Review of Core-shell structure zeolite-based catalysts for NOx emission control.

Nitrogen oxides (NOx) from diesel engine exhaust, is one of the major sources of environmental pollution. Currently, selective catalytic reduction with ammonia (NH3-SCR) is considered to be the most effective protocol for reducing NOx emissions. Nowadays, zeolite-based NH3-SCR catalysts have been industrialized and widespread used in this field. Nevertheless, with the increasingly stringent environmental regulations and implementation of the requirement of "zero emission" of diesel engine exhaust, it is extremely urgent to prepare catalysts with superior NH3-SCR activity and exceptional resistance to poisons (SO2, alkali metals, hydrocarbons, etc.). Core-shell structure zeolite-based catalysts (CSCs) have shown great promise in NH3-SCR of NOx in recent years by virtue of its relatively higher low-temperature activity, broader operation temperature window and outstanding resistance to poisons. This review mainly focuses on the recent progress of CSCs for NH3-SCR of NOx with three extensively investigated SSZ-13, ZSM-5, Beta zeolites as cores. The reaction mechanisms of resistance to sulfur poisoning, alkali metal poisoning, hydrocarbon poisoning, and hydrothermal aging are summarized. Moreover, the important role of interfacial effect between core and shell in the reaction of NH3-SCR was clarified. Finally, the future development and application outlook of CSCs are prospected.

Assessing biochar, clinoptilolite zeolite and zeo-char loaded nano-nitrogen for boosting growth performance and biochemical ingredients of peace lily (Spathiphyllum Wallisii) plant under water shortage.

BACKGROUND: Peace lily (Spathiphyllum wallisii Regel) is an ornamental indoor plant with promising cut flower market, as well as antiviral, pharmacological and ecological potentials. Water deficiency can have sound effects on the growth performance and aesthetic quality of such plant. The aim of this study was to investigate the consequences of zeolite, biochar, and zeo-char loaded nano-nitrogen application on the growth performance and biochemical components of peace lily under water shortage conditions. An experiment was conducted over two consecutive seasons (2021-2022) at the experimental nursery of Ornamental Horticulture Department, Faculty of Agriculture, Cairo University, Giza, Egypt. Soil amendments; zeolite, biochar, and zeo-char loaded nano-nitrogen were prepared and applied to soil before cultivation. RESULTS: Our results revealed that the new combination treatment (zeo-char loaded nano-N) had an exceeding significant effect on most of the studied parameters. Vegetative traits such as plant height (35.7 and 35.9%), leaf number per plant (73.3 and 52.6%), leaf area (40.2 and 36.4%), stem diameter (28.7 and 27.1%), root number (100 and 43.5%) and length (105.7 and 101.9%) per plant, and fresh weight of leaves (23.2 and 21.6%) were significantly higher than control (commercially recommended dose of NPK) with the application of zeo-char loaded nano-N during the two growing seasons, respectively. Similar significant increments were obtained for some macro- (N, P, K, Mg, Ca) and micro- (Fe, Zn, Mn) elements with the same treatment relative to control. Chlorophyll (18.4%) and total carotenoids (82.9 and 32.6%), total carbohydrates (53.3 and 37.4%), phenolics (54.4 and 86.9%), flavonoids (31.7% and 41.8%) and tannins (69.2 and 50%), in addition to the phytohormone gibberellic acid (GA3) followed the same trend with the application of zeo-char loaded nano-N, increasing significantly over control. Leaf histological parameters and anatomical structure were enhanced with the new combination treatment in comparison with control. Antioxidant enzymes (catalase and peroxidase), proline and abscisic acid (ABA) exhibited significant declines with zeo-char loaded nano-N treatment relative to control. CONCLUSION: These findings suggest that incorporating soil amendments with nano- nutrients could provide a promising approach towards improving growth performance and quality of ornamental, medicinal and aromatic species under water deficiency conditions.

Effect of orange pulp with or without zeolite on productive performance, nitrogen utilization, and antioxidative status of growing rabbits.

The current study was designed to investigate the effect of dried orange pulp inclusion (OP diet), natural zeolite addition (Z diet), or both (OPZ diet) compared to control (CON diet) on digestibility, growth performance, nitrogen utilization, blood biochemical, antioxidative status, and cecum microbiota of growing rabbits. Seventy-two V-line male rabbits (6 weeks old) were divided into 4 balanced experimental groups. Results showed that administration of dried orange pulp or zeolite especially the OPZ diet significantly improved nutrient digestibility and nutritive values. Rabbits fed the experimental diets (OP, Z, or OPZ) recorded significantly higher values of average daily gain, N-retention, and N-balance compared with those fed the CON diet. Data on blood biochemical, showed non-significant differences in globulin concentrations, and significant decreases in levels of cholesterol, LDL (low-density lipoproteins), triglycerides, and MDA (malondialdehyde) as an antioxidant biomarker with OP, Z, or OPZ diets. Moreover, the incorporation of orange pulp or zeolite in diets significantly decreased the cecal count of E. coli, with no significant difference in total bacterial count among the experimental groups. It could be concluded that a combination between dried orange pulp and natural zeolite in the diet can enhance the growth performance, antioxidant and health status of rabbits.

Noble metal-free plasmonic Cu/WO3-x@ZNC bi-functional composite for ciprofloxacin photocatalytic degradation and photothermal water evaporation via visible-infrared exposure.

Herein, coupling of noble metal-free plasmonic copper nanoparticles with tungsten suboxide and supporting on zeolite nanoclay (Cu/WO3-x@ZNC) composite will be introduced for bi-functional photocatalytic ciprofloxacin (CIP) degradation and water photothermal evaporation under visible/infrared (Vis/IR) exposure. Reduced band-gap of WO3-x via oxygen vacancies creation and localized surface plasmon resonance (LSPR) formation by Cu nanoparticles contributed significantly the extension and intensification of composite's photo-absorption range. Furthermore, small mesoporous structure of ZNC enhanced CIP adsorption and charge carriers separation where the reported photocatalytic efficiencies were 88.3 and 81.7% upon IR and Vis light exposure respectively. It was evidenced that plasmonic hot electrons (e-.s) and hydroxyl radicals (OH•-) performed the basic functions of the photocatalytic process. At the other side, oxygen vacancies existence, plasmonic effect, and confining thermal characteristics of WO3-x, Cu, and ZNC correspondingly induced water photothermal evaporation with efficiencies up to 97.5 and 72.8% under IR and Vis illumination respectively. This work introduces synthesis of a novel bi-functional photocatalytic-photothermal composite by metal sub-oxide and non-noble metal plasmonic coupling and supporting on naturally-derived carrier for water restoration under broad spectral exposure.

Boosting the Stability of Subnanometer Pt Catalysts by the Presence of Framework Indium(III) Sites in Zeolite.

Subnanometer metal clusters show advantages over conventional metal nanoparticles in numerous catalytic reactions owing to their high percentage of exposed surface sites, abundance of under-coordinated metal sites and unique electronic structures. However, the applications of subnanometer metal clusters in high-temperature catalytic reactions (>600 °C) are still hindered, because of their low stability under harsh reaction conditions. In this work, we have developed a zeolite-confined bimetallic PtIn catalyst with exceptionally high stability against sintering. A combination of experimental and theoretical studies shows that the isolated framework In(III) species serve as the anchoring sites for Pt species, precluding the migration and sintering of Pt species in the oxidative atmosphere at ≥650 °C. The catalyst comprising subnanometer PtIn clusters exhibits long-term stability of >1000 h during a cyclic reaction-regeneration test for ethane dehydrogenation reaction.

Comparison of the natural and surfactant-modified zeolites in the adsorption efficiency of sunset yellow food dye from aqueous solutions.

The removal of Sunset Yellow (E110) on natural zeolite and zeolite modified with the cationic surfactant cetyl pyridinium chloride (CPC) was studied using the adsorption method. The structural characteristics of the surfactant-modified zeolite (SMZ-CPC) were investigated using X-ray diffraction(XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) analysis, and the scanning electron microscopy (SEM) images. The effect of different parameters on the adsorption process, such as equilibration time and amount of adsorbent at 298 K, were determined using UV-Vis spectroscopy. The maximum dye removal percentage on SMZ-CPC was obtained with 0.08 g of adsorbent in 30 min. The results show that the zeolite modified with CPC surfactant (SMZ) has a higher adsorption capacity for Sunset Yellow than the unmodified zeolite (natural form). The experimental adsorption data were nonlinearly analyzed using isotherm equations such as Langmuir, Freundlich, Temkin, Langmuir-Freundlich (or Sips), and Extended Langmuir (EL). The experimental data were better fitted with the Sips isotherm. The adsorption kinetic data were analyzed using eight models in nonlinear forms: the pseudo-first-order (PFO), pseudo-second-order (PSO), integrated kinetic Langmuir (IKL), Elovich, intraparticle diffusion (IPD), mixed order rate equation (MOE), fractal-like pseudo-first-order (FL-PFO) and fractal-like pseudo-second-order (FL-PSO). According to the results of the coefficient of determination (R2), Elovich kinetic model well expressed E110 adsorption onto SMZ-CPC. Most of the dye removal takes place in less than 5 min and the maximum adsorption capacity is 5.06 mg/g. The results of this study show that zeolite modified with cationic surfactant is an effective adsorbent for removal anionic dyes from an aqueous solution.

Valorizing waste activated sludge incineration ash to S-doped Fe2+@Zeolite 4A catalyst for the treatment of emerging contaminants exemplified by sulfamethoxazole.

The global attention towards waste management and valorization has led to significant interest in recovering valuable components from sludge incineration ash (SIA) for the synthesis of functional environmental materials. In this study, the SIA was converted to an S-doped Fe2+-zeolite type catalyst (FZA) for the treatment of emerging contaminants (ECs), exemplified by sulfamethoxazole (SMX). Results demonstrate that FZA effectively catalyzed the activation of peracetic acid (PAA), achieving a remarkable degradation of 99.8% under optimized conditions. Mechanistic investigations reveal that the FZA/PAA system can generate ·OH, 1O2, O2·ï¼, and Fe(Ⅳ), with ·OH playing a dominant role in ECs degradation. Additionally, the doped S facilitated electrochemical performance, Fe2+ regeneration and fixation in FZA. Practical application elucidated that the FZA/PAA system can work in complex environments to degrade various ECs without generating high-toxicity ingredients. Overall, valorizing SIA to FZA provides dual achievement in waste management and ECs removal.

Enhanced and robust nitrogen removal using an integrated zeolite and partial denitrification anammox process.

Anammox has received increased attention due to its enhanced and cost-efficient approach to nitrogen removal. However, its practical application is complicated by strict influent NO2--N to NH4+-N ratio demands and an 11% nitrate production from the anammox process. This study was the first known research to propose and verify a system of zeolite integrated with partial denitrification and anammox (Z-PDA) in an up-flow anaerobic sludge bed (UASB) reactor. The enhanced and robust nitrogen removal resulted in an ultra-high nitrogen removal efficiency (NRE, 93.0 ± 2.0%). Zeolite adsorption and biological desorption of ammonium contributed to robust nitrogen removal with fluctuating influent NO2--N to NH4+-N ratios. Applying 16S rRNA gene sequencing found that Candidatus Brocadia and Thauera were the key bacteria responsible for anammox and partial denitrification (PD), respectively. Zeolite also acted as a biological carrier. This significantly enriched anammox bacteria with a higher relative abundance of Candidatus Brocadia, reaching 49.2%. Metagenomic analysis demonstrated that the multiple functional genes related to nitrogen removal (nrfA/H, narG/H/I) and the metabolic pathways (Biosynthesis of cofactors, the Two-component system, the Biosynthesis of nucleotide sugars, and Purine metabolism) ensured the resilience of the Z-PDA system despite influent fluctuations. Overall, this study provided novel insights into the impacts of zeolite in the PDA system. It described the fundamental mechanism of zeolite based on adsorption and biological desorption, and demonstrated a meaningful application of the anammox process in sewage treatment.

Comparative Study of PtM (M=Cu, Zn, Ga, Mn, Fe, In, Ce) Bimetals on Zincosilicate for Propane Dehydrogenation Reaction.

Silicoaluminate zeolites have relatively strong Brönsted (B) acid properties that can easily lead to deep cracking reactions, making them less favourable as carriers for propane dehydrogenation. Here, we utilise zincosilicate zeolite with less B-acid produced by the introduction of the heteroatom Zn into the framework as a carrier, followed by simultaneous ion exchange (IE) of M monometallic or PtM bimetallic (M = Cu, Zn and Ga, etc.). The optimized PtZn/Zn-4 exhibits a superior propane dehydrogenation performance over PtCu/Zn-4 and PtGa/Zn-4, which can achieve a propane conversion of about 30% in a pure propane atmosphere at 550 °C and can be operated for at least 168 h without significant deactivation. Characterization techniques such as spherical aberration corrected transmission electron microscopy, in situ X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared fourier transform spectroscopy with different gas adsorptions are used to investigate these PtM@zeolite catalysts in order to deepen the understanding of acid site identification, promoter effect and catalysis.

On the Origin of Enantioselectivity in Chiral Zeolite Asymmetric Catalyst GTM-3: Host-Guest Transfer of Chirality.

Knowledge of how extra-large-pore chiral zeolite asymmetric catalysts based on the -ITV framework imprint their chirality during a catalytic reaction is crucial in order to spread the scope for the catalytic enantioselective production of chiral compounds of interest. In this work, we have carried out a combined experimental and computational study on the catalytic activity of antipode GTM-3 catalysts during the ring-opening of trans-stilbene oxide with 1-butanol. Identification of the enantiomers of all the chiral species unraveled a surprising catalytic behavior: these chiral catalysts promote the transformation of one enantiomer of trans-stilbene oxide in the corresponding unlike product (with inversion of configuration of the attacked C) via an SN2 mechanism, and at the same time, the transformation of the other enantiomer of trans-stilbene oxide via an SN1-like mechanism into the like (with retention of configuration) and secondary products (diphenylacetaldehyde via Meinwald rearrangement and derived products). A computational study based on DFT + D methods suggested a potential explanation for this catalytic behavior, associated with a different orientation of trans-stilbene oxide enantiomers bound on the Ge(T7) positions in d4r units, which is stabilized by the development of intraframework H-bonds between the interrupted T7OH adjacent positions characteristic of this framework. Calculations suggest that each enantiomer of trans-stilbene oxide follows a different reaction pathway, one favoring the SN2 route by addition of butanol from the opposite side to form unlike-products, while the different orientation of the antipode enantiomer disfavors such SN2 route mainly by steric repulsions and at the same time favors the reaction toward the SN1 mechanism to give like- and secondary-products. Our study suggests that the strong enantioselectivity of GTM-3 catalysts for this reaction is associated with the particular orientation adopted by the chiral reactants within the chiral nanospace provided by the -ITV framework, similarly to what occurs with enzymes, and such preferential orientation is directly controlled by the asymmetric cavities where the reaction takes place, by the particular features of the Ge active sites in adjacent interrupted positions and by the presence of several framework OH groups in the nearby nanospace that interact with guest species. The experimental observations and the reaction mechanism proposed suggest that GTM-3 catalysts prepared from the (1S,2S) enantiomer of the N,N-ethyl-methyl-pseudoephedrinium organic agent should be enriched in the P4332 enantiomorphic space group of the -ITV framework and GTM-3 prepared from the (1R,2R) enantiomer in the antipode P4132. Interestingly, resolution of the absolute configuration of GTM-3 materials from 3D-electron diffraction data has been accomplished and confirms such an assignment, giving an average 82% enantio-enrichment in the corresponding chiral polymorph. Structure-solution of the location of the chiral structure-directing agents indicates that the transfer of chirality from the molecular component to the zeolite polymorph is governed by the development of strong H-bonds between the molecular hydroxyl group and the interrupted T(7)OH framework positions.