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Zeolites are a promising support for Pd catalysts in lean methane (CH4) combustion. Herein, three types of zeolites (H-MOR, H-ZSM-5 and H-Y) were selected to estimate their structural effects and deactivation mechanisms in CH4 combustion. We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states. Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity, with activation energy (Ea) at 73 kJ/mol, while Pd/H-ZSM-5 displayed the highest turnover frequency (TOF) at 19.6 × 10-3 sec-1, presumably owing to its large particles with more step sites providing active sites in one particle for CH4 activation. Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ ions on ion-exchange sites yielded the lowest apparent activity and TOF. Furthermore, Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition, but introducing 3 vol.% H2O caused the CH4 conversion rate on Pd/H-MOR drop from 100% to 63% and that on Pd/H-ZSM-5 decreased remarkably from 82% to 36%. The former was shown to originate from zeolite structural dealumination, and the latter principally owed to Pd aggregation and the loss of active PdO.

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In this study, we investigated the deactivation kinetics and mechanism of N-F-TiO2/SiO2 nanopowder as a model photocatalyst for the purpose of facilitating the photocatalytic degradation of acrylonitrile (AN) in aqueous environment. Prior research has already displayed the proficient degradation of AN through the utilization of N-F-TiO2/SiO2 catalysts, revealing a degradation efficiency of 81.2% within a span of 6 min at an initial AN concentration of 10 mg/L. Multiple variables including the initial AN concentration, illumination intensity, and initial pH value were extensively analyzed during the degradation process. The kinetics of photocatalytic degradation of AN, facilitated by the N-F-TiO2/SiO2 photocatalyst, were modeled by fitting the pseudo first-order reaction kinetics to each individual factor. Furthermore, the adverse effect of catalyst poisoning during the photocatalytic breakdown of AN using the N-F-TiO2/SiO2 photocatalyst was analyzed through a range of different techniques including SEM, XPS, BET, XRD, TG, and NH3-TPD. The incorporation of findings from these diverse techniques revealed that, the primary factors contributing to the photocatalyst's poisoning were as follows: (i) During the degradation process, the build-up of intermediate molecules on active sites hindered their functionality, leading to a decrease in the efficiency of the photocatalytic reaction, (ii) Carbonaceous deposits formed when the catalyst's pore structure was obstructed by pollutants or intermediate products that had not undergone timely photocatalytic breakdown and (iii) The persistent erosion of active sites due to hydraulic forces resulted in inadequate performance of the N-F-TiO2/SiO2 photocatalyst in aqueous solutions. A comprehensive analysis of the deactivation kinetics was conducted, deciding in the formulation of a detailed poisoning mechanism for the N-F-TiO2/SiO2 photocatalyst. Additionally, we explored the catalysts regeneration, involving thermal treatment, ultrasonic irradiation, and catalyst reloading. This study not only advances our insight into the waning performance of catalysts in aqueous media but also establishes a conceptual framework for extrapolating analogous deactivation dynamics in other catalysts, grounded in precedent experimental knowledge. This research contributes to the development of a deactivation model for catalysts in the aqueous environment, based on existing experimental research, providing a theoretical framework for understanding the deactivation process of photocatalysts.

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The competitive adsorption behavior, the synergistic catalytic reaction, and deactivation mechanisms under double components of sulfur-containing volatile organic compounds (VOCs) are a bridge to solve their actual pollution problems. However, they are still unknown. Herein, simultaneous catalytic decomposition of methyl mercaptan (CH3SH) and ethyl mercaptan (C2H5SH) is investigated over lanthanum (La)-modified ZSM-5, and kinetic and thermodynamic results confirm a great difference in the adsorption property and catalytic transformation behavior. Meanwhile, the new synergistic reaction and deactivation mechanisms are revealed at the molecular level by combining with in situ diffuse reflectance infrared spectroscopy (in situ DRIFTS) and density functional theory (DFT) calculations. The CH3CH2* and SH* groups are presented in decomposing C2H5SH, while the new species of CH2*, active H* and S*, instead of CH3* and SH*, are proved as the key elementary groups in decomposing CH3SH. The competitive recombining of SH* in C2H5SH with highly active H* in dimethyl sulfide (CH3SCH3), an intermediate in decomposing CH3SH, would aggravate the deposition of carbon and sulfur. La/ZSM-5 exhibits potential environmental application due to the excellent stability of 200 h and water resistance. This work gives an understanding of the adsorption, catalysis, reaction, and deactivation mechanisms for decomposing double components of sulfur-containing VOCs.

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With the looming goal of carbon neutrality and increasingly stringent environmental protection policies, gas purification in coal-fired power plants is becoming more and more intense. To achieve the NOx emission standard when coal-fired power plants are operating at full load, wide-temperature denitrification catalysts that can operate for a long time in the range of 260-420°C are worthy of study. This review focuses on the research progress and deactivation mechanism of selective catalytic reduction (SCR) denitration catalysts applied to a wide temperature range. With the increasing application of SCR catalysts, it also means that a large amount of spent catalysts is generated every year due to deactivation. Therefore, it is necessary to recycle the wide temperature SCR denitration catalyst. The challenges faced by wide-temperature SCR denitration catalysts are summarized by comparing their regeneration processes. Finally, its future development is prospected.

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The ß 2 adrenergic receptor (ß2AR), one of important members of the G protein coupled receptors (GPCRs), has been suggested as an important target for cardiac and asthma drugs. Two replicas of Gaussian accelerated molecular dynamics (GaMD) simulations are performed to explore the deactivation mechanism of the active ß2AR bound by three different substrates, including the agonist (P0G), antagonist (JTZ) and inverse agonist (JRZ). The simulation results indicate that the Gs protein is needed to stabilize the active state of the ß2AR. Without the Gs protein, the receptor could transit from the active state toward the inactive state. During the transition process, helix TM6 moves toward TM3 and TM5 in geometric space and TM5 shrinks upwards. The intermediate state is captured during the transition process of the active ß2AR toward the inactive one, moreover the changes in hydrophobic interaction networks between helixes TM3, TM5, and TM6 and the formation of a salt bridge between residues Arg3.50 and Glu6.30 drive the transition process. We expect that this finding can provide energetic basis and molecular mechanism for further understanding the function and target roles of the ß2AR.

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Small structural alterations of the purine/pyrimidine core have been related to important photophysical changes, such as the loss of photostability. Similarly to canonical nucleobases, solute-solvent interactions can lead to a change in the excited state lifetimes and/or to the interplay of different states in the photophysics of these modified nucleobases. To shed light on both effects, we here report a complete picture of the absorption spectra and excited state deactivation of deoxyguanosine and its closely related derivative, deoxydeazaguanosine, in water and methanol through the mapping of the excited state potential energy surfaces and molecular dynamics simulations at the TD-DFT level of theory. We show that the N by CH exchange in the imidazole ring of deoxyguanosine translates into a small red-shift of the bright states and slightly faster dynamics. In contrast, changing solvent from water to methanol implies the opposite, i.e., that the deactivation of both systems to the ground state is significantly hindered.

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Mn-based catalysts are expected to be applied for removing NOx due to its excellent low-temperature activity. However, the practical use of these catalysts is extremely restricted with the co-poisoning of alkali metal and SO2 in the flue gas. Here the MnO2/TiO2 catalyst was employed to elucidate the co-poisoning mechanisms of K and SO2 for the low temperature selective catalytic reduction (SCR) of NO. The physicochemical properties of catalysts under different toxicity conditions were studied by experiments. The adsorption of NH3, SO2, NO, and K on active component (MnO2) and support (TiO2) was studied by density functional theory. This work unravels a promotion effect of support on the alkali and sulfur resistance. The SO2&K co-poisoning catalyst had higher SCR activity than the SO2-poisoned and K-poisoned catalyst alone. For a single toxic condition: (1) SO2 was preferentially bonded with the terminated O site of MnO2 inhibiting the dehydrogenation of NH3 and redox cycle. (2) The presence of Lewis base (K atom) on the catalyst decreased the binding energy of a Lewis base (NH3) and hindered the adsorption of NH3. For the synergistic effect of K and SO2, the majority of K adsorbed on the support (TiO2) lead to increase alkalinity, which could promote the adsorption of SO2 on the TiO2 and reduce the toxicity of the active component (MnO2).

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Up to now, the member of zeolite family has expanded to more than 230. However, only little part of them have been reported as catalysts used in reactions. Discovering potential zeolites for reactions is significantly important, especially in industrial applications. A carbonylation zeolite catalyst Al-RUB-41 has special morphology and channel orientation. The 8-MR channel of Al-RUB-41 is just perpendicular to its thin sheet, making a very short mass-transfer distance along 8-MR. This specific nature endows Al-RUB-41 with efficient catalytic ability to dimethyl ether carbonylation reaction with beyond 95% methyl acetate selectivity. Compared with the most widely accepted carbonylation zeolite catalysts, Al-RUB-41 behaves a much better catalytic stability than H-MOR and a greatly enhanced catalytic activity than H-ZSM-35. A space-confined deactivation mechanism over Al-RUB-41 is proposed. By erasing the acid sites on outer surface, Al-RUB-41@SiO2 catalyst achieves a long-time and high-efficiency activity without any deactivation trend.

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In this work, γ-Al2O3-supported CuO (c-CuO/Al2O3) materials are successfully synthesized using a novel impregnation-precipitation-decomposition method. The obtained c-CuO/Al2O3 catalyst shows excellent catalytic activities for bisphenol A (BPA) degradation with sodium persulfate (PDS) as an oxidant. Radical quenching tests and electron paramagnetic resonance (EPR) studies indicate that PDS activation is a combined mechanism involving both free radical and nonfree radical pathways. In a continuous large-scale degradation process, about 1.78 L of 20 ppm BPA can be completely removed within 480 min. Although c-CuO/Al2O3 can be deactivated after several reaction cycles, the catalytic activity can be regenerated after simple aerobic calcination. X-ray photoelectron spectroscopy (XPS) and Raman analysis confirm that the deactivation of c-CuO/Al2O3 should be attributed to the conversion of Cu(II) to Cu(I). The aerobic calcination could oxidize Cu(I) back to Cu(II), thus recovering the catalytic activity. In addition, the density functional technology (DFT) and temperature-programmed oxidation (TPD) results reveal that γ-Al2O3 can not only serve as a carrier to anchor the CuO particles but also can adsorb and activate PDS by introducing more basic sites on the surface. c-CuO/Al2O3 has high activity and can be regenerated easily, thus having great potential applications for wastewater treatment.

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Alkylated waste vegetable oil is a versatile intermediate product in the synthesis of bio-based materials. Heterogeneous catalytic condition with high conversion rate in the direct alkylation of waste vegetable oil was reported and the deactivation mechanism of catalyst was revealed. The total exchange capacity, elemental composition and pyrolysis product of catalyst before and after the alkylation reaction were analysed by back titration, elemental analysis, electrospray ionization mass spectrometry, gas chromatography mass spectrometry and pyrolysis-gas chromatography/mass spectrometry, respectively. The results indicated that the metallic and non-metallic (C, H) elements contents of the catalyst have very much increased with great changes in pyrolysis product and a slight decrease in the total exchange capacity. The formation of insoluble polymers through Diels-Alder cycloaddition between triglycerides was proved to be the major factor causing the dysfunction of the catalytic centre. The metal ions from corrosion of the reactor were the minor factor causing about 2.56% loss of the catalytic centre. Moreover, the catalyst was able to maintain high catalytic efficiency when replacing the raw materials with other waste vegetable oil having low concentration of polyunsaturated fatty acids, which is significant for producing not only the aryl fatty acids derivatives but also the bio-based surfactants.

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In this study, the performance of catalytic ozonation in the treatment of bio-treated coking wastewater (BCW) using pilot- and full-scale systems was investigated. Additionally, the removal efficiency of organic pollutants from BCW, the deactivation mechanism of MnxCe1-xO2/γ-Al2O3, and backflushing optimization for in-situ catalyst regeneration, which have not been previously investigated, were analysed. Results of the 12-month pilot scale experiments showed that catalytic ozonation resulted in the effective removal of organic pollutants when backflushing was applied as an in-situ catalyst regeneration strategy. The effluent chemical oxygen demand (COD) content decreased from 150 to 78 mg L-1, and remained below a discharge limitation of 80 mg L-1, and the stable COD removal efficiencies (from 56.0% to 47.9%) indicated that catalyst deactivation, which primarily resulted from the deposition of inorganic salts on the surface of the catalyst that limited interaction between ozone and active sites and/or prevented electrons transfer, was primarily inhibited by backflushing. The catalyst regeneration via in-situ air- and water-backflushing was attributed to the scrubbing, collision, and/or the loosing effect. Additionally, in the full-scale experiment, the catalytic ozonation process with in-situ alternative backflushing exhibited a stable COD removal efficiency (above 45.6%) for 885 days when water- and air-flushing strengths of 10 L m-2 s-1 and 15 L m-2 s-1, respectively, were applied with a 7-day regeneration interval. Therefore, the results of this study provide new insights into catalytic ozonation and support its engineering application in BCW treatment.

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Ozone (O3), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O3 removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O3 removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O3 decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O3 decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O3 decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O3 decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O3 decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O3 decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O3 catalytic decomposition technology are put forward.

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Calcification and deactivation of high rate sludge bed reactors is a common and serious engineering problem in the application of anaerobic bioreactor. In this study, the characteristics and deactivation mechanism of calcified anaerobic granules were investigated. The results showed that the calcium content of calcified anaerobic granules was ten times higher than that of control anaerobic granules. A large part of the calcium accumulated in the center of anaerobic granules in the form of calcite, and a small part of the calcium distributed in the outer layer of anaerobic granules in the form of Ca-P deposit. The calcium core occupied a large space which was available for the functional microorganisms. The calcium salts deposited in the outer layer of granular sludge which led to the significant reduction of macropore volume. The porosity of calcified anaerobic granules decreased by 13% compared with that of control anaerobic granules, causing generally the decline of methanogenic activity (for example, by 13% at influent organic concentration of 6.6 g COD L-1). The substrate gradient created by methanation of organic salts, including organic calcium salts, was deduced to be the driving force of anaerobic granule calcification, while the gradual accumulation of calcium salts in anaerobic granules was deduced to be the dominant factor for the decline of anaerobic granule activity.

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NiFe-based layered double hydroxides (LDHs) are among the most efficient oxygen evolution reaction (OER) catalysts in alkaline medium, but their long-term OER stabilities are questionable. In this work, it is demonstrated that the layered structure makes bulk NiFe LDH intrinsically not stable in OER and the deactivation mechanism of NiFe LDH in OER is further revealed. Both operando electrochemical and structural characterizations show that the interlayer basal plane in bulk NiFe LDH contributes to the OER activity, and the slow diffusion of proton acceptors (e.g., OH- ) within the NiFe LDH interlayers during OER causes dissolution of NiFe LDH and therefore decrease in OER activity with time. To improve diffusion of proton acceptors, it is proposed to delaminate NiFe LDH into atomically thin nanosheets, which is able to effectively improve OER stability of NiFe LDH especially at industrial operating conditions such as elevated operating temperatures (e.g., at 80 °C) and large current densities (e.g., at 500 mA cm-2 ).

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The catalytic cracking upgrading reactions over HZSM-5 of different model compounds of bio-oil have been studied with a self-designed fluid catalytic cracking (FCC) equipment. Typical bio-oil model compounds, such as acetic acid, guaiacol, n-heptane, acetol and ethyl acetate, were chosen to study the products distribution, reaction pathway and deactivation of catalysts. The results showed: C6-C8 aromatic hydrocarbons, C2-C4 olefins, C1-C5 alkanes, CO and CO2 were the main products, and the selectivity of olefins was: ethylene>propylene>butylene. Catalyst characterization methods, such as FI-IR, TG-TPO and Raman, were used to study the deactivation mechanism of catalysts. According to the catalyst characterization results, a catalyst deactivation mechanism was proposed as follows: Firstly, the precursor which consisted of a large number of long chain saturated aliphatic hydrocarbons and a small amount CC of aromatics formed on the catalyst surface. Then the active sites of catalysts had been covered, the coke type changed from thermal coke to catalytic coke and gradually blocked the channels of the molecular sieve, which accelerated the deactivation of catalyst.

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The intramolecular proton transfer reaction of the 2-amino-3-(2'-benzoxazolyl)-quinoline (ABO) and 2-amino-3-(2'-benzothiazolyl)-quinoline (ABT) molecules in both S0 and S1 states at B3LYP/6-311++G(d,p) level in ethanol solvent have been studied to reveal the deactivation mechanism of the tautomers of the two molecules from the S1 state to the S0 state. The results show that the tautomers of ABO and ABT molecules may return to the S0 state by emitting fluorescence. In addition, the bond lengths, angles and infrared spectra are analyzed to confirm the hydrogen bonds strengthened upon photoexcitation, which can facilitate the proton transfer process. The frontier molecular orbitals (MOs) and natural bond orbital (NBO) are also calculated to indicate the intramolecular charge transfer which can be used to explore the tendency of ESIPT reaction. The potential energy surfaces of the ABO and ABT molecules in the S0 and S1 states have been constructed. According to the energy potential barrier of 9.12kcal/mol for ABO molecule and 5.96kcal/mol for ABT molecule, it can be indicated that the proton transfer may occur in the S1 state.

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The effects of typical inorganic impurities on the catalytic conversion of cellulose to ethylene glycol (EG) were investigated, and the mechanism of catalyst deactivation by certain impurities were clarified. It was found that most impurities did not affect the EG yield, but some non-neutral impurities or Ca and Fe ions greatly decreased the EG yield. Conditional experiments and catalyst characterization showed that some impurities changed the pH of the reaction solution and affected the cellulose hydrolysis rate; Ca and Fe cations reacted with tungstate ions and suppressed the retro-aldol condensation. To obtain a high EG yield, the pH of the reaction solution and the concentration of tungstate ions should be respectively adjusted to 5.0-6.0 and higher than 187ppm. For raw biomass conversion, negative effects were eliminated by suitable pretreatments, and high EG yields comparable to those from pure cellulose were obtained.

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