Liquid- liquid (Cyclohexanone: Cyclohexanol) separation using augmented tight nanofiltration membrane: A sustainable approach.

Organic solvent nanofiltration (OSN) is an incipient technology in the field of organic liquid-liquid separation. The incomplete separations and complexity involved in these, forces many organic liquids to be released as effluents and the adverse effects of these on environment is enormous and irreparable. The work prominences on the complete separation of industrially significant cyclohexanone: cyclohexanol (keto-alcohol oil) and heptane: toluene mixtures. The separations of these above-mentioned organic liquid mixtures were carried out using the fabricated Lewis acid modified graphitic carbon nitride (Cu2O@g-C3N4) incorporated polyvinylidene difluoride (PVDF) composite membranes. These fabricated membranes showed a separation factor of 18.16 and flux of 1.62 Lm-2h-1 for cyclohexanone: cyclohexanol mixture and separation of heptane and toluene mixture (with heptane flux of 1.52 Lm-2h-1) showed a separation factor of 9.9. The selectivity and productivity are based on the polarity and size of the organic liquids. The role of Cu2O@g-C3N4 is influencing the pore size distribution, increased divergence from solubility parameters, polarity, solvent uptake and porosity of the composite membranes. The developed composite membranes are thus envisioned to be apt for a wide range of liquid-liquid separations due to its implicit nature.

Exposure to benzene, toluene, ethylbenzene, and xylene (BTEX) at Nigeria's petrol stations: a review of current status, challenges and future directions.

Introduction: In Nigeria, because of increasing population, urbanization, industrialization, and auto-mobilization, petrol is the most everyday non-edible commodity, and it is the leading petroleum product traded at the proliferating Nigeria's petrol stations (NPSs). However, because of inadequate occupational health and safety (OHS) regulatory measures, working at NPSs exposes petrol station workers (PSWs) to a large amount of hazardous benzene, toluene, ethylbenzene, and xylene (BTEX) compounds. Methods: Studies on BTEX exposures among Nigerian PSWs are scarce. Thus, constraints in quantifying the health risks of BTEX limit stakeholders' ability to design practical risk assessment and risk control strategies. This paper reviews studies on the OHS of Nigerian PSWs at the NPSs. Results: Although knowledge, attitude, and practices on OHS in NPSs vary from one Nigeria's study setting to another, generally, safety practices, awareness about hazards and personal protective equipment (PPE), and the use of PPE among PSWs fell below expectations. Additionally, air quality at NPSs was poor, with a high content of BTEX and levels of carbon monoxide, hydrogen sulfide, particulate matter, and formaldehyde higher than the World Health Organization guideline limits. Discussion: Currently, regulatory bodies' effectiveness and accountability in safeguarding OHS at NPSs leave much to be desired. Understanding the OHS of NPSs would inform future initiatives, policies, and regulations that would promote the health and safety of workers at NPSs. However, further studies need to be conducted to describe the vulnerability of PSWs and other Nigerians who are occupationally exposed to BTEX pollution. More importantly, controlling air pollution from hazardous air pollutants like BTEX is an essential component of OHS and integral to attaining the Sustainable Development Goals (SDG) 3, 7, and 11.

Biofiltration of n-butyl acetate with three packing material mixtures, with and without biochar.

Two cost-effective packing materials were used for n-butyl acetate removal in lab-scale biofilters, namely waste spruce root wood chips and biochar obtained as a byproduct from a wood gasifier. Three biofilters packed with spruce root wood chips: without biochar (SRWC), a similar one with 10% of biochar (SRWC-B) and that with 10% of biochar impregnated with a nitrogen fertilizer (SRWC-IB) showed similar yet differing maximum elimination capacities of 206 ± 27, 275 ± 21 and 294 ± 20 g m-3 h-1, respectively, enabling high pollutant removal efficiency (>95% at moderate loads) and stable performance. The original biochar adsorption capacity was high (208 ± 6 mgtoluene g-1), but near 70% of it was lost after a 300-day biofilter operation. By contrast, the exposed impregnated biochar drastically increased its adsorption capacity in 300 days (149 ± 7 vs. 17 ± 5 mgtoluene g-1). Colony forming unit (CFU) and microscopic analyses revealed significant packing material colonization by microorganisms and grazing fauna in all three biofilters with an acceptable pressure drop, up to 1020 Pa m-1, at the end of biofilter operation. Despite a higher price (14 vs. 123 €m-3), the application of the best performing SRWC-IB packing can reduce the total investment costs by 9% due to biofilter volume reduction.

Catalytic oxidation of toluene by manganese oxides: Effect of K+ doping on oxygen vacancy.

Alkali metal potassium was beneficial to the electronic regulation and structural stability of transition metal oxides. Herein, K ions were introduced into manganese oxides by different methods to improve the degradation efficiency of toluene. The results of activity experiments indicated that KMnO4-HT (HT: Hydrothermal method) exhibited outstanding low-temperature catalytic activity, and 90% conversion of toluene can be achieved at 243°C, which was 41°C and 43°C lower than that of KNO3-HT and Mn-HT, respectively. The largest specific surface area was observed on KMnO4-HT, facilitating the adsorption of toluene. The formation of cryptomelane structure over KMnO4-HT could contribute to higher content of Mn3+ and lattice oxygen (Olatt), excellent low-temperature reducibility, and high oxygen mobility, which could increase the catalytic performance. Furthermore, two distinct degradation pathways were inferred. Pathway Ⅰ (KMnO4-HT): toluene → benzyl → benzoic acid → carbonate → CO2 and H2O; Pathway ⅠⅠ (Mn-HT): toluene → benzyl alcohol → benzoic acid → phenol → maleic anhydride → CO2 and H2O. Fewer intermediates were detected on KMnO4-HT, indicating its stronger oxidation capacity of toluene, which was originated from the doping of K+ and the interaction between KOMn. More intermediates were observed on Mn-HT, which can be attributed to the weaker oxidation ability of pure Mn. The results indicated that the doping of K+ can improve the catalytic oxidation capacity of toluene, resulting in promoted degradation of intermediates during the oxidation of toluene.

Characterization of Palm Fatty Acid Distillate, Diacylglycerol Regioisomers, and Esterification Products Using High-Performance Size Exclusion Chromatography.

High-performance size exclusion chromatography (HPSEC) equipped with an evaporative light scattering detector (ELSD) was utilized for characterization of palm fatty acid distillate (PFAD) and its esterified products, with a particular focus on lipid profiles and diacylglycerol (DAG) regioisomers. The separation of triacylglycerol (TAG), DAG, monoacylglycerol (MAG), and free fatty acid (FFA) was achieved through a single 100-Å Phenogel column, coupled with a 2-cm C18 guard, utilizing toluene/acetic acid (100:0.25, v/v) as the mobile phase. This separation was based on size sieving principles and the interactions between the hydroxyl group(s) and the Phenogel matrix. The limit of detection (LOD) and limit of quantification (LOQ) for the esterified PFAD products analyzed by this method fell within the range of 4.8-5.5 µg/mL and 14.7-16.7 µg/mL, respectively. Additionally, the same column, paired with a 2-cm silica guard and a mobile phase comprised of toluene/isooctane/acetic acid (35:65:0.15, v/v/v), was used for the characterization of DAG regioisomers within the esterified PFAD. LODs and LOQs for sn-1,3-DAG and sn- 1,2-DAG were determined to be 39.2 and 118.7 µg/mL, and 32.8 and 99.5 µg/mL, respectively. Investigation of esterified PFAD products prepared using 4% H2SO4 at 120°C. After 2 h, the analysis revealed the highest MAG content at 31.85%, accompanied by 51.54% DAG, 2.35% TAG, and a residual 14.27% FFA. Notably, as the reaction time extended, the MAG content decreased, while both DAG and TAG levels exhibited an increasing trend. Further examination of DAG regioisomers during PFAD esterification, under varying catalyst concentrations (2-10%) and reaction temperatures (80-140°C), demonstrated a significant increase in the percentage of sn-1,3-DAG, inversely correlated with the reduction in FFA from 2% H 2 SO 4 and 80°C onwards. Remarkably, the percentage of sn-1,2-DAG remained relatively stable regardless of changes in catalyst concentrations or temperatures, confirming its susceptibility to isomerization into the thermodynamically more stable sn-1,3-DAG form. This study provides valuable insights into the composition and behavior of esterified PFAD products.

Determination of the oil absorption value of inorganic powder by tracer-assisted headspace gas chromatography.

This paper reports a method for determining the oil absorption value of inorganic powder based on tracer-assisted headspace gas chromatographic (HS-GC) technique. The method was carried out by adding 25 µL droplet of toluene-Dioctyl Phthalate solution onto the surface of 1.0 g inorganic powder, then sealing the headspace vial and shaking it to make the powder spherical. The amount of toluene that not been adsorbed by inorganic powder was quantified using HS-GC with the optimal equilibrium temperature and time conditions of 100 °C and 7 min, respectively. A new mathematical model shows that the oil absorption value can be determined from the signal of toluene. The results show that the employed method has good precision (the relative standard deviation < 3.6 %) and accuracy (R2 = 0.993). This method is simple and accurate, and can be an reliable tool for testing the oil absorption value of inorganic powder sample.

Examination of Permeation Resistance of Chemical Protective Gloves Made of Laminate-Film Materials Against Chemical Substances.

This study investigated the permeation resistance of chemical protective gloves made of laminate film comprising nylon, ethylene-vinyl alcohol copolymer (EVOH), and other materials against different chemical substances to examine their usability in different work processes. The permeation resistance of the chemical protective glove was tested using the Japanese Industrial Standards (JIS) test method against twelve substances: acetone, acetonitrile, dichloromethane, ethyl acetate, n-hexane, methanol, tetrahydrofuran, toluene, 2-propanol, 1-butanol, 1,4-diethylene dioxide, and ethanol. After 480 min, no substance, except for methanol and ethanol, permeated at a standard permeation rate of 0.1 µg/cm2/min. Methanol and ethanol showed permeation at 1 min and 30 min elapsed, respectively. Hence, the gloves tested in this study exhibited permeation resistance to various chemical substances, and can thus be used in many work processes. Some film materials have short permeation time against certain chemical substances, but the chemical protective gloves tested in this study can be used at work sites, such as manufacturing sites, that require permeation resistance to different chemical substances.

Efficient Photothermal Catalytic Oxidation Enabled by Three-Dimensional Nanochannel Substrates.

Photothermal catalysis exhibits promising prospects to overcome the shortcomings of high-energy consumption of traditional thermal catalysis and the low efficiency of photocatalysis. However, there is still a challenge to develop catalysts with outstanding light absorption capability and photothermal conversion efficiency for the degradation of atmospheric pollutants. Herein, we introduced the Co3O4 layer and Pt nanoclusters into the three-dimensional (3D) porous membrane through the atomic layer deposition (ALD) technique, leading to a Pt/Co3O4/AAO monolithic catalyst. The 3D ordered nanochannel structure can significantly enhance the solar absorption capacity through the light-trapping effect. Therefore, the embedded Pt/Co3O4 catalyst can be rapidly heated and the O2 adsorbed on the Pt clusters can be activated to generate sufficient O2- species, exhibiting outstanding activity for the diverse VOCs (toluene, acetone, and formaldehyde) degradation. Optical characterization and simulation calculation confirmed that Pt/Co3O4/AAO exhibited state-of-the-art light absorption and a notable localized surface plasmon resonance (LSPR) effect. In situ diffuse reflectance infrared Fourier transform spectrometry (in situ DRIFTS) studies demonstrated that light irradiation can accelerate the conversion of intermediates during toluene and acetone oxidation, thereby inhibiting byproduct accumulation. Our finding extends the application of AAO's optical properties in photothermal catalytic degradation of air pollutants.

Investigation on the source of VOCs emission from indoor construction materials using electronic sensors and TD-GC-MS.

Indoor air quality (IAQ) is critical to the health and wellbeing of people. As the majority of people spend greater amounts of time indoors, either in office spaces or households, the level of air pollutants in such environments is critical. Building materials and furniture are known sources of air pollutants such as Volatile Organic Compounds (VOCs) and may be associated with discomfort, detrimental health of the occupants, etc. In this study, the VOCs found in a brand new office complex were monitored over a period of 6 months, with an emphasis on monitoring and quantifying harmful VOCs and identifying their emission source. Air samples were taken from a closed, unoccupied office space on a weekly basis and analysed using Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS), while continuous monitoring of the air quality was performed using two commercially available IAQ sensors. To identify the source of the emitted VOCs, pieces of all construction material that were used in the office, including flooring, finished wall material, and adhesive glues, were removed, and placed in air-tight glass containers prior to analysis confirming that the source of VOCs is indeed the flooring. Identified compounds included mainly material origin VOCs such as BTEX (benzene, toluene, ethylbenzene, xylene) and styrene, but also common VOCs such as acetone and propan-2-ol. Of significant importance was the concentration of toluene that was found to be the most abundant VOC in both the flooring material and the indoor air.

The Impact of Environmental Benzene, Toluene, Ethylbenzene, and Xylene Exposure on Blood-Based DNA Methylation Profiles in Pregnant African American Women from Detroit.

African American women in the United States have a high risk of adverse pregnancy outcomes. DNA methylation is a potential mechanism by which exposure to BTEX (benzene, toluene, ethylbenzene, and xylenes) may cause adverse pregnancy outcomes. Data are from the Maternal Stress Study, which recruited African American women in the second trimester of pregnancy from February 2009 to June 2010. DNA methylation was measured in archived DNA from venous blood collected in the second trimester. Trimester-specific exposure to airshed BTEX was estimated using maternal self-reported addresses and geospatial models of ambient air pollution developed as part of the Geospatial Determinants of Health Outcomes Consortium. Among the 64 women with exposure and outcome data available, 46 differentially methylated regions (DMRs) were associated with BTEX exposure (FDR adjusted p-value < 0.05) using a DMR-based epigenome-wide association study approach. Overall, 89% of DMRs consistently exhibited hypomethylation with increasing BTEX exposure. Biological pathway analysis identified 11 enriched pathways, with the top 3 involving gamma-aminobutyric acid receptor signaling, oxytocin in brain signaling, and the gustation pathway. These findings highlight the potential impact of BTEX on DNA methylation in pregnant women.

Mechanisms of benzene and benzo[a]pyrene biodegradation in the individually and mixed contaminated soils.

There is a lack of knowledge on the biodegradation mechanisms of benzene and benzo [a]pyrene (BaP), representative compounds of polycyclic aromatic hydrocarbons (PAHs), and benzene, toluene, ethylbenzene, and xylene (BTEX), under individually and mixed contaminated soils. Therefore, a set of microcosm experiments were conducted to explore the influence of benzene and BaP on biodegradation under individual and mixed contaminated condition, and their subsequent influence on native microbial consortium. The results revealed that the total mass loss of benzene was 56.0% under benzene and BaP mixed contamination, which was less than that of individual benzene contamination (78.3%). On the other hand, the mass loss of BaP was slightly boosted to 17.6% under the condition of benzene mixed contamination with BaP from that of individual BaP contamination (14.4%). The significant differences between the microbial and biocide treatments for both benzene and BaP removal demonstrated that microbial degradation played a crucial role in the mass loss for both contaminants. In addition, the microbial analyses revealed that the contamination of benzene played a major role in the fluctuations of microbial compositions under co-contaminated conditions. Rhodococcus, Nocardioides, Gailla, and norank_c_Gitt-GS-136 performed a major role in benzene biodegradation under individual and mixed contaminated conditions while Rhodococcus, Noviherbaspirillum, and Phenylobacterium were highly involved in BaP biodegradation. Moreover, binary benzene and BaP contamination highly reduced the Rhodococcus abundance, indicating the toxic influence of co-contamination on the functional key genus. Enzymatic activities revealed that catalase, lipase, and dehydrogenase activities proliferated while polyphenol oxidase was reduced with contamination compared to the control treatment. These results provided the fundamental information to facilitate the development of more efficient bioremediation strategies, which can be tailored to specific remediation of different contamination scenarios.

Prefeeding of Clarias gariepinus with Spirulina platensis counteracts petroleum hydrocarbons-induced hepato- and nephrotoxicity.

Petroleum aromatic hydrocarbons are considered one of the most dangerous aquatic pollutants due to their widespread across water bodies, persistence, and extension to the food chain. To our knowledge, there hasn't been any research investigating the hepatorenoprotective effects of Spirulina platensis (SP) against toxicity induced by these environmental toxicants in fish. Thus, we decided to explore its potential safeguarding against benzene and toluene exposure in adult Clarias gariepinus. To achieve this objective, fish were divided into five groups (60 per group; 20 per replicate). The first group served as a control. The second and third groups were intoxicated with benzene and toluene at doses of 0.762 and 26.614 ng/L, respectively for 15 days. The fourth and fifth groups (SP + benzene and SP + toluene, respectively) were challenged with benzene and toluene as previously mentioned following dietary inclusion of SP at a dose of 5 g/kg diet for 30 days. The marked increase in liver metabolizing enzymes, glucose, total protein, albumin, globulin, albumin/globulin ratio, and creatinine confirmed the hepato- and nephrotoxic impacts of benzene and toluene. These outcomes were coupled with cytopathological affections and excessive collagen deposition. The incorporation of SP in ration formulation, on the contrary, restored the previously mentioned toxicological profile due to its antioxidant and cytoprotective attributes. Regardless of SP intervention, the renal tissues still displayed histo-architectural lesions, because of insufficient dose and timeframe. Additional research will be required to identify the ideal SP remediation regimen.

Unsymmetrical Benzothieno-Fused BODIPYs as Efficient NIR Heavy-Atom-Free Photosensitizers.

Heavy-atom-free photosensitizers are potentially suitable for use in photodynamic therapy (PDT). In this contribution, a new family of unsymmetrical benzothieno-fused BODIPYs with reactive oxygen efficiency up to 50% in air-saturated toluene was reported. Their efficient intersystem crossing (ISC) resulted in the generation of both 1O2 and O2-• under irradiation. More importantly, the PDT efficacy of a respective 4-methoxystyryl-modified benzothieno-fused BODIPY in living cells exhibited an extremely high phototoxicity with an ultralow IC50 value of 2.78 nM. The results revealed that the incorporation of an electron-donating group at the α-position of the unsymmetrical benzothieno-fused BODIPY platform might be an effective approach for developing long-wavelength absorbing heavy-atom-free photosensitizers for precision cancer therapy.

Synthesis and characterization of fluorescent poly(α-cyclodextrin)/carbon quantum dots composite for efficient removal and detection of toluene and xylene from aqueous media.

This study reports the synthesis and characterization of a supramolecular composite comprised of carbon dots (CDots) embedded within net-poly[(α-cyclodextrin)-ν-(citric acid)] (α-CD/CA/CDots) for the removal and detection of toluene and xylene from aqueous media. The remarkable stability of CDots within the composite enables the preservation of photoluminescence properties for prolonged storage and extended UV-light irradiation. As demonstrated, following the adsorption of both organic compounds, the composite detected them in the aqueous medium due to a fluorescence quenching mechanism. Spectroscopic analyses reveal that the accessible Stern-Volmer quenching constants for toluene and xylene are KSVa = 15.4 M-1 and KSVa = 10.3 M-1, respectively. As a result, the α-CD/CA/CDots composite were sensitive to the tested volatile organic compounds (LODtoluene = 3.7 mg/L and LODxylene = 4.9 mg/L). Optimal conditions for toluene and xylene adsorption were found, allowing to achieve noticeable adsorption capabilities (qe(toluene) = 68.9 and qe(xylene) = 48.2 mg/g) and removal efficiencies exceeding 70%. Different characterization techniques confirmed the successful synthesis of the composite and elucidated the interaction mechanisms between the adsorbent and the tested compounds. In summary, the multifunctionality demonstrated by the α-CD/CA/CDots composite ranks it as an efficient and promising adsorbent and detection probe for this class of water contaminants.

Elucidating contributions of volatile organic compounds to ozone formation using random forest during COVID-19 pandemic: A case study in China.

Ozone has been reported to increase despite nitrogen oxides reductions during the COVID-19 pandemic, and ozone formation needs to be revisited using volatile organic compounds (VOCs), which are rarely measured during the pandemic. Here, a total of 98 VOCs species were monitored in an economy-active city in China from January 2021 to August 2022 to assess contributions to ozone formation during the pandemic. Total VOCs concentrations were 35.55 ± 21.47 ppb during the entire period, among which alkanes account for the largest fraction (13.78 ppb, 38.0%), followed by aromatics (6.16 ppb, 16.8%) and oxygenated VOCs (OVOCs, 5.69 ppb, 15.7%). Most VOCs groups (e.g., alkenes, OVOCs) and individual species (e.g., isoprene, methyl vinyl ketone) display obvious seasonal and diurnal variations, which are related to their sources and reactivities. No weekend effects of VOCs suggest limited influences from traffic emissions during pandemic. Aromatics and alkenes are the major contributors (39% and 33%) to ozone formation potential, largely driven by o/m/p-xylene (21%), ethylene (15%), toluene (9%). Secondary organic aerosol formation potential is dominated by toluene (>50%) despite its low proportion (5%). Further inclusion of VOCs and meteorology in the Random Forest model shows good ozone prediction performance (R2 = 0.77-0.86, RMSE = 11.95-19.91 µg/m3, MAE = 8.89-14.58 µg/m3). VOCs and NO2 contribute >50% of total importance with the largest difference in importance ratio of VOCs/NO2 in the summer and winter, implying ozone formation regime may vary. No seasonal variations in importance of meteorology are observed, while importance of other variables (e.g., PM2.5) is highest in the summer. This work identifies critical VOCs groups and species for ozone formation during the pandemic, and demonstrates the feasibility of machine learning algorithms in elucidation of ozone formation mechanisms.

Co-exposure of petrochemical workers to noise and mixture of benzene, toluene, ethylbenzene, xylene, and styrene: Impact on mild renal impairment and interaction.

Epidemiological evidence concerning effects of simultaneous exposure to noise and benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) on renal function remains uncertain. In 2020, a cross-sectional study was conducted among 1160 petrochemical workers in southern China to investigate effects of their co-exposure on estimated glomerular filtration rate (eGFR) and mild renal impairment (MRI). Noise levels were assessed using cumulative noise exposure (CNE). Urinary biomarkers for BTEXS were quantified. We found the majority of workers had exposure levels to noise and BTEXS below China's occupational exposure limits. CNE, trans, trans-muconic acid (tt-MA), and the sum of mandelic acid and phenylglyoxylic acid (PGMA) were linearly associated with decreased eGFR and increased MRI risk. We observed U-shaped associations for both N-acetyl-S-phenyl-L-cysteine (SPMA) and o-methylhippuric acid (2-MHA) with MRI. In further assessing the joint effect of BTEXS (ß, -0.164 [95% CI, -0.296 to -0.033]) per quartile increase in all BTEXS metabolites on eGFR using quantile g-computation models, we found SPMA, tt-MA, 2-MHA, and PGMA played pivotal roles. Additionally, the risk of MRI associated with tt-MA was more pronounced in workers with lower CNE levels (P = 0.004). Multiplicative interaction analysis revealed antagonisms of CNE and PGMA on MRI risk (P = 0.034). Thus, our findings reveal negative dose-effect associations between noise and BTEXS mixture exposure and renal function in petrochemical workers. With the exception of toluene, benzene, xylene, ethylbenzene, and styrene are all concerning pollutants for renal dysfunction. Effects of benzene, ethylbenzene, and styrene exposure on renal dysfunction were more pronounced in workers with lower CNE.

Impact of diluents on the calibration of direct dynamic thermal desorption prior to gas chromatography.

A thermal desorber (TD) can be used in different ways to introduce samples in a gas chromatographic (GC) system. Besides its conventional use where the collected analytes are released from the sorbent in the sample tube, direct dynamic desorption (DDD) is an interesting option where a solid sample is put directly in the TD tube. However, since no sorbent is used for the sample, proper calibration is not straightforward. This issue was investigated in the present work using offline liquid calibration (OLC) and inline liquid calibration (ILC). Unexpectedly, ILC yielded a lower response than OLC. This could be related to the adsorption kinetics of the analytes and water on the cold trap of the TD. More insight was gained performing double injection ILC experiments with toluene as diluent for the analytes and injecting water before or after the toluene solution. This revealed a clear influence of the diluent. The influence of water was further explored applying two cold trap temperatures (4 °C and -30 °C). Inserting a LiCl trap in the TD tube to capture the water was found to be an effective solution for the problem. Finally, quantitative aspects of this approach were demonstrated.

Surface Hydroxyl and Oxygen Vacancies Engineering in ZnSnAl LDH: Synergistic Promotion of Photocatalytic Oxidation of Aromatic VOCs.

Photocatalytic oxidation has gained great interest in environmental remediation, but it is still limited by its low efficiency and catalytic deactivation in the degradation of aromatic VOCs. In this study, we concurrently regulated the surface hydroxyl and oxygen vacancies by introducing Al into ZnSn layered double hydroxide (LDH). The presence of distorted Al species induced local charge redistribution, leading to the remarkable formation of oxygen vacancies. These oxygen vacancies subsequently increased the amount of surface hydroxyl and elongated its bond length. The synergistic effects of surface hydroxyl and oxygen vacancies greatly enhanced reactant adsorption-activation and facilitated charge transfer to generate •OH, •O2-, and 1O2, resulting in highly efficient oxidation and ring-opening of various aromatic VOCs. Compared with commercial TiO2, the optimized ZnSnAl-50 catalyst exhibited about 2-fold activity for the toluene and styrene degradation and 10-fold activity for the chlorobenzene degradation. Moreover, ZnSnAl-50 demonstrated exceptional stability in the photocatalytic oxidation of toluene under a wide humidity range of 0-75%. This work marvelously improves the photocatalytic efficiency, stability, and adaptability through a novel strategy of surface hydroxyl and oxygen vacancies engineering.

Establishing efficient toluene elimination over cobalt-manganese bimetallic oxides via constructing strong Co-Mn interaction.

Doping proves to be an efficacious method of establishing intermetallic interactions for enhancing toluene oxidation performance of bimetallic oxides. However, conventional bimetallic oxide catalysts are yet to overcome their inadequacy in establishing intermetallic interactions. In this work, the dispersion of Mn-Co bimetallic sites was improved by hydrolytic co-precipitation, strengthening the intermetallic interactions which improved the structural and physicochemical properties of the catalysts, thus significantly enhancing its catalytic behavior. MnCo-H catalysts fabricated by the hydrolytic co-precipitation method showed promising catalytic performance (T50 = 223 °C, T90 = 229 °C), robust stability (at least 100 h) and impressive water resistance (under 10 vol.% of water) for toluene elimination. Hydrolytic co-precipitation has been found to improve dispersion of MnCo elements and to enhance interaction between Co and Mn ions (Mn4+ + Co2+ = Mn3+ + Co3+), resulting in a lower reduction temperature (215 °C) and a weaker Mn-O bond strength, creating more lattice defects and oxygen vacancies, which are responsible for superior catalytic properties of MnCo-H samples. Furthermore, in situ DRIFTs showed that gaseous toluene molecules adsorbed on the surface of MnCo-H were continuously oxidized to benzyl alcohol → benzaldehyde → benzoate, followed by a ring-opening reaction with surface-activated oxygen to convert to maleic anhydride as the final intermediate, which further generates water and carbon dioxide. It was also revealed that the ring-opening reaction for the conversion of benzoic acid to maleic anhydride is the rate-controlling step. This study reveals that optimizing active sites and improving reactive oxygen species by altering the dispersion of bimetals to enhance bimetallic interactions is an effective strategy for the improvement of catalytic behavior, while the hydrolytic co-precipitation method fits well with this corollary.

Effect of commutation on pressure drop and microbial diversity in a horizontal biotrickling filter for toluene removal.

A horizontal biotrickling filter (HBTF) was designed to understand the toluene removal process and microbial community structures. The start-up time of the HBTF, immobilized by the dominant fungi was only about 6 days and the toluene removal efficiency was found to be more than 95% when the inlet toluene concentration remained at around 1560.0 mg/m3. In the stable operation stage of the HBTF, based on not greatly reducing the removal efficiency, a simple and convenient periodic commutation was adopted to reduce the pressure drop (△P) and regulate the distribution of microorganisms in the packing area of the HBTF. The △P decreased from about 90 Pa to 10 Pa after the commutation, which indicated its feasibility. The performance of the HBTF was improved by changing the inlet direction of waste gas flow. When the inlet concentration of toluene was about 640 mg/m3, the removal efficiency was nearly 70.0% before commutation and it remained 95.0-98.0% after commutation. Microbial abundance and diversity analysis showed that the corresponding Shannon-Weiner index was 2.73 and 1.84, respectively. The front section of the HBTF, which was exposed to toluene earlier, consistently exhibited higher microbial diversity than that in the back section. Following commutation, microbial diversity decreased in both the front and back sections, with a maximum decline of around 50%. The main fungi treating toluene were Aplanochytrium, Boletellus, and Exophiala.