Efficient Exciton Dissociation on Ceria Chelated Cerium-Based MOF Isogenous S-Scheme Photocatalyst for Acetaldehyde Purification.

Long-term exposure to low concentration indoor VOCs of acetaldehyde (CH3CHO) is harmful to human health. Thus, a novel isogenous heterojunction CeO2/Ce-MOF photocatalyst is synthesized via a one-step hydrothermal method for the effective elimination of CH3CHO in this work. This CeO2/Ce-MOF photocatalyst performs well in CH3CHO removal and achieves an apparent quantum efficiency of 7.15% at 420 nm, which presents ≈6.7 and 3.4 times superior to those generated by CeO2 and Ce-MOF, respectively. The enhanced efficiency is due to two main aspects including i) an effective photocarrier separation ability and the prolonged reaction lifetime of excitons play crucial roles and ii) the formation of an internal electric field (IEF) is sufficient to overcome the considerable exciton binding energy, and increases the exciton dissociation efficiency by up to 50.4%. Moreover, the reasonable pathways and mechanisms of CH3CHO degradation are determined by in situ DRIFTS analysis and simulated DFT calculations. Those results demonstrated that S-scheme heterojunction successfully increases the efficiency of harmful volatile organic compounds elimination, and it offers essential guidance for designing rare earth-based MOF photocatalysts.

Oxygen induced enhancement of NIR emission in brookite TiO2 powders: comparison with rutile and anatase TiO2 powders.

Brookite TiO2 attracts considerable attention in photocatalysis owing to its superior performance in several photocatalytic reactions. In this work, we investigated the behavior of charge carriers in brookite, rutile, and anatase TiO2 by using photoluminescence (PL) and transient absorption (TA) spectroscopies. PL measurements revealed that brookite TiO2 exhibits a visible and a NIR emission at ∼520 nm and ∼860 nm, respectively. Addition of methanol vapor quenched both the visible and NIR emissions by the hole-consuming reaction of methanol. However, exposure to O2 shows curious behaviors: the visible emission was quenched but the NIR emission was enhanced. These results can be accounted for by the enhancement of upward band bending resulting in the effective separation of electrons and holes into the bulk and the surface, respectively. Furthermore, the shallowly trapped electrons, which are responsible for visible PL, are consumed by O2; hence, the visible emission is quenched. However, in the case of NIR emission, the deeply trapped electrons are responsible and they are mainly located at the surface defects. The O2 adsorption promotes the hole accumulation at the surface and then assists the recombination of these deeply trapped electrons, resulting in the enhancement of the NIR emission. We also found that the lifetime of NIR emission (τ1 = 43 ± 0 ns and τ2 = 589 ± 1 ns) was much longer than that of visible emission (τ1 = 15 ± 0 ns and τ2 = 23 ± 0 ns), since the mobility of these deeply trapped electrons to encounter with holes is lower than that of the shallowly trapped electrons. However, even for this slow NIR emission, the actual lifetime of the deeply trapped electrons estimated by TA (1.5 ± 0.0 µs and 17 ± 0 µs) was one or two orders of magnitude longer, confirming that non-radiative recombination is dominant and it is much slower than radiative recombination: TAS and PL provide detailed information on the radiative and non-radiative recombination processes. The PL of anatase and rutile TiO2 powders was also measured and the difference from brookite TiO2 was discussed.

Partial Delignification as Pretreatment for Nanoporous Carbon Material from Biomass.

For the pretreatment in order to nano prepare porous carbon from biomass such as bamboo, a mixture of acetic acid and hydrogen peroxide was used for the partial delignification of bamboo. The pretreatment should be effective for the removal of lignin because the lignin percentage after the pretreatment depended on the treatment time and the treatment temperature. For the concentration of the mixture used for the pretreatment in this study, a small amount of lignin (ca. 2 wt%) remained even after a sufficiently-long treatment time. The BET specific surface area of the carbon material prepared by the heat treatment at 800 degrees C for 1 h under flowing N2 was related to the pretreatment conditions, and the specific surface areas of the samples were found to be related to the lignin percentage. The removal of lignin while maintaining the microstructure derived from plant tissue could be the reason for the local maximum of the specific surface area at ca. 5% of the lignin.

Atomically isolated Sb(CN)3 on sp2-c-COFs with balanced hydrophilic and oleophilic sites for photocatalytic C-H activation.

Activation of carbon-hydrogen (C-H) bonds is of utmost importance for the synthesis of vital molecules. Toward achieving efficient photocatalytic C-H activation, our investigation revealed that incorporating hydrophilic C≡N-Sb(CN)3 sites into hydrophobic sp2 carbon-conjugated covalent organic frameworks (sp2-c-COFs) had a dual effect: It simultaneously enhanced charge separation and improved generation of polar reactive oxygen species. Detailed spectroscopy measurements and simulations showed that C≡N-Sb(CN)3 primarily functioned as water capture sites, which were not directly involved in photocatalysis. However, the potent interaction between water molecules and the Sb(CN)3-modified framework notably enhanced charge dynamics in hydrophobic sp2-c-COFs. The reactive species ·O2- and ·OH (ad) subsequently combined with benzyl radical, leading to the formation of benzaldehyde, benzyl alcohol, and lastly benzyl benzoate. Notably, the Sb(CN)3-modified sp2-c-COFs exhibited a 54-fold improvement in reaction rate as compared to pristine sp2-c-COFs, which achieved a remarkable 68% conversion rate for toluene and an 80% selectivity for benzyl benzoate.

The powerful combination of 2D/2D Ni-MOF/carbon nitride for deep desulfurization of thiophene in fuel: Conversion route, DFT calculation, mechanism.

2D/2D Ni-MOF/g-C3N4 nanocomposite was utilized for desulfurization. The multilayer pore structure and high specific surface area of Ni-MOF/g-C3N4 promote the adsorption and conversion of thiophene. In addition, the two-dimensional structure exposes more active centers and shortens photogenerated carrier migration to the material surface distance, it enhances photogenerated charge transfer. The Ni-MOF and g-C3N4 construct a Z-scheme heterojunction structure with tight contact, it effectively enhances the material's photocatalytic redox ability. In the light, the material generates more photocarriers for the production of free radicals including hydroxyl radicals, holes, and superoxide radicals. The higher carrier concentration of Ni-MOF/g-C3N4 promotes the activation and oxidation of thiophene, consequently enhancing the photocatalytic desulfurization capability. The results showed that the conversion of thiophene was 98.82 % in 3 h under visible light irradiation. Radical capture experiments and analysis using electron paramagnetic resonance spectroscopy demonstrated that superoxide radicals, holes, and hydroxyl radicals played crucial roles in PODS (photocatalytic oxidative desulfurization). In addition, DFT (density functional theory) calculations were conducted to determine the paths of electron migration and TH (thiophene) adsorption energy. Finally, a mechanism for photocatalytic desulfurization was proposed based on the comprehensive analysis of theoretical calculations and experimental studies.

Atomically dispersed low-valent Au boosts photocatalytic hydroxyl radical production.

Providing affordable, safe drinking water and universal sanitation poses a grand societal challenge. Here we developed atomically dispersed Au on potassium-incorporated polymeric carbon nitride material that could simultaneously boost photocatalytic generation of ·OH and H2O2 with an apparent quantum efficiency over 85% at 420 nm. Potassium introduction into the poly(heptazine imide) matrix formed strong K-N bonds and rendered Au with an oxidation number close to 0. Extensive experimental characterization and computational simulations revealed that the low-valent Au altered the materials' band structure to trap highly localized holes produced under photoexcitation. These highly localized holes could boost the 1e- water oxidation reaction to form highly oxidative ·OH and simultaneously dissociate the hydrogen atom in H2O, which greatly promoted the reduction of oxygen to H2O2. The photogenerated ·OH led to an efficiency enhancement for visible-light-response superhydrophilicity. Furthermore, photo-illumination in an onsite fixed-bed reactor could disinfect water at a rate of 66 L H2O m-2 per day.

Spatial charge separated two-dimensional/two-dimensional Cu-In2S3/CdS heterojunction for boosting photocatalytic hydrogen production.

Two-dimensional (2D) beta indium sulfide (ß-In2S3) shows great potential in photocatalytic hydrogen production due to its broad-spectrum response, relatively negative conduction band edge, high carrier mobility and low toxicity. However, the high charge recombination rate limits the application of In2S3. Here, we in-situ grew 2D cadmium sulfide (CdS) on the surface of In2S3 doped with copper ions (Cu2+) to construct a heterojunction photocatalyst that suppresses charge recombination. The in-situ grown method and shared sulfur composition were conducive to forming the efficient interface contact between In2S3 and CdS, promoting charge transfer and showing the high spatial charge separation rate, resulting in a hydrogen production rate of 868 µmol g-1h-1. The induced Cu2+ extended the light absorption range and stabilized the photocatalyst. By creating stable 2D/2D heterojunction photocatalysts with high charge separation efficiency, this work opens new possibilities for applying In2S3 materials in photocatalytic hydrogen production.

Improvement of electrical conductivity while maintaining a high-transmittance of graphene oxide/MWCNT film by hydrazine reduction.

In this study, we attempted to synthesize a transparent electrode with a composite of along graphene with multi-walled carbon nanotubes (MWCNT). Hydrazine was used for the reduction process. After the treatment with hydrazine, the sheet resistance was reduced from over 10 Momega/sq. The longest dip time sample (reduced GO/MWCNT-5, RGO/MWCNT-5) had the lowest sheet resistance (114 komega/sq). The reason for this decrease is likely due to the fact that the concentration of MWCNT in the deposited film increased with increases in the deposition time based on the higher density of the MWCNT. Although the transmittance decreased with decreases in the sheet resistance, the transmittances of all the samples were approximately 80% at 550 nm. We succeed in synthesizing a film that maintains transmittance (80%) despite a decreasing sheet resistance.

Cu2O/TiO2 decorated on cellulose nanofiber/reduced graphene hydrogel for enhanced photocatalytic activity and its antibacterial applications.

Photocatalysis has gained attention as a viable wastewater remediation technique. However, the difficulty of recovering powder-based photocatalyst has often become a major limitation for their on-site practical application. Herein, we report on the successful in-situ preparation of a novel three-dimensional (3D) photocatalyst consisting of Cu2O/TiO2 loaded on a cellulose nanofiber (CNF)/reduced graphene hydrogel (rGH) via facile hydrothermal treatment and freeze-drying. The 3D macrostructure not only provides a template for the anchoring of Cu2O and TiO2 but also provides an efficient electron transport pathway for enhanced photocatalytic activity. The results showed that the Cu2O and TiO2 were uniformly loaded onto the aerogel framework resulting in the composites with large surface area with exposed actives sites. As compared to bare rGH, CNF/rGH, Cu2O/CNF/rGH and TiO2/CNF/rGH, the Cu2O/TiO2/CNF/rGH showed improved photocatalytic activity for methyl orange (MO) degradation. MO degradation pathway is proposed based on GC-MS analysis. The enhanced photoactivity can be attributed to the charge transfer and electron-hole separation from the synergistic effect of Cu2O/TiO2 anchored on CNF/rGH. In terms of their anti-bacterial activity towards Staphylococcus aureus and Escherichia coli, the synergistic effect of the Cu2O/TiO2 anchored on the CNF/rGH framework showed excellent activity towards the bacteria.

Visible-light-driven photocatalytic disinfection of raw surface waters (300-5000 CFU/mL) using reusable coated Ru/WO3/ZrO2.

We selected ruthenium (Ru) to improve the photocatalytic activity of a WO3/ZrO2 composite. The synthesized Ru/WO3/ZrO2 was then compared to a benchmark photocatalyst (S-TiO2) in terms of photocatalytic disinfection of raw surface waters collected from the Nile Delta region, Egypt. The photocatalysts were immobilized on aluminum plates with polysiloxane to test them in repetitive cycles under the irradiation of a metal-halide lamp. Bacterial concentrations in the raw waters ranged from 300 to 5000 CFU/mL (CFU: colony-forming units) and different species and genus were detected including gram-negative (e.g., shigella, salmonella, vibrio parahaemolyticus, and vibrio cholera) and gram-positive bacteria (e.g., enterococcus). Ru/WO3/ZrO2 deactivated over 90 % of the bacterial content within 120 min for most sources, whereas S-TiO2 did not perform as highly. The bacterial count after 240 min of irradiation was below the detection limit for all different water sources. Moreover, the inhabitation of photocatalytic disinfection by natural organic matter (NOM) was investigated. Ru/WO3/ZrO2 was stable for four continuous cycles (960 min in total), suggesting the viability for practical application.

Titanium Dioxide/Polyvinyl Alcohol/Cork Nanocomposite: A Floating Photocatalyst for the Degradation of Methylene Blue under Irradiation of a Visible Light Source.

Photocatalytic degradation by the titanium dioxide (TiO2) photocatalyst attracts tremendous interest due to its promising strategy to eliminate pollutants from wastewater. The floating photocatalysts are explored as potential candidates for practical wastewater treatment applications that could overcome the drawbacks posed by the suspended TiO2 photocatalysis system. The problem occurs when the powdered TiO2 applied directly into the treated solution will form a slurry, making its reuse become a difficult step after treatment. In this study, the immobilization of titanium dioxide nanoparticles (TiO2 NPs) on the floating substrate (cork) employing polyvinyl alcohol (PVA) as a binder to anchor TiO2 NPs on the surface of the cork was carried out. Characterizations such as Fourier transformer infrared, X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis), zeta potential, photoluminescence spectroscopy, femtosecond to millisecond time-resolved visible to mid-IR absorption spectroscopy, ion chromatography, and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) analyses were employed. XRD analysis revealed the formation of anatase-phase TiO2 NPs. The results demonstrated that the crystallite size was 9.36 nm. The band gap energy of TiO2 NPs was determined as 3.0 eV. PL analysis verified that TiO2 NPs possessed a slower recombination rate of electron-hole pairs as compared to anatase TiO2. The result was attributed by the behavior of photogenerated charge carriers on TiO2 NPs, which existed as shallowly trapped electrons that could survive longer than a few milliseconds in this study. Furthermore, SEM-EDX analysis indicated that TiO2 NPs were well distributed on the surface of the cork. At the optimal mole ratio of TiO2/PVA (1:8), the TiO2/PVA/cork floating photocatalyst degraded at 98.43% of methylene blue (MB) under a visible light source which performed better than under sunlight irradiation (77.09% of MB removal) for 120 min. Besides, the mineralization result has measured the presence of sulfate anions after photocatalytic activities, which achieved 86.13% (under a visible light source) and 65.34% (under sunlight). The superior photodegradation performance for MB was mainly controlled by the reactive oxygen species of the superoxide radical (•O2 -). The degradation kinetics of MB followed the first-order kinetics. Meanwhile, the Langmuir isotherm model was fitted for the adsorption isotherm. The floating photocatalyst presented good reusability, resulting in 78.13% of MB removal efficiency even after five cycles. Our TiO2/PVA/cork floating photocatalyst fabrication and high photocatalytic performance are potentially used in wastewater treatment, especially under visible light irradiation.

The role of Ce addition in catalytic activity enhancement of TiO2-supported Ni for CO2 methanation reaction.

In this work, various amounts of Ce were added to TiO2 to form a mixed oxide support; Ce x Ti1-x O2 (x = 0, 0.003, 0.05, 0.10 and 0.15) and then those synthesized supports were impregnated by 10 wt% Ni to produce a catalysts. The 10 wt% Ni-Ce x Ti1-x O2 (x = 0, 0.003, 0.05, 0.10 and 0.15) catalysts were tested for CO2 methanation reaction by using a fixed-bed reactor in the temperature range of 100-500 °C. The sample was pretreated at 450 °C under H2 and then a mixed feed gas of CO2 and H2 was switched into the reactor to start the reaction. The results showed that 10 wt% Ni-Ce0.003Ti0.997O2 catalyst (the lowest Ce content) exhibited the highest CO2 conversion and CH4 yield. Moreover, 10 wt% Ni-Ce0.003Ti0.997O2 showed highly stable during the stability test (50 h.). The results indicated that upon addition of small amount of Ce into TiO2-supported Ni, the surface, structural, electrical and redox properties of the catalyst were improved to the extent that these properties can promote the catalytic activities for CO2 methanation. The Ce addition can improve the CO2 methanation catalytic activity by several ways. First, higher dispersion of Ni on catalysts surface upon addition of Ce was observed which resulted in higher adsorption rate of H2 on this metal active site. Second, formation of a larger amounts of oxygen vacancies as well as basicity improvement upon addition of Ce were occurred which can increase the CO2 adsorption on catalyst surface. Third, incorporation of Ce resulted in improving of a starting reduction temperature of Ni2+ to Ni0 for TiO2-supported Ni catalyst which can indicate that the reducibility of Ce-doped TiO2-supported Ni catalyst was enhanced and then alter its catalytic activity. However, increasing of Ce content led to lowering of CO2 methanation activities which resulted from increasing of basicity by Ce addition. The excess amounts of adsorbed CO2 would lead to competitive adsorption to H2 and then lead to a decrease of catalytic activity. Therefore, an appropriate amount of H2 and CO2 adsorption ability on catalyst surface was a prominent factor to dominate the catalytic activity.

Preparation, testing and characterization of doped TiO2 active in the peroxidation of biomolecules under visible light.

Doped TiO2 samples using different preparative procedures were synthesized using either urea or thiourea leading to N- or S-doped TiO2. Photocatalytic peroxidation and oxidation (mineralization) of phosphatidylethanolamine (PE) lipid with doped TiO2 were carried out under light irradiation lambda > 410 nm. The formation of conjugated double bonds in PE molecules was followed to detect the formation of peroxy radicals (peroxidation index) under light excitation (lambda > 410 nm) when doped TiO2 was used. The kinetics of CO2 production was monitored during the mineralization of PE. Colored TiO2 powders were studied in detail by different and complementary physicochemical techniques. The band gap energies of colored TiO2 were determined by diffuse reflectance spectroscopy (DRS). The visible absorption shoulder of TiO2 was observed to follow Urbach's law. The variation of the transient decay after 354 nm laser pulse excitation does not correlate with the different N- and S-TiO2 doping levels introduced by the addition of urea or thiourea. This suggests that the states (recombination centers or traps) introduced by the doping are not effective in varying the decay kinetics within the nanosecond and microsecond time scale. Elemental analysis shows comparable amounts of S- and N-doping of TiO2 when thiourea is used as dopant. X-ray diffraction reveals no rutile in S-TiO2 samples heated to 600 degrees C, suggesting that the addition of sulfur precludes rutilization during sample crystallization. X-ray photoelectron spectroscopy (XPS) of the S-TiO2 samples confirms the preferential localization of S on the 20 topmost layers of S-TiO2 upon calcination at 500 degrees C for 2 h.

Attempt of Deposition of Ag-Doped Amorphous Carbon Film by Ag-Cathode DC Plasma with CH4 Flow.

A simple DC plasma apparatus having large Ag cathode with CH4 flow was used for the attempt to prepare Ag-doped amorphous carbon film. As the gaseous source, CH4 and the additive (N2 or Ar) were used for the plasma process. When N2 was the additive, the substrate surfaces after the plasma process were electrical conductor although high electrical resistance. The growth rate of the deposits decreased with increasing the amount of N2, and the deposits contained nitrogen. Although the small amount of silver was detected by XPS, the peak for Ag may not be in the carbon deposit but be in interlayer formed at Ar etching process. When Ar was the additive, the substrate surfaces after the plasma process were also electrical conductor although high electrical resistance. The growth rate of the deposits was almost independent of the amount of Ar, and the deposits contained no argon. The small XPS peaks for Ag may not be in the carbon deposit but be in interlayer formed at Ar etching process. Both the prepared samples had high antibiotic property. The method of this study could be used for the surface reforming with amorphous carbon coating having electrical conductivity and antibiotic property.

Improvement of visible light photocatalytic acetaldehyde decomposition of bismuth vanadate/silica nanocomposites by cocatalyst loading.

Photocatalytic activity of bismuth vanadate (BiVO(4)) for acetaldehyde decomposition under visible light irradiation was improved by inclusion of a nanocomposition of silica as an adsorbent material and loading of platinum (Pt) or trivalent iron ion (Fe(3+)) as reduction cocatalysts. Addition of silica enhanced photocatalytic activity due to improvement of adsorption ability, but total decomposition of acetaldehyde was not observed within 24h of visible light irradiation. For further improvement of photocatalytic activity, BiVO(4) with an optimized amount of silica composition were modified with Pt or Fe(3+). Photodeposition of Pt greatly increased photocatalytic activity, and acetaldehyde was totally decomposed within 24h of visible light irradiation.