Search Results (84)

This review examines the research progress on non-noble-metal-based catalysts for formaldehyde (HCHO) oxidation at room temperature. It begins with an introduction to the hazards of HCHO as an indoor pollutant and the urgency of its removal, comparing several HCHO removal technologies and highlighting the advantages of room-temperature catalytic oxidation. It delves into the classification, preparation methods, and regulation strategies for non-precious metal catalysts, with a focus on manganese-based, cobalt-based, and other transition metal-based catalysts. The effects of catalyst preparation methods, morphological structure, and specific surface area on catalytic performance are discussed, and the catalytic oxidation mechanisms of HCHO, including the Eley–Rideal, Langmuir–Hinshelwood, and Mars–van Krevelen mechanisms, are analyzed. Finally, the challenges faced by non-precious metal catalysts are summarized, such as issues related to the powder form of catalysts in practical applications, lower catalytic activity at room temperature, and insufficient research in the presence of multiple VOC molecules. Suggestions for future research directions are also provided. Full article

The DFT method was used to evaluate the adsorption of methyl radicals and the evolution of ethane on the M(111) (M = Co, Ni, Pd, Pt) surfaces, eight metal atoms, in aqueous medium. A maximum of five and four radicals can be adsorbed on Co(111) and Ni(111), respectively, and six on Pd(111) and Pt(111) (top site). The ethane evolution occurs via the Langmuir–Hinshelwood (LH) or Eley–Rideal (ER) mechanisms. The production of ethane through the interaction of two adsorbed radicals is thermodynamically feasible for high coverage ratios on the four surfaces; however, kinetically, it is feasible at room temperature only on Co(111) at a coverage of (5/5) and on Pd(111) at a coverage ratio of 4/6, 5/6, and 6/6. Ethane production occurs via the ER mechanism: a collision with solvated methyl radical produces either C₂H₆ or ${\mathrm{C}\mathrm{H}}_2^{\ast }+{\mathrm{C}\mathrm{H}}_{4\left(\mathrm{a}\mathrm{q}\right)}$. On Pd(111) the product is only C₂H₆, on Pt(111), both products (C₂H₆ or ${\mathrm{C}\mathrm{H}}_2^{\ast }$) are plausible, and on Co(111) and Ni(111), only ${\mathrm{C}\mathrm{H}}_2^{\ast }+{\mathrm{C}\mathrm{H}}_{4\left(\mathrm{a}\mathrm{q}\right)}$ is produced. Further reactions of ${\mathrm{C}\mathrm{H}}_2^{\ast }$ with ${\mathrm{C}\mathrm{H}}_2^{\ast }$ or ${\mathrm{C}\mathrm{H}}_3^{\ast }$ to give ${\mathrm{C}}_2{\mathrm{H}}_4^{\ast }$ or ${\mathrm{C}}_2{\mathrm{H}}_5^{\ast }$ are thermodynamically plausible only on Pt(111); however, they are very slow due to high energy barriers, 1.48 and 1.36 eV, respectively. Full article

Ferrous oxalate dihydrate (α-FOD) was synthesized from Ecuadorian black sands for phenol removal from aqueous solutions. Visible light-driven photodegradation kinetics were studied by varying the initial pollutant concentration, solution pH, and α-FOD dosage and by adding peroxydisulfate (PDS), including quenching tests. A representative model of phenol photodegradation was obtained by the Langmuir–Hinshelwood mechanism over a large range of concentrations (apparent kinetic constant, k = 0.524 h⁻¹). Almost complete removal was reached within 1 h under dark + 9 h under visible irradiation. The degradation rate was slightly affected by pH in the range of 3 to 9, with a significant improvement at pH 11 (k = 1.41-fold higher). The optimal α-FOD dosage was ~0.5 g/L. Two regimes were observed when using PDS: first, a heterogeneous Fenton-like process during the first few minutes after PDS addition; second, pure photocatalysis to completely remove the phenol. When comparing the two systems, without and with PDS, the half-life time for pure photocatalysis was 2.5 h (after the lamp was switched on). When adding PDS (1.0 mM), the half-life time was reduced to a few minutes (5 min after PDS addition, phenol removal was 66%). The photocatalyst presented remarkable degradation efficiency up to five repeated cycles. Full article

Mn-based oxides are promising catalysts for the selective catalytic reduction (SCR) of NO_x by NH₃ at low temperatures. However, fundamental NH₃-SCR mechanisms and resistance mechanisms against SO_x remain controversial. This study employed density functional theory (DFT) calculations to explore the intrinsic mechanisms of NH₃-SCR and SO_x poisoning on Mn₃O₄(001). Both NH₃ and NO adsorb atop the surface Mn site (the Lewis acid site). In contrast to the traditional Langmuir–Hinshelwood (L-H) mechanism in which gaseous NO is first oxidized to form adsorbed nitrites or nitrates and then react with adsorbed NH_x species to produce H₂O and N₂, a new potential L-H pathway is proposed that involves gaseous NO first adsorbing and then reacting with NH* to generate the key intermediate NHNO*, followed by the formation of H₂O and N₂. This L-H pathway is more efficient as it bypasses the NO oxidation step and is more selective for N₂ formation by avoiding N₂O production. In addition, the L-H mechanism is more favorable than the Eley–Rideal (E-R) mechanism because of the lower free energy profile. SO₂ exhibits limited poisoning effects, whereas SO₃ strongly poisons the Mn₃O₄(001) surface by occupying adsorption sites, hindering intermediate formation and producing ammonium bisulfate. Full article

Tetrafluoromethane (CF₄) is the simplest perfluorocarbon, a class of compounds with very high greenhouse gas potential. Catalytic hydrolysis offers an opportunity to convert these compounds to manageable CO₂ and HF. Recently published data showed the effectiveness of Ga-doping to overcome the fluorine poisoning of various Al₂O₃ catalysts at relatively modest temperatures. This prior work offered a partial catalytic mechanism together with kinetic and conversion data. The current paper completes the catalytic mechanism, and then analyzes it using the Langmuir–Hinshelwood algorithm for both the initial CF₄ conversion, and the catalyst site regeneration. The resulting derived rate expression, together with a catalyst activity coefficient expression, are then used in flow reactor configurations to simulate both relatively short exposure time runs with little loss of activity, as well as longer runs with severe activity loss. The reasonable agreement with the published laboratory data suggests that these expressions can be used for a larger-scale practical reactor design. Full article

Carbonyl sulfide (COS), an organosulfur compound commonly present in industrial gases, poses significant challenges for environmental protection and industrial processes due to its toxicity. This paper reviews recent advancements in the development of catalysts for COS hydrolysis, emphasizing the effects of various supports and active components on catalyst performance, as well as the mechanisms underlying the hydrolysis reaction. Traditional supports like γ-Al₂O₃ demonstrate high activity for COS hydrolysis but are susceptible to deactivation. In contrast, novel supports such as activated carbon, TiO₂, and ZrO₂ have garnered attention for their unique structures and properties. The incorporation of active components, including alkali metals, alkaline earth metals, transition metals, and rare earth metals, significantly enhances the hydrolysis efficiency and resistance to deactivation of the catalysts. Additionally, this paper outlines three primary mechanisms for COS hydrolysis: the alkali-catalyzed mechanism, the Langmuir–Hinshelwood model, and the Eley–Rideal model mechanism, as well as the thiocarbonate intermediate mechanism, which collectively elucidate the conversion of COS into the H₂S and CO₂ catalyzed by these systems. Future research efforts will concentrate on developing high-activity, high-stability, and cost-effective COS hydrolysis catalysts, along with a more in-depth exploration of the reaction mechanisms to facilitate the efficient removal of COS from industrial emissions. Full article

The wastewater generated by the pharmaceutical industry poses a risk to the environment due to undesirable characteristics such as low biodegradability, high levels of contaminants, and the presence of suspended solids, in addition to the high load of organic matter due to the presence of drugs and other emerging products in the effluent. This study aims to reduce the impact of wastewater pollution by removing amoxicillin (AMO) antibiotics as an organic pollutant. In this concept, two synthesized catalysts, NiAl₂O₄ and ZnO, are sensitive oxides to light energy. The prepared materials were then characterized using X-ray diffraction, UV–vis solid reflectance diffuse, Raman spectroscopy, scanning electron microscopy, BET, and ATR-FTIR spectroscopy. The effects of principal operating parameters under sunlight, namely, the percentage of the mixture of NiAl₂O₄ and ZnO, the pH of the medium, and the initial concentration of the antibiotic were studied experimentally to determine the optimal conditions for achieving a high degradation rate. The results showed that photodegradation is higher at a pH of 6, with a weight percentage of the mixture of 50% for both catalysts in 1 g/L of the total catalyst dose. Then, the effect of the initial concentration of AMO on the photodegradation reaction showed an important influence on the photodegradation process; as the degradation rate decreases, the initial AMO concentration increases. A high degradation rate of 92% was obtained for an initial AMO concentration of 10 mg/L and a pH of 6. The kinetic study of degradation established that the first-order model and the Langmuir–Hinshelwood (LH) mechanism fit the experimental data perfectly. The study showed the success of using heterosystem photocatalysts and sustainable energy for effective pharmaceutical removal, which can be extended to treat wastewater with other organic emerging pollutants. On the other hand, modeling was introduced using Gaussian process regression (GPR) to predict the degradation rate of AMO under sunlight in the presence of heterogeneous ZnO and NiAl₂O₄ systems. The model evaluation criteria of GPR in terms of statistical coefficients and errors show very interesting results and the performance of the model used. Where statistical coefficients were close to one (R = 0.9981), statistical errors were very small (RMSE = 0.1943 and MAE = 0.0518). The results suggest that the model has a strong predictive power and can be used to optimize the process of AMO removal from wastewater. Full article

Community drinking water sources are increasingly contaminated by various point and non-point sources, with emerging organic contaminants and microbial strains posing health risks and disrupting ecosystems. This study explores the use of zinc oxide nanoparticles (ZnO-NPs) as a non-specific agent to address groundwater contamination and combat microbial resistance effectively. The ZnO-NPs were synthesized via a green chemistry approach, employing a sol-gel method with lemon peel aqueous extract. The catalyst was characterized using techniques including XRD, ATR-FTIR, SEM-EDAX, UV-DRS, BET, and Raman spectroscopy. ZnO-NPs were then tested for photodegradation of quinoline yellow dye (QY) under sunlight irradiation, as well as for their antibacterial and antioxidant properties. The ZnO-NP photocatalyst showed significant photoactivity, attributed to effective separation of photogenerated charge carriers. The efficiency of sunlight dye photodegradation was influenced by catalyst dosage (0.1–0.6 mg L⁻¹), pH (3–11), and initial QY concentration (10–50 mg L⁻¹). The study developed a first-order kinetic model for ZnO-NPs using the Langmuir–Hinshelwood equation, yielding kinetic constants of equilibrium adsorption and photodegradation of Kc = 6.632 × 10⁻² L mg⁻¹ and kH = 7.104 × 10⁻² mg L⁻¹ min⁻¹, respectively. The results showed that ZnO-NPs were effective against Gram-positive bacterial strains and showed moderate antioxidant activity, suggesting their potential in wastewater disinfection to achieve sustainable development goals. A potential antibacterial mechanism of ZnO-NPs involving interactions with microbial cells is proposed. Additionally, Gaussian Process Regression (GPR) combined with an improved Lévy flight distribution (FDB-LFD) algorithm was used to model QY photodegradation by ZnO-NPs. The ARD-Exponential kernel function provided high accuracy, validated through residue analysis. Finally, an innovative MATLAB-based application was developed to integrate the GPR_FDB-LFD model and FDB-LFD algorithm, streamlining optimization for precise photodegradation rate predictions. The results obtained in this study show that the GPR and FDB-LFD approaches offer efficient and cost-effective methods for predicting dye photodegradation, saving both time and resources. Full article

Three MnCeTiO_x catalysts with the same composition were prepared by conventional co-precipitation (MCT-C), reverse co-precipitation (MCT-R), and parallel co-precipitation (MCT-P), respectively, and their low-temperature SCR performance for de-NO_x was evaluated. The textural and structural properties, surface acidity, redox capacity, and reaction mechanism of the catalysts were investigated by a series of characterizations including N₂ adsorption and desorption, XRD, SEM, XPS, H₂-TPR, NH₃-TPD, NO-TPD, and in situ DRIFTs. The results revealed that the most excellent catalytic performance was achieved on MCT-R, and more than 90% NO_x conversion can be obtained at 100–300 °C under a high GHSV of 80,000 mL/(g_cat·H). Furthermore, MCT-R possessed optimal tolerance to H₂O and SO₂ poisoning. The excellent catalytic performance of MCT-R can be attributed to its larger BET specific surface area; higher contents of Mn⁴⁺, Ce³⁺, and adsorbed oxygen species; and more adsorption capacity for NH₃ and NO. Moreover, in situ DRIFTs results indicated that the NH₃-SCR reaction follows simultaneously the Langmuir–Hinshelwood and Eley–Rideal mechanisms at 100 °C. By adjusting the adding mode during the co-precipitation process, excellent low-temperature de-NO_x activity of MCT-R can be obtained simply and conveniently, which is of great practical value for the preparation of a MnCeTiO_x catalyst for denitrification. Full article

Ketoprofen is a non-biodegradable drug and is not removed by conventional treatments. The need to remove pharmaceutical compounds from water and wastewater has aroused considerable interest in advanced oxidation processes (AOP), whose effectiveness depends on the generation of reactive free radicals capable of oxidizing and decomposing numerous compounds. Heterogeneous photocatalysis is an efficient method if an active semiconductor is used. In this work, the photodegradation reaction of ketoprofen promoted by TiO₂ was studied, analyzing the kinetics obtained by changing variables such as temperature, initial concentration, and quantity of photocatalyst. It was determined that the mechanism is of the Langmuir–Hinshelwood type and that the system is operating in the kinetic regime, while tests at different temperatures have shown that the adsorption of ketoprofen and byproducts are both exothermic. Experimental data were interpreted with reliable models that allow to retrieve quantitatively the kinetic and thermodynamic parameters. Full article

The use of graphene oxide (GO) photogenerated electron–hole (e–h⁺) pairs to degrade pollutants is a novel green method for wastewater treatment. However, the interaction between photosensitive pollutants and a GO–light system remains unclear. In this work, the mechanism of degradation of photosensitive pollutant tetracycline (TC) promoted by GO photogenerated e–h⁺ pairs was studied. Our studies encompassed the determination of TC removal kinetics, analysis of active substances for TC degradation, identification of degradation products, and computational modeling. Clear evidence shows that a new reaction mechanism of enhanced adsorption and induced generation of reactive oxygen species (ROS) was involved. This mechanism was conducive to significantly enhanced TC removal. Kinetic studies showed a first-order behavior that can be well described by the Langmuir–Hinshelwood model. Radical scavenging experiments confirmed that ¹O₂, •O₂⁻, and holes (h⁺) were the main active substances for TC degradation. Electron spin resonance analysis indicated that photoexcited TC molecules may transfer electrons to the conduction band of GO to induce the generation of additional ROS. A major transformation product (m/z 459) during TC degradation was identified with liquid chromatography–mass spectrometry. Density functional theory calculation indicated a stronger adsorption between TC and GO under photoirradiation. This mechanism of photo-enhanced adsorption and synergistic induced generation of ROS provides a new strategy for the removal of emerging pollutants in water. Overall, the new mechanism revealed in this work expands the knowledge of applying GO to wastewater treatment and is of great reference value for research in this field. Full article

In this study we perform a comparison of the reaction mechanism and the activation barrier for the rate-determining step in various metal nitrides (Ta₃N₅, Mn₆N₅, Fe₃Mo₃N, Co₃Mo₃N) for the ammonia synthesis reaction. The reactions are explained with simplified schematics and the energy profiles for the various reaction mechanisms are given in order to screen the catalytic activity of the catalysts for the ammonia synthesis reaction. We find that the catalytic activity ranks in the following order: Co₃Mo₃N > Fe₃Mo₃N > Ta₃N₅ > Mn₆N_5. We also find that the reaction mechanism proceeds either by a Langmuir–Hinshelwood and an Eley–Rideal/Mars–van Krevelen mechanism. This is an overview of about 10 years of computational research conducted to provide an overview of the progress established in this field of study. Full article

Since the signing of the Minamata Convention in 2013, attempts have been primarily focused on reducing the emission of elemental mercury (Hg⁰) from coal-fired power plants (CFPPs). The most cost-effective measure for controlling the emission of mercury involves oxidizing Hg⁰ to mercury oxides, which are then removed using wet flue gas desulfurization (WFGD). Thus, novel photocatalysts with the best properties of photocatalytic ability and thermal stability need to be developed urgently. In this study, titanium dioxide (TiO₂)-based photocatalysts were synthesized through the modification of three metal oxides: CuO, CeO₂, and Bi₂O₃. All the photocatalysts were further characterized using X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence, and ultraviolet-visible spectrometry. The photocatalytic oxidation efficiencies of Hg⁰ were evaluated under an atmosphere of N₂ + Hg⁰ at 100–200 °C. The photocatalytic reactions were simulated by kinetic modeling using the Langmuir–Hinshelwood (L–H) mechanism. The results showed that Bi₂O₃/TiO₂ exhibited the best thermal stability, with the best oxidation efficiency at 200 °C and almost the same performance at 100 °C. L–H kinetic modeling indicated that photocatalytic oxidation reactions for the tested photocatalysts were predominantly physical adsorption. Additionally, the activation energy (E_a), taking into account Arrhenius Law, decreased dramatically after modification with metal oxides. Full article

Silica (SiO₂), accounting for the main component of fly ash, plays a vital role in the heterogeneous formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs) in high-temperature industrial processes. Silica clusters, as the basic units of silica, provide reasonable models to understand the general trends of complex surface reactions. Chlorothiophenols (CTPs) are the most crucial precursors for PCTA/DT formation. By employing density functional theory, this study examined the formation of 2-chlorothiophenolate from 2-CTP adsorbed on the dehydrated silica cluster ((SiO₂)₃) and the hydroxylated silica cluster ((SiO₂)₃O₂H₄). Additionally, this study investigated the formation of pre-PCTA/DTs, the crucial intermediates involved in PCTA/DT formation, from the coupling of two adsorbed 2-chlorothiophenolates via the Langmuir–Hinshelwood (L–H) mechanism and the coupling of adsorbed 2-chlorothiophenolate with gas-phase 2-CTP via the Eley–Rideal (E–R) mechanism on silica clusters. Moreover, the rate constants for the main elementary steps were calculated over the temperature range of 600–1200 K. Our study demonstrates that the 2-CTP is more likely to adsorb on the termination of the dehydrated silica cluster, which exhibits more effective catalysis in the formation of 2-chlorothiophenolate compared with the hydroxylated silica cluster. Moreover, the E–R mechanism mainly contributes to the formation of pre-PCTAs, whereas the L–H mechanism is prone to the formation of pre-PCDTs on dehydrated and hydroxylated silica clusters. Silica can act as a relatively mild catalyst in facilitating the heterogeneous formation of pre-PCTA/DTs from 2-CTP. This research provides new insights into the surface-mediated generation of PCTA/DTs, further providing theoretical foundations to reduce dioxin emission and establish dioxin control strategies. Full article

Lignocellulosic biomass can uptake CO₂ during growth, which can then be pyrolysed into three major products, biochar (BC), syngas, and bio-oil. Due to the presence of oxygenated organic compounds, the produced bio-oil is not suitable for direct use as a fuel and requires upgrading via hydrodeoxygenation (HDO) and hydrogenation. This is typically carried out over a supported metal catalyst. Regarding circular economy and sustainability, the BC from the pyrolysis step can potentially be activated and used as a novel catalyst support, as reported here. A 15 wt% Ni/BC catalyst was developed by chemically modifying BC with sulfuric acid to improve mesoporous structure and surface area. When compared to the pristine Ni/BC catalyst, sulfuric activated Ni/BC catalyst has excellent mesopores and a high surface area, which increases the dispersion of Ni nanoparticles and hence improves the adsorptive effect and thus catalytic performance. A liquid phase hydrogenation of furfural to 2-methylfuran was performed over the developed 15 wt% Ni/BC catalyst. Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic type models for adsorption of dissociative H₂ were screened based on an R² value greater than 99%, demonstrating that the experimental data satisfactorily fit to three plausible models: competitive (Model I), competitive at only one type of adsorption site (Model II), and non-competitive with two types of adsorption sites (Model III). With a correlation coefficient greater than 99% between the experimental rates and the predicted rate, Model III, which is a dual-site adsorption mechanism involving furfural adsorption and hydrogen dissociative adsorption and surface reaction, is the best fit. The Ni/BC catalyst demonstrated comparative performance and significant cost savings over previous catalysts; a value of 24.39 kJ mol⁻¹ was estimated for activation energy, −11.43 kJ mol⁻¹ for the enthalpy of adsorption for H₂, and −5.86 kJ mol⁻¹ for furfural. The developed Ni/BC catalyst demonstrated excellent stability in terms of conversion of furfural (96%) and yield of 2-methylfuran (54%) at the fourth successive experiments. Based on furfural conversion and yield of products, it appears that pores are constructed slowly during sulfuric acid activation of the biochar. Full article