Realizing high hydrogen evolution activity under visible light using narrow band gap organic photocatalysts

The design and synthesis of conjugated semiconducting polymers for photocatalytic hydrogen evolution have engendered intense recent interest. However, most reported organic polymer photocatalysts show a relatively broad band gap with weak light absorption ability in the visible light region, which commonly leads to a low photocatalytic activity under visible light. Herein, we synthesize three novel dithieno[3,2-b:2′,3′-d]thiophene-S,S-dioxide (DTDO) containing conjugated polymer photocatalysts by a facile C–H arylation coupling polymerization reaction. The resulting polymers show a broad visible light absorption range up to 700 nm and a narrow band gap down to 1.81 eV due to the introduction of the DTDO unit. Benefiting from the donor–acceptor polymer structure and the high content of the DTDO unit, the three-dimensional polymer PyDTDO-3 without the addition of a Pt co-catalyst shows an attractive photocatalytic hydrogen evolution rate of 16.32 mmol h⁻¹ g⁻¹ under visible light irradiation, which is much higher than that of most reported organic polymer photocatalysts under visible light.

Narrow band gap conjugated polymer photocatalysts containing dithieno[3,2-b:2′,3′-d]thiophene-S,S-dioxide show an attractive photocatalytic hydrogen evolution rate of 16.32 mmol h⁻¹ g⁻¹ under visible light irradiation.     

Chitosan-modified TiO<Subscript>2</Subscript> as photocatalyst for ethanol reforming under visible light

This work reports the reforming of bio-ethanol on chitosan–TiO₂ hybrid photocatalysts at ambient temperature. The influence of chitosan composition on the photocatalytic performance of chitosan–TiO₂ hybrid was studied. The hybrids were characterized by CHN elemental analysis, nitrogen adsorption–desorption isotherms, thermogravimetric analysis, diffuse reflectance spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results showed that the preparation variables used for the incorporation of chitosan on TiO₂ promoted changes in the morphology, superficial area, crystal size and porosity of the photocatalyst, affecting the band gap of this semiconductor and consequently the reactivity of the chitosan–TiO₂ hybrids. The catalysts were evaluated for hydrogen production from ethanol under visible light. It was demonstrated that the calcination temperature of 623 K and a chitosan content of 20% were the most appropriate preparation conditions and the resulting product displays a pore size of 1.9 nm, crystal size of 11.3 nm, BET area of 178 m² g^?1 and band gap of 2.92 eV. The calcination temperature of 623 K and incorporation of 20% of chitosan obtained the same results in the conversion rate of hydrogen in comparison to the pure TiO₂ P25.     

Understanding the synergistic effects,optical and electronic properties of ternary Fe/C/S‐doped TiO2 anatase within the DFT + U approach

Although TiO₂ is an efficient photocatalyst, its large band gap limits its photocatalytic activity only to the ultraviolet region. An experimentally synthesized ternary Fe/C/S‐doped TiO₂ anatase showed improved visible light photocatalytic activity. However, a theoretical study of the underlying mechanism of the enhanced photocatalytic activity and the interaction of ternary Fe/C/S‐doped TiO₂ has not yet been investigated. In this study, the defect formation energy, electronic structure and optical property of TiO₂ doped with Fe, C, and S are investigated in detail using the density functional theory + U method. The calculated band gap (3.21 eV) of TiO₂ anatase agree well with the experimental band gap (3.20 eV). The defect formation energy shows that the co‐ and ternary‐doped systems are thermodynamically favorable under oxygen‐rich condition. Compared to the undoped TiO₂, the absorption edge of the mono‐, co‐, and ternary‐doped TiO₂ is significantly enhanced in the visible light region. We have shown that ternary doping with C, S, and Fe induces a clean band structure without any impurity states. Moreover, the ternary Fe/C/S‐doped TiO₂ exhibit an enhanced photocatalytic activity, a smaller band gap and negative formation energy compared to the mono‐ and co‐doped systems. Moreover, the band edges of Fe/C/S‐doped TiO₂ align well with the redox potentials of water, which shows that the ternary Fe/C/S‐doped TiO₂ is promising photocatalysts to split water into hydrogen and oxygen. These findings rationalize the available experimental results and can assist the design of TiO₂‐based photocatalyst materials.     

Defect induced nickel,nitrogen-codoped mesoporous TiO2 microspheres with enhanced visible light photocatalytic activity

Nickel, nitrogen-codoped mesoporous TiO₂ microspheres (Ni–N–TiO₂) with high surface area, and an effective direct band gap energy of ∼2.58 eV. Nickel sulfate used as the Ni source and ammonia gas as the N source here. The efficiency of the as-prepared samples was investigated by monitoring the degradation of Rhodamine B under visible light irradiation. The experimental results indicate that Ni-doped mesoporous TiO₂ microspheres show higher photocatalytic activity than mesoporous TiO₂ microspheres under visible light irradiation. It mainly due to that the electron trap level (Ni²⁺/Ni⁺) promoting the separation of charge carriers and the oxygen vacancies inducing the visible light absorption. In addition, Ni–N–TiO₂ shows enhanced activity compared with Ni–TiO₂. Codopants and dopants are found to be uniformly distributed in TiO₂ matrix. Among the all samples the 0.5% molar quantity of Ni dopant and 500 °C 2 h nitriding condition gives the highest photocatalytic activity. The treatment of ammonia gas on Ni–TiO₂ sample induced oxygen vancancies, substitutional and interstitial N. A suitable treatment by ammonia gas also promote separation of charge carriers and the absorption of visible light. The active species generated in the photocatalytic system were also investigated. The strategy presented here gives a promising route towards the development of a metal and non-metal codoped semiconductor materials for applied photocatalysis and related applications.     

Characterization and photocatalytic activity of Fe- and N-co-deposited TiO2 and first-principles study for electronic structure

Titanium dioxide (TiO₂), co-deposited with Fe and N, is first implanted with Fe by a metal plasma ion implantation (MPII) process and then annealed in N₂ atmosphere at a temperature regime of 400-600 °C. First-principle calculations show that the (Fe, N) co-deposited TiO₂ films produced additional band gap levels at the bottom of the conduction band (CB) and on the top of the valence band (VB). The (Fe, N) co-deposited TiO₂ films were effective in both prohibiting electron-hole recombination and generating additional Fe-O and N-Ti-O impurity levels for the TiO₂ band gap. The (Fe, N) co-deposited TiO₂ has a narrower band gap of 1.97 eV than Fe-implanted TiO₂ (3.14 eV) and N-doped TiO₂ (2.16 eV). A significant reduction of TiO₂ band gap energy from 3.22 to 1.97 eV was achieved, which resulted in the extension of photocatalytic activity of TiO₂ from UV to Vis regime. The photocatalytic activity and removal rate were approximately two-fold higher than that of the Fe-implanted TiO₂ under visible light irradiation.     

Enhanced photocatalytic hydrogen production performance of pillararene-doped mesoporous TiO2 with extended visible-light response

Pillararenes are a new type of supramolecular hosts,and they have been widely applied in drug delivery,catalysis,separation process,and sensors.However,they have rarely been used to produce hydrogen.Here,we report that pillararenes were used as functional molecules to explore photocatalysts and efficiently promoted hydrogen production from water.The most common and easily synthesized pdimethoxy pillar[5]arene（PI-OMe） was employed to form an organic-inorganic hybrid material with titanium dioxide...     

Photocatalytic performance of BiFeO3 based on MOFs precursor

BiFeO₃ (BFO) is considered to be a potential visible light photocatalytic material for organic degradation due to its narrow band gap. In this work, the BFO with smaller band gap and better photocatalytic performance was prepared by thermal decomposition of we prepared smaller band gap and better photocatalytic performance BFO by thermal decomposition of MOFs precursor Bi[Fe (CN)₆]·5H₂O. Among them, BFO‐0.5 has the best photocatalytic activity, which the photocatalytic degradation rate of methyl orange (MO) aqueous solution is 98.1% within 60 minutes. The photocatalytic activity is almost unchanged after four cycles of use. The enhanced photocatalytic activity of BFO could be attributed to the enhanced optical absorption and smaller particles. It may be conducive to design more efficient photocatalysts for photocatalytic degradation of organic dyes.     

Ag3PO4的可见光光催化性能及机理分析

采用沉淀置换法制备了可见光光催化剂Ag3PO4,利用XRD、UV-Vis及XPS等对其进行了结构特性分析,以水中微污染有机物的降解评价了Ag3PO4的光催化活性,并通过活性物种及能带结构的分析对催化剂的光催化机理进行了推测。结果表明,Ag3PO4的带隙能约为1.9 eV、催化剂表面存在的Ag+可捕获光生e-、催化剂的价带电位较低,这有利于Ag3PO4在可见光照射下产生的e--h+的分离及活性物种.OH的形成。经60 min可见光光催化反应,15 mg.L-1的甲基橙和腐殖酸的降解率分别达97%和82%,比同等条件下TiO2-P25的降解率还高40%和25%,光催化剂Ag3PO4的用量为0.6 g.L-1。     

三元杂化TiO2-SiO2-POMs催化剂的合成及其在可见光降解罗丹明B中的应用

采用分步溶胶-凝胶法制备的三元杂化催化剂TiO₂-SiO₂-杂多酸(POMs)在可见光降解工业染料罗丹明B中表现出了高效反应活性. 利用时间分辨微波传导(TRMC)和漫反射光谱(DRS)研究了催化剂在可见光区的光催化性能, 实验结果表明: 在三元杂化催化剂内, 二氧化钛和二氧化硅的键合加强了催化剂在可见光区的响应和吸收, 二氧化钛和杂多酸的结合提高了反应活性位(空穴-电子对)的稳定性. 三元杂化催化剂TiO₂-SiO₂-POMs中组分之间的协同效应促进了可见光光催化性能的提高.     

Sulfur and Ti3+ co‐Doping of TiO2 Nanotubes Enhance Photocatalytic H2 Evolution Without the Use of Any co‐catalyst

TiO₂ nanotubes were successfully co‐doped with sulfur and Ti³⁺ states using a facile annealing treatment in H₂/H₂S gas mixture. The obtained nanotubes were investigated for their photocatalytic performance and characterized by SEM, XRD, XPS, EPR, IPCE, IMPS and Mott‐Schottky measurements. The synthesized co‐doped TiO₂ nanotubes show an enhanced photocatalytic hydrogen production rate compared to tubes that were treated only in pure H₂ or H₂S atmosphere—this without the presence of any co‐catalyst. It was found that sulfur in co‐doped TiO₂ exists in the form of S^2? and a small quantity of S⁴⁺/S⁶⁺, which leads to a narrowing of the band gap. However, the enhanced absorption of light in the visible range is not the key reason for the improved photocatalytic performance. We ascribe the enhanced photocatalytic activity to a synergetic effect of S mid‐gap states and disordered Ti³⁺ defects that facilitate photo generated electron transfer.     

Effect of Co-catalyst CdS on the Photocatalytic Performance of ZnMoO4 for Hydrogen Production

Zinc molybdate (ZnMoO₄), a layer perovskite material, has the advantages of high stability, excellent optical and charge properties. However, its high band gap and high electron–hole recombination efficiency limit its application in the photocatalytic reduction field like hydrogen production. In this study, we used CdS as a co-catalyst and successfully prepared CdS/ZnMoO₄ composite photocatalysts with different loadings. The hydrogen evolution rate of CdS/ZnMoO₄ reached 530.2 µmol h^?1 g^?1, which was approximately 11 and 100 times more than rates of pure CdS and ZnMoO₄ under the same conditions, respectively. It is the presence of CdS that contributed to this improved performance, which acted as an electron acceptor to separate electrons and holes. Besides, a reasonable mechanism was provided based on photoelectrochemical characterizations. CdS loading greatly improved the hydrogen evolution performance of ZnMoO₄ under visible light, providing a direction to improving the performance of perovskite based photocatalysts.

     

Photocatalytic properties of CuO/(001)‐TiO2 composites synthesized by the vapor–thermal method

Composites of (001)‐face‐exposed TiO₂ ((001)‐TiO₂) and CuO were synthesized in water vapor environment at 250°C with various Cu/Ti molar ratios (R_Cu/Ti). The resulting CuO/(001)‐TiO₂ composites were characterized using a variety of techniques. The synthesis under high‐temperature vapor allows close contact between CuO and (001)‐TiO₂, which results in the formation of heterojunctions, as evidenced by the shift of valence band maximum towards the forbidden band of TiO₂. An appropriate ratio of CuO can enhance the absorption of visible light and promote the separation of photogenerated carriers, which improve the photocatalytic performance. The degradation rate constant K_app increased from 5.5 × 10^?2 to 8.1 × 10^?2 min^?1 for R_Cu/Ti = 0.5. Additionally, the results showed that superoxide radicals (^?O₂^?) play a major role in the photocatalytic degradation of methylene blue.     

A Semi‐Conductive Copper–Organic Framework with Two Types of Photocatalytic Activity

Based on the newly designed ligand 4′‐(3,5‐dicarboxyphenyl)‐4,2′:6′,4′′‐terpyridine (DCTP), a unique semi‐conductive 3D framework {[Cu^ΙCu^ΙΙ₂(DCTP)₂]NO₃?1.5 DMF}_n ( 1 ) with a narrow band gap of 2.1 eV, was obtained and structurally characterized. DFT calculations with van de Waals correction employed to explore the electronic structure of 1 , clearly revealed its semi‐conductive behavior. Furthermore, we found that 1 exhibits a superior band alignment with water to produce hydrogen and degrade organic pollutants. Without adding any photosensitizers, 1 displays an efficiently photocatalytic hydrogen production in water based on the photo‐generated electrons under UV/Vis light. 1 also exhibits excellent photo‐degradation of methyl blue under visible‐light owing to the strong oxidization of excited holes. It is the first example of MOFs with doubly photocatalytic activities related to photo‐generated electrons and holes, respectively.     

光催化剂Sm2FeSbO7的制备及光物理和光催化性能表征

首次采用固相反应法制备了新型光催化剂Sm₂FeSbO₇,有效地降解了水中有机污染物。利用X射线衍射、扫描电镜、X射线光电子能谱、傅里叶变换红外光谱、透射电子显微镜和紫外－可见光谱仪对Sm₂FeSbO₇的结构和光催化性能进行了表征。Sm₂FeSbO₇为烧绿石型结构,立方晶系和空间群Fd3m结晶。Sm₂FeSbO₇的晶格参数a为1.035 434 nm。Sm₂FeSbO₇的带隙经估算为2.46 eV。用Sm₂FeSbO₇作为光催化剂在可见光照射下降解靛蓝胭脂红,并与氮掺杂TiO₂对比。结果表明,与掺氮TiO₂相比,Sm₂FeSbO₇在可见光照射下光催化降解靛蓝胭脂红显示出较高的光催化活性。总有机碳的减少,无机产物的逐渐形成,SO₄^2-和NO₃^-以及CO₂的演变揭示了在光催化过程中靛蓝胭脂红的连续矿化。检测了一些来自光催化降解靛蓝胭脂红的中间体,如邻硝基苯甲酸和邻硝基苯甲醛,并获得了可能的靛蓝胭脂红光催化降解路径。     

Improved photoelectrochemical hydrogen production over decorated titania with copper and nickel oxides by optimizing the photoanode and reaction characteristics

We optimized photocatalytic hydrogen production over TiO₂-based photocatalyst by varying the dopant (nickel and copper oxide), thin film active area, nature and concentration of sacrificial agents, and light intensity in a photoelectrochemical (PEC) cell/dye-sensitized solar cell (DSSC). Various characterization techniques have been used to investigate the structural, morphological, optical, and PEC behavior of single and codoped TiO₂. The TiO₂ decorated with both Cu and Ni oxides with active area of 1 cm² in a mixture of 5 vol % glycerol and 1 M KOH under light intensity of 100 mWcm^?2 produced the maximum hydrogen of 338.4 μmol cm^?2 for 2 h. The superior photocatalyst performance of this photocatalyst is attributed to its small crystallite size and large pore size, as confirmed by X-ray diffractometer, Transmission electron microscopy (TEM), and surface area of Brunauer-Emmet-Teller (S_BET). The absorption edges of this photocatalyst had the highest red shift compared with single doped and pure TiO₂ because of more indirect transitions of the photoexcited electrons, greater charge carrier separation, and lower recombination rate. The photoanode active area of 1 cm² with better photocatalytic performance correlated with the number of defects and grain boundaries. Glycerol shifted the conduction band of the photocatalyst to more negative flat potential compared with others. Increasing the concentration of glycerol further than 5 vol% saturated the photocatalyst active sites, increased photooxidation intermediates of glycerol, and reduced the hydrogen production. The light intensity had the maximum impact on the hydrogen production and could strongly control the number of charge carriers in both the PEC cell and the DSSC.     

Heterostructural BiOI/TiO2 composite with highly enhanced visible light photocatalytic performance

Binary BiOI/TiO₂ hybrid material was synthesized via a sol-gel method combined with chemical etching. The as-prepared powders were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DRS), photoluminescence spectra (PLS) and photocurrent response tests. Under visible light (λ > 420 nm), BiOI/TiO₂ degraded methyl orange (MO) efficiently and displayed much higher photocatalytic activity than that of pure BiOI. Moreover, BiOI/TiO₂ can effectively promote photooxidation of other organic dyes like rhodamine B (RhB), crystal violet (CV) and methylene blue (MB). In addition, the quenching effects of different scavengers proved that reactive O ₂ ^? and h⁺ played the major role in the MO degradation. The photocatalytic activity enhancement of BiOI/TiO₂ is closely related to the strong absorption in the visible region, and the efficient charge separation derived from the matching band potentials between BiOI and TiO₂, as well as the low recombination rate of the electron-hole pairs due to the heterojunction formed between BiOI and TiO₂.     

Preparation and photocatalytic activity of visible light-active sulfur and nitrogen co-doped SrTiO3

Nitrogen and sulfur co-doped SrTiO₃ was prepared by high energy grinding of the mixture of SrTiO₃ and thiourea. A new band gap in visible light region (522 nm) corresponding to 2.37 eV could be formed by the co-doping. The photocatalytic activity for nitrogen monoxide oxidation of SrTiO₃ in visible light region especially in the long wavelength range (λ > 510 nm) could be improved greatly. Under the irradiation of light with wavelength larger than 510 nm, the photocatalytic activity of nitrogen and sulfur co-doped SrTiO₃ was 10.9 times greater than that of pure SrTiO₃. The high visible light photocatalytic activity of this substance may be due to the formation of a new band gap that enables to absorb visible light effectively.     

Semiconducting and quartz microbalance (QCM) humidity sensor properties of TiO2 by sol gel calcination method

Titanium dioxide (TiO₂) material was synthesized using the sol gel calcination method. The structural properties of the TiO₂ semiconductor were investigated by atomic force microscopy. The electrical conductivity of the TiO₂ was measured as a function of temperature and TiO₂ exhibits a conductivity of 2.55 × 10⁻⁶ S/m at room temperature with activation energy of 104 meV. The electrical conductivity of the TiO₂ at room temperature is higher than that of nanocrystalline TiO₂ (3 × 10⁻⁷ S/m) and TiO₂ thin film in air (5 × 10⁻⁹ S/m) and in vacuum (8.8 × 10⁻¹⁰ S/m). It was found that the electrical transport mechanism of the TiO₂ is controlled by thermally activated mechanism. The optical band gap of the TiO₂ powder sample was determined to be 3.17 eV, which is good in agreement with the bulk TiO₂ (E_g = 3.2 eV). Up to our knowledge, there is no any reported data about the band gap of TiO₂ nanopowder based on the diffused reflectance calculation. Quartz crystal microbalance (QCM) TiO₂ humidity sensor was prepared. The sensor indicates a large frequency change with an interaction occurred between TiO₂ and humidity molecules. The sensor exhibits a good repeatability when it was exposed to the moist air of 65% RH.     

Performance of a photocatalytic hybrid system coupled with a stainless steel membrane for removal of humic acid

The objective of this study was to evaluate the performance of a photocatalysis/H₂O₂/metal membrane hybrid system in the degradation of humic acid. A metal membrane of nominal pore size 0.5 μm was used in the experiment for separation of TiO₂ particles. Hydrogen peroxide was tested as an oxidant. The efficiency of removal of COD_Cr and color increased rapidly for initial hydrogen peroxide concentrations up to 50 mg L⁻¹. The efficiency of removal of COD_Cr and color by 50 mg L⁻¹ initial hydrogen peroxide concentration was approximately 95 and 98%, respectively. However, addition of hydrogen peroxide over 50 mg L⁻¹ inhibited the efficiency of the system. Addition of hydrogen peroxide to a UV/TiO₂ system enhanced efficiency of removal of COD_Cr and color compared with no addition of hydrogen peroxide. This may be ascribed to capture electrons ejected from TiO₂ and to the production of OH radicals. Application of the metal membrane in the UV/TiO₂/H₂O₂ system enhanced the efficiency of removal of COD_Cr and color because of adsorption by the metal membrane surface and the production of OH radicals. By application of a metal membrane with a nominal pore size of 0.5 μm, TiO₂ particles were effectively separated from the treated water by metal membrane rejection. The photocatalytic metal membrane had much less resistance than the humic acid, TiO₂, and humic acid/TiO₂ because of the degradation of humic acid by the photocatalytic reaction.     

光催化剂Sm2FeSbO7的制备及光物理和光催化性能表征

首次采用固相反应法制备了新型光催化剂Sm₂FeSbO₇,有效地降解了水中有机污染物。利用X射线衍射、扫描电镜、X射线光电子能谱、傅里叶变换红外光谱、透射电子显微镜和紫外-可见光谱仪对Sm₂FeSbO₇的结构和光催化性能进行了表征。Sm₂FeSbO₇为烧绿石型结构,立方晶系和空间群Fd3m结晶。Sm₂FeSbO₇的晶格参数a为1.035 434 nm。Sm₂FeSbO₇的带隙经估算为2.46 eV。用Sm₂FeSbO₇作为光催化剂在可见光照射下降解靛蓝胭脂红,并与氮掺杂TiO₂对比。结果表明,与掺氮TiO₂相比,Sm₂FeSbO₇在可见光照射下光催化降解靛蓝胭脂红显示出较高的光催化活性。总有机碳的减少,无机产物的逐渐形成,SO₄^2-和NO₃^-以及CO₂的演变揭示了在光催化过程中靛蓝胭脂红的连续矿化。检测了一些来自光催化降解靛蓝胭脂红的中间体,如邻硝基苯甲酸和邻硝基苯甲醛,并获得了可能的靛蓝胭脂红光催化降解路径。