Benzene Conversion Research Articles

Remote Activation Catalysis: Interparticle Hydrogen Spillover-Assisted Cumene Synthesis from Propane and Benzene.

Hydrogen spillover, particularly when involving "interparticle" hydrogen spillover, offers a unique opportunity to enhance catalytic efficiency by remote activation of surface acidity. Building on this concept, this study aims to investigate physically mixed alumina-supported platinum nanoparticles (Pt/Al2O3) and zirconia-supported tungsten oxide (WO3/ZrO2) in promoting the direct synthesis of cumene from benzene and propane at 300 °C. The reaction with Pt/Al2O3 alone afforded propylene as the only product, indicating the successive reaction route of Pt-catalyzed dehydrogenation of propane, followed by acid-catalyzed alkylation. WO3/ZrO2 with 18 wt.% WO3 loading resulted in high benzene conversion (≈5.0%) and cumene selectivity (≈87.5%), which possesses poly tungstate species on the surface that is active for the acid-catalyzed alkylation. UV-vis-near infrared spectroscopy, X-ray photoelectron spectroscopy, and in situ Fourier-transform infrared spectroscopy analyses revealed that atomic hydrogen abstracted from propane spills over from Pt/Al2O3 particles to WO3/ZrO2 particles to form Brønsted acid sites on the poly tungstate species, whose activity for alkylation between benzene and propylene is double that of the parent WO3/ZrO2.

Experimental and kinetic modeling study of oxidative degradation of benzene and phenol in supercritical water.

Benzene and phenol are representative aromatic compounds existing commonly in wastewater. The kinetics of oxidative degradation of benzene and phenol in supercritical water have been investigated in a flow reactor at 823K and 250atm, with the excess oxygen ratio ranging from 0.5 to 2.0. For supercritical water oxidation of benzene, CO2 was observed as the main product accounting for the largest fraction of the reacted carbon. Its concentration was higher than that of CO under all conditions, even at the initial reaction periods where benzene conversions were low. The phenol conversion was found to accelerate with increasing excess oxygen ratio, exhibiting strong dependence on oxygen concentration. CO2 and CO were the major gaseous products with comparable concentrations, and C2H2 was also formed in considerable amounts. A comprehensive chemical kinetic model was developed based on a gas-phase mechanism, and its performance was further validated by comparing to experimental data from different sources. The model reproduced the benzene and phenol conversions and CO concentration fairly well, but underpredicted the CO2 yield and overpredicted the C2H2 yield slightly. Reaction mechanisms were then inferred through kinetic analyses, emphasizing the importance of C6H5OO and C6H5O radicals. Finally, the kinetic characteristics of benzene and phenol oxidation in supercritical water and gas-phase environments were compared.

Acid washing-assisted synthesis of porous Co3O4 nanosheet catalyst featuring efficient benzene oxidation performance

Co-based catalysts exhibit considerable catalytic activity in oxidative reactions, yet challenges remain in synthesizing Co3O4 materials featuring both large surface area and high activity. Here, ultrathin La0.029CoOx nanosheets were post-treated with various concentrations of dilute nitric acid to obtain the two-dimensionally geometric Co3O4-H nanosheets catalysts. Among them, the resultant Co3O4-0.1H catalyst disclosed significantly enhanced catalytic activity, enabling to achieve 100 % conversion of benzene at 230 °C under an ultrahigh weight hourly space velocity (WHSV) of 60,000 mL·g−1·h−1. Additionally, the catalyst also displayed excellent catalytic durability and well catalytic stability over 5 cyclic tests and 45 h of long-period operation. A thorough characterization results revealed that the superior catalytic performance of Co3O4-0.1H was attributed to its distinct nanosheet morphology, high specific surface area and abundant surface defect sites. This work highlights the effectiveness and simplicity of acid washing treatment strategy in improving the catalytic oxidation activity of transition metal oxide catalysts.

Selective hydroxylation of benzene via enhanced generation and utilization of hydroxyl radicals with CuZnSbO photocatalyst

Photocatalytic selective benzene hydroxylation via activation of C(sp2)–H under visible light remains a challenging reaction. Copper-incorporated mixed metal oxide photocatalysts have shown promise in addressing this difficulty by enabling visible light harvesting, controlled reactive oxygen species (ROS) generation, effective ROS utilization, and reactant adsorption. However, copper incorporated metal oxide catalysts were suffered from poor catalytic activity and selectivity due to leaching of Cu species. To solve this problem, herein, a novel stable mixed metal oxide (CuZnSbO) was prepared for the first time by applying a facile method. Copper introduction brought about the suitable band gap energy for a wide range of visible light harvesting of the CuZnSbO catalyst. The copper species play a key role in activating H2O2 to produce hydroxyl radicals (•OH) for benzene oxidation by controlling charge recombination. The mixed metal oxide of zinc and antimony supports the included copper strongly enabling copper stability. The CuZnSbO not only generates available hydroxyl radicals but also facilitates efficient hydroxyl radical consumption to initiate C(sp2)–H activation, forming benzene radical intermediates en route to phenol. That is ever reported. CuZnSbO delivered 31.51 % benzene conversion and 100 % phenol selectivity. This work demonstrates the promise of engineered mixed metal oxide that boosts Cu species utilization for H2O2 and benzene activation. The photocatalyst showed good activity in selective oxidative hydroxylation reactions through harnessing visible light and controlled ROS generation. Importantly, Cu cations govern the photocatalytic •OH generation mechanisms as shown by XPS and active site deactivation analysis.

Sonochemical preparation of Fe-Y zeolite catalyst for the conversion of benzene to phenol

Enzyme-mimetic materials such as Fe-containing zeolites are of research interest due to the high selectivity for the one-step selective oxidation of benzene to phenol over the Fe-catalytic active center at room temperature and ambient pressure. This study investigates a Fe-modified Y zeolite catalysts prepared via a sonochemical method for the oxidation of benzene-to-phenol using water as solvent. These catalysts were subjected to a screening and optimization experiment by a response surface methodology (RSM), evaluating their potential for the synthesis of phenol. Achieving the preparation of a catalyst with an increased phenol selectivity from 3 % to ∼91 % and almost 100 % when evaluated at 30 ºC. Various Fe species, including the α-Fe(II) active site, were detected using UV-Vis spectroscopy, FTIR spectroscopy, and magnetic thermal gravimetric analysis (MTGA). Highlighting the potential of sonochemistry for preparing at mild temperatures (<100 ºC) iron-modified zeolite Y catalysts with room temperature catalytic active in water-based systems.

Visible-Light-Driven Oxidation of Benzene to Phenol with O2 over Photoinduced Oxygen-Vacancy-Rich WO3.

Direct photocatalytic conversion of benzene to phenol with molecular oxygen (O2) is a green alternative to the traditional synthesis. The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O2 activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO3) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O2 as they readily capture photogenerated electrons from the reductive sites of WO3 to activate adsorbed O2. The oxygen-isotope-labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O2 into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high-performance OVs-rich photocatalysts for solar-induced chemical conversion.

Visible‐Light‐Driven Oxidation of Benzene to Phenol with O2 over Photoinduced Oxygen‐Vacancy‐Rich WO3

AbstractDirect photocatalytic conversion of benzene to phenol with molecular oxygen (O2) is a green alternative to the traditional synthesis. The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O2 activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO3) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O2 as they readily capture photogenerated electrons from the reductive sites of WO3 to activate adsorbed O2. The oxygen‐isotope‐labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O2 into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high‐performance OVs‐rich photocatalysts for solar‐induced chemical conversion.

An Innovative Biphasic Reaction System for Highly Selective Benzene Hydroxylation based on Photocatalytic Polymer Composites

AbstractThe hydroxylation of benzene to phenol in presence of hydrogen peroxide was performed using a new biphasic system consisting of a solid phase, a photocatalytically active monolithic polymer composite, immersed in an aqueous phase in which H2O2 is dissolved. In detail, ZnO photocatalytic particles were embedded into the hydrophobic syndiotactic polystyrene (sPS) polymer. Zinc oxide nanostructures (ZnO NSs) were synthesized by an electrochemical procedure. The surface morphology and structure of ZnO nanoparticles and ZnO‐sPS monolithic aerogel composite (ZnO/sPS) were investigated by scanning electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy analysis. Photocatalytic results evidenced that, under UV irradiation, both ZnO NSs and biphasic system water‐photocatalytic composites had a high benzene oxidative property but with very low phenol yield (&lt;2 %) at pH=7. To enhance the phenol selective formation, the pH of the aqueous solution surrounding the photocatalytic polymer composite was modified. A phenol yield of about 94 % and benzene conversion higher than 99 % was obtained in alkaline conditions (pH=11).

Nitration of Benzene to Nitrobenzene Using NO2 as Nitro Source Under Mild and Solvent‐Free Conditions

AbstractIn this work, a green and efficient method has been developed to catalyze the nitration of benzene to nitrobenzene in NO2‐O2 system by using acidic ion exchange resin as catalyst under mild (0 °C and atmospheric pressure) and solvent‐free conditions. Based on experimental screening, commercial acid ion exchange resin Amberlite FPC3500 was identified as the optimal catalyst. Under the optimized reaction conditions, 99.9 % conversion of benzene was obtained with 99.1 % selectivity of nitrobenzene. Furthermore, the catalyst is easily reusable. The results demonstrate a greener route for the production of nitrobenzene.

Efficient ethylbenzene production from CO2 and benzene in a single-bed reactor

The selective synthesis of specific value-added aromatic hydrocarbons through CO2 hydrogenation holds significant strategic importance in mitigating energy and climate issues. However, the process of forming ethylated side chains on benzene rings is challenging, and the methods reported are often limited by multi-bed systems. Here, we show the first CO2 hydrogenation in tandem coupling with benzene alkylation to synthesize ethylbenzene over a single-bed system containing ZnFeOx and nano ZSM-5 catalysts. The results indicated that the bifunctional catalyst composed of ZnFeOx with a Zn/Fe ratio of 0.5 and nano-HZSM-5 exhibits excellent catalytic performance under optimized conditions. The benzene conversion reaches 28.0 %, ethylbenzene selectivity is 61.3 % and the conversion of CO2 is remarkably high, achieving 45.0 %. This single-bed system significantly promotes the in-situ utilization of ethylation intermediates. The introduction of zinc promoted the formation of ZnFe2O4 spinel, which increased the number of active sites due to its superior dispersibility and reducibility. Nano-HZSM-5 demonstrated outstanding ethylbenzene selectivity and catalytic stability owing to its unique shape selectivity, moderate acidity, and superior diffusion properties. This study further explores the reaction network and mechanism through GC–MS analysis and various model reactions, elucidating the formation pathways of primary products in detail. This research provides a new strategy for the controllable synthesis of ethylbenzene using CO2 as a C1 source in a single-bed system.

Multidimensional Engineering to Construct Ru/TiO2 Catalysts Enriched with Pores and Ti3+ Defects for Highly Efficient Selective Hydrogenation of Benzene

AbstractStructural engineering, coupled with crystalline phase engineering and surface engineering, serves as a practical and effective strategy for enhancing catalytic performance through the fine design of catalysts in terms of their structure, physical phases and surface defects. In this work, a set of strategies were employed for structural transformation and crystalline phase transition of Ru/TiO2 catalysts, utilizing multidimensional regulation. Ru nanoparticles loaded on a unique TiO2 nanosheet flowers (Ru/TSFs) enriched with pores and Ti3+ defects were prepared by solvothermal and impregnation‐chemical reduction methods. The Ru/TSFs exhibited an outstanding catalytic performance in the reaction of selective hydrogenation of benzene for the preparation of cyclohexene, with a selectivity of 79 % and a maximum yield of 52.8 % along with a benzene conversion of 45.9 % and a good stability. The excellent catalytic performance attributes to the distinctive structure of three‐dimensional nanosheet flowers, which offers a high specific surface area and improvs the effective contact between the catalyst and the reaction substrate. Meanwhile, the porous Ru/TSFs exhibit exceptional hydrophilicity and abundant Ti3+ defects on their surface, which is quite favorable for the desorption of cyclohexene from the reaction system, thus improving the selectivity of cyclohexene. The multidimensional engineering may provide an efficient approach for constructing high‐performance loaded catalysts for potential industrial applications.

Confined Cu Single Sites in ZSM-5 for Photocatalytic Hydroxylation of Benzene to Phenol.

Zeolites with band-like charge transport properties have exhibited their potential activities in sensing, optics, and electronics. Herein, a precisely designed Cu@ZSM-5 catalyst is presented with an ultra-wide bandgap of 4.27eV, showing excellent photocatalytic activity in hydroxylation of benzene with benzene conversion 27.9% and phenol selectivity 97.6%. The SXRD and Rietveld refinement results illustrate that Cu@ZSM-5 has an average of 0.8 Cu atoms per unit cell and the single Cu atoms located in the cross-section of the sinusoidal and straight channels. XANES and EXAFS further demonstrate that the Cu atoms have an oxidation state of +2, coordinated with three OMFI-framework atoms and one ─OH group. Detailed characterizations demonstrate that the Cu@ZSM-5 with tailored bandgap is able to enhance the photoinduced electron-hole separation and hence promote selective hydroxylation of benzene to phenol via the superoxide radical route. This work may open a new way for designing electrically conductive zeolite-supported photocatalysts.

Production of Jet Fuel Range Aromatics by Alkylation of Benzene with Olefins over Bifunctional Ga/ZSM-5 Catalyst.

Aromatic components of C8-C15 are playing indispensable roles in multi-functional properties of jet fuel. Here, we reported the controllable alkylation of benzene with mixed olefins of ethylene and propylene toward C8-C15 aromatic hydrocarbons for jet fuels over the bifunctional Ga/ZSM-5 catalyst. The resultant 2Ga/ZSM-5 exhibited a superior selectivity of 86.4% (yield of 55.5%) to C8-C15 range aromatics, at benzene conversion of 40.3%, ethylene and propylene conversion of 99.5% and 99.2%, respectively. The incorporation of Ga species could effectively weaken the strong acid sites of ZSM-5 and endow 2Ga/ZSM-5 catalyst with appropriate acidity, therefore facilitating the benzene alkylation process and suppressing the undesired hydrogen transfer or aromatization side reactions as well, thus improving the yield of desired C8-C15aromatics for jet fuels. This work provided insight into the development of promising bifunctional catalyst for the oriented transformation of biomass-derived chemicals to aviation fuels.

Unravelling High Water Vapor-Induced Inhibitory Effects on Pt/Co3O4 Catalysts toward Benzene Oxidation.

Water vapor inevitably exists in the environment, which causes adverse impacts on many crucial chemical reactions. However, high water vapor of up to 10 vol %─relevant to a broad spectrum of industrial practices-for catalytic implications has been less investigated or neglected. As such, we explored an industry-relevant, humidity-highly sensitive benzene oxidation only in the presence of 10 vol % water vapor using the well-established Pt/Co3O4 catalysts, to bring such an important yet ignored topic to the forefront. Results revealed that Pt/Co3O4 catalysts possessing higher contents of Pt nanoparticles exhibited marked tolerance to water vapor interference. Under an incomplete benzene conversion condition, the input of 10 vol % water vapor indeed impaired the catalytic performance of Pt/Co3O4 catalyst significantly, which, in fact, was caused by the unfavorable formation of carboxylate species covering the catalyst's surface engendering irrecoverable activity loss, instead of the well-accepted water competitive adsorption. While such activity loss can be restored by elevating the reaction to a higher temperature. This study helps us to understand the compromised catalytic activity caused by high humidity, urging the systematic evaluation of well-established catalyst systems in high water vapor-contained conditions and pressing the development of water-tolerant catalysts for real-life application consideration.

Synergistic catalytic degradation of benzene and toluene on spinel MMn2O4 (M[dbnd]Co, Ni, Cu) catalysts

Owing to the complexity of multicomponent gases, developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging. The spinel MMn2O4 (MCo, Ni, or Cu) catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene. The CuMn2O4 sample exhibited the best catalytic performance, the conversion of benzene reached 100 % at 350 °C, and toluene conversion reached 100 % at 250 °C. XRD, N2 adsorption-desorption, HRTEM-EDS, ED-XRF, Raman spectroscopy, H2-TPR, NH3-TPD, O2-TPD and XPS were used to characterize the physical and chemical properties of MMn2O4 catalysts. The excellent redox properties, high concentration of surface Mn4+, and adsorption of oxygen species over the CuMn2O4 sample facilitated the simultaneous and efficient removal of benzene and toluene. Additionally, in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene. Notably, as an effective catalytic material, spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene, providing some insight for the development of efficient multicomponent VOC catalysts.

Boosting Pt utilization via strategic Co Integration: Structural and mechanistic investigation of High-Performance Pt-Co alloy nanocatalysts for catalytic benzene combustion

Platinum (Pt)-based catalysts exhibit notable efficacy in reducing emissions of hazardous volatile organic compounds (VOCs), such as benzene. Nevertheless, the high cost and limited availability of Pt necessitate exploring reasonable strategies to optimize Pt utilization and enhance catalytic efficiency. Thus, pressing needs emerge to develop efficient Pt-based catalysts. This study investigates the catalytic combustion of benzene utilizing an antimony-doped tin oxide (ATO) supported platinum-cobalt (Pt-Co) alloy catalyst. The incorporation of cobalt into Pt nanoparticles leads to Co atoms occupying bulk sites in the Pt-Co alloy, elevating the surface exposure of Pt atoms and enriching Pt on the surface, thereby providing additional active sites for catalysis. Advanced characterization techniques provide critical insights into the morphology, size distribution, crystallinity and valence states of Pt upon strategic Co alloying. Pt-Co/ATO exhibits exceptional low-temperature activity, achieving 95 % benzene conversion at 170 °C, which is 30 °C lower than the 200 °C required for Pt/ATO. Pressure-dependent kinetic analysis reveals a Langmuir-Hinshelwood mechanism involving the co-adsorption of benzene and oxygen reactants on active Pt-Co alloy sites. This study contributes insights into tuning bimetallic alloy nanostructures to optimize noble metal utilization and catalytic performance for VOC abatement, establishing a foundation for advancing sustainable emissions control technology.

Benzene Oxidation in Air by an Amine-Functionalized Metal-Organic Framework-Derived Carbon- and Nitrogen-Loaded Zirconium Dioxide-Supported Platinum Catalyst.

To learn more about the behavior of amine (NH2)-functionalized metal-organic framework (MOF)-derived noble metal catalysts in the removal of aromatic volatile organic compounds in air, benzene oxidation at low temperatures has been investigated using 0.2-, 0.8-, and 1.5%-platinum (Pt)/Universitetet i Oslo (UiO)-66-NH2. The benzene conversion (XB) of x%-Pt/UiO-66-NH2-R under dry conditions (175 °C) was 23% (x = 0.2%) < 52% (x = 0.8%) < 100% (x = 1.5%): 'R' suffix denotes reduction pretreatment using a hydrogen (10 vol %) and nitrogen mixture at 300 °C for the generation of metallic Pt (Pt0) sites and simultaneous partial MOF decomposition into carbon- and nitrogen-loaded zirconium dioxide. The prominent role of reduction pretreatment was apparent in benzene oxidation as 1.5%-Pt/UiO-66-NH2 did not exhibit catalytic activity below 175 °C (dry condition). The promotional role of moisture in benzene oxidation by 1.5%-Pt/UiO-66-NH2-R was evident with a rise in the steady-state reaction rate (r) at 110 °C (21 kPa molecular oxygen (O2)) from 1.3 × 10-3 to 5.0 × 10-3 μmol g-1 s-1 as the water (H2O) partial pressure increased from 0 to 1.88 kPa. In contrast, the activity was lowered with increasing RH due to catalyst poisoning by excess moisture (r (110 °C) of 6.6 × 10-04 μmol g-1 s-1 at 2.83 kPa H2O (21 kPa O2)). Kinetic modeling suggests that XB proceeds through the Langmuir-Hinshelwood mechanism on the Pt/UiO-66-NH2-R surface (dissociative O2 chemisorption and the involvement of two oxygen species in benzene oxidation). According to the density functional theory simulation, the carbon and nitrogen impurities are to make the first XB step (i.e., hydrogen migration from the benzene molecule to the substrate) energetically favorable. The second hydrogen atom from the benzene molecule is also extracted effectively, while the oxygen derived from O2 facilitates further XB. The Pt0 sites dissociate the O2 and H2O molecules, while the product of the latter, i.e., free hydrogen and hydroxyl, makes the subsequent XB steps energetically favorable.

Selective benzene hydroalkylation: Ni/Ni PS/HY catalysts for enhanced cyclohexylbenzene formation

The potential for synthesizing cyclohexylbenzene through one-step hydroalkylation of benzene is significant, but the selectivity is hindered by the deep hydrogenation of benzene to cyclohexane. In this study, Ni-containing phyllosilicate (Ni PS) was incorporated between Ni nanoparticles and zeolite (HY) using the deposition–precipitation technique, thereby creating Ni/Ni PS/HY. A conventional Ni/HY catalyst was also prepared using the impregnation method for comparison. Ni/Ni PS/HY demonstrates outstanding catalytic performance even at a low temperature of 130 °C and a high WHSV of up to 42.21 h−1, achieving a benzene conversion of ∼25 % and a cyclohexylbenzene selectivity of ∼85 %, which remained stable for 300 h. By contrast, the conventional Ni/HY catalyst yields a mere 2.5 % benzene conversion under identical conditions. Comprehensive characterizations and density functional theory (DFT) calculations reveal that Ni PS plays crucial roles in the hydroalkylation of benzene to cyclohexylbenzene. The formation of Ni PS leads to high Ni dispersion, generating more active sites for hydrogenation. Concurrently, the robust interaction between Ni PS and Ni reduces the reactivity of adsorbed H species, impeding the deep hydrogenation of benzene to cyclohexane, while still effectively allowing the formation of cyclohexene. After being adsorbed by the strong acid sites within Ni PS, the intermediate cyclohexene can be smoothly transported through the mesoporous structure of Ni PS to HY for alkylation. All these factors culminate in the exceptional catalytic performance of Ni/Ni-PS/HY.

Experimental and theoretical studies on effective synergistic low-temperature removal of NO and typical volatile organic compounds (VOCs) from flue gas based on Cu@VWTi catalyst

The transition metal-modified VWTi structural catalysts hold great promise for simultaneously removing nitrogen oxides (NOx) and volatile organic compounds (VOCs) from industrial flue gases. A series of Cu@VWTi catalysts were prepared to investigate their synergistic low-temperature removal performance towards NO and typical VOCs, including toluene, benzene, chlorobenzene (CB), p-chlorotoluene (p-CT), and dichloromethane (DCM). The copper-enhanced samples prepared via ultrasound-assisted impregnation exhibited irregular globular and varying crystallinity. The catalysts displayed a typical anatase crystal structure with high TiO2 content or high dispersion of V and W species along with a certain adjustment effect on the morphology. Various controlling factors affecting the synergistic removal of NO and VOCs were evaluated. It was observed that the presence of VOCs in flue gas has weak impact on NO removal, except for the waste incineration using the Cu@VWTi catalyst. However, a high initial NO concentration had an adverse effect on VOCs removal. Impressively, the optimized copper-doped catalyst (5 wt% Cu loaded of smelting plant and coal-fired power plant used catalyst) exhibited excellent performance for p-CT, toluene and DCM removal of 95.0%, 99.6% and 100% at 300 °C, respectively. The toluene and p-CT conversion efficiencies were highest over the catalyst used in the smelting plant after Cu loading, surpassing the benzene conversion efficiency. Cu@VWTi demonstrated excellent performance for p-CT, toluene, and DCM removal at 250 °C. Although 5 wt% Cu loading on the catalysts significantly enhanced the stability and anti-jamming of VOCs removal, as well as their tolerance to both SO2 and water vapor. The enhanced mechanism of Cu decoration attributed to the enhanced intensity of acid sites and the stable relative proportion of Oads/Olatt species in the used 5% Cu loaded catalyst due to the redox cycles of Cu and V species. Compared with Brønsted acid, which primarily adsorbs NH4+, Lewis acid mainly adsorbs gas phase acid and forms coordinated NH3 in gas phase. The bonding between toluene and the Cu site was enhanced with an adsorption energy of −130.9 kJ mol−1, as well as the cracking adsorption of the CH2Cl2 on the Ti site with a bonding energy of −436.7 kJ mol−1, both indicating strong chemical adsorption. The first step of dechlorination and demethylation was thermodynamically and kinetically favorable for DCM and toluene decomposition.

Performance evolution and mechanism of asphalt crack sealant under UV aging: A continuity study

Asphalt crack repair materials, known as crack sealants, are directly exposed to ultraviolet (UV) radiation in asphalt pavements. This exposure causes the gradual aging and deterioration of both their surface and internal properties. To study this phenomenon, the sealant was subjected to UV irradiation for a range of 0–385 hours, with the basic properties of the aged sealant tested every 55 hours. Several techniques were employed to investigate the changes in the internal chemical composition of the sealant, including Fluorescence microscopy (FM), gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FT-IR). The results revealed that the UV aging of the sealant mainly occurs in the thinner surface layer, which becomes progressively lighter in color. Notably, obvious surface cracks form after aging process. The cone penetration and softening point of the sealant exhibit an exponential or logarithmic change corresponding to the aging time. The most pronounced changes occur during the early stages of UV aging, with the properties tending to stabilize after approximately 220 h of aging. In addition, the FM images showed that the dispersed polymer particles within the sealant gradually transform into a continuous network structure after aging over time. The GPC spectrum of the aged sealant shifts to the left, indicating an increase in molecular weight, particularly in the polymer modifier. This is consistent with the transformation observed in the FT-IR analysis, which demonstrates that UV irradiation leads to the breaking and recombination of polymer chemical bonds in the sealant. The FT-IR analysis reveals the conversion of monosubstituted benzene to polysubstituted benzene in the polymer modifier, which also correlates with the formation of the network structure observed in the FM images and the increase in molecular weight detected in the GPC spectrum of the polymer modifier.