Decorating Ag/AgCl on UiO-66-NH2: Synergy between Ag plasmons and heterostructure for the realization of efficient visible light photocatalysis

UiO-66-NH2, as typical visible light responsive Zr-based metal-organic frameworks (MOFs), has attracted great interest in recent years. However, rapid combination of the photoinduced carriers limits its further application. Here, we designed a facile precipitation-photoreduction method to post-synthetically decorate Ag/AgCl on the surface of UiO-66-NH2 and form a heterostructure. Metallic Ag can not only transmit electrons between UiO-66-NH2 and AgCl but also absorb visible light, because of the surface plasmon resonance (SPR) effect. The rhodamine B photodegradation rate of UiO-66-NH2/Ag/AgCl (16.2 wt.% Ag) is about 10 and 4 times those of UiO-66-NH2 and Ag/AgCl, respectively. The SPR effect of Ag NPs and the formation of a heterostructure synergistically increase the absorbability of visible light, accelerate the separation of photoinduced charges, and promote the formation of superoxide radicals. We expect that our work could provide a new viewpoint for constructing efficient MOF-based photocatalytic systems.

Preparation of Nitrogen-doped TiO2 Nanoparticle Catalyst and Its Catalytic Activity under Visible Light

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.

Simple Method to Fabricate Au Nanoparticle-Decorated TiO2 Nanotube Arrays for Enhanced Visible Light Photocurrent

Au nanoparticle-decorated TiO2 nanotube arrays are prepared by a simple method, which is a thermal annealing thin gold film deposited on anodie oxidized TiO2 nanotube arrays. These electron microscope images present that Au nanoparticles are well dispersed within the wall and on the surface of the XiO2 nanotubes. Meanwhile, the morphologies of Au nanoparticles can be controlled by changing the thickness of the deposited gold film. Associ- ated with the excitation of localized surface plasmon resonances, the prepared Au nanoparticle-decorated TiO2 nanotube arrays could work as visible light responsive photocatalysts to produce a greatly enhanced photocurrent density. By varying the initial gold film thickness, such Au nanoparticle-decorated TiO2 nanotube arrays could be optimized to obtain the highest photocurrent generation efficiency in the visible and UV light regions.

Novel Bi2MoO6 Nanosheets/Vertical TiO2 Nanorods Arrays Heterojunction with Enhanced Photoelectrochemical Performance under Visible Light Irradiation

Novel Bi2MoO6/TiO2 heterojunction was fabricated by growing Bi2MoO6 nanosheets arrays on the vertically aligned TiO2 nanorods arrays via a two-step solvothermal method. The obtained Bi2MoO6/TiO2 hierarchical heterojunction showed excellent visible light photoelectrochemical performance. Compared with the pure TiO2 and Bi2MoO6, the photocurrent density of the heterojunction was increased 57 and 29 times, respectively. Furthermore, the hydrogen generation rate of the Bi2MoO6/TiO2 for photoelectrocatalytic water-splitting was about 6 times higher than that of the pure Bi2MoO6. The improved performance can be attributed to the synergistic effects of enhanced absorption of visible light, increase of migration rate and separation efficiency of photo-induced carriers.

Structure, photocatalytic and antibacterial activity study of Meso porous Ni and S co-doped TiO2 nano material under visible light irradiation

Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.

Synthesis of La/N Co-Doped SrTiO₃Using Polymerized Complex Method for Visible Light Photocatalysis

Lanthanum and nitrogen co-doped SrTiO3 was synthesized using polymerized complex method with Ti(OC3H7)4, SrCl2·6H2O and La(NO3)3·6H2O as starting materials followed by calcinations in NH3. Ethylene glycol and anhydrous citric acid were used as the precursors of synthesis. The samples were characterized using XRD, TEM, DRS, BET, EDX and XPS. The cubic-perovskite type of La/N co-doped SrTiO3 nanoparticle could be successfully synthesized. The photocatalytic activity of SrTiO3 for DeNOx ability in visible light region (λ > 510 nm) could be improved by co-doping of La3+ and N3_. The high visible light photocatalytic activity of this substance was caused by a narrow band gap energy that enables to absorb visible light.

Coupling of Cu Catalyst and Phosphonated Ru Complex Light Absorber with TiO2 as Bridge to Achieve Superior Visible Light CO2 Photoreduction

Visible light photocatalytic CO2 conversion is a promising solution to global warming and energy shortage.Herein,we build a well-designed bridge-like nanostructure,that is,the phosphonated Ru complex(RuP)light absorber–TiO2 bridge–Cu catalyst.In this nanostructure,brookite TiO2 serving as a bridge is spatially connected to the RuP and Cu on each of its sides and could thus physically separate the photoexcited holes and electrons over the RuP and Cu,respectively.Given its eff ective charge separation,this RuP–TiO2–Cu assembly exhibits superior CO2 photoreduction activity relative to RuP–SiO2–Cu under visible light irradiation(λ>420 nm).The catalytic activity is further optimized by adopting brookite TiO2 with various electronic band structures.Results reveal the rapid movement of electrons from the RuP through the conduction band of TiO2 and fi nally to the Cu surface.This property is crucial in CO2 photoreduction activity.

Synergic effects of Cu_xO electron transfer co-catalyst and valence band edge control over TiO_2 for efficient visible-light photocatalysis

Bandgap engineering by doping and co‐catalyst loading are two primary approaches to designing efficient photocatalysts by promoting visible‐light absorption and charge separation,respectively.Shifting of the TiO2conduction band edge is frequently applied to increase visible‐light absorption but also lowers the reductive properties of photo‐excited electrons.Herein,we report a visible‐light‐driven photocatalyst based on valance band edge control induced by oxygen excess defects and modification with a CuxO electron transfer co‐catalyst.The CuxO grafted oxygen‐rich TiO2microspheres were prepared by ultrasonic spray pyrolysis of the peroxotitanate precursor followed by a wet chemical impregnated treatment.We found that oxygen excess defects in TiO2shifted the valence band maximum upward and improved the visible‐light absorption.The CuxO grafted onto the surface acted as a co‐catalyst that efficiently reduced oxygen molecules to active intermediates(i.e.,O2??radial and H2O2),thus consuming the photo‐generated electrons.Consequently,the CuxO grafted oxygen‐rich TiO2microspheres achieved a photocatalytic activity respectively8.6,13.0and11.0as times high as those of oxygen‐rich TiO2,normal TiO2and CuxO grafted TiO2,for degradation of gaseous acetaldehyde under visible‐light irradiation.Our results suggest that high visible‐light photocatalytic efficiency can be achieved by combining oxygen excess defects to improve visible‐light absorption together with a CuxO electron transfer co‐catalyst.These findings provide a new approach to developing efficient heterojunction photocatalysts.

Visible Light-Responsive N-Doped TiO_(2) Photocatalysis:Synthesis,Characterizations,and Applications

Photocatalysis based on semiconductors has recently been receiving considerable research interest because of its extensive applications in environmental remediation and renewable energy generation.Various semiconductor-based materials that are vital to solar energy utilization have been extensively investigated,among which titanium oxide(TiO_(2))has attracted considerable attention because of its exceptional physicochemical characteristics.However,the sluggish responsiveness to visible light in the solar spectrum and the inefficient separation of photoinduced electron-hole pairs hamper the practical application of TiO_(2) materials.To overcome the aforementioned serious drawbacks of TiO_(2),numerous strategies,such as doping with foreign atoms,particularly nitrogen(N),have been improved in the past few decades.This review aims to provide a comprehensive update and description of the recent developments of N-doped TiO_(2) materials for visible lightresponsive photocatalysis,such as(1)the preparation of N-doped/co-doped TiO_(2) photocatalysts and(2)mechanistic studies on the reasons for visible light response.Furthermore,the most recent and significant advances in the field of solar energy applications of modified N-doped TiO_(2) are summarized.The analysis indicated the critical need for further development of these types of materials for the solar-to-energy conversion,particularly for water splitting purposes.

Degradation of Gesaprim Herbicide by Heterogeneous Photocatalysis Using Fe-Doped TiO2

Fe-doped TiO2 was prepared by the sol gel method and characterized by X-ray diffraction. All the Fe-doped TiO2 were composed of an anatase crystal form. The activity of the Fe-doped TiO2 for the degradation of the gesaprim commercial herbicide (which contains atrazine as active compound and formulating agents) was studied by varying the iron content during UV (15 W), visible light and solar irradiations. The visible light came from commercial saving energy lamps (13, 15 and 20 Watts). The gesaprim degradation rate depended on the iron content in the photo catalyst. The Fe-doped TiO2 (0.5% by weight of TiO2) showed higher TOC removal under visible light and was more active than the undoped TiO2 photo catalyst under the light irradiation sources tested. Over 90% of chemical oxygen demand abatement was achieved with both UV and visible light but less time was required to decrease the chemical oxygen demand content by using the catalyst doped with iron at 0.5% under visible light. It was observed that the degradation of gesaprim increased by increasing the iron content in the catalyst under visible light.

Construction of novel TiO2/Bi4Ti3O(12)/MoS2 core/shell nanofibers for enhanced visible light photocatalysis

TiO2/Bi4 Ti3 O12 hybrids have been widely prepared as promising photocatalysts for decomposing organic contaminations.However,the insufficient visible light absorption and low charge separation efficiency lead to their poor photocatalytic activity.Herein,a robust methodology to construct novel TiO2/Bi4 Ti3 O12/MoS2 core/shell structures as visible light photocatalysts is presented.Homogeneous bismuth oxyiodide(BiOI) nanoplates were immobilized on electrospun TiO2 nanofiber surface by successive ionic layer adsorption and reaction(SILAR) method.TiO2/Bi4 Ti3 O12 core/shell nanofibers were conveniently prepared by partial conversion of TiO2 to high crystallized Bi4 Ti3 O12 shells through a solid-state reaction with BiOI nanoplates,which is accompanied with certain transition of TiO2 from anatase to rutile phase.Afterwards,MoS2 nanosheets with several layers thick were uniform decorated on the TiO2/Bi4 TiO3 O12 fiber surface resulting in TiO2/Bi4 Ti3 O12/MoS2 structures.Significant enhancement of visible light absorption and photo-generated charge separation of TiO2/Bi4 Ti3 O12 were achieved by introduction of MoS2.As a result,the optimized TiO2/Bi4 Ti3 O12/MoS2-2 presents 60% improvement for photodegrading RhB after 120 min irradiation under visible light and 3 times higher of apparent reaction rate constant in compared with the TiO2/Bi4 Ti3 O12.This synthetic method can also be used to establish other photocatalysts simply at low cost,therefore,is suitable for practical applications.

Magnetically Separable Straw@Fe_(3)O_(4)/Cu_(2)O Composites for Photocatalytic Degradation of Methyl Orange under Visible Light Irradiation

Fe_(3)O_(4)and Cu_(2)O were successively immobilized on alkali-treated straw,and the magnetically separable straw@Fe_(3)O_(4)/Cu_(2)O composite was obtained.The straw@Fe_(3)O_(4)/Cu_(2)O was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,scanning electron microscopy,X-ray photoelectron spectroscopy and vibrating sample magnetometry,respectively.Photocatalytic performance of the straw@Fe_(3)O_(4)/Cu_(2)O was evaluated by measuring the degradation of methyl orange(MO)under irradiation of visible light.The introduction of Fe3O4 not only endowed the straw@Fe_(3)O_(4)/Cu_(2)O with magnetic separation feature but also significantly enhanced photocatalytic activity because Fe3O4 could prevent recombination of hole-electron pairs.The active species capture experiment showed that holes(h+),hydroxyl(∙OH)and superoxide(∙O2ˉ)radicals all took part in the MO degradation.In addition,the photocatalytic mechanism of straw@Fe_(3)O_(4)/Cu_(2)O was proposed based on the experimental results.After five cycles for the photodegradation of MO,the straw@Fe_(3)O_(4)/Cu_(2)O still displayed good photocatalytic activity,suggesting that the as-prepared composite had great potential for practical use in wastewater treatment.

Preparation,Characterization and Visible Light Photocatalytic Activity of Nitrogen-doped TiO_2

The N-doped TiO2 polycrystalline powder was synthesized through calcining the hydrolysis prodact of tetra-butyl titanate with ammonia. The photocatalytic activity of N-doped TiO2 powder with anatase phone calcined at 400℃ was 2.7 times higher than that of Degussa P25 for phenol decomposition under visible light. All samples had mesoporoas structures. X- ray photoelectron spectroscopy confirmed that a trace amount of N atoms remained in the anatase polycrystaUine TiO2 powder when calcined at 400 ℃ as substitutional atoms at the oxygen sites. UV-Vis and EPR analyses indicated that oxygen vacancy states were created during the course of N-doped TiO2 powder formation. It is considered that substitutional N atoms, oxygen vacancy, states, large BET surface areas and mesoporoas structure are important facwrs for the N-doped photocatalyst to present a high vis-activity.

Preparation of spherical activated carbon-supported and Er^(3+):YAlO_3-doped TiO_2 photocatalyst for methyl orange degradation under visible light

In order to develop the high photocatalytic activity of TiO2 under visible light as that under ultraviolet light and make it easy to be separated from treated liquor, a visible light response and spherical activated carbon （SAC） supported photocatalyst doped with upconversion luminescence agent Er3＋：YAlO3 was prepared by immobilizing Er3＋：YAlO3/TiO2, which was obtained by combination of Er3＋：YAlO3 and TiO2 using sol-gel method, on the surface of SAC. The crystal phase composition, surface structure and element distribution, and light absorption of the new photocatalysts were examined by X-ray diffraction （XRD）, energy dispersive X-ray spectra （EDS） analysis, scanning electron microscopy （SEM） and fluorescence spectra analysis （FSA）. The photocatalytic oxidation activity of the photocatalysts was also evaluated by the photodegradation of methyl orange （MO） in aqueous solution under visible light irradiation from a LED lamp （λ400 nm）. The results showed that Er3＋：YAlO3 could perform as the upconversion luminescence agent which converts the visible light up to ultraviolet light. The Er3＋：YAlO3/TiO2 calcinated at 700 °C revealed the highest photocatalytic activity. The apparent reaction rate constant could reach 0.0197 min-1 under visible light irradiation.

Preparation of NaYF_4:Er^(3+)/TiO_2 composite and up-conversion luminescence properties under visible light excitation

The up-conversion luminescence composite NaYF4：Er3＋/TiO2 is prepared using the sol-gel method. The specimen has good crystallinity and two shapes, i.e., viereck and round, while the sizes of viereck and round particles are both micron-sized. The TiO2 has an anatase structure, while the NaYF4 has a hexagonal phase, which can be hardly obtained through the common sol-gel method. Due to the big particle size and the high crystallinity of pure NaYF4： Er3＋, the composite has a small specific surface area that is less than Degussa P25 TiO2. The NaYF4：Er3＋/TiO2 composite shows several emission peaks at 211, 237, and 251 nm under the excitation of 388 nm, at 395 nm and 411 nm under the excitation of 500 nm, and at 467, 481,492, and 508 nm under the excitation of 570 nm.

Degradation of dyestuff wastewater using visible light in the presence of a novel nano TiO_2 catalyst doped with upconversion luminescence agent

A new upconversion luminescence agent, 40CdF2·60BaF2·0.8ErO3, was synthesized and its fluorescent spectra were determined. This upconversion luminescence agent can emit five upconversion fluorescent peaks shown in the fluorescent spectra whose wavelengths are all below 387 nm under the excitation of 488 nm visible light. This upconversion luminescence agent was mixed into nano rutile TiO2 powder by ultrasonic and boiling dispersion and the novel doped nano TiO2 photocatalyst utilizing visible light was firstly prepared. The doped TiO2 powder was charactered by XRD and TEM and its photocatalytic activity was tested through the photocatalytic degradation of methyl orange as a model compound under the visible light irradiation emitted by six three basic color lamps. In order to compare the photocatalytic activities, the same experiment was carried out for undoped TiO2 powder. The degradation ratio of methyl orange in the presence of doped nano TiO2 powder reached 32.5% under visible light irradiation at 20 h which was obviously higher than the corresponding 1.64% in the presence of undoped nano TiO2 powder, which indicate the upconversion luminescence agent prepared as dopant can effectively turn visible lights to ultraviolet lights that are absorbed by nano TiO2 particles to produce the electron-cavity pairs. All the results show that the nano rutile TiO2 powder doped with upconversion luminescence agent is a promising photocatalyst using sunlight for treating the industry dye wastewater in great force.

Photocatalytic Activity of Lanthanum and Sulfur Co-doped TiO_2 Photocatalyst under Visible Light

A novel lanthanum and sulfur co-doped TiO2 photocatalyst was synthesized by precipitation- dipping method, and characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and UV-Vis diffuse reflectance spectroscopy. Compared with the S-doped TiO, La-doped TiO2 and the standard Degussa P25 photocatalysts, the lanthanum and sulfur co-doped TiO2 photocatalyst （the molar percentage of La is 3.0%） calcined at 450 ℃ for 2 h showed the strongest absorption for visible light and highest activities for degradation of reactive blue 19 dye in aqueous solution under visible light（λ〉400 nm） irradiation. It was also discovered that the co-doping of lanthanum and sulfur hindered the aggregation and growth of TiO2 particles, and the doping of lanthanum reduced slightly the phase transition temperature ofTiO2 from anatase to rutile.

Detection of intermediates in the TiO_2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.

Enhanced Photocatalytic Activity of Nanoparticle-Aggregated Ag–AgX(X=Cl, Br)@TiO_2 Microspheres Under Visible Light

Ag–AgX(X = Cl, Br)@TiO_2 nanoparticle-aggregated spheres with different mass ratio of R = TiO2/Ag(X) from 35:1 to 5:1 were synthesized by a facile sol–gel technique with post-photoreduction. The photocatalytic activities of both Ag–Ag Cl@TiO_2 and Ag–Ag Br@TiO_2 under visible light are effectively improved by ~3 times relative to TiO_2 NPAS under the simulated sunlight for the decomposition of methyl orange(MO). Ag–AgBr@TiO_2 showed 30% improvement and less stable in photocatalytic activity than that of AgCl@TiO_2. The role of Ag and Ag X nanoparticles on the surface of Ag–Ag X(X = Cl,Br)@TiO_2 was discussed. Ag on these samples not onlycan efficiently harvest visible light especially for Ag Cl, but also efficiently separate excited electrons and holes via the fast electron transfer from Ag X(X = Cl, Br) to metal Ag nanoparticles and then to TiO_2-aggregated spheres on the surface of heterostructure. On the basis of their efficient and stable photocatalytic activities under visible-light irradiation, these photocatalysts could be widely used for degradation of organic pollutants in aqueous solution.

(N,F)-codoped TiO_2 Nanocrystals as Visible Light-activated Photocatalyst

（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The （N, F）- codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.