Accelerating Toluene Oxidation over Boron-Titanium-Oxygen Interface: Steric Hindrance of the Methyl Group Induced by the Plane-Adsorption Configuration.

Elimination of dilute gaseous toluene is one of the critical concerns within the field of indoor air remediation. The typical degradation route on titanium-based catalysts, "toluene-benzaldehyde-carbon dioxide", necessitates the oxidation of the methyl group as a prerequisite for photocatalytic toluene oxidation. However, the inherent planar adsorption configuration of toluene molecules, dominated by the benzene rings, leads to significant steric hindrance for the methyl group. This steric hindrance prevents the methyl group from contacting the active species on the catalyst surface, thereby limiting the removal of toluene under indoor conditions. To date, no effective strategy to control the steric hindrance of the methyl group has been identified. Herein, we showed a B-Ti-O interface that exhibits significantly enhanced toluene removal efficiency under indoor conditions. In-depth investigations revealed that, compared to typical Ti-based photocatalysts, the steric hindrance between the methyl group and the catalyst surface decreased from 3.42 to 3.03 Å on the designed interface. This reduction originates from the matching of orbital energy levels between Ti 3dz2 and C 2pz of the benzene ring. The decreased steric hindrance improved the efficiency of toluene being attacked by surface active species, allowing for rapid conversion into benzaldehyde and benzoic acid species for subsequent reactions. Our work provides novel insights into the steric hindrance effect in the elimination of aromatic volatile organic compounds.

Electrocatalytic oxidation of gaseous toluene in an all-solid cell using a foam Ti/Sb-SnO2/ß-PbO2 anode.

Mineralization of benzene, toluene, and xylene (BTX) with high efficiency at room temperature is still a challenge for the purification of indoor air. In this work, a foam Ti/Sb-SnO2/ß-PbO2 anode catalyst was prepared for electrocatalytically oxidizing gaseous toluene in an all-solid cell at ambient temperature. The complex Ti/Sb-SnO2/ß-PbO2 anode, which was prepared by sequentially deposing Sb-SnO2 and ß-PbO2 on a foam Ti substrate, shows high electrocatalytic oxidation efficiency of toluene (80%) at 7 hr of reaction and high CO2 selectivity (94.9%) under an optimized condition, i.e., a cell voltage of 2.0 V, relative humidity of 60% and a flow rate of 100 mL/min. The better catalytic performance can be ascribed to the high production rate of ⋅OH radicals from discharging adsorbed water and the inhibition of oxygen evolution on the surface of foam Ti/Sb-SnO2/ß-PbO2 anode when compared with the foam Ti/Sb-SnO2 anode. Our results demonstrate that prepared complex electrodes can be potentially used for electrocatalytic removal of gaseous toluene at room temperature with a good performance.

Fabrication of novel Ag4Bi2O5-x towards excellent photocatalytic oxidation of gaseous toluene under visible light irradiation.

In this work, a novel oxide combined with bismuth (Bi) and silver (Ag) was prepared via simple ball milling. This substance was optimized by adjusting the amount of pre-source. Preliminary characterization results confirmed the successful synthesis of Ag4Bi2O5. Subsequently, gaseous toluene was selected as model compound to evaluate the photocatalytic activity of Ag4Bi2O5 photocatalyst. According to the degradation results, Ag4Bi2O5 performed excellent visible light-driven photocatalytic activity with high stability. For the oxidation process of gaseous compound, reactive oxygen species (ROS) were responsible for the achievement, and the formation of oxygen vacancies on Ag4Bi2O5 were involved in the generation of ROS to promote the transfer of photogenerated electrons, and improving photocatalytic activity. DFT calculations revealed the theoretical band gap of Ag4Bi2O5 bulk is 1.758 eV. And the work function of Ag4Bi2O5 (112)ov was ca. at 4.447 eV. The material was easily fabricated and a reliable path was provided for the synthesis of new and efficient photocatalyst for the remediation of polluted indoor air.

Acid-assisted hydrothermal synthesis of nanocrystalline TiO2 from titanate nanotubes: influence of acids on the photodegradation of gaseous toluene.

In order to efficiently remove volatile organic compounds (VOCs) from indoor air, one-dimensional titanate nanotubes (TiNTs) were hydrothermally treated to prepare TiO2 nanocrystals with different crystalline phases, shapes and sizes. The influences of various acids such as CH3COOH, HNO3, HCl, HF and H2SO4 used in the treatment were separately compared to optimize the performance of the TiO2 nanocrystals. Compared with the strong and corrosive inorganic acids, CH3COOH was not only safer and more environmentally friendly, but also more efficient in promoting the photocatalytic activity of the obtained TiO2. It was observed that the anatase TiO2 synthesized in 15 mol/L CH3COOH solution exhibited the highest photodegradation rate of gaseous toluene (94%), exceeding that of P25 (44%) by a factor of more than two. The improved photocatalytic activity was attributed to the small crystallite size and surface modification by CH3COOH. The influence of relative humidity (20%-80%) on the performance of TiO2 nanocrystals was also studied. The anatase TiO2 synthesized in 15 mol/L CH3COOH solution was more tolerant to moisture than the other TiO2 nanocrystals and P25.

Construction of CdS@g-C3N4 heterojunction photocatalyst for highly efficient degradation of gaseous toluene.

Exploring efficient photocatalysts for the degradation of VOCs under visible light is a challenge. CdS@g-C3N4 heterojunction photocatalytic materials were developed in this study using a microwave-assisted sol-gel process. CdS@g-C3N4(0.2) photocatalyzed the maximum degradation of gaseous toluene under visible light irradiation, and the time required to achieve the same degradation rate was reduced by 270 min when compared to pure CdS. The morphological characterization, photoelectric property analysis, and DFT calculations all verified that the CdS nanoparticles were uniformly disseminated on the surface of g-C3N4, and that the interfaces were closely contacted to form a heterojunction interface with a built-in field. This enhances charge transfer from CdS to g-C3N4 while successfully decreasing electron-hole pair recombination caused by light. Furthermore, the energy band structure was altered to absorb longer wavelengths of light and extend the absorption spectral range, improving the photocatalytic material's efficacy for broad-spectrum light such as sunshine. This paper proposes methods for predicting and optimizing the surface structure of catalysts, as well as developing high-performance multi-heterojunction photocatalysts for the degradation of indoor VOCs.

Semi-solid electrolyte with layered heterometallic low-valent electron-mediator enabling indirect destruction of gaseous toluene.

The electrochemical degradation of air pollutants, particularly volatile organic compounds (VOCs), at their gaseous state is a promising method. However, it remains at an infant stage due to sluggish solid-gas electron transfers at room temperature. We established a triphase reaction condition using a semi-solid electrolyte layer between the electrode and membrane to enhance the electron transfer at room temperature. A polyvinyl alcohol (PVA) gel layer was inserted between a bimetallic layered CuNi(CN)4 complex coated Cu foam electrode (TCNi-Cu) and Nafion 324 membrane for the degradation of gaseous toluene. The cyclic voltammetry of TCNi-Cu using a sodium hydroxide-coated copper mesh electrode at a triphase showed Cu1+ and Ni1+ stabilization at -0.7 and -0.9 V, respectively, which was similar to the liquid phase electron transfer behavior. The degradation capacity of gaseous toluene without using electrogenerated TCNi-Cu + PVA gel was 0.54 mg cm2 min-1, whereas that of TCNi-Cu + PVA gel layers was 1.17 mg cm-2min-1, which revealed the mediation effect at a triphase condition. Toluene was converted into oxygen-containing products, such as butanol, propanol, and acetone (without reduction products), which revealed that indirect oxidation occurred at the cathode using an in-situ generated oxidant, such as OH˙ radical. As an electron-mediator, Cu1+ was used to form oxidants for the degradation of toluene at -0.7 V. The toluene removal rate reached 1.4 µmol h-1, with an energy efficiency of 0.15 Wh L-1. This study is the first attempt to describe a liquid-electrolyte-free cathodic half-cell in electrochemical application to VOCs degradation, highlighting the electron transfer at room temperature.

Flavin mononucleotide-stimulated microbial fuel cell for efficient gaseous toluene abatement.

Chemical park is regarded as a major contributor of VOCs emissions in China. Currently, a green and safe technology, microbial fuel cells (MFCs), is being developed for the VOCs abatement. Noting that effective electron transfer is critical to the MFC performance. In this work, flavin mononucleotide (FMN) was dosed as an electron shuttle to improve the removal of the typical toxic VOCs, toluene. The experimental results revealed that the performance of toluene removal and power generation were accelerated with the dosage of 0.2-2 µM FMN. With the addition of 1 µM FMN, the removal efficiency, the maximum output voltage and the coulombic efficiency of MFC were increased by 18.4%, 64.4% and 56.3%, respectively. However, a further increase in FMN concentration to 2 µM caused a reduction in the removal efficiency and coulombic efficiency. The images of scanning electron microscopy and confocal laser scanning microscopy showed that the presence of FMN greatly promoted the microbial growth and its activity. Furthermore, microbial community analysis also implied that the moderate dosage of FMN (0.2-1 µM) was beneficial for the growth of the typical exoelectrogens, Geobacter sp., and thus the coulombic efficiency was increased. In addition, an electron transfer pathway involving in cytochrome b, OMCs, cytochrome c, and MtrA was proposed based on the cyclic voltammetry analysis. This work will provide a fundamental theoretical support for its application of toxic VOCs abatement from the chemical park.

Mechanisms for removal of gaseous toluene in headspace using sonophysical and sonochemical effects at the gas-liquid interface.

We developed a new method for removing gaseous substances by using high frequency (200 kHz) ultrasonic irradiation of water, and the effects of ultrasonic irradiation on gas-phase toluene were evaluated quantitatively for the first time. The removal ratio of gaseous toluene increased with increasing ultrasonic power, but the reaction was inhibited by the addition of radical scavengers, indicating that ultrasonic irradiation not only accelerated the dissolution of gaseous toluene but also induced toluene decomposition. The contribution made by OH radicals to the decomposition of gaseous toluene at the gas-liquid interface was confirmed by the difference in removal ratios between addition of KI and addition of tert-butyl alcohol. The toluene removal mechanism was investigated by studying the logarithmic plots for toluene concentration at specified times. The results of this study clearly showed the promotion of gaseous toluene dissolution and the reaction via OH radicals at the gas-liquid interface by sonophysical and sonochemical effects with both effects contributing to the removal of gaseous toluene. Furthermore, the total organic carbon concentration in the aqueous phase increased with increasing reaction time, indicating that the toluene degradation products were trapped and decomposed into low-molecular-weight organic compounds in the aqueous phase.

Exogenous electron transfer mediator enhancing gaseous toluene degradation in a microbial fuel cell: Performance and electron transfer mechanism.

Effective electron transfer (ET) between microorganisms and electrodes is essential for the toluene degradation and power generation in a microbial fuel cell (MFC). In this work, the neutral red, with excellent electrochemical reversibility and compatible redox potential as NADH/NAD+, was selected as electron mediator to boost the performance of the MFC. Experimental results revealed that, with the 0.5 µM neutral red, the removal efficiency and coulombic efficiency of the gaseous toluene powered MFC was increased by ~19% and ~400%, respectively. However, further increase in neutral red concentration resulted in a decreased in removal efficiency and coulombic efficiency, which was attributed by the toxicity of neutral red to the microbes. The microbial community analysis indicated that, with the dosage of the neutral red, the dominated bacteria shifted from Geobacter to Ignavibacteriales, resulting in a high coulombic efficiency. With the further increase in the neutral red, the amount of Ignavibacteriales gradually decreased and thus the coulombic efficiency declined at a high neutral red concentration. Based on the cyclic voltammetry analysis, an electron transport pathway involving neutral red, cytochromes, and OMCs in neutral red mediated MFC was proposed. Overall, the dosage of neutral not only enhanced the electron transfer but also induced the growth of the exoelectrogens, and thus significantly improve the MFC performance.

The roles of wavelength in the gaseous toluene removal with OH from UV activated Fenton reagent.

The UV lights of different wavelengths were performed in boosting hydroxyl radicals (OH) generation from traditional Fenton reagent for the gaseous toluene removal. The Fenton, UV254/Fenton and UV365/Fenton processes were first adopted to eliminate gaseous toluene through the bubble column reactor, respectively. The stable toluene removal efficiency in 60 min was 85.31% in the UV365/Fenton process, which was higher than other processes. The gaseous toluene was mainly oxidized into CO2 rather than other gaseous intermediates in the UV365/Fenton process. For UV365/Fenton process, the GC-MS tests were carried out to figure out the aqueous intermediates of gaseous toluene removal. The OH concentration in the UV365/Fenton process was the highest among all the parallel tests via the EPR experiments and the quantificational measurements with coumarin as the probe. The iron ion in the aqueous solution was systematically evaluated with the experiments proceeding. The evolution of iron ion in the aqueous solution indicated that the fast reduction of Fe3+ to Fe2+ was assisted with 365 nm UV rather than 254 nm UV, which played a key point in the high gaseous toluene removal efficiency. This study demonstrated that the combination of UV365 irradiation and Fenton in the wet scrubbing reactor performed a synergistic effect on the gaseous toluene removal.

A vertically configured photocatalytic-microbial fuel cell for electricity generation and gaseous toluene degradation.

A vertically configured photocatalytic-microbial fuel cell (photo-MFC) is developed by combining a nanodiamond-decorated ZnO (ZnO/ND) photocathode with a bioanode. The system can effectively couple the light energy with bioenergy to enhance the degradation of volatile organic compounds (VOCs) and boost electricity output. Results show that the composite system exhibits increased performance for toluene removal (60.65%), higher than those of individual parts (ZnO/ND-photocatalysis: 37.16%, MFC: 17.81%). Furthermore, its electrochemical performance is dramatically increased. The peak power density of 120 mW/m2 and the current density of 1.07 A/m2 are generated under light illumination, which are about 1.57-fold and 1.37-fold higher than that under dark (76 mW/m2, 0.78 A/m2), respectively. Microbial community analysis demonstrates Proteobacteria and Firmicute are dominant phyla, implying they play important roles on accelerating the extracellular-electron transfer and toluene degradation. In addition, the underlying mechanism for toluene degradation in the photo-MFC system is preliminary explored. Our results suggest that the photo-MFC has great potential for simultaneous treatment of VOCs with energy recovery.

A novel high-performance CeO2-CuMn2O4 catalyst for toluene degradation.

A series of spinel CuM2O4 (M = Mn, Fe, and Al) was used as the catalyst to investigate the effective degradation of toluene, and then CuMn2O4 with better catalytic activity was selected as the research object to study its activity at different ratios of Cu and Mn. Meanwhile, CeO2 was introduced to modify CuMn bimetallic oxide to improve its catalytic performance. The structure, morphology, and valence states of surface elements of as-prepared catalysts were characterized by XRD, TEM, SEM, N2 adsorption-desorption, XPS, and H2-TPR. Using toluene as a probe molecule, the catalytic activity of the catalyst was tested and the results showed that the conversion rate of toluene catalyzed by CeO2-CuMn2O4 catalyst can reach 90% at 200 °C (T90) and 100% at 240 °C (T100). The CO2 yield can also reach 100% at 248 °C. Moreover, the possible catalytic mechanism for toluene by the CeO2-CuMn2O4 was briefly explored. The catalytic oxidation of toluene over the oxide follows the Mars-van Krevelen mechanism.

Efficient photocatalytic oxidation of gaseous toluene in a bubbling reactor of water.

Conventional gas-solid photocatalytic oxidation (SPCO) of VOCs has drawbacks such as accumulation of intermediates and catalytic deactivation. In this study, gas-liquid photocatalytic oxidation (LPCO) was exploited to improve the catalytic activity and stability by continuously bubbling VOCs into water. Toluene and commercial TiO2 (P25) were chosen as the representative VOC pollutant and photocatalyst, respectively. Toluene removal efficiency in LPCO was about 6 times of that in conventional SPCO, and no intermediates were detected in the exhaust of LPCO probably due to its high degradation and mineralization rates. However, plentiful intermediates were identified by GC-MS and ITMS both in the gas outlet and on the surface of catalyst in SPCO, which may lead to photocatalytic deactivation. Moreover, LPCO exhibited superior catalytic activity towards typical soluble VOCs such as formaldehyde compared to SPCO. The soluble intermediates formed from toluene degradation can be easily removed by sustaining UV irradiation to avoid water pollution and the water after purification can be reused in LPCO. This study provides a novel gas-liquid photocatalytic oxidation to replace conventional gas-solid photocatalytic oxidation for the sake of better catalytic activity and fewer by-products.

Adsorption/desorption kinetics and breakthrough of gaseous toluene for modified microporous-mesoporous UiO-66 metal organic framework.

In this work, micro-mesoporous UiO-66 was successfully prepared with P123 (EO20PO70EO20) as structure-directing agent by a simple solvothermal method. Adsorption/desorption kinetics of gaseous toluene over pristine UiO-66 and micro-mesoporous UiO-66 were investigated by breakthrough experiments, toluene vapor adsorption isotherm measurements and temperature programmed desorption (TPD) experiments. The interactions between toluene and UiO-66 samples were assessed through the Henry's law constant (KH) and the isosteric adsorption heat (ΔHads). The micro-mesoporous UiO-66 crystal demonstrated 2.6 times toluene adsorption capacity of the pristine UiO-66 when the P123/Zr4+ molar ratio was 0.2. Results showed that micropore adsorption was the main adsorption process and the larger pores in micro-mesoporous UiO-66 increased molecular diffusion rate and reduced the mass transfer resistance. This result indicated that micro-mesoporous structures and defect sites had a positive effect on toluene molecules capture. The breakthrough times and the working capacities decreased with the increase of the relative humidity and adsorption temperature. A good thermal stability and reproducibility were revealed over the micro-mesoporous UiO-66 in this paper.

Efficient gaseous toluene photoconversion on graphene-titanium dioxide nanocomposites with dominate exposed {001} facets.

A series of GnTiO2 {001} nanocomposites (GTN) with dominate exposed {001} facets has been synthesized by various dosage of graphite oxide (GO) and hydrofluoric acid (HF) during a facile solvothermal process successfully. The photocatalytic degradation efficiency (PDE) of the optimal sample reached up to 98.7% for liquids methyl orange and up to 78.6% for gaseous toluene under the UV-light irradiation for 30 min, which is much higher than P25. The effects mechanism of HF and GO on the percentage of {001} facets exposed and the crystal morphology are investigated by XRD, SEM, TEM, UV-Vis, XPS and BET measurement, particularly. Cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS) were used to explore the electron transfer mechanisms of GnTiO2 {001} nanocomposites. These results reveal the enhanced photocatalytic properties attribute to the excellent electron transport of Gn and highly reactive {001} facets can facilitate the separation of photo-generated charge carriers. Moreover, Gn can extend the absorption range of light and improve the adsorptivity of pollutant molecules.