Oxidation Of Benzene Research Articles

Oxidative two-state photoreactivity of a manganese(IV) complex using near-infrared light.

Highly reducing or oxidizing photocatalysts are a fundamental challenge in photochemistry. Only a few transition metal complexes with Earth-abundant metal ions have so far advanced to excited state oxidants. All these photocatalysts require high-energy light for excitation, and their oxidizing power has not been fully exploited due to energy dissipation before reaching the photoactive state. Here we demonstrate that the complex [Mn(dgpy)2]4+, based on Earth-abundant manganese and the tridentate 2,6-diguanidylpyridine ligand (dgpy), evolves to a luminescent doublet ligand-to-metal charge transfer (2LMCT) excited state (1,435 nm, 0.86 eV) with a lifetime of 1.6 ns after excitation with low-energy near-infrared light. This 2LMCT state oxidizes naphthalene to its radical cation. Substrates with extremely high oxidation potentials up to 2.4 V enable the [Mn(dgpy)2]4+ photoreduction via a high-energy quartet 4LMCT excited state with a lifetime of 0.78 ps, proceeding via static quenching by the solvent. This process minimizes free energy losses and harnesses the full photooxidizing power, and thus allows oxidation of nitriles and benzene using Earth-abundant elements and low-energy light.

Generation and Reactivity of μ-1,2-Peroxo CuIICuII and Bis-μ-oxo CuIIICuIII Species and Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide.

Tetradentate-N4 ligands stabilize dinuclear {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} species, and CuII complexes of these ligands were reported to catalyze the oxidation of benzene with H2O2. Here, we report {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} intermediates of dinucleating bis(tetradentate-N4) ligands depending on the absence or presence of 6-methyl substituents on the terminal pyridine donors, respectively, generated either from {CuICuI} precursors with O2 or from {CuIICuII} precursors with H2O2 and NEt3. Both intermediates are not stable even at low temperatures, but they show no electrophilic HAT reactivity with DHA. Catalytic investigations on the hydroxylation of benzene with excess H2O2 between 30 and 50 °C indicate that both radical-based and {Cu2On}-based mechanisms depend strongly on the catalytic conditions. In the presence of a radical scavenger, TONs of ∼920/∼720 have been achieved without/with the 6-methyl group of the ligand. Although {CuII(μ-OH)CuII} reacts with excess H2O2 at -40 °C to {CuII(OOH)}2 species, these are only stable for seconds at 20 °C and cannot account for catalytic oxidations over a period of 24 h at 30-50 °C.

Promoted catalytic oxidation of benzene over Mn-Ni solid solutions: Effect of metal oxygen bond parameters

In this work, Mn-Ni solid solutions were obtained by doping Ni into MnOx via solution combustion synthesis and the resulting catalysts were then applied to benzene oxidation. Various characterizations revealed that Ni doping changed the metal oxygen bond parameters, such as coordination numbers (CNs) and bond length. Both Mn-O and Ni-O bonds in Mn-Ni solid solutions exerted reduced CNs, while the bond length of Mn-O bonds was extended, making the oxygen species more chemically reactive., which further improved physicochemical properties (such as reducibility, oxygen mobility, surface active oxygen species etc.) and catalytic performance. Remarkably, the solid solutions with a Mn/Ni molar ratio of 4:1 (named Mn4Ni1) showed Mn-O and Ni-O bonds with lower CNs and longer bond lengths, which enhanced the activity and mobility of oxygen species, reducibility and chemisorption capacity of benzene. Therefore, Mn4Ni1 demonstrated optimal benzene oxidation activity and showed the lowest T90 (192 °C). The potential reaction mechanism was proposed according to the analysis results of C6H6-TPSR and in-situ FTIR. Furthermore, promoted oxidation of benzene and phenolate species on Mn4Ni1 could inhibit accumulation of intermediates and avoid catalyst poisoning and deactivation. This strategy shed light to the design of catalysts in environmental catalysis and thermal catalysis.

Oxygen-dependent catalytic activity of mesoporous MnCO3-based catalysts for highly effective benzene oxidation

The catalytic activities of mesoporous MnCO3-based catalysts synthesized with a simple precipitation method were investigated for the oxidation of benzene. The calcination temperature was confirmed to have significant influences on physicochemical structure and catalytic performance of samples. MnCO3-based catalysts prepared at the calcination temperature below 400 °C showed higher activity for benzene oxidation compared with manganese oxides (Mn5O8, MnxOy and MnO2), which was mainly ascribed to abundant reactive oxygen species, large specific surface areas and rich oxygen vacancies. The optimal MnCO3-300 with good durability and strong water resistance ability achieved 90% benzene conversion at 184 °C. In situ DRIFTS spectra results suggested that both lattice oxygen and adsorbed oxygen could participate in the benzene oxidation. The possible reaction pathway of benzene oxidized into CO2 and H2O was involved with phenolate, benzoquinone, maleic anhydride, maleate and acetate intermediates, where the transformation from phenolate to benzoquinone was identified as the rate-limiting step.

Tailoring local environment of oxygen vacancies by molybdenum doping on MnO2 for enhanced catalytic oxidation of VOCs

The microenvironment of oxygen vacancies plays an important role in metal oxide catalysts for VOCs catalytic oxidation. A simple strategy was provided to tailor the local environment of oxygen vacancies over MnO2 via Mo doping engineering to enhance its catalytic activity. The 0.3MoMnO2 with Mo/Mn quality ratio of 0.3 showed superior catalytic oxidation performance of benzene and anti-toxicity (H2O, SO2, and particulate matter). Its benzene oxidation rate at 190℃ was 1.95 × 10−4 mol/g/h, which was about three and two times higher than that of MnO2 and 0.9MoMnO2, respectively. The Mn-Ov-Mo sites were experimentally verified as the dominant active centers on 0.3MoMnO2. Through DFT calculation, Mo doping could enhance the oxygen adsorption on oxygen vacancies of MnO2. The remarkably well activity of Mn-Ov-Mo was rationally explained by the moderate oxygen adsorption energy to maintain a dynamic equilibrium of oxygen adsorption and desorption, which enhanced the oxygen activation, thereby promoting the benzene catalytic oxidation. However, excessive Mo doping induced the formation of Mo-Ov-Mo, and its side-on oxygen adsorption configuration was not conducive to oxygen transfer. This work broadens the understanding of the relationship between the local environment of oxygen vacancies and catalytic activities, which is beneficial for the rational design of efficient VOCs catalysts.

Low-temperature oxidative removal of benzene from the air using titanium carbide (MXene)-Supported platinum catalysts

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%–2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2–R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g−1·h−1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2–R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2–R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.

Auto-ignition characteristics of oxygenated aromatic compounds: Benzyl alcohol, benzaldehyde, and phenol

The growing attention towards biomass and biomass-derived fuels for transportation, energy production, forest fire prevention, and safety applications stimulated significant research activities focused on understanding the chemical kinetics of oxygenated aromatic hydrocarbons, which represent important reference components for biofuels. This motivates the current investigation of the ignition behavior of benzyl alcohol, benzaldehyde, and phenol, which exhibit intertwined reaction pathways. Novel ignition delay time data were measured in a shock tube and a rapid compression machine covering pressures from 10 to 40 bar and temperatures from 860–1250 K. In addition, a kinetic model was developed and used to analyze critical reaction pathways in comparison to models from literature. It is shown that the phenyl-phenoxy-phenyl peroxy subsystem plays a key role not only in the oxidation of benzaldehyde, but also in the oxidation of benzene and phenol. Comparison of the current model with a recent version of the CRECK mechanism reveals that differences are present with respect to the dominant reaction pathways that have a strong influence on the formation of Ö radicals. Further investigations are required to resolve this discrepancy reconciling theory, modelling, and the unfortunately limited number of systematic experimental data to which this work significantly contributes.

A theoretical study of the oxidation of benzene by manganese oxide clusters: formation of quinone intermediates.

Manganese oxides (MnxOy) have been widely applied in various chemical industrial processes owing to their long lifetime, low cost and high abundance. They have been used as co-reactants for the elimination of volatile organic compounds (VOCs); however, their oxidation mechanism is not clearly established. In this theoretical study, interaction capacities between benzene (C6H6) and MnxOy clusters, which were modeled with MnO2 and Mn2O3 molecules, were investigated by quantum chemical computations using density functional theory (DFT) with the PBE-D3 functional. The interaction capacity between C6H6 and MnxOy was evaluated, and the probing of the initial stage of the C6H6 oxidation at a molecular level offers an in-depth oxidation reaction path. Interaction energies computed in several spin states, along with the analysis of the electron distribution using the quantum theory of atoms in molecules, natural bond orbital and Wiberg bond index techniques as well as local softness values and MO energies of fragments, point out that the interaction between C6H6 and Mn2O3 is stronger than that with MnO2, amounting to -43 and -35 kcal mol-1, respectively, and the metal atom is identified as the primary active site. During the oxide cluster-assisted oxidation, benzene firstly undergoes an oxidation reaction by active oxygen to generate intermediates such as hydroquinone and benzoquinone. The pathway involving p-benzoquinone as the product (noted as PR1) is the most energetically favored one through a transition structure lying at 19 kcal mol-1, below the energy reference of the reactants, leading to an energy barrier significantly lower than that of 36 kcal mol-1 found for the gas phase oxidation reaction with molecular oxygen without the assistance of the oxide clusters. Potential energy profiles illustrating the reaction paths and molecular mechanisms were described in detail.

Preparation of a Ce/N-MOF(Fe)@P-C3N4 composite photocatalyst and efficient oxidation of benzene to phenol

The selective photocatalytic oxidation of benzene to phenol under mild conditions is of great significance for the next-generation phenol industry.

Enhanced detection of aromatic oxidation products using NO3 - chemical ionization mass spectrometry with limited nitric acid.

Nitrate ion-based chemical ionization mass spectrometry (NO3 --CIMS) is widely used for detection of highly oxygenated organic molecules (HOMs). HOMs are known to participate in molecular clustering and new particle formation and growth, and hence understanding the formation pathways and amounts of these compounds in the atmosphere is essential. However, the absence of analytical standards prevents robust quantification of HOM concentrations. In addition, nitrate-based ionization is usually very selective towards the most oxygenated molecules and blind to less oxygenated compounds hindering the investigation of molecular formation pathways. Here, we explore varying concentrations of nitric acid reagent gas in the sheath flow of a chemical ionization inlet as a method for detecting a wider range of oxidation products in laboratory-simulated oxidation of benzene and naphthalene. When the concentration of reagent nitric acid is reduced, we observe an increase in signals of many oxidation products for both precursors suggesting that they are not detected at the collision limit. The sensitivity of naphthalene oxidation products is enhanced to a larger extent than that of benzene products. This enhancement in sensitivity has a negative relationship with molecular oxygen content, the oxygen-to-carbon ratio, the oxidation state of carbon, and lowered volatility. In addition, the sensitivity enhancement is lower for species that contain more exchangeable H-atoms, particularly for accretion products. While more experimental investigations are needed for providing the relationship between enhancement ratios and instrumental sensitivities, we suggest this method as a tool for routine check of collision-limited sensitivities and enhanced detection of lower-oxygenated species.

Towards automated inclusion of autoxidation chemistry in models: from precursors to atmospheric implications.

In the last few decades, atmospheric formation of secondary organic aerosols (SOA) has gained increasing attention due to their impact on air quality and climate. However, methods to predict their abundance are mainly empirical and may fail under real atmospheric conditions. In this work, a close-to-mechanistic approach allowing SOA quantification is presented, with a focus on a chain-like chemical reaction called "autoxidation". A novel framework is employed to (a) describe the gas-phase chemistry, (b) predict the products' molecular structures and (c) explore the contribution of autoxidation chemistry on SOA formation under various conditions. As a proof of concept, the method is applied to benzene, an important anthropogenic SOA precursor. Our results suggest autoxidation to explain up to 100% of the benzene-SOA formed under low-NO x laboratory conditions. Under atmospheric-like day-time conditions, the calculated benzene-aerosol mass continuously forms, as expected based on prior work. Additionally, a prompt increase, driven by the NO3 radical, is predicted by the model at dawn. This increase has not yet been explored experimentally and stresses the potential for atmospheric SOA formation via secondary oxidation of benzene by O3 and NO3.

Enhancing direct hydroxylation of benzene to phenol on Fe1/PMA single-atom catalyst: a comparative study of H2O2vs. O2-assisted reactions

This study enhances benzene oxidation to phenol using Fe1/PMA catalyst under ambient conditions, providing insights for sustainable catalytic processes, especially regarding selection of oxidant.

An iron-containing POM-based hybrid compound as a heterogeneous catalyst for one-step hydroxylation of benzene to phenol.

It is a major challenge to perform one-pot hydroxylation of benzene to phenol under mild conditions, which replaces the environmentally harmful cumene method. Thus, finding highly efficient heterogeneous catalysts that can be recycled is extremely significant. Herein, a (POM)-based hybrid compound {[FeII(pyim)2(C2H5O)][FeII(pyim)2(H2O)][PMoV2MoVI9VIV3O42]}·H2O (pyim = 2-(2-pyridyl)benzimidazole) (Fe2-PMo11V3) was successfully prepared by hydrothermal synthesis using typical Keggin POMs, iron ions and pyim ligands. Single-crystal diffraction shows that the Fe-pyim unit in Fe2-PMo11V3 forms a stable double-supported skeleton by Fe-O bonding to the polyacid anion. Remarkably, due to the introduction of vanadium, Fe2-PMo11V3 forms a divanadium-capped conformation. Benzene oxidation experiments indicated that Fe2-PMo11V3 can catalyze the benzene hydroxylation reaction to phenol in a mixed solution of acetonitrile and acetic acid containing H2O2 at 60 °C, affording a phenol yield of about 16.2% and a selectivity of about 94%.

Enhanced catalytic oxidation of benzene though the synergistic Pt-Ni bimetallic single-atom catalyst

Excellent catalysts for the catalytic oxidation of benzene (C6H6) require active sites with robust oxidation capabilities. Heteronuclear dual-single atom catalysts can exhibit enhanced catalytic activity through synergistic interactions between the dual single atoms (SAs). Herein, we successfully engineered a bimetallic single-atom catalyst, Pt1-Ni1/TiO2-NW, which demonstrates exceptional performance in C6H6 oxidation. Various technologies, including X-ray absorption fine structure and Z-type spherical aberration-corrected transmission electron microscopy, were used to identify the bimetallic single atoms within the catalyst. The catalytic oxidation of C6H6 by Pt1-Ni1/TiO2-NW was comprehensively investigated. Finally, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) were employed to reveal the underlying mechanism for the synergetic effect of the bimetallic single atoms. The results indicate that the introduction of Ni SA favors the formation of Pt SA. The T90% of Pt1-Ni1/TiO2-NW reached 185 °C, a remarkable 40 °C lower than that of the single-atom catalyst Pt1/TiO2-NW. More importantly, the active center of Pt-O-Ni, formed by the collaboration of Pt SA and Ni SA with bridging oxygen, plays a crucial role in reducing the energy barrier during the conversion of C6H6 to phenol and further to benzoquinones. This research provides a valuable methodology for constructing heteronuclear bimetallic single-atom catalysts tailed specifically for C6H6 oxidation.

Theoretical study of the local environment of Co-NxCy structure for selective oxidation of benzene to phenol

Adjusting the local environment of single-atom catalysts (SACs) is a promising approach to enhance the catalytic performance in benzene oxidation reaction (BOR). Herein, a range of Co-based SACs with N2/3/4-coordination numbers on graphene were constructed to investigate the effect of the electronic structure of SACs on BOR via density function theory (DFT). Expectedly, the electron density and charge amount of the Co active sites in the overall reaction path on the CoNxCy catalyst can be regulated by coordination environment. In particular, the as-formed *O=CoN4=O* intermediate displays the strongest electron interaction between Co atom and O*, thus O* has the largest electron density and the most negative charge number, resulting in a lower energy barrier of 0.69 eV for the rate-determining step of CO bond formation. The methodology in this work provides a certain theory supporting and guidance for developing highly efficient SACs with controllable coordination structures to enhance hydrocarbon oxidation reactions.

Assessing the environmental risk of fire and explosion events associated with chemical process routes

The development of inherently environmentally friendly chemical process plants is one approach to reduce or avoid potential harmful environmental consequences that could occur due to chemical plant accidents. This can be achieved by selecting the chemical process route involving the least environmental risk, during preliminary design stage. To assist the route selection process a risk-based index called Inherent Environmental Risk Index for Fires and Explosions (F&E-IERI) is proposed. The F&E-IERI assesses and ranks chemical process routes considering environmental impacts caused by accidental fires and explosions that could occur in a chemical plant. This index considers the environmental impact magnitude, fire or explosion event occurrence frequency, and the environmental element vulnerability. A higher index associated with the route indicates a higher environmental risk. The proposed index has been applied in four possible routes to produce acetone. The p-diisopropyl benzene oxidation process route to produce acetone showed the lowest F&E-IERI value indicating the route having the lowest environmental risk.

Copper nanoparticles embedded into nitrogen-doped carbon fiber felt as recyclable catalyst for benzene oxidation under mild conditions

Herein, an active and stable nanocatalyst based on copper nanoparticles embedded into nitrogen-doped carbon fiber felts (NCFFs) was fabricated through a co-assembly protocol. The catalytic performance of Cu (20 wt.%)/NCFF was contributed to its structural and morphological features, which were studied by various characterization techniques. The data illustrated that the catalyst showed reasonable activity and excellent selectivity in oxidation of benzene-to-phenol (25.2 and 100% for yield and selectivity respectively) in the presence of an environmentally-friendly oxidant. Furthermore, the microscopic catalyst kept its long-term performance until nine successive runs, which turns it into a bulk alternative in large-scale schemes.

Boosting H2O2 utilization efficiency in benzene hydroxylation to phenol via isolated single VO4 site on hydrophobic poly(ionic liquid)-derivative

Hydrogen peroxide (H2O2)-mediated benzene hydroxylation is one of the most attractive avenues towards green synthesis of phenol, a crucial industrial feedstock. Nonetheless, it remains one challenge to explore efficient catalysts, especially the one allowing high H2O2 utilization efficiency to fulfill the safety production. In this work, isolated single VO4 sites were constructed on the hydrophobic poly(ionic liquid)-derivative through copolymerization of dinuclear imidazolyl ionic liquid and polyhedral oligomeric silsesquioxane (POSS), ion change with ammonium metavanadate (NH4VO3), and the pyrolysis under moderate temperature. The combination of V(IV) single sites and a hydrophobic surface made the catalyst effectively catalyzing the phenol synthesis from benzene oxidation with H2O2, giving phenol selectivity above 99 %, H2O2 utilization efficiency of 92 %, and turnover frequency (TOF) beyond 900 h−1. The catalyst was stably recycled and exhibited broad substrate compatibility. The pyrolysis step strengthened both stability and activity, significantly contributing to the high catalytic efficiency.

Catalytic removal of harmful volatile organic compounds by reutilizing zinc rods waste from spent batteries as a palladium catalyst support

The emission of volatile organic compounds (VOCs) has led to significant deterioration in air quality, making it imperative to ensure that these compounds are removed from emission sources before they are released into the atmosphere. In this context, the present study recycled spent primary batteries to use their zinc rods waste (ZRW) as a palladium catalyst support for the removal of harmful VOCs. To this end, palladium supported on ZRW (Pd/ZRW) catalysts were prepared and tested for the catalytic oxidation of benzene, methylbenzene and 1,2-dimethylbenzene. The physicochemical properties of the Pd/ZRW catalysts were carefully characterized by ICP-OES, BET, SEM, XRD, FE-TEM, XPS, and H2-TPR analyses. The main component of ZRW was identified as ZnO. Consistent with expectations, increases in the loading of Pd from 0.1 to 1.0 wt% in the Pd/ZRW catalysts resulted in enhanced VOCs removal efficiency. The reaction temperature required for the complete oxidation (100% removal efficiency) of methylbenzene and 1,2-dimethylbenzene on the 1.0 wt% Pd/ZRW catalyst was below 340 °C at a gas hourly space velocity of 50,000 h−1. TEM, XPS, and H2-TPR results implied that the enhancement of catalytic activity with the addition of Pd could be attributed to the readily movable surface lattice oxygen as well as the active component (Pd species). Ultimately, ZRW of spent primary batteries appear to show promise as a catalyst support for VOCs removal. This study has introduced a novel strategy for reducing air pollutants by utilizing waste, which promotes the disposal of hazardous solid waste and ensures clean air quality.

Potential for the anaerobic oxidation of benzene and naphthalene in thermophilic microorganisms from the Guaymas Basin.

Unsubstituted aromatic hydrocarbons (UAHs) are recalcitrant molecules abundant in crude oil, which is accumulated in subsurface reservoirs and occasionally enters the marine environment through natural seepage or human-caused spillage. The challenging anaerobic degradation of UAHs by microorganisms, in particular under thermophilic conditions, is poorly understood. Here, we established benzene- and naphthalene-degrading cultures under sulfate-reducing conditions at 50°C and 70°C from Guaymas Basin sediments. We investigated the microorganisms in the enrichment cultures and their potential for UAH oxidation through short-read metagenome sequencing and analysis. Dependent on the combination of UAH and temperature, different microorganisms became enriched. A Thermoplasmatota archaeon was abundant in the benzene-degrading culture at 50°C, but catabolic pathways remained elusive, because the archaeon lacked most known genes for benzene degradation. Two novel species of Desulfatiglandales bacteria were strongly enriched in the benzene-degrading culture at 70°C and in the naphthalene-degrading culture at 50°C. Both bacteria encode almost complete pathways for UAH degradation and for downstream degradation. They likely activate benzene via methylation, and naphthalene via direct carboxylation, respectively. The two species constitute the first thermophilic UAH degraders of the Desulfatiglandales. In the naphthalene-degrading culture incubated at 70°C, a Dehalococcoidia bacterium became enriched, which encoded a partial pathway for UAH degradation. Comparison of enriched bacteria with related genomes from environmental samples indicated that pathways for benzene degradation are widely distributed, while thermophily and capacity for naphthalene activation are rare. Our study highlights the capacities of uncultured thermophilic microbes for UAH degradation in petroleum reservoirs and in contaminated environments.