ZnO/TiO_2改性催化剂在阳光照射下对溴氨酸水溶液的催化降解

采用溶胶-凝胶法制备了具有可见光响应的ZnO/TiO2催化剂.考察了煅烧温度、煅烧时间、ZnO掺杂量对ZnO/TiO2催化剂性能的影响及阳光下不同紫外线强度对ZnO/TiO2催化剂降解溴氨酸水溶液的影响.结果表明:当煅烧温度为400,℃,煅烧时间为2h,ZnO掺杂比为1%时,催化剂性能较佳;紫外线指数为5,光照5,h时,溴氨酸水溶液的褪色率达到100%,在太阳光直射下3,h后,溴氨酸水溶液的褪色率为97.73%,TOC去除率为82.88%.

具有高活性宽光谱响应的新型光催化材料

以二氧化钛为代表的传统光催化材料只能利用短波长的紫外光,太阳光利用率和量子效率低,其广泛应用受到极大限制.针对这一问题,近年来我们开展了一系列具有高活性和(或)宽光谱响应(包括紫外及可见光)的新型纳米光催化材料的研究.本文简要总结了相应工作的进展,并对可能影响光催化材料的活性和光谱响应的相关因素进行了探讨.

NiFe layered double-hydroxide nanoparticles for efficiently enhancing performance of BiVO_4 photoanode in photoelectrochemical water splitting

A bismuth vanadate(BiVO4)photoanode with a cocatalyst consisting of NiFe layered double‐hydroxide(NiFe‐LDH)nanoparticles was fabricated for photoelectrochemical(PEC)water splitting.NiFe‐LDH nanoparticles,which can improve light‐absorption capacities and facilitate efficient hole transfer to the surface,were deposited on the surface of the BiVO4 photoanode by a hydrothermal method.All the samples were characterized using X‐ray diffraction,scanning electron microscopy,and diffuse‐reflectance spectroscopy.Linear sweep voltammetry and current‐time plots were used to investigate the PEC activity.The photocurrent response of NiFe‐LDH/BiVO4 at 1.23 V vs the reversible hydrogen electrode was higher than those of Ni(OH)2/BiVO4,Fe(OH)2/BiVO4 and pure BiVO4 electrodes under visible‐light illumination.NiFe‐LDH/BiVO4 also gave a superior PEC hydrogen evolution performance.Furthermore,the stability of the NiFe‐LDH/BiVO4 photoanode was excellent compared with that of the bare BiVO4 photoanode,and offers a novel method for solar‐assisted water splitting.

Preparation of BiOCl0.9I0.1/β-Bi2O3 composite for degradation of tetracycline hydrochloride under simulated sunlight

A novel and effective BiOCl0.9I0.1/x%β-Bi2O3 composite catalyst was synthesized through a precipitation method. The structure, morphology, and optical properties of the samples were certified by X-ray diffraction, UV-Vis diffuse reflectance, scanning electron microscopy, and X-ray photoelectron spectroscopic characterizations. Photocatalytic experiments demonstrated that the synthesized BiOCl0.9I0.1/x%β-Bi2O3 composite catalyst exhibited excellent photocatalytic performance toward the degradation of tetracycline hydrochloride(TCH) under simulated sunlight. Furthermore, the TCH degradation rate of BiOCl0.9I0.1/15%β-Bi2O3 increased by 27.6% and 61.4% compared with those of the pure BiOCl0.9I0.1 and pure β-Bi2O3, respectively. Due to the multiple vacancies and valence states possessed by BiOCl0.9I0.1/x%β-Bi2O3, namely Bi5+, Bi(3-x)+, Bi5+–O, Bi3+–O, I- and I3-, the charge separation in photocatalysis reactions can be effectively promoted. The Mott-Schottky measurements indicate that the conduction band(CB) level of BiOCl0.9I0.1/15%β-Bi2O3 becomes more negative relative to that of BiOCl0.9I0.1, guaranteeing an advantageous effect on the redox ability of the photocatalyst. This study provides a new bright spot for the construction of high-performance photocatalysts.

One-step fabrication of TiO2/graphene hybrid mesoporous film with enhanced photocatalytic activity and photovoltaic performance

We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.

Surface-sulfurized Ag_2O nanoparticles with stable full-solar-spectrum photocatalytic activity

Ag2O has attracted much recent attention,because of its high photocatalytic activity in the ultraviolet(UV)‐visible region.However,there have been few reports on the near‐infrared(NIR)photocatalytic activity of Ag2O.This paper reports the high NIR photocatalytic activity of Ag2O nanoparticles.Ag2O is unsuitable for application in full‐solar‐spectrum photocatalysis,because it is unstable under UV irradiation.A surface sulfurization process was carried out to address this issue.Specifically,a layer of Ag2S2O7nanoparticles was grown on the surface of the Ag2O nanoparticles,to improve the stability of the Ag2O photocatalyst and enhance its photocatalytic activity in the UV,visible and NIR regions.The Ag2O/Ag2S2O7heterostructure is a stable and efficient full‐solar‐spectrum photocatalyst.It has potential application in the photodegradation of organic pollutants,and more generally in environmental engineering where full utilization of the solar spectrum is required.

Preparation of N-Doped TiO_2-Loaded Halloysite Nanotubes and Its Photocatalytic Activity under Solar-Light Irradiation

The N-doped TiO2-loaded halloysite nanotubes(N-Ti O2/HNTs) nanocomposites were prepared by using chemical vapor deposition method which was realized in autoclave. The photocatalytic activity of nanocomposites was evaluated by virtue of the decomposition of formaldehyde gas under solar-light irradiation. The XRD patterns verified that the anatase structured TiO2 was deposited on HNTs. The TEM images showed that the surface of HNTs was covered with nanosized TiO2 with a particle size of ca. 20 nm. The UV-vis spectra indicated that the N-Ti O2/HNTs presented a significant absorption band in the visible region between 400 nm and 600 nm. Under solar-light irradiation, the highest degradation rate of formaldehyde gas attained 90% after 100 min of solar-light irradiation. The combination of the photocatalytic property of TiO2 and the unique structure of halloysite would assert a promising perspective in degradation of organic pollutants.

Metastable-phaseβ-Fe_(2)O_(3) photoanodes for solar water splitting with durability exceeding 100 h

Planar films of pure and Ti^(4+)-dopedβ-Fe_(2)O_(3)were prepared by a spray pyrolysis method.X-ray diffraction patterns and Raman spectra of the metastableβ-Fe_(2)O_(3)film showed that its thermal stability was significantly improved because of covalent bonds in the interfaces between the film and substrate,while only weak Van der Waals bonds existed at the interfaces within the particle-assembledβ-Fe_(2)O_(3)film prepared by electrophoretic deposition.The as-prepared planar films were thus able to withstand higher annealing temperature and stronger laser irradiation power in comparison with theβ-Fe_(2)O_(3)particle-assembly.Ti^(4+)doping was used to increase the concentration of carriers in the metastableβ-Fe_(2)O_(3)film.Compared with pureβ-Fe_(2)O_(3)photoanodes,the highest saturated photocurrent for water splitting over the Ti^(4+)-dopedβ-Fe_(2)O_(3)photoanode was increased by a factor of approximately three.Theβ-Fe_(2)O_(3)photoanode exhibited photochemical stability for water splitting for a duration exceeding 100 h,which indicates its important potential application in solar energy conversion.

Photocatalytic H_2 evolution activity of CuO/ZrO_2 composite catalyst under simulated sunlight irradiation

Zirconia-supported CuO （CuO/ZrO2） composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO2 materials were also prepared by solid state reaction and co-precipitation method. The as-prepared powders were characterized by X-ray diffractometry （XRD）, transmission electron microscopy （TEM）, and thermogravimetric-differential thermal analysis （TG-DTA）. The photocatalytic activity of CuO/ZrO2 catalyst was investigated based on the H2 evolution from oxalic acid solution under simulated sunlight irradiation. The effects of molar ratio of CuO to ZrO2, preparation method, phase change with the calcination temperature and the durability on the photocatalytic activity of the photocatalyst were investigated in detail. It is found that the optimal activity of photocatalytic H2 evolution （2.41 mmol.h i.g-~） can be obtained when CuO/ZrO2 composite photocatalyst is synthesized by sol-gel technique and the mole ratio of CuO to ZrO2 is 40%. The activity of copper oxide supported on monoclinic ZrO2 calcined at higher temperature is much higher than that on tetragonal ZrO2 calcined at lower temperature, and the best calcination temperature is 900 ℃.

Promoting charge carrier utilization by integrating layered double hydroxide nanosheet arrays with porous BiVO_4 photoanode for efficient photoelectrochemical water splitting

The increasing exploration of renewable and clean power sources have driven the development of highly active materials for photoelectrochemical （PEC） water splitting. However, it is still a great challenge to enhance the charge utilization. Herein, we report a facile method to fabricate composite photoanode with porous BiVO4 film as the photon absorber and layered double hydroxide （LDH） nanosheet arrays as the oxygen-evolution cocatalysts （OECs）. The as-prepared BiVO4/NiFe-LDH photoanode shows an excellent performance for PEC water splitting benefitting from the synergistic effect of the superior charge separation efficiency facilitated by porous BiVO4 film and the excellent water oxidation activity resulting from LDH nanosheet arrays. A photocurrent density is 4.02 mA cm^-2 at 1.23 V vs. the reversible hydrogen electrode （RHE）. Furthermore, the O2 evolution rate at the surface of BiVO4/NiFe-LDH photoanode is as high as 29.6 μmol h^-1 cm^-2 and the high activity for water oxidation is maintained for over 30 h. Impressively, the performance of the as-fabricated composite photoanode for PEC water splitting can be further enhanced through incorporating a certain amount of Co^2＋ cation into NiFe-LDH as OEC. The photocurrent density is achieved up to 4.45 mA cm^-2 at 1.23 V vs. RHE. This value is the highest yet reported for un-doped BiVO4-based photoanodes so far.

An integrated thermoelectric-assisted photoelectrochemical system to boost water splitting

Common solar-driven photoelectrochemical(PEC) cells for water splitting were designed by using semiconducting photoactive materials as working photoelectrodes to capture sunlight. Due to the thermodynamic requirement of 1.23 eV and kinetic energy loss of about 0.6 eV, a photo-voltage of 1.8 V produced by PEC cells is generally required for spontaneous water splitting. Therefore, the minimum bandgap of1.8 eV is demanded for photoactive materials in single-photoelectrode PEC cells, and the bandgap of about 1 eV for back photoactive materials is appropriate in tandem PEC cells. All these PEC cells cannot effectively utilize the infrared light from 1250 to 2500 nm. In order to realize the full spectrum utilization of solar light, here, we develop a solar-driven PEC water splitting system integrated with a thermoelectric device. The key feature of this system is that the thermoelectric device produces a voltage as an additional bias for the PEC system by using the temperature difference between the incident infrared-light heated aqueous electrolyte in the PEC cell as the hot source and unirradiated external water as the cold source. Compared to a reference PEC system without the thermoelectric device, this system has a significantly improved overall water splitting activity of 1.6 times and may provide a strategy for accelerating the application of full spectrum solar light-driven PEC cells for hydrogen production.