于Ar等离子体处理显著提高了TiO_2∶Er薄膜中的氧空位浓度,不但增强了与氧空位相关的电致发光,而且增强了以氧空位为敏化中心的从TiO_2基体向Er3+离子的能量传递,从而增强了Er3+离子的发光。     

TiO<Subscript>2</Subscript> nanocrystals grown on graphene as advanced photocatalytic hybrid materials

A graphene/TiO₂ nanocrystals hybrid has been successfully prepared by directly growing TiO₂ nanocrystals on graphene oxide (GO) sheets. The direct growth of the nanocrystals on GO sheets was achieved by a two-step method, in which TiO₂ was first coated on GO sheets by hydrolysis and crystallized into anatase nanocrystals by hydrothermal treatment in the second step. Slow hydrolysis induced by the use of EtOH/H₂O mixed solvent and addition of H₂SO₄ facilitates the selective growth of TiO₂ on GO and suppresses growth of free TiO₂ in solution. The method offers easy access to the GO/TiO₂ nanocrystals hybrid with a uniform coating and strong interactions between TiO₂ and the underlying GO sheets. The strong coupling gives advanced hybrid materials with various applications including photocatalysis. The prepared graphene/TiO₂ nanocrystals hybrid has superior photocatalytic activity to other TiO₂ materials in the degradation of rhodamine B, showing an impressive three-fold photocatalytic enhancement over P25. It is expected that the hybrid material could also be promising for various other applications including lithium ion batteries, where strong electrical coupling to TiO₂ nanoparticles is essential.     

二氧化钛纳米棒的制备及其晶体生长机理分析

采用溶剂热法合成具有高结晶性与单分散性的TiO₂纳米棒. 采用TEM、XRD、HRTEM等对样品的微观结构进行表征, 并考察了TiO₂纳米棒对亚甲基蓝的光催化性能. 通过控制反应时间、反应温度, 研究纳米棒的形貌演变规律.结果表明, 可以通过“奥斯特瓦尔德熟化”和“取向接触”两种晶体生长过程制备出棒状TiO₂纳米晶, 降低纳米晶的表面能是晶体生长与形貌演变的主要驱动力; 高结晶性的TiO₂纳米棒具有高于P25的光催化能力.