Visible light responsive photocatalysts developed by substitution with metal cations aiming at artificial photosynthesis

To solve resource,energy,and environmental issues,development of sustainable clean energy system is strongly required.In recent years,hydrogen has been paid much attention to as a clean energy.Solar hydrogen production by water splitting using a photocatalyst as artificial photosynthesis is a promising method to solve these issues.Efficient utilization of visible light comprised of solar light is essential for practical use.Three strategies,i.e.,doping,control of valence band,and formation of solid solution are often utilized as the useful methods to develop visible light responsive photocatalysts.This minireview introduces the recent work on visible-light-driven photocatalysts developed by substitution with metal cations of those strategies.

Construction of 2D-2D TiO_2 nanosheet/layered WS_2 heterojunctions with enhanced visible-light-responsive photocatalytic activity

Constructing nanocomposites that combine the advantages of composite materials,nanomaterials,and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO2.In this study,2D‐2D TiO2 nanosheet/layered WS2(TNS/WS2)heterojunctions were prepared via a hydrothermal method.The structure and morphology of the photocatalysts were systematically characterized.Layered WS2(~4 layers)was wrapped on the surface of TiO2 nanosheets with a plate‐to‐plate stacked structure and connected with each other by W=O bonds.The as‐prepared TNS/WS2 heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible‐light irradiation,than pristine TiO2 nanosheets and layered WS2.The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency,which originated from the perfect 2D‐2D nanointerfaces and intimate interfacial contacts between TiO2 nanosheets and layered WS2.Based on experimental results,a double‐transfer photocatalytic mechanism for the TNS/WS2 heterojunctions was proposed and discussed.This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.

Photocatalytic degradation of tetracycline hydrochloride with visible light-responsive bismuth tungstate/conjugated microporous polymer

Conjugated microporous polymer(CMP)is an emerging organic semiconductor withπ-conjugated skeletons,and the bandgap of CMP can be flexibly modulated to harvest visible light.Based on the diversity and adjustability of monomers in CMP,we designed and synthesized donor-accepter(D-A)type BTNCMP through Sonogashira-Hagihara cross-coupling polymerization,further in-situ constructing series of inorganic/organic Z-scheme BW/BTN-n composite in the presence of Bi_(2)WO_(6).After optimization,the tetracycline hydrochloride(C0=10 mg·L^(-1))degradation efficiency reached 84%with BW/BTN-2 as catalyst in 90 min under visible light irradiation,the apparent rate constant k1 is 0.017 min^(-1),which is 1.7 and 5.7 times higher than bare Bi_(2)WO_(6) and BTN-CMP.X-ray photoelectron spectra and UV-Vis diffuse spectra showed that the enhanced photocatalytic activity originated from the tight heterojunction between Bi_(2)WO_(6) and BTN-CMP,which can extend the light absorption range and facilitate the separation and transport of photogenerated charges in the interface of heterojunction.The active species trapping experiments and electron spin resonance technique revealed that h+was the dominant active species during the photodegradation process of tetracycline hydrochloride(TCH).The present study demonstrated the feasibility to construct inorganic/organic composite for the photocatalytic degradation of environmental pollutants.

One-pot topotactic synthesis of Ti^(3+) self-doped 3D TiO_2 hollow nanoboxes with enhanced visible light response

Ti^（3＋） self-doped anatase three-dimensional（3D） TiO_2 hollow nanoboxes were synthesized via a topological transformation process involving template participation by a facile one-pot hydrothermal treatment with an ethanol solution of zinc powder and TiOF_2. It is worth noting that the 3D TiO_2 hollow nanoboxes are assembled from six single-crystal nanosheets and have dominant exposure of the {001} facets. It is found from EPR spectra that adding zinc powder is an environment-friendly and effective strategy to introduce Ti^（3＋） and oxygen vacancy（Ov） into the bulk of 3D hollow nanoboxes rather than the surface, which is responsible for their enhanced visible photocatalytic properties.The photocatalytic activity was evaluated by measuring the formation rate of hydroxide free radicals using 7-hydroxycoumarin as a probe. The sample prepared with zinc/TiOF_2 mass ratio of0.25 exhibited the highest RhB photodegradation activity under visible-light irradiation with a degradation rate of 96%, which is 4.0-times higher than that of pure TiO_2. The results suggest a novel approach to construct in-situ 3D hierarchical TiO_2 hollow nanoboxes doped with Ti^（3＋） and Ov without introducing any impurity elements for superior visible-light photocatalytic activity.

Preparation and Photostriction Properties of BiFeO_(3)-BaTiO_(3)Ceramics

Under illumination by 405,520 and 655 nm monochromatic visible light(light intensity of 30 kW/m^(2)),large photostriction(ΔL/L)of 0.19%,0.13%and 0.26%for 67BiFeO_(3)-33BaTiO_(3)(67BF-33BT)lead-free ferroelectric ceramics are obtained,respectively.By studying the ferroelectric and photoelectric properties in conjunction with in situ Raman spectroscopy,it is found that the photostrictive effect of 67BF-33BT is not caused by the electrical strain induced by abnormal photovoltaic voltage,but related to the optical induced oxygen octahedral distortion.The 67BF-33BT lead-free ferroelectric material with excellent photostrictive response in the visible light region is expected to play an important role in the field of optical drive electromechanical devices.

The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO_(2) thin film

The effects of radio frequency(RF)atmospheric pressure(AP)He/H_(2)plasma and thermal treatment on the hydrogenation of TiO_(2)thin films were investigated and compared in this work.The color of the original TiO_(2)film changes from white to black after being hydrogenated in He/H_(2)plasma at160 W(gas temperature~381℃)within 5 min,while the color of the thermally treated TiO_(2)film did not change significantly even in pure H_(2)or He/H_(2)atmosphere with higher temperature(470℃)and longer time(30 min).This indicated that a more effective hydrogenation reaction happened through RF AP He/H_(2)plasma treatment than through pure H_(2)or He/H_(2)thermal treatment.The color change of TiO_(2)film was measured based on the Commission Internationale d’Eclairage L*a*b*color space system.Hydrogenated TiO_(2)film displayed improved visible light absorption with increased plasma power.The morphology of the cauliflower-like nanoparticles of the TiO_(2)film surface remained unchanged after plasma processing.X-ray photoelectron spectroscopy results showed that the contents of Ti3+species and Ti-OH bonds in the plasma-hydrogenated black TiO_(2)increased compared with those in the thermally treated TiO_(2).X-ray diffraction(XRD)patterns and Raman spectra indicated that plasma would destroy the crystal structure of the TiO_(2)surface layer,while thermal annealing would increase the overall crystallinity.The different trends of XRD and Raman spectra results suggested that plasma modification on the TiO_(2)surface layer is more drastic than on its inner layer,which was also consistent with transmission electron microscopy results.Optical emission spectra results suggest that numerous active species were generated during RF AP He/H_(2)plasma processing,while there were no peaks detected from thermal processing.A possible mechanism for the TiO_(2)hydrogenation process by plasma has been proposed.Numerous active species were generated in the bulk plasma region,accelerated in the sheath region,and bumped toward the TiO_(2)film,which will react with the TiO_(2)surface to form OVs and disordered layers.This leads to the tailoring of the band gap of black TiO_(2)and causes its light absorption to extend into the visible region.

Charge transfer between biogenic jarosite derived Fe^3＋ and TiO2 enhances visible light photocatalytic activity of TiO2

In this work, we have shown that mining waste derived Fe^3＋can be used to enhance the photocatalytic activity of TiO2. This will allow us to harness a waste product from the mines, and utilize it to enhance TiO2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO2 and biogenic jarosite. Evidence of Fe／O／Ti bonding in the TiO2/jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO2, biogenic jarosite and mechanically mixed sample of jarosite and TiO2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO2 and jarosite derived Fe^3＋as was shown from the EELS and ELNEFS. Generation of OHU was supported by photoluminesence（PL） experiments.

Template-free large-scale synthesis of g-C3N4 microtubes for enhanced visible light-driven photocatalytic H2 production

A template-free hydrothermal-assisted thermal polymerization method has been developed for the large-scale synthesis of one-dimensional （1D） graphitic carbon nitride （g-C3N4） microtubes. The g-C3N4 microtubes were obtained by simple thermal polymerization of melamine-cyanuric acid complex microrods under N2 atmosphere, which were synthesized by hydrothermal treatment of melamine solution at 180℃ for 24 h. The as-obtained g-C3N4 microtubes exhibited a large surface area and a unique one-dimensional tubular structure, which provided abundant active sites for proton reduction and also facilitated the electron transfer processes. As such, the g-C3N4 microtubes showed enhanced photocatalytic H2 production activity in lactic acid aqueous solutions under visible light irradiation （A 〉 420 nm）, which was - 3.1 times higher than that of bulk g-C3N4 prepared by direct thermal polymerization of the melamine precursor under the same calcination conditions.

Smart adsorbents for CO2 capture:Making strong adsorption sites respond to visible light

Due to the good controllability and high energy efficiency in adsorption processes,photoresponsive adsorbents are intriguing for CO2 capture.Nevertheless,most reported photoresponsive adsorbents are designed based on weak adsorption sites,regulating CO2 adsorption through structural change or steric hindrance.In addition,ultraviolet(UV)light is commonly involved in the regulation of adsorption capacity.Here we report for the first time the smart adsorbents for CO2 capture,which makes strong adsorption sites respond to visible(Vis)light.The adsorbents were fabricated by introducing primary amine and Dispersed Red 1(DR1,a kind of push-pull azobenzene that responds to Vis light rapidly)units to mesoporous silica,which act as strong adsorption sites and triggers,respectively.The primary amine sites make the adsorbents highly selective in the adsorption of CO2 over CH4.Without light irradiation,azobenzene is in the form of trans configuration,which leads to decreased electrostatic potential of primary amines and subsequently,exposure of active sites and liberal adsorption of CO2.Upon Vis-light irradiation,cis isomers are formed,which results in increased electrostatic potential of primary amines and subsequently shelter of active sites.Even on such strong adsorption sites,the alteration of CO2 adsorption capacity can reach 40%for the adsorbent with and without Vis-light irradiation.Moreover,the trans/cis isomerization of DR1 units can be triggered reversibly by Vis light.The present smart system endows adsorbents with selective adsorption capacity and avoids the employment of UV light,which is unlikely to be achieved by conventional photoresponsive adsorbents.

Visible Light and Temperature Regulated Reflection Colors in Self-supporting Cholesteric Liquid Crystal Physical Gels

Photo-responsive cholesteric liquid crystals(CLCs)have attracted much attention in recent years due to their wide applications in filters,tun able optical lasers,dyn amic display devices,etc.However,UV light is usually used as the exter nal stimulus source,which is not envir on ment-frie ndly enough.On the other hand,the mecha nical properties of CLCs are not strong eno ugh for these practical applications.Therefore,it still remains a challenge to endow the CLCs with visible light response and high mechanical properties at the same time.Herein,an axially chiral tetra-fluorinated binaphthyl azobenzene gelator(S-4F-AG)is synthesized.Upon 550 and 450 nm light irradiations,S-4F-AG exhibits excellent photo-switchable behaviors.Notably,the maximum con tent of c/s-isomer and its half-life are as high as 35%and 89 h in acet on itrile,respectively.A self-supporting CLC physical gel with a storage modulus around 104 Pa can be obtained when 3wt%S-4F-AG and 12wt%binaphthyl azobenzene derivative(dopant 2)are co-doped into a nematic LC host P0616A.This CLC physical gel exhibits a temperature-driven blue,green,and red reflection colors reversibly.Importantly,such three primary RGB colors can also be realized by adjusting the exposure time of 550 nm green light.This work lays a solid foundation for the applications ranging from information storage to high-tech anticounterfeit.

In situ preparation of visible-light-driven carbon quantum dots/NaBiO3 hybrid materials for the photoreduction of Cr(Ⅵ)

In this study,different carbon quantum dots(CQDs)/NaBiO3 hybrid materials were synthesized as photocatalysts to effectively utilize visible light for the photocatalytic degradation of contaminants effectively.These hybrid materials exhibit an enhanced photocatalytic reduction of hexavalent chromium(Cr(Ⅵ))in the aqueous medium.Zero-dimensional nanoparticles of CQDs were embedded within the two-dimensional NaBiO3 nanosheets by the hydrothermal process.Compared with that of the pure NaBiO3 nanosheets,the photocatalytic performance of the hybrid catalysts was significantly high and 6 wt.%CQDs/NaBiO3 catalyst exhibited better photocatalytic performance.We performed the first-principles density functional theory calculations to study the interfacial properties of pure NaBiO3 nanosheets and hybrid photocatalysts,and confirmed the CQDs played an important role in the CQDs/NaBiO3 composites.The experimental results indicated that the enhanced reduction of Cr(Ⅵ)was probably due to the high loading of CQDs(electron acceptor)on NaBiO3,which made NaBiO3 nanomaterials to respond in visible light and significantly improved their electron-hole separation efficiency.