Improving the hydrothermal stability of Al-rich Cu-SSZ-13 zeolite via Pr-ion modification.

Al-rich (Si/Al = 4-6) Cu-SSZ-13 has been recognized as one of the potential catalysts to replace the commercial Cu-SSZ-13 (Si/Al = 10-12) towards ammonia-assisted selective catalytic reduction (NH3-SCR). However, poor hydrothermal stability is a great obstacle for Al-rich zeolites to meet the catalytic applications containing water vapor. Herein, we demonstrate that the hydrothermal stability of Al-rich Cu-SSZ-13 can be dramatically enhanced via Pr-ion modification. Particularly, after high-temperature hydrothermal aging (HTA), CuPr1.2-SSZ-13-HTA with an optimal Pr content of 1.2 wt% exhibits a T80 (temperature window of NO conversion above 80%) window of 225-550 °C and a T90 window of 250-350 °C. These values are superior to those of Cu-SSZ-13-HTA (225-450 °C for T80 and no T90 window). The results of X-ray diffraction Rietveld refinement, electron paramagnetic resonance (EPR) and spectral characterization reveal that Pr ions mainly located in the eight-membered rings (8MRs) in SSZ-13 zeolite can inhibit the generation of inactive CuOx during hydrothermal aging. This finding is further supported by density functional theory (DFT) calculations, which suggest that the presence of Pr ions restrains the transformation from Cu2+ ions in 6MRs into CuOx, resulting in enhanced hydrothermal stability. It is also noted that an excessive amount of Pr ions in Cu-SSZ-13 would result in the production of CuOx that causes the decline of catalytic performance. The present work provides a promising strategy for creating a hydrothermally stable Cu-SSZ-13 zeolite catalyst by adding secondary metal ions.

Exogenous compound bacteria enhance the nutrient removal efficiency of integrated bioremediation systems: Functional genes and microorganisms play key roles.

With the continuous development of intensive mariculture, the application of the integrated bioremediation system of aquaculture wastewater (IBSAW) is increasingly promoted. However, the process and nutrients removal performance of the IBSAW need to be further optimized due to its immature technologies. In this study, exogenous compound bacteria (ECB) were added to IBSAW to investigate its pollutants removal efficiency and the relevant mechanisms. High-throughput sequencing and Geochip gene array were used to analyze the correlation between nutrients and bacteria, and the abundance of N and P cycling genes were quantified. Multivariable statistics, dimensionality reduction analysis, and network analysis were applied to explore the mechanisms of IBSAW operation. The results showed that the nutrients decreased significantly after adding ECB, with the brush treatment group significantly outperforming the ceramsite in removing NO3- and PO43-. Ceramsite has an advantage in removing NO2--N. The addition of ECB and different substrates significantly affected the composition of bacterial communities. The contents of nosZ and nirKS related to denitrification in the treatment groups were significantly higher than those in the control group, and the contents in the brush treatment group were significantly higher than that of ceramsite. The biomarkers Psychroserpens and Ruegeria on the biofilm of the brush treatment group were positively correlated with nirKS, while Mycobacterium, Erythrobacter and Paracoccus, Pseudohaliea in the ceramsite group were positively correlated with nirS and nirK, respectively. Therefore, it is speculated that the ECB significantly promoted the increase of denitrification bacteria by affecting the composition of bacterial communities, and the ECB combined with functional genera improved the efficiency of nutrients removal in the system. This study provided a reference for understanding the process and mechanism of nutrients removal, optimizing the wastewater purification technology of the IBSAW and improving the performance of the system.

InSitu Integrated Fabrication for Multi-Interface Stabilized and Highly Durable Polyaniline@Graphene Oxide/Polyether Ether Ketone Special Separation Membranes.

Special separation membranes are widely employed for separation and purification purposes under challenging operating conditions due to their low energy consumption, excellent solvent, and corrosion resistance. However, the development of membranes is limited by corrosion-resistant polymer substrates and precise interfacial separation layers. Herein, polyaniline (PANI) is employed to achieve insitu anchoring of multiple interfaces, resulting in the fabrication of polyaniline@graphene oxide/polyether ether ketone (PANI@GO/PEEK) membranes. Insitu growth of PANI achieves the adequate bonding of the PEEK substrate and GO separation interface, which solves the problem of solution processing of PEEK and the instability of GO layers. By bottom-up confined polymerization of aniline, it could control the pore size of the separation layer, correct defects, and anchor among polymer, nano-separation layer, and nano-sheet. The mechanism of membrane construction within the confined domain and micro-nano structure modulation is further explored. The membranes demonstrate exceptional stability realizing over 90% rejection in 2 m HCl, NaOH, and high temperatures. Additionally, -membranes exhibit remarkable durability after 240 days immersion and 100 h long-term operation, which display the methanol flux of 50.2 L m-2 h-1 and 92% rejection of AF (585 g mol-1 ). This method substantially contributes to special separation membranes by offering a novel strategy.

Coaxial 3D Printing of Zeolite-Based Core-Shell Monolithic Cu-SSZ-13@SiO2 Catalysts for Diesel Exhaust Treatment.

Core-shell catalysts with functional shells can increase the activity and stability of the catalysts in selective catalytic reduction of NOx with ammoniax . However, the conventional approaches based on multistep fabrication for core-shell structures encounter persistent restrictions regarding strict synthesis conditions and limited design flexibility. Herein, a facile coaxial 3D printing strategy is for the first time developed to construct zeolite-based core-shell monolithic catalysts with interconnected honeycomb structures, in which the hydrophilic noncompact silica serves as shell and Cu-SSZ-13 zeolite acts as core. Compared to a Cu-SSZ-13 monolith which suffers from the interfacial diffusion, the SiO2 shell layer can increase the accessibility of active sites over Cu-SSZ-13@SiO2 , resulting in a 10-20% higher NO conversion at200-550 °C under 300 000 cm3 g-1 h-1 . Meanwhile, a thicker SiO2 shell enhances the hydrothermal stability of the aged catalyst by inhibiting the dealumination and the formation of CuOx . Other representative monolithic catalysts with different topological zeolites as shell and diverse metal oxides as the core can be also realized by this coaxial 3D printing. This strategy allows multiple porous materials to be directly integrated, which allows for flexible design and fabrication of various core-shell monolithic catalysts with customized functionalities.

Unveiling Secondary-Ion-Promoted Catalytic Properties of Cu-SSZ-13 Zeolites for Selective Catalytic Reduction of NOx.

The incorporation of secondary metal ions into Cu-exchanged SSZ-13 zeolites could improve their catalytic properties in selective catalytic reduction of NOx with ammonia (NH3-SCR), but their essential roles remain unclear at the molecular level. Herein, a series of Cu-Sm-SSZ-13 zeolites have been prepared by ion-exchanging Sm ions followed by Cu ions, which exhibit superior NH3-SCR performance. The NO conversion of Cu-Sm-SSZ-13 is nearly 10% higher than that of conventional Cu-SSZ-13 (175-250 °C) after hydrothermal ageing, showing an enhanced low-temperature activity. The Sm ions are found to occupy the six-membered rings (6MRs) of SSZ-13 by X-ray diffraction Rietveld refinement and aberration-corrected scanning transmission electron microscopy. The Sm ions at 6MRs can facilitate the formation of more active [ZCu2+(OH)]+ ions at 8MRs, as revealed by temperature-programmed reduction of hydrogen. X-ray photoelectron spectroscopy and density functional theory (DFT) calculations indicate that there exists electron transfer from Sm3+ to [ZCu2+(OH)]+ ions, which promotes the activity of [ZCu2+(OH)]+ ions by decreasing the activation energy of the formation of intermediates (NH4NO2 and H2NNO). Meanwhile, the electrostatic interaction between Sm3+ and [ZCu2+(OH)]+ results in a high-reaction energy barrier for transforming [ZCu2+(OH)]+ ions into inactive CuOx species, thus enhancing the stability of [ZCu2+(OH)]+ ions. The influence of the ion-exchanging sequence of Sm and Cu ions into SSZ-13 is further investigated by combining both experiments and theoretical calculations. This work provides a mechanistic insight of secondary ions in regulating the distribution, activity, and stability of Cu active sites, which is helpful for the design of high-performance Cu-SSZ-13 catalysts for the NH3-SCR reaction.

Polarity-Dominated Stable N97 Respirators for Airborne Virus Capture Based on Nanofibrous Membranes.

The longevity and reusability of N95-grade filtering facepiece respirators (N95 FFRs) are limited by consecutive donning and disinfection treatments. Herein, we developed stable N97 nanofibrous respirators based on chemically modified surface to enable remarkable filtration characteristics via polarity driven interaction. This was achieved by a thin-film coated polyacrylonitrile nanofibrous membrane (TFPNM), giving an overall long-lasting filtration performance with high quality factor at 0.42 Pa-1 (filtration efficiency: over 97 %; pressure drop: around 10 Pa), which is higher than that of the commercial N95 FFRs (0.10-0.41 Pa-1 ) tested with a flow rate of 5 L min-1 and the 0.26 µm NaCl aerosol. A coxsackie B4 virus filtration test demonstrated that TFPNM also had strong virus capture capacity of 97.67 %. As compared with N95 FFRs, the TFPNM was more resistant to a wider variety of disinfection protocols, and the overall filtration characteristics remained N97 standard.

Three-Dimensional-Printed Core-Shell Structured MFI-Type Zeolite Monoliths for Volatile Organic Compound Capture under Humid Conditions.

Crystalline aluminosilicate zeolites with high sorption capacity and low production cost have been recognized as a promising adsorbent for volatile organic compound (VOC) capture. However, the ubiquitous water vapor in the VOC streams may compete with VOCs during the practical separation process because of the hydrophilic property of aluminosilicate zeolites. Herein, a self-supporting core-shell structured MFI-type zeolite monolith was fabricated by 3D-printing aluminosilicate ZSM-5 zeolites as the core, followed by coating silicalite-1 zeolites as a hydrophobic shell via post-hydrothermal crystallization. Natural sepiolite nanofibers (SNFs) were employed as printing ink additives for reinforcing the mechanical stability of 3D-printed ZSM-5 monoliths. Colloidal silica was also introduced into the printing inks, affording continuous growth of silicalite-1 layers (with a thickness of ∼200 nm) over ZSM-5 crystals. Such core-shell structured MFI-type zeolite monoliths exhibited superior dynamic adsorption performance for toluene at 298 K under humid conditions (relative humidity: 50%), with a saturated adsorption capacity of 44.3 mg/g. This work provides a facile strategy for designing self-supporting zeolite monoliths with core-shell architectures for adsorption/separation and other advanced applications.