Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

Controllable synthesis of SnO2 photocatalyst with superior photocatalytic activity for the degradation of methylene blue dye solution

SnO₂ photocatalyst was successfully synthesised by novel chemical route in hydrothermal environment and annealed at two different temperatures viz 550 and 600 °C, respectively. The crystal structure, optical properties, surface and bulk morphology have been characterised using various tools like X-ray diffraction (XRD), UV visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscope (TEM) and scanning electron microscope (SEM). Cubic, spheres and porous like morphology of SnO₂ photocatalyst was successfully confirmed using SEM micrographs and TEM. In addition to this the photocatalytic activity was evaluated towards the degradation of methylene blue dye solution. SnO₂ photocatalyst annealed at 600 °C exhibits excellent photocatalytic efficiency which may be attributed to the unique morphology, high crystalline nature and charge separation. The photocatalyst efficiency was further tested towards the concentration of dye, catalyst dosage and pH of the dye. The involvement of ?OH in the photocatalytic reaction was evidenced using trapping experiment by employing different scavengers. The photocatalyst was moderately active, stable upto its fifth usage and stability of the photocatalyst before and after the photocatalytic reaction was also been studied using XRD and SEM.     

g-C3N4/g-C3N4 isotype heterojunction as an efficient platform for direct photodegradation of antibiotic

A visible-light-driven g-C₃N₄/g-C₃N₄ isotype heterojunction photocatalyst was synthesized by one-step thermal treatment using urea and thiourea as the precursor. The photocatalytic activity of as-prepared photocatalyst was evaluated through the degradation of rhodamine B (RhB) and tetracycline hydrochloride (TC) under the visible light irradiation. The hybrid showed enhanced photocatalytic activity in photodegradating the applied pollutants as compared with single g-C₃N₄. When the ratio of urea to thiourea was 2:1, the prepared isotype heterojunction exhibited the highest photocatalytic activity and the photodegradation rates for RhB and TC were 99.8% and 95.1% after being visible light irradiated for 1 h and 4 h respectively. The enhanced photocatalytic performance of the isotype heterojunction is ascribed to the enhanced charge separation efficiency. After being reused for 5 times, the hybrid still showed excellent recyclability and chemical stability. Furthermore, NaI, BQ and IPA were used as the sacrificial agents for studying the surface reactions in the photocatalytic process. The method used in this work provides a new pathway to achieve more efficient degradation of antibiotics and to stimulate further studies in this important field.     

Catalytic reduction of CO2 to alcohol with Cu2Se-combined graphene binary nanocomposites

Photocatalytic reduction of CO₂ over a Cu₂Se–graphene nanocatalyst has been investigated. The nanocomposite material was successfully prepared via a modified hydrothermal method. The structure and properties of the prepared composite were characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray microscopy, transmission electron microscopy, Raman spectroscopic analysis, and X-ray photoelectron spectroscopy. A synergetic effect of the combination of Cu₂Se and graphene appeared in the form of excellent photocatalytic reduction capability of CO₂. The photocatalytic efficiencies of the samples were characterized by testing for the photoreduction of CO₂ to alcohol under visible light irradiation, which produced results such as to suggest that there is a significant potential for graphene-based semiconductor hybrid materials to be used as photocatalysts for reduction of CO₂.     

Novel method for doping nano TiO2 photocatalysts by chemical vapour deposition

Highly active photocatalytic Fe-doped nano TiO₂ was successfully synthesised by chemical vapour deposition (CVD) method using FeCl₃ as Fe source. CVD was carried out by evaporating FeCl₃ at 350°C in nitrogen flow during 30–90?min. The amount of Fe incorporated into TiO₂ framework is adjusted by the amount of FeCl₃ used and the evaporation time. The obtained sample was characterised by X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), energy dispersive X-ray spectroscopy (EDS), UV-Vis, Fourier transform-infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activities of the samples were tested in photocatalytic decomposition of 2-propanol in liquid phase using visible light instead of UV light irradiation. Non-doped TiO₂ and high Fe loading TiO₂ samples showed very low photocatalytic activity, whereas the low Fe loading TiO₂ sample exhibited high photocatalytic activity under visible light. The high photocatalytic activity of this sample was rationalised by the existence of defects (Ti–OH groups) as the active sites.     

A Hierarchical Z‐Scheme CdS–WO3 Photocatalyst with Enhanced CO2 Reduction Activity

The development of an artificial photosynthetic system is a promising strategy to convert solar energy into chemical fuels. Here, a direct Z‐scheme CdS–WO₃ photocatalyst without an electron mediator is fabricated by imitating natural photosynthesis of green plants. Photocatalytic activities of as‐prepared samples are evaluated on the basis of photocatalytic CO₂ reduction to form CH₄ under visible light irradiation. These Z‐scheme‐heterostructured samples show a higher photocatalytic CO₂ reduction than single‐phase photocatalysts. An optimized CdS–WO₃ heterostructure sample exhibits the highest CH₄ production rate of 1.02 μmol h^?1 g^?1 with 5 mol% CdS content, which exceeds the rates observed in single‐phase WO₃ and CdS samples for approximately 100 and ten times under the same reaction condition, respectively. The enhanced photocatalytic activity could be attributed to the formation of a hierarchical direct Z‐scheme CdS–WO₃ photocatalyst, resulting in an efficient spatial separation of photo‐induced electron–hole pairs. Reduction and oxidation catalytic centers are maintained in two different regions to minimize undesirable back reactions of the photocatalytic products. The introduction of CdS can enhance CO₂ molecule adsorption, thereby accelerating photocatalytic CO₂ reduction to CH₄. This study provides novel insights into the design and fabrication of high‐performance artificial Z‐scheme photocatalysts to perform photocatalytic CO₂ reduction.     

Fabrication of ultrafine ZnFe2O4 nanoparticles for efficient photocatalytic reduction CO2 under visible light illumination

A one-pot, solvent-thermal process was used to create the ultrafine ZnFe₂O₄ nanoparticles photocatalyst. During the solvent-thermal process, the in situ self-forming NaCl not only served as a “cage” to confine the ion diffusion, but also acted as a microreactor for nanocrystallite growth. An average particle size of ～10 nm and a high-specific surface area of ～112.9 m²/g were observed for the ultrafine ZnFe₂O₄ nanoparticles Owing to the synergistic effect of ultrafine particle size, the full utilization of the visible light region and high conduction band (CB) position, ultrafine ZnFe₂O₄ photocatalyst displayed an efficient photocatalytic CO₂ reduction under visible light illumination. Besides, the ultrafine ZnFe₂O₄ photocatalyst showed high production selectivity for CH₃CHO and C₂H₅OH generation in aqueous CO₂/NaHCO₃ solution. This work may provide a new idea for the synthesis of new high-efficiency photocatalysts.     

Photocatalytic degradation of formaldehyde by nanostructured TiO2 composite films

Interest in the photocatalytic oxidation of formaldehyde from contaminated wastewater is growing rapidly. The photocatalytic activity of the nanocrystalline Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film for the degradation of formaldehyde solution under visible light was discussed in this study. The films were characterised by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy, X-ray diffraction (XRD), BET surface area, UV–Vis absorption spectroscopy, and photoluminescence spectroscopy. The FE-SEM results revealed that the Fe³⁺/F^? co-doped TiO₂–SiO₂ film was composed of uniform round-like nanoparticles or aggregates with the size range of 5–10 nm. The XRD results indicated that only the anatase phase was observed in the film. Compared with a pure TiO₂ film and a singly modified TiO₂ film, the Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film showed the best photocatalytic properties due to its strong visible light adsorption and diminished electrons-holes recombination.     

Preparation,characterisation and activity evaluation of CaCO3/ZnO photocatalyst

The photocatalyst CaCO₃/ZnO with high activity was prepared by coprecipitation method using (NH₄)₂CO₃, Zn(NO₃)₂ and Ca(NO₃)₂ as raw materials. The photocatalyst was characterised by X-ray powder diffraction, terephthalic acid photoluminescence probing technique (TA-PL), UV–vis diffuse reflectance spectroscopy and the fluorescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic oxidation of methyl orange and rhodamine B. The results showed that the photocatalytic activity of the photocatalyst was much higher than that of pure ZnO. The best mole ratio of Ca/Zn in the sample was 1?:?2, and its intensity of TA-PL was the strongest. The effect of heat treatment condition on the photocatalytic activity of the photocatalyst was investigated. The best preparation condition was about 650°C for 7?h. Compared with pure ZnO, the photoabsorption wavelength range of the CaCO₃/ZnO extends towards visible light and improves the utilisation of the total spectrum. The possible mechanisms of influence of CaCO₃ on the photocatalytic activity of CaCO₃/ZnO were also discussed.     

Structural and Photocatalytic Activity of Mesoporous N-Doped TiO2 with Band-to-Band Visible Light Absorption Ability

White colored N-doped TiO₂ and a neat TiO₂ powder were synthesized via sol–gel method. Prepared samples were characterized by means of x-ray diffractions, Brunauer–Emmet–Teller and Barrett–Joyner–Halenda methods, x-ray photoelectron spectroscopy, ultraviolet-visible analysis, scanning electron microscopy, and energy dispersive x-ray spectroscopy. Both of the N-doped TiO₂ and neat TiO₂ consisted of anatase phase of titania with mesoporous nature and according to XPS analysis prepared N-doped TiO₂ is a substitutional nitrogen containing sample. The band gap of N-doped TiO₂ and neat TiO₂ were estimated from ultraviolet-visible spectroscopy data to be 2.7 and 3.2 eV, respectively. Prepared substitutional N-doped TiO₂ featured steep light absorption edge with an approximately parallel characteristic of its absorption edge to that neat TiO₂. This is due to its band-to-band visible light absorption ability. Synthesized N-doped TiO₂ had a large surface area value of 193 m²/g and high photon absorption ability causing superior photocatalytic properties towards Congo red azo dye compared to neat TiO₂ either under ultraviolet or visible light illumination.     

Synthesis and characterization of N-doped TiO2/ZrO2 visible light photocatalysts

Zirconia and nitrogen-doped TiO₂ powder was synthesized using a polymer complex solution method for the preparation of an enhanced visible light photocatalyst. The produced catalysts were characterized via the Brunauer, Emmett, and Teller method (BET), X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectra, and UV–Vis spectrophotometry analyses. The N-doped TiO₂/ZrO₂ photocatalyst showed a high specific surface area and small crystal sizes. The XPS spectra of the N-doped TiO₂/ZrO₂ sample indicated that nitrogen was doped into the TiO₂ lattice and enhanced the photocatalytic activity. The UV–Vis absorption spectra of the N-doped TiO₂/ZrO₂ sample noticeably shifted to the visible light region compared to that of the TiO₂. The photocatalytic activities of the prepared catalysts were evaluated for the decomposition of gaseous NO_x under UV and visible light irradiations. The photocatalytic activities of N-doped TiO₂/ZrO₂ were much greater than those of commercial Degussa P25 in both the UV and visible light regions. The high photocatalytic activity can be attributed to stronger absorption in the visible light region, a greater specific surface area, smaller crystal sizes, more surface OH groups, and to the effect of N-doping, which resulted in a lower band gap energy.     

Visible-light photocatalysis in nitrogen-carbon-doped TiO2 films obtained by heating TiO2 gel-film in an ionized N2 gas

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO₂ films were obtained by heating a TiO₂ gel in an ionized N₂ gas. The as-synthesized TiO_2−x−yN_xC_y films have shown an improvement over titanium dioxide in optical absorption and photocatalytic activity such as photodegradation of methyl orange under visible light. The process of the oxygen atom substituted by nitrogen and carbon was discussed. Oxygen vacancy induced by the formation of Ti³⁺ species and nitrogen and carbon doped into substitution sites of TiO₂ have been proven to be indispensable for the enhance of photocatalytic activity, as assessed by UV-Vis Spectroscopy and X-ray photoemission spectroscopy.     

CeO2-Cu2O composite nanofibers: Synthesis,characterization photocatalytic and electrochemical application

The present study describes fabrication and electrochemical classification of one-dimensional CeO₂-Cu₂O nanofibers for photocatalysis and supercapacitor application. The utilized CeO₂-Cu₂O composite was prepared by sol–gel electrospinning method using Polyvinylpyrrolidone (PVP), Ce(NO₃)₃?6H₂O and Cu(CH₃COO)₂ as precursors. The physicochemical properties of the synthesized samples were characterized using special characterization approaches such as X-ray diffractometer (XRD), energy dispersive X-ray analysis (EDX), electron probe microanalysis (EPMA) and scanning electron microscopy (SEM). As compared to pristine CeO₂, the UV–vis spectrum of CeO₂-Cu₂O composite exhibited the absorption peak which shifted to higher wavelength. The photocatalytic activity results indicated the substantial degradation of MB dye by ～92% over the surface of CeO₂-Cu₂O nanocomposite catalyst under visible light illumination. The CeO₂-Cu₂O composite possessed higher photocatalytic activity and electrochemical capacitance than the pristine samples as supercapacitor electrode materials. The CeO₂-Cu₂O composite exhibits a specific capacitance of 329.64 F g^?1 at 5 mV s^?1, which is higher than that of the pristine CeO₂ (192.5 F g^?1) nanofibers. These results suggest the applicability of fabricated composite nanofibers as visible light active photocatalyst and as electrode material for supercapacitors.     

Iron promotion of the TiO2 photosensitization process towards the photocatalytic oxidation of azo dyes under solar-simulated light irradiation

The photocatalytic oxidation of the azo dye Orange-II (Or-II) using Fe loaded TiO₂ (Fe–TiO₂) was studied under ultraviolet (UV), visible (vis) and simultaneous UV–vis irradiations using a solar light simulator. Photocatalysts were characterized by means of XRD, SEM-EDX, FTIR and DRS. Fe³⁺ species, identified in XPS analyses, were responsible of the increased absorption of visible light. Moreover, DRS analyses showed a decrease in the bandgap due to Fe³⁺ loading. Photocatalystic tests proved that Fe modification enhanced the TiO₂ photocatalytic activity towards Or-II photodegradation under simultaneous UV–vis irradiation. Even so, the performance of the Fe–TiO₂ samples towards the photodegradation of phenol, under UV irradiation, was lower than TiO₂ suggesting the recombination of the UV photogenerated electron–hole pair. Therefore, results evidence a Fe³⁺ promotion of the electron caption in the photosensitization process of TiO₂ by Or-II acting as a sensitizer. Such process leads to the Or-II photooxidation under UV–vis irradiation by losing energy in electron transferring processes to sensitize TiO₂, and, the formation of reactive oxygen species promoted by the injected electron to the TiO₂ conduction band.     

Grafting Hypercrosslinked Polymers on TiO2 Surface for Anchoring Ultrafine Pd Nanoparticles: Dramatically Enhanced Efficiency and Selectivity toward Photocatalytic Reduction of CO2 to CH4

Metal deposition with photocatalyst is a promising way to surmount the restriction of fast e^?/h⁺ recombination to improve the photocatalytic performance. However, the improvement remains limited by the existing strategies adopted for depositing metal particles due to the serious aggregation and large unconnected area on photocatalyst surface. Here, a strategy is proposed by directly grafting hypercrosslinked polymers (HCPs) on TiO₂ surface to construct Pd-HCPs-TiO₂ composite with uniform dispersion of ultrafine Pd nanoparticles on HCPs surface. This composite with surface area of 373 m² g^?1 exhibits improved photocatalytic CO₂ conversion efficiency to CH₄ with an evolution rate of 237.4 µmol g^?1 h^?1 and selectivity of more than 99.9%. The enhancement can be ascribed to the grafted porous HCPs with high surface area and N heteroatom on TiO₂ surface for the stabilization of Pd nanoparticles, favoring the electron transfer and CO₂ adsorption for selective CH₄ production. This strategy may hold the promise for design and construction of porous organic polymer with semiconductor for efficient photocatalytic conversion.     

A polymeric complex method to nanocrystalline BiCu2VO6 with visible light photocatalytic activity

Nanocrystalline BiCu₂VO₆ was successfully synthesized by a facile polymeric citrate complex method. The samples were characterized by X-ray diffraction (XRD) analyses, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectra (DRS), thermogravimetric analyses (TG) and differential thermal analyses (DTA). BiCu₂VO₆ showed photocatalytic activity for the degradation of RhB under visible light irradiations with the coexistence of H₂O₂. As compared to BiCu₂VO₆ prepared via a solid state reaction, BiCu₂VO₆ prepared via a polymeric citrate complex method showed higher photocatalytic activity. The visible light photocatalytic activity of BiCu₂VO₆ was also proposed.     

Highly Selective Photoreduction of CO2 with Suppressing H2 Evolution by Plasmonic Au/CdSe–Cu2O Hierarchical Nanostructures under Visible Light

Here, the photocatalytic CO₂ reduction reaction (CO₂RR) with the selectivity of carbon products up to 100% is realized by completely suppressing the H₂ evolution reaction under visible light (λ > 420 nm) irradiation. To target this, plasmonic Au/CdSe dumbbell nanorods enhance light harvesting and produce a plasmon‐enhanced charge‐rich environment; peripheral Cu₂O provides rich active sites for CO₂ reduction and suppresses the hydrogen generation to improve the selectivity of carbon products. The middle CdSe serves as a bridge to transfer the photocharges. Based on synthesizing these Au/CdSe–Cu₂O hierarchical nanostructures (HNSs), efficient photoinduced electron/hole (e^?/h⁺) separation and 100% of CO selectivity can be realized. Also, the 2e^?/2H⁺ products of CO can be further enhanced and hydrogenated to effectively complete 8e^?/8H⁺ reduction of CO₂ to methane (CH₄), where a sufficient CO concentration and the proton provided by H₂O reduction are indispensable. Under the optimum condition, the Au/CdSe–Cu₂O HNSs display high photocatalytic activity and stability, where the stable gas generation rates are 254 and 123 µmol g^?1 h^?1 for CO and CH₄ over a 60 h period.     

Synthesis of Mixed-Phase TiO2 Powders in Salt Matrix and Their Photocatalytic Activity

Three mixed-phase TiO₂ powders, containing ～80 volume % anatase and ～20 volume % rutile, were prepared from amorphous titanium hydroxide and three different salt matrices—pure sodium chloride, pure Na₂CO₃, and pure disodium hydrogen phosphate (DSP). Amorphous titanium hydroxide and salt mixtures were heat treated at 875°C in a rapid thermal annealing system for different times, according to the time–temperature phase transformation graphs. Time-dependent UV degradation of aqueous solutions of methylene blue dye (15 ppm) in the presence of mixed-phase powders was used to monitor the activity of the catalysts. Microstructural study of the powders by scanning electron microscope and transmission electron microscope combined with phase analysis by XRD and optical absorbance by UV-absorption spectroscopy indicated that the higher photocatalytic activity of the powder obtained from pure DSP salt could be explained by its smaller rutile particle size and anatase–rutile interparticle bonding.     

Photocatalytic degradation of 2,4-dichlorophenol wastewater using porphyrin/TiO2 complexes activated by visible light

The use of TiO₂ as photocatalyst to degrade the organic compounds is an effective method of oxidation process and has been widely studied in environmental engineering. However, TiO₂ absorbed the UV light which is only small part of sunlight reaching earth surface to activate photocatalytic procedure effectively is a major disadvantage. Therefore, studies on the development of new TiO₂ wherein its photocatalytic activity can be activated by visible light which is the major part of sunlight will be valuable for field application. In this study, we evaluate the photocatalytic degrading efficiency of porphyrins/TiO₂ complexes on the organic pollutants under irradiation with visible light (λ = 419 nm). The results showed that the photodecomposition efficiency of 2,4-dichlorophenol (2,4-DCP) wastewater by using porphyrin/TiO₂ irradiated under visible light for 4 h was up to 42-81% at pH 10. These evidences reveal that the system of porphyrin/TiO₂ complexes has also significantly efficiency of photocatalytic degradation for some hazardous or recalcitrant pollutants under visible light irradiation.