附载光催化剂TiO_2/活性炭光催化氧化NO_2^-的研究

探讨了光催化剂TiO2/C的制备条件和不同制备条件对NO2-的光催化氧化效果.研究表明,制备TiO2/C的最佳条件为:Ti(OCH3)4的用量为10ml,附载光催化剂样品在400℃下焙烧5h,TiO2/C的用量为0.5g时光催化效果最好.

g-C_3N_4基光催化剂的制备和应用

石墨相氮化碳(g-C_3N_4)半导体材料具有无毒、带隙小(2.7 e V)、在太阳光谱中能较好吸收可见光的优点,是近年来迅速发展的新型可见光催化剂.然而,纯的g-C_3N_4还存在可见光捕获能力有限、电荷载流子易重组和比表面积小的缺点,其光催化效率不够理想,离实际工业大规模应用还有一段距离.文中总结了g-C_3N_4的合成方法.阐述了进一步提高g-C_3N_4活性的方法,包括孔道和比表面积的调控、贵金属沉积、非金属元素掺杂、半导体复合形成复合材料等.分析了g-C_3N_4基光催化剂在降解有机污染物、光解水制氢、还原六价铬三方面的研究进展,并对g-C_3N_4基光催化剂的研究方向进行了展望.

Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2) reduction pathway for efficient H_(2)O_(2) production using water and air

The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

Facile synthesis and enhanced photocatalytic H_2-evolution performance of NiS_2-modified g-C_3N_4 photocatalysts

NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature（80 ℃） impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups（such as-OH and-C0NH-） to the surface of g-C3N4.Then,the Ni^2＋ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2＋ ions upon the addition of Ni（NO3）2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate（116.343 μmol h^-1 g^-1）,which is significantly higher than that of the pure g-C3N4（3 μmol h^-1 g^-1）.Moreover,the results of a recycling test for the NiS2/g-C3N4（3 wt%）sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.

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.

Ternary Ag/AgCl/BiOIO_3 composites for enhanced visible-light-driven photocatalysis

Ternary Ag/AgC l/BiO IO3 composite photocatalysts are prepared by a facile method. Enhanced visible-light absorption and charge carrier separation are achieved after the introduction of Ag/AgC l particles into BiO IO3 systems,as revealed by ultraviolet-visible diffuse-reflectance spectrometry,photocurrent response and electrochemical impedance spectroscopy. The Ag/AgC l/BiO IO3 composites are applied to the visible-light photocatalytic oxidization of NO in air and exhibit an enhanced activity for NO removal in comparison with Ag/AgC l and pure BiO IO3. A possible photocatalytic mechanism for Ag/AgC l/BiO IO3 is proposed,which is related to the surface plasmon resonance effects of Ag metal and the effective carrier separation ability of BiO IO3. This work provides insight into the design and preparation of BiO IO3-based materials with enhanced visible-light photocatalysis ability.

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.

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.

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.

In situ synthesis of Ti^(3+) self-doped mesoporous TiO_2 as a durable photocatalyst for environmental remediation

This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.

Thermal nitridation of triazine motifs to heptazine-based carbon nitride frameworks for use in visible light photocatalysis

A thermal nitridation route for the assembly and polymerization of molecular triazine units to heptazine-based covalent frameworks has been successfully established. The obtained conjugated carbon nitride polymers feature nanostructures that show enhanced photocatalytic reactivity for hydrogen production under visible light irradiation.

Enhanced plasmonic photocatalysis by SiO_2@Bi microspheres with hot-electron transportation channels via Bi–O–Si linkages

The semimetal Bi has received increasing interest as an alternative to noble metals for use in plasmonic photocatalysis. To enhance the photocatalytic efficiency of metallic Bi, Bi microspheres modified by SiO2 nanoparticles were fabricated by a facile method. Bi-O-Si bonds were formed between Bi and SiO2, and acted as a transportation channel for hot electrons. The SiO2@Bi microspheres exhibited an enhanced plasmon-mediated photocatalytic activity for the removal of NO in air under 280 nm light irradiation, as a result of the enlarged specific surface areas and the promotion of electron transfer via the Bi-O-Si bonds. The reaction mechanism of photocatalytic oxidation of NO by SiO2@Bi was revealed with electron spin resonance and in situ diffuse reflectance infrared Fourier transform spectroscopy experiments, and involved the chain reaction NO -> NO2 -> NO3- with center dot OH and center dot O-2(-) radicals as the main reactive species. The present work could provide new insights into the in-depth mechanistic understanding of Bi plasmonic photocatalysis and the design of high-performance Bi-based photocatalysts. (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Enhanced photocatalytic H_2 production over dual-cocatalyst-modified g-C_3N_4 heterojunctions

Ag nanoparticles (NPs) were deposited on the surface of g-C3N4 (CN) by an in situ calcination method. NiS was successfully loaded onto the composites by a hydrothermal method. The results showed that the 10 wt%-NiS/1.0 wt%-Ag/CN composite exhibits excellent photocatalytic H2 generation performance under solar-light irradiation. An H2 production rate of 9.728 mmol·g^-1·h^-1 was achieved, which is 10.82-, 3.45-, and 2.77-times higher than those of pure g-C3N4, 10 wt%-NiS/CN, and 1.0 wt%-Ag/CN composites, respectively. This enhanced photocatalytic H2 generation can be ascribed to the co-decoration of Ag and NiS on the surface of g-C3N4, which efficiently improves light harvesting capacity, photogenerated charge carrier separation, and photocatalytic H2 production kinetics. Thus, this study demonstrates an effective strategy for constructing excellent g-C3N4-related composite photocatalysts for H2 production by using different co-catalysts.

S-scheme Sb2WO6/g-C3N4 photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance

Normal photocatalysts cannot effectively remove low-concentration NO because of the high recombination rate of the photogenerated carriers.To overcome this problem,S-scheme composites have been developed to fabricate photocatalysts.Herein,a novel S-scheme Sb2WO6/g-C3N4 nanocomposite was fabricated by an ultrasound-assisted method,which exhibited excellent performance for photocatalytic ppb-level NO removal.Compared with the pure constituents of the nanocomposite,the as-prepared 15%-Sb2WO6/g-C3N4 photocatalyst could remove more than 68%continuous-flowing NO(initial concentration:400 ppb)under visible-light irradiation in 30 min.The findings of the trapping experiments confirmed that•O2^–and h+were the important active species in the NO oxidation reaction.Meanwhile,the transient photocurrent response and PL spectroscopy analyses proved that the unique S-scheme structure of the samples could enhance the charge separation efficiency.In situ DRIFTS revealed that the photocatalytic reaction pathway of NO removal over the Sb2WO6/g-C3N4 nanocomposite occurred via an oxygen-induced route.The present work proposes a new concept for fabricating efficient photocatalysts for photocatalytic ppb-level NO oxidation and provides deeper insights into the mechanism of photocatalytic NO oxidation.

SPR effect of bismuth enhanced visible photoreactivity of Bi_2WO_6 for NO abatement

Bi2WO6 is a typical visible-light-responsive semiconductor photocatalyst with a layered structure.However,the relatively large bandgap(2.6–2.8 eV)and quick recombination of photo-generated carriers result in its low quantum efficiency.In this paper,Bi-nanospheres-modified flower-like Bi2WO6 was successfully prepared by solvothermal treatment of Bi2WO6 powders in Bi(NO3)3 solution using ethylene glycol as reductant.The photoreactivity of this photocatalyst was evaluated by the oxidation of NO in a continuous-flow reactor under irradiation by a visible LED lamp(λ>400 nm).It was found that both Bi nanospheres and flower-like Bi2WO6 precursor exhibit very poor photocatalytic activity with NO removal rates of only 7.7%and 8.6%,respectively.The photoreactivity of Bi/Bi2WO6 was found to steadily increase from 12.3%to 53.1%with increase in the amount of Bi nanospheres from 0 to 10 wt%.However,with further increase in the loading amount of Bi nanospheres,the photoreactivity of Bi/Bi2WO6 hybridized photocatalyst begins to decrease,possibly due to the light filtering by the Bi nanospheres.The enhanced visible photoreactivity of Bi/Bi2WO6 towards NO abatement was attributed to surface plasmon resonance driven interfacial charge separation.The excellent stability of Bi/Bi2WO6 hybridized photocatalyst towards NO oxidation demonstrates its potential for applications such as air purification.

Design of p-n homojunctions in metal-free carbon nitride photocatalyst for overall water splitting

Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes.Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity.The rate of hydrogen production using these CN photocatalysts reached 17028.82μmol h^(−1)g^(−1),and the apparent quantum efficiency was 11.2%at 420 nm.The ns-level time-resolved photoluminescence(PL)spectra provided information about the time-averaged lifetime of fluorescence charge carriers;the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns.Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents.The average hydrogen and oxygen production rates were 270.95μmol h^(−1)g^(−1)and 115.21μmol h^(−1)g^(−1)in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes.We investigated the high efficiency of the prepared CN photocatalysts via a series of tests(UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis).Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests.The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency.Therefore,this work can promote the development of CN photocatalysts.

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Fabrication of highly dispersed platinum-deposited porous g-C_3N_4 by a simple in situ photoreduction strategy and their excellent visible light photocatalytic activity toward aqueous 4-fluorophenol degradation

A series of highly dispersed platinum‐deposited porous g‐C3N4 (Pt/pg‐C3N4) were successfully fabricated by a simple in situ photoreduction strategy using chloroplatinic acid and porous g‐C3N4 as precursors. Porous g‐C3N4 was fabricated by a pretreatment strategy using melamine as a raw material.The morphology, porosity, phase, chemical structure, and optical and electronic properties ofas‐prepared Pt/pg‐C3N4 were characterized. The photocatalytic activity of as‐prepared Pt/pg‐C3N4was preliminarily evaluated by the degradation of aqueous azo dyes methyl orange under visible light irradiation. The as‐prepared Pt/pg‐C3N4 were further applied to the degradation and mineralization of aqueous 4‐fluorophenol. The recyclability of Pt/pg‐C3N4 was evaluated under four consecutive photocatalytic runs.

Efficient photocatalytic degradation of NO by ceramic foam air filters coated with mesoporous TiO_2 thin films

Ceramic foam air filters with three-dimensional（3D） porous structures and high surface areas were coated with mesoporous TiO 2 thin films by the reverse micellar method. The mesoporous TiO 2 thin films efficiently photocatalytically degraded nitrogen oxide（NO）. More than 92.5% of NO was degraded in a single pass for air filter samples containing different pore densities. The 3D porous structure of the ceramic air filters enhanced flow turbulence and mixing. This provided the catalytic system with excellent gas-dynamic properties,and sufficient contact between the reactant gas and catalyst surface. The higher pore density of the ceramic foam filters resulted in a higher photocatalytic rate. More adsorption sites for water vapor and the reactant and product gases improved the photocatalytic activity. The porous ceramic air filters coated with mesoporous TiO 2 had large surface areas,and thus high photocatalytic activity. This overcame the common disadvantages associated with using powdered TiO 2 photocatalysts on substrates. The 3D porous ceramic foam filters coated with mesoporous TiO 2 thin films exhibited a higher photocatalytic degradation rate of NO in air than the same thin film deposited on flat ceramic tiles. No deactivation was observed. A consistently high NO degradation rate was obtained between reaction cycles for the TiO 2-coated 3D porous ceramic filters.