Close Intimacy between PtIn Clusters and Zeolite Channels for Ultrastability toward Propane Dehydrogenation.

Propane dehydrogenation (PDH) serves as a pivotal intentional technique to produce propylene. The stability of PDH catalysts is generally restricted by the readsorption of propylene which can subsequently undergo side reactions for coke formation. Herein, we demonstrate an ultrastable PDH catalyst by encapsulating PtIn clusters within silicalite-1 which serves as an efficient promoter for olefin desorption. The mean lifetime of PtIn@S-1 (S-1, silicalite-1) was calculated as 37317 h with high propylene selectivity of >97% at 580 °C with a weight hourly space velocity (WHSV) of 4.7 h-1. With an ultrahigh WHSV of 1128 h-1, which pushed the catalyst away from the equilibrium conversion to 13.3%, PtIn@S-1 substantially outperformed other reported PDH catalysts in terms of mean lifetime (32058 h), reaction rates (3.42 molpropylene gcat-1 h-1 and 341.90 molpropylene gPt-1 h-1), and total turnover number (14387.30 kgpropylene gcat-1). The developed catalyst is likely to lead the way to scalable PDH applications.

Time-Dependent and Excitation-Dependent Afterglow Color Evolution from the Assembly of Dual Carbon Dots in Zeolite.

Afterglow materials with time-dependent color output emerge as huge prospects in advanced optical information encryption but remain a formidable challenge due to the limited exciton transfer from a single emission center. Here, multiple time-dependent afterglow color evolutions are achieved by the strategy of controllable assembly of dual carbon dots (CDs) with an individual afterglow color and decay rate into an RHO zeolite. The strategy possesses high controllability such that B-CDs and G-CDs can be independently generated and in situ embedded into a matrix; in particular, the doped amount of two kinds of CDs can be adjusted conveniently to produce interesting variable afterglow colors. Triggered by different excitations, the prepared B&G-CDs@RHO composites exhibit the conversion of TADF and RTP behaviors, as well as time-dependent afterglow color output from deep-blue to green (365 nm excitation) and static cyan (254 nm excitation). The unique luminescence and excellent stability allow the composite applied in information encryption with high-security levels.

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.

Designable Synthesis of Layered Silicates and Tunable Interlayer Expanded to Zeolites.

Layered zeolitic silicates and corresponding interlayer-expanded porous materials exhibit attractive application potential in wide fields. Nonetheless, designable synthesis and structure analysis of layered silicates remain challenging. Herein, two kinds of layered silicates are synthesized using different di-quaternary ammonium-type organic structure-directing agents (OSDAs). Their crystal structures are analyzed and verified by 3D electron diffraction (3D ED) and high-resolution TEM imaging. The suitable configurations of OSDA can lead to desirable interlayer states. Additionally, two new zeolite structures both with 12-membered ring (MR) channels intersected by 8 MR channels and larger interlayer spaces are constructed from layered silicate precursors by interlayer silylation. The new zeolitic material exhibits potential application in adsorption of organic pollution and catalytic reaction. This study is expected to develop versatile ways for the design and synthesis of layered silicates even zeolites and provide references in characterizing layered materials and zeolites as well.

Zeolite Crystallization Inside Chemically Recyclable Ordered Nanoporous Co3O4 Scaffold: Precise Replication and Accelerated Crystallization.

The synthesis of mesoporous zeolites has garnered attention with regard to improving their catalytic and adsorption performances. While the hard-templating method provides opportunities to design precisely controlled hierarchical micro- and mesoporous structures, synthesizing mesoporous zeolites without external precipitation requires significant work. This is mainly due to the absence of usable templates other than carbon with hydrophobic surfaces. Herein, it is demonstrated that the Co3O4 template is valuable in preparing mesoporous silicalite-1 and ZSM-5 with a precisely controlled porous structure through hydrothermal synthesis. Unlike conventional carbon templates, the Co3O4 template is relatively hydrophilic, effective in suppressing external precipitation, and is reusable by dissolving in an acidic solution. The crystallization process also differs from that of the carbon template, as the silicate precipitates on a 3D ordered nanoporous Co3O4 scaffold, followed by crystallization and crystal growth. Furthermore, it is unexpectedly observed that the zeolite crystallization is accelerated in the Co3O4 template. The synthetic approach utilizing nanoporous metal oxides opens new doors for the control of the hierarchical structure of zeolites, as well as for the design of metal oxide-zeolite nanocomposite catalysts, due to the potential extensibility of the combination of metal oxides and zeolites.

Unveiling Ru(bpy)3 2+-Encapsulated Zeolite Y as Photocatalyst: Harnessing Photocatalytic Singlet Oxygen Generation for Mustard Gas Simulant Detoxification.

This study explores the encapsulation of Ru(bpy)3 2+ within Zeolite Y (ZY) to improve photocatalytic singlet oxygen generation for the degradation of a mustard gas simulant, namely 2-chloroethyl ethyl sulfide (CEES). Mustard gas simulants are known to disrupt several biological processes; thus, their effective degradation is essential. Zeolite Y, with its hierarchical structure and adjustable Si/Al ratios, is an ideal host for Ru(bpy)3 2+, significantly improving its photocatalytic efficiency and stability. It is demonstrated through XRD and spectroscopic analyses that encapsulated Ru(bpy)3 2+ maintains its structural and photophysical properties, which are essential for generating singlet oxygen. Ru(bpy)3(1.0) loaded ZY(15) (where 1.0 and 15 represent the encapsulated amount of Ru(bpy)3 2+ and Si/Al ratio, respectively) outperforms other investigated photocatalytic systems in the oxidation of CEES, demonstrating high conversion rates and selectivity toward nontoxic sulfoxide products. Immobilization of Ru(bpy)3 2+-encapsulated zeolite Y onto cotton fabric results in effective degradation of CEES. The experimental results, validated by theoretical calculations, indicate an improved oxygen affinity and accessibility in zeolites with higher Si/Al ratios. This study advances the design of photocatalytic materials for environmental and defense applications, providing sustainable solutions for hazardous chemical degradation.

Construction of Hierarchical Films via Layer-by-Layer Assembly of Exfoliated Unilamellar Zeolite Nanosheets.

Zeolites have been widely applied as versatile catalysts, sorbents, and ion exchangers with unique porous structures showing molecular sieving capability. In these years, it is reported that some layered zeolites can be delaminated into molecularly thin 2-dimensional (2D) nanosheets characterized by inherent porous structures and highly exposed active sites. In the present study, two types of zeolite nanosheets with distinct porous structures with MWW topology (denoted mww) and ferrierite-related structure (denoted bifer) are deposited on a substrate through the solution process via electrostatic self-assembly. Alternate deposition of zeolite nanosheets with polycation under optimized conditions allows the layer-by-layer growth of their multilayer films with a stacking distance of 2-3 nm. Furthermore, various hierarchical structures defined at the unit-cell dimensions can be constructed simply by conducting the deposition of mww and bifer nanosheets in a designed sequence. Adsorption of a dye, Rhodamine B, in these films, is examined to show that adsorption is dependent on constituent zeolite nanosheets and their assembled nanostructures. This work has provided fundamental advancements in the fabrication of artificial zeolite-related hierarchical structures, which may be extended to other zeolite nanosheets, broadening their functionalities, applications, and benefits.

Accelerated Synthesis of TS-2 Zeolite via 2D Heterogeneous Nucleation for Efficient H2O2 Production.

MEL type c is crucial for addressing energy and environmental crises, yet efficient synthesis remains a challenge due to thermodynamic and kinetic limitations. In this work, TS-2 as typical zeolite is successfully synthesized with high efficiency (12 h with 92% yield) by introducing titanate acid (TA) 2D nanosheet into a hydrothermal synthesis system. A newly defined TA/TS-2 heterostructure is precisely identified as being incorporated into the zeolite framework via a heterogeneous nucleation mechanism. Ab initio molecular dynamics simulations deeply revealed the nucleation and growth mechanisms of the TA/TS-2 heterostructure. The formation energy barrier of Ti─O─Si structural units (88 kJ mol-1) is much lower than that of Si─O─Si units (119 kJ mol-1), leading to more efficient growth of the Ti─O─Si structure. The polarized electronic properties of Ti─O─Si (negative LUMO orbital and larger polarization) further enhanced the reaction probability and stability of Ti─Si bonding. This obtained TA/TS-2 heterostructure also demonstrated superior activity for photocatalytic production of hydrogen peroxide, which can be attributed to the abundant conductive band holes and narrow bandgap. This research provides an effective strategy for using 2D nanosheets to accelerate zeolite production, as well as an in-depth molecular-level insight into the nucleation and growth processes.

PEPICO analysis of catalytic reactor effluents towards quantitative isomer discrimination: DME conversion over a ZSM-5 zeolite.

The methanol-to-hydrocarbons (MTH) process involves the conversion of methanol, a C1 feedstock that can be produced from green sources, into hydrocarbons using shape-selective microporous acidic catalysts - zeolite and zeotypes. This reaction yields a complex mixture of species, some of which are highly reactive and/or present in several isomeric forms, posing significant challenges for effluent analysis. Conventional gas-phase chromatography (GC) is typically employed for the analysis of reaction products in laboratory flow reactors. However, GC is not suitable for the detection of highly reactive intermediates such as ketene or formaldehyde and is not suitable for kinetic studies under well defined low pressure conditions. Photoelectron-photoion coincidence (PEPICO) spectroscopy has emerged as a powerful analytical tool for unraveling complex compositions of catalytic effluents, but its availability is limited to a handful of facilities worldwide. Herein, PEPICO analysis of catalytic reactor effluents has been implemented at the FinEstBeAMS beamline of MAX IV Laboratory. The conversion of dimethyl ether (DME) on a zeolite catalyst (ZSM-5-MFI27) is used as a prototypical model reaction producing a wide distribution of hydrocarbon products. Since in zeolites methanol is quickly equilibrated with DME, this reaction can be used to probe vast sub-networks of the full MTH process, while eliminating or at least slowing down methanol-induced secondary reactions and catalyst deactivation. Quantitative discrimination of xylene isomers in the effluent stream is achieved by deconvoluting the coincidence photoelectron spectra.

Unexpected Low Temperature Activity with Low N2 O Emission of Stabilized Al-rich Zeolite Beta for Selective Catalytic Reduction of NOx.

The low temperature activity of Fe-loaded zeolites as selective catalytic reduction of NOx by NH3 (NH3 -SCR) catalysts is a critical drawback for practical application. Here, we found unexpected improvement of low temperature activity by our proposed post-synthetic treatment. An Al-rich zeolite beta (Si/Al=5) is employed as the catalyst support, and the parent sample is dealuminated for higher hydrothermal stability, followed by the liquid-mediated stabilization treatment and impregnation. It is found that stabilized samples feature excellent low temperature activity and high N2 selectivity even for a long-term operation, along with the ability to maintain high NOx conversion after aging. The improved SCR activity should be attributed to abundant acid sites in Al-rich framework and better stabilization of monomeric iron species after the stabilization treatment. Furthermore, the low yield of side product N2 O is probably due to the absence of the generation of NH4 NO3 during NH3 -SCR catalyzed by Fe-loaded zeolites.

Accelerated Synthesis of Nanolayered MWW Zeolite by Interzeolite Transformation.

Hierarchical zeolites can offer substantial benefits over bulk zeolites in catalysis. A drawback towards practical implementation is their lengthy synthesis, often requiring complex organic templates. This work describes an accelerated synthesis of nanolayered MWW zeolite based on the combination of interzeolite transformation (IZT) with a dual-templating strategy. FAU zeolite, hexamethyleneimine (HMI), and cetyltrimethylammonium bromide (CTAB) were respectively employed as Al source and primary zeolite, structure directing agent, and exfoliating agent. This approach allowed to reduce the synthesis of nanolayered MWW to 48 h, which is a considerable advance over the state of the art. Tracking structural, textural, morphological, and chemical properties during crystallization showed that 4-membered-ring (4MR) units derived from the FAU precursor are involved in the faster formation of MWW in comparison to a synthesis procedure from amorphous precursor. CTAB restricts the growth of the zeolite in the c-direction, resulting in nanolayered MWW. Moreover, we show that this approach can speed up the synthesis of nanolayered FER. The merits of nanolayered MWW zeolites are demonstrated in terms of improved catalytic performance in the Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to p-xylene compared to bulk reference MWW sample.

High Yield of L-Sorbose via D-Glucose Isomerization in Ethanol over a Bifunctional Titanium-Boron-Beta Zeolite.

D-Glucose-to-L-sorbose isomerization on Lewis acidic zeolite is a highly attractive avenue for sorbose production. But the L-sorbose yield is limited by the competing D-glucose-to-D-fructose isomerization and reaction equilibrium. In this work, it is suggested that ethanol directs the glucose conformation for selective D-glucose-to-L-sorbose isomerization. It also reacts with the produced L-sorbose to form ethyl-sorboside, which allows the D-glucose-to-L-sorbose isomerization to proceed beyond the thermodynamic equilibrium limit.  It is shown that a bifunctional zeolite Beta containing framework titanium (Ti) and boron (B) is a selective catalyst for this tandem reaction: Lewis acidic framework Ti catalyzes the D-glucose-to-L-sorbose isomerization via an intramolecular 5,1-hydride shift process as confirmed by isotopic tracing experiments followed by 13C-NMR, while weak Brønsted acid framework B selectively promotes the sorbose ketalization with ethanol. A remarkably high yield of L-sorbose with a high fraction of sugar (>95%: 27% unreacted glucose, 11.4% fructose, 57% sorbose) was obtained after the mixture produced in ethanol was hydrolyzed.

Hexagonal Prismatic Siloxanes Functionalized with Organosilyl Groups as Building Blocks of Nanoporous Materials.

Utilization of well-defined siloxane molecules allows for the construction of functional siloxane-based nanoporous materials based on the molecular design. Herein, a novel class of siloxane-based porous materials is synthesized via cross-linking of dimethylsilyl- and dimethylvinylsilyl-functionalized cage siloxanes with double-6-ring (D6R) geometry. Compared with the conventional double-4-ring cage siloxane, this study highlights the characteristics of D6R siloxanes as building blocks, demonstrating their high surface area and chemical stability. Furthermore, density functional theory calculations show their unique cation encapsulation ability.

Zeolite/Polymer Composites Prepared by Photopolymerization: Effect of Compensation Cations on Opacity and Gas Adsorption Applications.

The fabrication of structured zeolite adsorbents through photopolymerization-based 3D printing which offers a solution to the limitations of conventional shaping techniques has been demonstrated but many parameters still need to be optimized. In this study, we studied the influence of zeolite compensation cations on the photopolymerization and the composite's properties. Modified zeolites (LTA 4 A and FAU 13X exchanged with K+ , Li+ , Sr2+ , Ca2+ or Mg2+ ) were incorporated in PEGDA with BDMK as photoinitiator, and the formulation was cured under mild conditions (LED@405 nm, room temperature, under air). Our results indicate that the nature of zeolite compensation cations affects the colorimetric properties of polymer/zeolite composites: a better translucency parameter results in higher depth of cure. After calcination at 650 °C and complete removal of PEGDA, pure zeolitic monoliths were tested for adsorption of gas molecules of interest (carbon dioxide, dichlorobenzene and water). Structured 4 A and 13X monoliths obtained by 3D printing exhibit comparable adsorption capacity to commercial beads prepared from the same zeolites. This study enhances our understanding of the photopolymerization process involved in the production of polymer/zeolite composites. These composites are used in the fabrication of zeolitic objects through 3D printing, offering potential solutions to various environmental and dental challenges.

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.

TS-1@MCM-48 Core-Shell Catalysts for Efficient Oxidation of p-Diethylbenzene to High Value-Added Derivatives.

To expand the market capacity of p-diethylbenzene (PDEB), core-shell zeolite (TS-1@MCM-48) is designed as a catalyst for PDEB oxidation. TS-1@MCM-48 catalyst is synthesized by in-situ crystallization method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, in-situ electron paramagnetic resonance (EPR) and 29Si nuclear magnetic resonance (29Si MAS-NMR). Oxidation of PDEB by H2O2 was investigated systematically in liquid phase. The conversion of PDEB over TS-1@MCM-48 was 28.1 % and the total selectivity was 72.6 %, where the selectivity of EAP (p-ethylacetophenone) and EPEA (4-ethyl-α-methylbenzyl alcohol) was 28.6 % and 44.0 %, respectively. Compared with TS-1 and MCM-48 zeolite, the conversion rate of reactants and the selectivity of products have been significantly improved. The catalytic performance of TS-1@MCM-48 is derived from its well-crystallized microporous core and mesoporous shell with regular channels, which make active sites of TS-1 zeolite in the catalyst be fully utilized and mass transfer resistance be largely reduced. Further through theoretical calculation, we propose that the oxidation of PDEB is the result of the combination and mutual transformation of free radical process and carbocation process. Core-shell structure ensures the conversion rate of raw materials and improves the selectivity of products.

Interplay Between Ni and Brønsted and Lewis Acid Sites in the Hydrodesulfurization of Dibenzothiophene.

Ni-MoS2/γ-Al2O3 catalysts are commonly used in hydrotreating to enhance fossil fuel quality. The extensive research on these catalysts reveals a gap in understanding the role of Ni, often underestimated as an inactive sulfide phase or just a MoS2 promoter. In this work, we focused on analyzing whether well-dispersed supported nickel nanoparticles can be active in the hydrodesulfurization of dibenzothiophene. We dispersed Ni by Strong Electrostatic Adsorption (SEA) method across four supports with different types of acidity: silica (~ neutral acidity), γ-Al2O3 (Lewis acidity), H+-Y zeolite, and microporous-mesoporous H+-Y zeolite (both with Brønsted-Lewis acidity). Our findings reveal that Ni is indeed active in dibenzothiophene hydrodesulfurization, even with alumina and silica as supports, although their catalytic activity declines abruptly in the first hours. Contrastingly, the acid nature of zeolites imparts sustained stability and performance, attributed to robust metal-support interactions. The efficacy of the SEA method and the added mesoporosity in zeolites further amplify catalytic efficiency. Overall, we demonstrate that Ni nanoparticles may perform as a hydrogenating metal in the same manner as noble metals such as Pt and Pd perform in hydrodesulfurization. We discuss some of the probable reasons for such performance and remark on the role of Ni in hydrotreatment.

Effect of NO2 on N2 O production and NOx emission reduction in NH3 Selective Catalytic Reduction.

With the introduction of increasingly strict emission regulations, reducing nitrogen oxide (NOx ) emissions and nitrous oxide (N2 O) production from diesel engines have become the focus of research. At high temperature, the reaction of NO2 in the catalyst generates the intermediate product NH4 NO3 , which first crystallizes below 300 °C. These crystals tend to block the pores and inhibit the reaction. Subsequently, N2 O is produced through the decomposition of NH4 NO3 , leading to additional pollution. Therefore, the concentration of NO2 has a direct impact on both the NOx conversion efficiency and the generation of N2 O, requiring consideration of the optimal proportion of NO2 in SCR. Considering these two factors, it is concluded that the optimal amount of NO2 varies with temperature. To improve the NOx conversion rate of the Cu-SSZ-13 catalyst at low temperatures and reduce N2 O generation, the optimal NO2 ratio of the Cu-SSZ-13 catalyst under various operating conditions is studied using numerical simulations. As the temperature rises, the optimal NO2 /NOx ratio first increases and then decreases. Under the optimal NO2 /NOx ratio, the NOx conversion rate significantly increases, while N2 O generation decreases considerably. The optimal NO2 /NOx ratio also provides suggestions for the optimization of the DOC-DPF-DCR system.

Unlocking Mixed-Metal Oxides Active Centers via Acidity Regulation for K&SO2 Poisoning Resistance: Self-Detoxification Mechanism of Zeolite-Confined deNOx Catalysts.

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) is an efficient NOx reduction strategy, while the denitrification (deNOx) catalysts suffer from serious deactivation due to the coexistence of multiple poisoning substances, such as alkali metal (e.g., K), SO2, etc., in industrial flue gases. It is essential to understand the interaction among various poisons and their effects on the deNOx process. Herein, the ZSM-5 zeolite-confined MnSmOx mixed (MnSmOx@ZSM-5) catalyst exhibited better deNOx performance after the poisoning of K, SO2, and/or K&SO2 than the MnSmOx and MnSmOx/ZSM-5 catalysts, the deNOx activity of which at high temperature (H-T) increased significantly (>90% NOx conversion in the range of 220-480 °C). It has been demonstrated that K would occupy both redox and acidic sites, which severely reduced the reactivity of MnSmOx/ZSM-5 catalysts. The most important, K element is preferentially deposited at -OH on the surface of ZSM-5 carrier due to the electrostatic attraction (-O-K). As for the K&SO2 poisoning catalyst, SO2 preferred to be combined with the surface-deposited K (-O-K-SO2ads) according to XPS and density functional theory (DFT) results, the poisoned active sites by K would be released. The K migration behavior was induced by SO2 over K-poisoned MnSmOx@ZSM-5 catalysts, and the balance of surface redox and acidic site was regulated, like a synergistic promoter, which led to K-poisoning buffering and activity recovery. This work contributes to the understanding of the self-detoxification interaction between alkali metals (e.g., K) and SO2 on deNOx catalysts and provides a novel strategy for the adaptive use of one poisoning substance to counter another for practical NOx reduction.

Enhancing Water Tolerance and N2 Selectivity in NH3-SCR Catalysts by Protecting Mn Oxide Nanoparticles in a Silicalite-1 Layer.

Mn-based catalysts are promising candidates for eliminating harmful nitrogen oxides (NOx) via selective catalytic reduction with ammonia (NH3-SCR) due to their inherent strong redox abilities. However, poor water tolerance and low N2 selectivity are still the main limitations for practical applications. Herein, we succeeded in preparing an active catalyst for NH3-SCR with improved water tolerance and N2 selectivity based on protecting MnOx with a secondary growth of a hydrophobic silicalite-1. This protection suppressed catalyst deactivation by water adsorption. Interestingly, impregnating MnOx on MesoTS-1 followed by silicalite-1 protection allowed for a higher dispersion of MnOx species, thus increasing the concentration of acid sites. Consequently, the level of N2O formation is decreased. These improvements resulted in a broader operating temperature of NOx conversion and a modification of the NH3-SCR mechanism. Diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that unprotected Mn/MesoTS-1 mainly followed the Eley-Rideal mechanism, while Mn/MesoTS-1@S1 followed both Langmuir-Hinshelwood and Eley-Rideal mechanisms.