Search Results (295)

In wet flue gas desulfurization and denitrification processes, nitrite accumulation inhibits denitrification efficiency and induces secondary pollution due to its acidic disproportionation. This study developed a Mn-modified ZSM-5 zeolite catalyst, achieving efficient resource conversion of nitrite in nitrogen-containing wastewater through an O₃ + Mn/ZSM-5 catalytic system. Mn/ZSM-5 catalysts with varying SiO₂/Al₂O₃ ratios (prepared by wet impregnation) were characterized by BET, XRD, and XPS. Experimental results demonstrated that Mn/ZSM-5 (SiO₂/Al₂O₃ = 400) exhibited a larger specific surface area, enhanced adsorption capacity, abundant surface Mn³⁺/Mn⁴⁺ species, hydroxyl oxygen species, and chemisorbed oxygen, leading to superior oxidation capability and catalytic activity. Under the optimized conditions of reaction temperature = 40 °C, initial pH = 4, Mn/ZSM-5 dosage = 1 g/L, and O₃ concentration = 100 ppm, the $\mathrm{N}{\mathrm{O}}_2^{-}$ oxidation efficiency reached 94.33%. Repeated tests confirmed that the Mn/ZSM-5 catalyst exhibited excellent stability and wide operational adaptability. The synergistic effect between Mn species and the zeolite support significantly improved ozone utilization efficiency. The O₃ + Mn/ZSM-5 system required less ozone while maintaining high oxidation efficiency, demonstrating better cost-effectiveness. Mechanism studies revealed that the conversion pathway of $\mathrm{N}{\mathrm{O}}_2^{-}$ followed a dual-path catalytic mechanism combining direct ozonation and free radical chain reactions. Practical spray tests confirmed that coupling the Mn/ZSM-5 system with ozone oxidation flue gas denitrification achieved over 95% removal of liquid-phase $\mathrm{N}{\mathrm{O}}_2^{-}$ byproducts without compromising the synergistic removal efficiency of NO_x/SO₂. This study provided an efficient catalytic solution for industrial wastewater treatment and the resource utilization of flue gas denitrification byproducts. Full article

As widely used peroxidase-like nanozymes, Fe-based nanozymes still suffer from an unclear reaction mechanism, which limits their further application. In this work, through alkaline treatment and then the replacement or occupation of strong acid sites by isolated Fe species, porous ZSM-5-confined atomic Fe species nanozymes with separated medium acid sites (Al-OH) and isolated Fe-O₄ sites were prepared. And the structure and the state of Fe-O₄ confined by ZSM-5 were determined by AC-HAADF-STEM, XPS, and XAS. In the oxidation of 3, 3′, 5, 5′-tetramethylbenzidine (TMB) by the hydrogen peroxide (H₂O₂) process, the heterolysis of H₂O₂ to ∙OH mainly occurs at the isolated Fe-O₄ sites, and then the generated ∙OH can spill over to the Al-OH sites to oxidize the adsorbed TMB. The synergistic effect between Fe-O₄ sites and medium acid sites can significantly benefit the catalytic performance of Fe-based nanozymes. Full article

ZSM-22 zeolites with different Si/Al ratios (38, 50, 80) were prepared via a hydrothermal synthesis method, investigated for the catalytic dehydration of 1,3-butanediol (1,3-BDO) to butadiene (BD) at 300 °C. The catalytic performance of the synthesized materials was related to their properties and compared to a commercial ZSM-22 zeolite (Si/Al = 30). ZSM-22 (50) exhibited a quick decline in conversion, a lower BD selectivity, and higher propylene selectivity compared to the other materials, which could be attributed to the presence of strong Lewis acid sites and silanol nests. The Lewis sites favor the cracking of the intermediate 3-buten-1-ol (3B1OL) into propylene, while the silanol nests interact with the free hydroxyl group of 3B1OL, potentially inhibiting further dehydration towards BD. The highest initial BD yield of 74% was observed over ZSM-22 (80), while the highest initial BD productivity of 2.7 g_BD·g⁻¹_cata·h⁻¹ was achieved over ZSM-22 (38). After 22 h time on stream (TOS), c-ZSM-22 and ZSM-22 (38) outperformed previously reported catalysts from the literature, with productivities amounting to 1.3 g_BD·g⁻¹_cata·h⁻¹ and 1.2 g_BD·g⁻¹_cata·h⁻¹, respectively, at a site time of 6.6 mol_H+·s·mol⁻¹_1,3-BDO. Full article

A cheap, environmentally friendly, easily scalable post-treatment of Na-ZSM-5 (Si/Al molar ratio = 20 or 30) via electron-beam irradiation to produce hierarchical H-ZSM-5 as a propylene-increasing fluid catalytic cracking additive was performed. Higher specific surface areas and highly accessible porous systems were obtained among the irradiated samples. A combination of ²⁷Al, ¹H magic angle spinning nuclear magnetic resonance and NH₃-temperature-programmed desorption methods showed that upon irradiation, some of the framework’s tetrahedral Al atoms were removed as non-framework Al atoms via flexible coordination with Si-OH groups (either framework or non-framework defects), thus increasing the H-ZSM-5 acidity and stability during hydrothermal dealumination. The enhanced selectivity and stability toward propylene production over the irradiated H-ZSM-5 samples were attributed to the integration of the reserved population of medium acid sites into the highly accessible hierarchical network. N₂ adsorption–desorption isotherm data showed that the Si-rich H-ZSM-5 samples possessed an obvious ink-bottle-shaped micro-mesopore network and a greater degree of disordered orientation of the straight pore systems toward the exterior surfaces. Micro-activity test data suggested that with an increasing Si/Al ratio, the H-ZSM-5 additives lost some extent of their cracking activity due to the constricted hierarchical pore network toward the exterior surface but gained more stability and selectivity for propylene due to the reserved medium acid sites. Full article

ZSM-5 zeolites are primarily used in acid-catalyzed hydrocracking reactions in the petrochemical industry, and it is very important to ensure an adequate number of acidic sites for more efficient catalytic activity. This study investigated the possibility of exchanging sodium ions with hydrogen ions on ZSM-5 zeolite with a molar ratio of (SiO₂/Al₂O₃ = 1000) using an ion-exchange process with acetic acid. By employing the XRD and FT-IR methods, along with chemical analysis of ZSM-5 zeolite samples, the influence of hydrogen ion concentration on the chemical composition and structural characteristics of ZSM-5 zeolite was monitored at different acid concentrations and exchange times. It was shown that ion exchange with acetic acid leads to a significant reduction in sodium content even with less concentrated solutions while maintaining the stability of the crystal structure of ZSM-5 (SiO₂/Al₂O₃ = 1000) and a high degree of crystallinity. Full article

Platinum was supported on ZSM5 at loadings from 0.1 to 1 wt% and tested for the Selective Catalytic Reduction of NO with H₂ under excess O₂ in a fixed bed reactor to address the issue of NO_x emission abatement from H₂-fueled internal combustion engines avoiding the additional devices for urea storage and injection. To reduce the undesired NO oxidation to NO₂, which is activated by platinum at T > 200 °C, the 0.1%Pt/ZSM5 catalyst was further promoted with sodium. 5 wt% loading of Na strongly inhibited the NO oxidation while giving only a limited impact on the H₂-SCR activity. Unpromoted and Na-promoted catalysts were characterized by XRD, SEM/EDX, N₂ physisorption, and NH₃-TPD to investigate the morphological, structural, and acid properties; H₂ pulse chemisorption and DRIFTS of CO chemisorption were used to investigate the nature of Pt active species. Steady-state and transient operando DRIFTS experiments under NO+H₂+O₂ flow were employed to identify the adsorbed NO_x species interacting with H₂, and reaction intermediates as a function of the reaction conditions. The formation of ammonium intermediates via the reduction of surface nitrate species, playing a key role in H₂-SCR catalyzed by 0.1Pt/ZSM5, was preserved at low Na load whilst NO₂ formation was largely inhibited. Full article

The pulp and paper industry is one of the leading waste-generating industries globally. With the rich energy content of these wastes and many of these mills not paying attention/implementing efficient waste disposal methods, it has become imperative that research efforts on pulp and paper waste valorization be performed; hence this paper. Hydrothermal liquefaction (HTL) technology was adopted due to its ability to transform wet biomass into biocrude. The research studied the effects of reaction parameters such as temperature, residence time, feed concentration, and catalysts on the yield of biocrude. While central composite design (CCD) was used in the design of the experiments, response surface methodology (RSM) was utilized for their optimization. The optimum parametric conditions obtained were the following: temperature: 340 °C; residence time: 56min; and feed concentration: 5%. Zeolite (HZSM-5), gamma-alumina (γ-Al₂O₃), and activated carbon were utilized as catalysts, and their performances with respect to biocrude yield improvement were evaluated. The order of catalytic effect on the biocrude yield was γ-Al₂O₃ (25.65%) > HZSM-5 (23.18%) > activated carbon (21.94%). Catalyst characterization was performed on the fresh and spent catalysts to study their properties and to make informed inferences on their impacts on biocrude yield. Based on the findings from this research, necessary conclusions and recommendations for future work are presented. Full article

The esterification of terephthalic acid (PTA) with methanol to dimethyl terephthalate (DMT) was investigated using commercially available zeolite catalysts as the eco-friendly solid acids. Six typical zeolites (ZSM-5-25, ZSM-5-50, ZSM-5-100, ZSM-35, MOR, and β) were systematically evaluated. Among them, β zeolite showed excellent catalytic performance, achieving nearly 100% PTA conversion and 76.1% DMT selectivity under the conditions of 200 °C, of 0.5 MPa N₂ pressure, m(PTA):V(methanol) of 1:40 (g/mL), m(PTA):m(catalyst) of 10:1 over 4 h. The characterization results show that the catalytic efficiency was correlated with acid site strength, specific surface area, and mesoporous structure of the zeolite. After optimization, β zeolite achieved 100% PTA conversion and 94.1% DMT selectivity under the conditions of 200 °C, of 1 MPa N₂ pressure, m(PTA)/V(methanol) of 1:30 (g/mL), m(PTA)/m(catalyst) of 8:1 over 8 h. Moreover, β zeolite exhibited superior stability, maintaining over 92% of its initial activity after five cycles, highlighting its potential for sustainable DMT production. Full article

Despite significant advancements in designing tandem catalysts for CO₂ hydrogenation to aromatics, the role of zeolite acid property in regulating the selectivity of light aromatics (benzene, toluene, and xylene, abbreviated as BTX) remains unclear. Herein, we report H-ZSM-5 zeolite (denoted as HZ-X, where X represents the Si/Al ratio) integrated with a Na-promoted FeCo-based catalyst (NaFeCo) for CO₂ hydrogenation into aromatics via a modified Fischer–Tropsch synthesis pathway. This study systematically modulates the Si/Al ratio of acidic zeolite and examines its critical role in influencing the light aromatics selectivity. The optimized NaFeCo/HZ-50 catalyst achieves a CO₂ conversion of 43% with an aromatics selectivity of 41%, including a BTX fraction of 57% in total aromatics. Multiple characterization techniques (NH₃-TPD, Py/DTBPy-IR, ²⁷Al NMR, etc.) clarify that acidic zeolite HZ-50 exhibits appropriate acid density and lower external surface acid sites, which synergistically boost the efficient aromatics and BTX synthesis while suppressing the undesirable alkylation and isomerization reactions on the external acid sites. This work develops a highly efficient multifunctional catalyst for CO₂ hydrogenation to light aromatics, especially offering guidance for the rational design of acidic zeolite with unique shape-selective functions. Full article

The formation of unstable solid electrolyte interphases (SEIs) on the surface of lithium metal anodes poses a significant barrier to the commercialization of lithium metal batteries (LMBs). Rational modulation of solvation structures within the electrolytes emerged as one of the most effective strategies to enhance interfacial stability in LMBs; however, this approach often compromises the structural stability of the bulk electrolyte. Herein, we present an innovative method that improves interface stability without adversely affecting the bulk electrolyte’s structural stability. By employing ZSM molecular sieves as efficient ion channels on the lithium metal anode surface—termed ZSM electrolytes—a more aggregated solvation structure is induced at the lithium metal interface, resulting in an anion-rich interphase. This anion-enriched environment promotes the formation of an SEI derived from anions, thereby enhancing the stability of the lithium metal interface. Consequently, Li||Cu cells utilizing the ZSM electrolyte achieve an average coulombic efficiency (CE) of 98.76% over 700 h. Moreover, LiFePO₄||Li batteries exhibit stable cycling performance exceeding 900 cycles at a current density of 1 C. This design strategy offers robust support for effective interfacial regulation in lithium metal batteries. Full article

Gallium-modified Zeolite Socony Mobil-5 (ZSM-5) zeolites were synthesized using wetness impregnation and hydrothermal synthesis methods. The structural and acidic properties of the zeolites were characterized through an analytical instrument, which demonstrated that Gallium-modified HZSM-5 zeolites retain the Mobil five instructure (MFI) framework structure, but exhibit a reduction in Brønsted acid sites and a decrease in micropore size. The catalytic performance of these zeolites in the pyrolysis of cellulose biomass and polyethylene was tested. Compared with HZSM-5, Ga-modified HZSM-5 zeolites considerably increased monoaromatic yields while reducing alkanes production. In particular, gallium-impregnated HZSM-5 increased the monoaromatic yield from 37.6% for ZSM-5 to 43.2%, while hydrothermal synthesized Ga-HMFI reduced polyaromatic and alkane yields from 6.6% and 24.6% for HZSM-5 to 2.9% and 11.4%, respectively. These results indicated that Ga-modified HZSM-5 zeolites can improve the synergy between cellulose-derived oxygenates and polyethylene-derived olefins, enhancing the yield of petrochemical hydrocarbons compared to that predicted by theoretical calculations. Full article

Room-temperature complete oxidation of formaldehyde (HCHO) is an important orientation of research programs, yet challenges remain. The development of efficient catalysts with high activity and excellent stability is of great significance for such practical application. Inspired by this whole catalytic process, we, therefore, chose HZSM-5 zeolite with abundant acidic sites as catalyst support and lactic acid (LA) as modifier to regulate the properties. The use of LA simultaneously enhances the hydroxyls density and increases the dispersion of Pt nanoparticles, which are better than the reference catalyst prepared via direct wetness impregnation method. Most satisfying of all, the lactic acid-modified HZSM-5-supported Pt catalyst demonstrates a remarkable reaction performance for room-temperature HCHO oxidation at a high concentration HCHO of 80 ppm and a large space velocity of 360,000 mL/g/h (especially with a low Pt loading of 0.5%). In addition, a 120 h test further confirms the favorable stability of the designed catalyst. This pre-modified strategy using organic acid might provide potential approach in the construction of efficient zeolite-supported catalysts. Full article

Biomass, as a renewable carbon resource, holds broad application prospects. Among various bio-based platform molecules, furan derivatives play a significant role in green chemical production. Notably, the conversion of 2-methylfuran (2-MF) to 3-acetyl-1-propanol (3-AP) over bifunctional catalysts has attracted considerable interest. In this study, a Pd@PHZSM-5 catalyst was prepared by encapsulating Pd nanoparticles within P-doped HZSM-5 for 2-MF conversion. The encapsulation improved Pd dispersion and metal–acid synergy, enhancing both catalytic activity and 3-AP selectivity. Additionally, phosphorus doping increased HZSM-5 crystallinity, resulting in excellent stability. This work provides a feasible strategy for optimizing metal–acid cooperation, offering theoretical guidance for bifunctional catalysis and biomass valorization. Full article

This study focuses on optimizing the Reverse Water Gas Shift (RWGS) reaction system using a membrane reactor to improve CO₂ conversion efficiency. A one-dimensional simulation model was developed using FlexPDE Professional Version 8.01/W64 software to analyze the performance of ZSM-5 membranes integrated with 0.5 wt% Ru-Cu/ZnO/Al₂O₃ catalysts. The results show that the membrane reactor significantly outperforms the conventional Packed Bed Reactor by achieving higher CO₂ conversion (0.61 vs. 0.99 with optimized parameters), especially at lower temperatures, due to its ability to remove H₂O and shift the reaction equilibrium selectively. Key operational parameters, including temperature, pressure, and sweep gas flow rate, were optimized to maximize membrane reactor performance. The ZSM-5 membrane showed strong H₂O selectivity, with an optimum operating temperature of around 400–600 °C. The problem is that many reactants permeate at higher temperatures. Subsequently, a Half-MPBR design was introduced. This design was able to overcome the reactant permeation problem and increase the conversion. The conversion ratios for PBR, MPBR, and Half-MPBR are 0.71, 0.75, and 0.86, respectively. This work highlights the potential of membrane reactors to overcome the thermodynamic limitations of RWGS reactions and provides valuable insights to advance Carbon Capture and Utilization technologies. Full article

Catalytic conversion of bioethanol is a promising production method for preparing light olefin. However, the role of acid sites in different pore channels of HZSM-5 catalyst is not clear. The roles of acid sites in different channels of HZSM-5 catalyst on the conversion of ethanol to ethylene and propylene was investigated by density functional theory (DFT). The results show that the conversion of ethanol to ethylene mainly occurs at the acid site of the sinusoidal channel (T11) of HZSM-5, and the conversion of ethanol to propylene mainly occurs at the acid site of the straight channel (T10) of HZSM-5 catalyst. The adsorption and diffusion behaviors of ethylene and propylene in straight and sinusoidal channels of HZSM-5 were simulated by the molecular dynamics method. The results show that for the adsorption of ethylene and propylene, the acid sites of sinusoidal channel (T11) with SiO₂/Al₂O₃ = 128 is more conducive to improving the selectivity of ethylene, and the acid sites of straight channel (T10) with SiO₂/Al₂O₃ = 128 is more conducive to improving the propylene selectivity. For the diffusion of ethylene and propylene, the acid sites in the straight channel (T10) of HZSM-5 (SiO₂/Al₂O₃ = 128) are more beneficial to improve propylene selectivity. Full article