A novel freeze-drying steam-assisted crystallization protocol fabricates multistage porous ZSM-5 zeolites, incorporating multiscale channel architectures (0.5 nm-10 mu m) to alleviate mass-transfer constraints inherent in conventional microporous zeolites. This eco-friendly, scalable methodology pioneers catalytic polyethylene pyrolysis by augmenting catalytic activity, achieving exceptional monocyclic aromatic hydrocarbons selectivity of 97.3 % and BTEX (benzene/toluene/ethylbenzene/xylene) selectivity of 94.9 %, surpassing commercial and nanosized counterparts. Demonstrating operational stability, the catalyst maintains 23.7-30.0 wt% oil yields and 71.3-74.9 % BTEX selectivity, attributed to enhanced intracrystalline diffusivity that mitigates coke deposition. Computational simulations reveal that multistage porous structures facilitate reactant diffusion and regulate C-C bond cleavage via steric confinement, synergizing with acid sites to promote cracking-aromatization cascades. Life-cycle analysis confirms the technology's economic superiority over conventional pyrolysis through improved product value and reduced separation costs. This advancement establishes a sustainable paradigm for zeolite synthesis and plastic-to-aromatics conversion, aligning with circular economy goals.

Hydroisomerization plays a significant role in improving the low-temperature fluidity of diesel fuel, producing gasoline with a high-octane number, and lowering the pour point of lubricating oil. Therefore, the development of hydroisomerization catalysts is crucial. Herein, two steps are utilized to this end for synthesizing a hierarchical ZSM-48 zeolite (Z48-0.2CA) continuously: the growth modifier cetyltrimethylammonium bromide (CTAB) is utilized first to limit the growth of ZSM-48 crystals and introduce rich intercrystalline mesopores. Then, the nano-ZSM-48 crystals are treated with citric acid to form intracrystalline mesopores. Furthermore, the acidity of the synthesized Z48-0.2CA is effectively reduced. The test of the catalytic performance of n-hexadecane hydroisomerization over the Pd-loaded Pd/Z48-CA bifunctional catalysts demonstrates that the Pd/Z48-0.2CA catalysts prepared with a CTAB/Al mole ratio of 0.2 and treated with citric acid has the highest iso-hexadecane yield of 68.8 %, which is 12.0 % greater at lower reaction temperature in contrast to the conventional microporous Pd/Z48 catalyst because of the improved diffusion of hydrocarbons in the channel of the zeolite and the increased CPd/CH+ value. Therefore, the use of a growth modifier and acid treatment for the synthesis of hierarchical zeolite effectively enhances the catalytic performance of bifunctional catalysts.

The development of hydrodeoxygenation catalysts with outstanding catalytic performance and stability is key to improving the performance of hydrodeoxygenation reactions. In this work, the bimetallic Ni-Mo/ZSM-22 catalysts supported on ZSM-22 zeolite were prepared for the methyl palmitate (MP) hydrodeoxygenation. Owing to the formation of Ni-MoOx species, electron transfer between metallic Ni and MoOx species effectively enhances metal dispersion, promotes the H-spillover effect and increases the number of oxygen vacancies. Among all catalysts, the 5Ni5Mo/ZSM-22 catalysts with Ni and Mo loadings of 5 wt% respectively exhibit the best catalytic performance. According to the test results, the total yield of isomer C15 and C16 is 91.88%. Compared with the 10Ni/ZSM-22 catalyst with 10 wt% Ni loading, the introduction of MoOx species results in a higher C16/C15 ratio, indicating that hydrodeoxygenation occurs mainly via the direct deoxygenation pathway. A long-term test of 100 h demonstrates the excellent catalytic stability of the 5Ni5Mo/ZSM-22 catalyst, which originates from more stable deposited metal nanoparticles. Therefore, the formation of Ni-MoOx species significantly improves the catalytic behaviour for methyl palmitate hydrodeoxygenation, which is critical for upgrading the fuel quality of second-generation biodiesel.

ABSTRACT Although covalent organic frameworks (COFs) have garnered significant attention as versatile scaffolds in photocatalysis, it is constrained by the sluggish charge‐carrier dissociation inherent to organic semiconductors. Moreover, how subtle changes in atomic topology within an otherwise similar framework translate into macroscopic optoelectronic behavior remains insufficiently understood. Herein, we demonstrate that precise nitrogen‐site isomerism within the framework backbone serves as a critical lever to manipulate exciton dynamics. By synthesizing two regioisomeric vinylene‐linked COFs, PzDA‐TMT‐COF (pyrazine‐based, para‐N) and DzDA‐TMT‐COF (pyridazine‐based, ortho‐N), we reveal that a subtle translocation of nitrogen atoms induces a profound divergence in charge‐separation efficiency. Despite identical chemical compositions and porosities, the para‐configured PzDA‐TMT‐COF delivers a significantly enhanced hydrogen evolution rate of 13.2 mmol g −1 h −1 , significantly outperforming its ortho‐analogue. It is elucidated that this “atomic editing” fundamentally reshapes the intramolecular potential landscape: the para‐substitution maximizes donor–acceptor polarization and minimizes exciton binding energy, thereby accelerating the transition from bound excitons to free charge carriers. Our findings establish a rigorous structure–activity relationship, highlighting that rational control over heteroatom placement is a paramount design principle for organic photocatalysts.

The high-value utilization of coal tar represents one of the most promising approaches to addressing global energy shortages and mitigating environmental degradation. Herein, four types of Ni-W-La-HZSM-5/gamma-Al2O3 composite catalysts were rationally designed using the silica sol encapsulation method (HZSM-5 &gamma-Al2O3), the liquid phase coating method (HZSM-5#gamma-Al2O3), the polyelectrolyte treatment method (HZSM-5 gamma-Al2O3), the template-treatment method (HZSM-5@gamma-Al2O3), respectively, for the directly conversion of alpha-naphthol from coal tar into light aromatics. 1Ni-5W-0.2La combining with HZSM-5@gamma-Al2O3 catalyst could reach 42.39% for the selectivity of BTEXN (SBTEXN), which was higher than those of other composite catalysts, due to its rich mesoporous structure and less few weak surface acid sites. The SBTEXN becomes largely unaffected by changes in the content of medium strong acid to the weak acid ratio (CMSA/CWA), when the volume ratio of mesopore to micropore (Vmeso/Vmicro) reaches a certain threshold. Furthermore, higher ratios of Vmeso/Vmicro and CMSA/CWA are beneficial for enhancing the conversion rate of alpha-naphthol (R alpha-naphthol). The as-synthesized capsule-like catalyst opens a new pathway for the efficient conversion of alpha-naphthol into BTEXN and offers a convenient method for modulating the pore structure and surface acid properties of HZSM-5/gamma-Al2O3.

Piezoresistive sensors are widely used in a variety of fields due to their high sensitivity, low cost, and ease of integration. As technology advances, new materials and structures are designed to continue driving the improvement of piezoresistive sensor performance and the expansion of their fields of application. A unique functionalized multi-walled carbon nanotube (MWNTs-g-TPU) with thermoplastic polyurethane (TPU) chains was prepared by chemical grafting in this study. Conductive composites with piezoresistive properties were prepared by the solution blending method with TPU as the polymer matrix and MWNTs-g-TPU as the reinforcing filler. MWNTs-g-TPU interacts more strongly with TPU than non-functionalized MWNTs, significantly improving the mechanical, electrical, and piezoresistive properties of MWNTs-g-TPU/TPU composites. A sensor was fabricated using a 5.0 wt% MWNTs-g-TPU/TPU composite, demonstrating high sensitivity to external pressure. The composite material exhibited a stable piezoresistive response after multiple cycles, which indicates its great potential in the piezoresistive sensor field.

ZSM-48 shows excellent performance in shape selective catalysis, especially in hydroisomerization reaction. However, adjusting the acidity of ZSM-48 and improving the synergy of acidic and metal sites are still major challenges in the application of ZSM-48 in hydroisomerization reaction. The dispersing Nb species on support can better utilize the active Nb species and regulate support surface acidity. In this paper, we develop a new route to regulate ZSM-48 surface acidity through Nb modified. The different Nb modified ZSM-48 is prepared under mild conditions and is characterized by physico-chemical characterization techniques such as XRD, N2 physisorption, NH3-TPD, SEM, Py-IR. Owing to its unique acidity, Nb-modified Pt/ZSM-48 exhibits better performance on the hexadecane hydroisomerization compared with Pt/ZSM-48. The selectivity of i-C16 can reach 87 wt% over Pt/ 20Nb/ZSM-48. The addition of Nb not only improves i-C16 selectivity but also enhances the stability of the catalyst. Our results provide a facile strategy to adjust the surface acidity of ZSM-48 as solid acids for catalytic applications.

Hierarchically structured high-silica ZSM-5 nanozeolites with an average particle size of about 115 nm and abundant inter/intra-crystal mesopores were successfully synthesized via a new combination of dry-gel crystallization (DGC) and subsequent alkali-etching treatment. The alkali-etching process effectively introduced auxiliary intracrystal mesopores into the nanozeolite precursors, significantly increasing the specific surface area and total pore volume while maintaining appropriate surface acidity, which had been confirmed by comprehensive characterizations, e.g., XRD, N2 sorption isotherms, SEM, TEM, NMR, ICP-OES, and NH3-TPD. Benefiting from the developed three-dimensional interconnected micro/mesoporous structure, the resultant nanoZSM-5(200)_D catalyst exhibited superior performance in the methanol-to-propylene (MTP) reaction. It achieved 46% propylene selectivity and an exceptionally prolonged catalyst lifetime for 90% methanol conversion of 224 h (t 90), which is approximately 3 times and 16 times that of the nanoZSM-5(200) precursor and purely microporous ZSM-5(200) counterpart, respectively. Additionally, the universality of the here-reported two-step procedure has also been proven, which offers a new choice for preparation of high-performance hierarchically structured zeolite catalysts.

The development of highly effective bifunctional catalysts for n-hexadecane hydroisomerization is still essential to produce second-generation biodiesel. Herein, a Pt-Pd/ZSM-22-G (abbreviated as Pt-Pd/Z22-G) bimetallic catalyst was prepared by employing a room temperature electron reduction (RTER) method with glow discharge as the electron source. As a contrast, a series of Pt/Z22-H, Pd/Z22-H and Pt-Pd/Z22-H catalysts were prepared by the conventional hydrogen reduction method. The Pt-Pd/Z22-G catalyst reveals more exposed metal sites, larger CMe/CH+ values and an enhanced distribution of Pt-Pd(111) facets compared with the Pt/Z22-H, Pd/Z22-H and Pt-Pd/Z22-H catalysts. These modifications are originated from the stronger electron interactions and the smaller metal nanoparticles because of the effects of highly energetic reducing electrons. The n-hexadecane hydroisomerization results show that the iso-hexadecane yield over the Pt-Pd/Z22-G catalyst is 82.9%, which is the highest among four investigated catalysts in this work. This phenomenon occurs because more exposed Pt-Pd(111) facets and larger CMe/CH+ ratios are beneficial for the adsorption and hydrogenation of iso-alkene intermediates at metal sites to increase the iso-alkanes yield based on density functional theory (DFT) calculations. Furthermore, the iso-alkanes yield over the Pt-Pd/Z22-G catalyst also keeps steady after long-term tests for 120 h because of the limited metal aggregation and carbon deposition.

Interfacial solar steam generation (ISSG) has recently received much attention as a low-carbon-footprint and high-energy-efficient strategy for seawater desalination and wastewater treatment. However, achieving the goals of a high evaporation rate, ecofriendliness, and high tolerance to salt ions in brine remains a bottleneck. Herein, a novel hydrogel-based evaporator for effective solar desalination was synthesized on the basis of sodium alginate (SA) and carboxymethyl chitosan (CMCS) incorporating a carbon nanotube (CNT)-wrapped melamine sponge (MS) through a simple dipping-drying-cross-linking process. The hydrogel-based evaporator reaches a high evaporation rate of 2.18 kg m-2 h-1 in 3.5 wt % brine under 1 sun irradiation. Furthermore, it demonstrated excellent salt ion rejection in high-concentration salt water. Simultaneously, it exhibits excellent purification functionality toward heavy metals and organic dyes. This study provides a simple and efficient strategy for seawater desalination and wastewater treatment.

The ZSM-12 zeolite has attracted attention as the promising acid component of bifunctional catalysts for the n -alkane hydroisomerization because of its large size of micropore openings (0.57 nm × 0.61 nm) with 12-membered-ring and one-dimensional channels. However, the larger crystal size and stronger Brønsted acid strength of microsized ZSM-12 zeolite will lead to cracking of iso -olefin intermediates and decrease the iso -alkane yield. In this study, ZSM-12 zeolite samples partially and completely isomorphously substituted with gallium ([Ga,Al]Z12 and GaZ12) were in situ synthesized. The characteristic results indicate that isomorphous substitution by Ga can effectively reduce the crystal size to increase the mesoporosity and weaken the Brønsted acidity of the [Ga,Al]Z12 and GaZ12 samples. In addition, bifunctional catalysts with more appropriate metal-acid proximity for n -hexadecane hydroisomerization were prepared by mixing the 0.6Pd/A sample with 0.6 wt.% Pd loaded on γ-Al2O3 and the ZSM-12, [Ga,Al]Z12 and GaZ12 samples, respectively. The 0.3Pd/A-[Ga,Al]Z12 and 0.3Pd/A-GaZ12 catalysts both promote the maximum iso -hexadecane yield and distribution of multi-branched iso -hexadecane products due to their enhanced mesoporosity, reduced Brønsted acid strength, increased CPd/CH+ ratios and improved metal-acid balance. Especially for the 0.3Pd/A-GaZ12 catalyst, when the n -hexadecane conversion is 93.5%, the maximum iso -hexadecane yield reaches 80.6%, and the proportion of multi-branched iso -hexadecane products is 64.6%, which are both the highest among all investigated catalysts. Accordingly, Ga isomorphous substitution is an effective strategy to develop the efficient bifunctional catalysts for hydroisomerization.

The ZSM-22 zeolite has become an effective support for the hydroisomerization of n-alkanes due to its onedimensional pore structure, good hydrothermal stability and simple synthesis process. However, the diffusion resistance of hydrocarbons in the microporous channel still limits the further industrial application of the traditional microporous ZSM-22 zeolites. To overcome the diffusion limitation, the different amounts of polyhexamethylene biguanide (PHMB) was added into the initial gel as the only template instead of 1,6-diaminohexane (DAH) to synthesize a series of hierarchcal ZSM-22 zeolites (Z22-xP), and the corresponding Pd/ZSM-22 catalysts with 0.5 wt% Pd loading were then prepared for n-hexadecane hydroisomerization in this work. The characteristic results show that, the Z22-xP samples exhibit improved mesoporous volume and external surface than those of the traditional microporous Z22 -D sample. Additionally, the Z22-xP samples also demonstrates significantly lower Bronsted acid density in comparison with the microporous Z22 -D sample because of the proportion decrease of T1 -T3 skeleton Al atoms. The catalytic tests results indicate that the employment of PHMB instead of DAH can effectively promote the catalytic performance. The Pd/Z22-0.002P catalyst reveals the highest iso-hexadecane yield of 76.6 % among all catalysts. Therefore, this work provides a more convenient and effective way for the development of potential bifunctional catalysts with promoted catalytic performance.

Rheumatoid arthritis (RA) is a systemic immune-mediated disease characterized by joint inflammation and destruction. The disease typically affects small joints in the hands and feet, later progressing to involve larger joints such as the knees, shoulders, and hips. While the reasons for these joint-specific differences are unclear, distinct epigenetic patterns associated with joint location have been reported. In this study, we evaluated the unique epigenetic landscapes of fibroblast-like synoviocytes (FLS) from hip and knee synovium in RA patients, focusing on the expression and regulation of Homeobox (HOX) transcription factors. These highly conserved genes play a critical role in embryonic development and are known to maintain distinct expression patterns in various adult tissues. We found that several HOX genes, especially HOXD10, were differentially expressed in knee FLS compared with hip FLS. Epigenetic differences in chromatin accessibility and histone marks were observed in HOXD10 promoter between knee and hip FLS. Histone modification, particularly histone acetylation, was identified as an important regulator of HOXD10 expression. To understand the mechanism of differential HOXD10 expression, we inhibited histone deacetylases (HDACs) with small molecules and siRNA. We found that HDAC1 blockade or deficiency normalized the joint-specific HOXD10 expression patterns. These observations suggest that epigenetic differences, specifically histone acetylation related to increased HDAC1 expression, play a crucial role in joint-specific HOXD10 expression. Understanding these mechanisms could provide insights into the regional aspects of RA and potentially lead to therapeutic strategies targeting specific patterns of joint involvement during the course of disease.

Utilizing inexhaustible solar energy and seawater resources, solar-driven interfacial steam generation (SSG) offers a straightforward and efficient solution to freshwater scarcity and wastewater reuse. The present study provides a seawater desalination strategy through carbon nanotubes/thermoplastic polyurethane/polydimethylsiloxane (CNTs/TPU/PDMS) composite sponge. This material is engineered for enhanced solar-driven interfacial evaporation, explicitly targeting the mitigation of salt deposition which is detrimental to the efficiency of traditional solar evaporator. Using a commercially available melamine sponge as the base structure, an impregnation-drying technique was adopted for the optimization of light absorber CNTs. The formation of a Janus structure by incorporating a composite layer of PDMS, melamine sponge, and CNTs enhances the salt resistance and water transport capability of the evaporator. Owing to light absorption properties and Janus structure, a maximal evaporation rate of 5.02 kg m− 2 h− 1, with a sustained average rate of 4.8 kg m− 2 h− 1, as well as proficient ion rejection and organic dye purification efficacy was achieved.

The hydroisomerization of long-chain n -alkanes proves to be an effective approach for the production of renewable second-generation biodiesel, and the development of bifunctional catalysts with synergistic effect between metal and acidic sites was the key to increase the yield of iso -alkanes. Herein, novel hierarchical SAPO31 nanoparticles (S31 -H i ) were synthesized with varied amounts of the growth inhibitor 1-octyl-3-methylimidazolium chloride ionic liquid (OMIMCl IL) in a one-stage crystallization, and a proposed formation process was discussed. The 0.1Pd/S31-H i bifunctional catalysts were prepared by loading only 0.1 wt% Pd based on the S31H i by wetness impregnation method and their catalytic performances were evaluated for the hydroisomerization of n -hexadecane. The catalytic performance of 0.1Pd/S31-H based on the S31 -H synthesized by adding an appropriate amount of OMIMCl ILs was significantly improved, which can be attributed to the enhanced diffusion originating from its smaller crystal size, higher Pd dispersion, and larger C Pd /C H + value, which was beneficial for achieving synergistic catalysis. The iso -hexadecane yield of 77.8% and proportion of multibranched isomers of 51.5%, and catalytic stability within 100 h time on stream was obtained over the 0.1Pd/ S31 -H at n -hexadecane conversion of 89.3%. These catalysts have application potential for the production of second-generation clean biodiesel with excellent low temperature fluidity.

Solar-driven steam generation membranes have garnered increasing attention for freshwater production. Nonetheless, the adverse impact of salt accumulation on membrane surfaces directly undermines the efficacy of solar evaporation. In this work, one type of composite membrane comprised of carbon nanotubes (CNTs)-styrene-ethylene-butadiene-styrene (SEBS) was fabricated by modified vapor phase pore-forming technique. Through the grafting of maleic anhydride (MAH), the CNTs-SEBS-MAH composite membrane was successfully hydrolyzed. As a consequence, the composite membrane exhibits evaporation rate as high as 1.28 kg m(-2) h(-1 )under one sun solar irradiation, accompanied by an outstanding solar vapor conversion efficiency of 87.5%. In addition, the fabricated composite membrane has high resistance to salt accumulation, as well as self-cleaning capability. This work provides a route for manufacturing hydrophilic polymer composite membrane towards solar energy driven seawater desalination.

Propylene, as an important chemical basic raw material, is in increasing demand year by year. Au/ZSM-5 as a bifunctional catalyst exhibits excellent catalytic performance and propylene selectivity in low-temperature catalytic cracking to propylene reaction. The smaller Au size (5.8-8.2 nm) is prepared through deposition precipitation, but the characteristics of support will also undergo partial changes at the same time. The support characteristics have been confirmed to have changed through a series of characterizations. The propylene yield could reach 42% at 410 oC when the value of CH/CM is 40. A proposed metal-acid synergistic catalysis mechanism for octane catalytic cracking to produce propylene is elucidated. The higher propylene yield is attributed to the synergy between acid sites and Au species. Our research results provide a reasonable and effective correlation between the metal-acid activity of bifunctional catalysts and catalytic activity in catalytic cracking reactions to produce propylene.

In recent years, solar energy interfacial evaporation technology has been extensively explored for seawater desalination and wastewater treatment. However, salt accumulation and complex fabrication of evaporator largely constrains the applications of this technology in practice. Here, one type of interpenetrating polymer network hydrogel composing of agarose (AG) and polyvinylpyrrolidone (PVP) using polypyrrole (PPy) as the light absorbent was fabricated via "hot-ice" template method, which was featured with pitted-surface and microchannels structure. The evenly arranged pits on the surface of the hydrogel can absorb the sunlight as much as possible and convert it into heat energy, improving the efficiency of photothermal absorption. The water channels generated by the formation of CaCl2 center dot 6H(2)O crystals can transport water from the bottom to the evaporation interface elevating the transmission rate and accelerating the exchange of gradient salt concentration. As consequences, excellent salt resistance of the hydrogel can be obtained, achieving seawater evaporation rate as high as 3.2 kg m(-2) h(-1). In addition, the outstanding ion rejection performance, strong acid/alkali purification capability, and good treatment capacity for heavy metal ions and dye wastewater were also demonstrated.

The development of highly effective metal–zeolite bifunctional catalysts for the hydroisomerization of n -alkanes is a paramount strategy to produce second-generation biofuels with high quality. In this study, polyhexamethylene biguanide hydrochloride (PHMB) is precisely added to the initial gel to synthesize nanosized ZSM-23 zeolites (Z23- x PH). Due to orientation adsorption and steric hindrance effects of PHMB, each sample of Z23- x PH demonstrates enhanced mesoporosity in comparison with the conventional Z23-C zeolite. Furthermore, the Brønsted acid density of the Z23- x PH samples is also significantly reduced due to a reduction in the distribution of framework Al at T2–T5 sites. The corresponding Pd/23-C and Pd/Z23- x PH bifunctional catalysts with 0.5 wt% Pd loading for n -hexadecane hydroisomerization are prepared by incorporating ZSM-23 zeolites as acid supports. According to the catalytic test results, the suitable addition of PHMB can effectively promote the iso -hexadecane yield. The Pd/Z23-2PH catalyst with an n PHMB / n Si molar ratio of 0.002 demonstrates the highest maximum iso -hexadecane yield of 74.1% at an n -hexadecane conversion of 88.3%. Therefore, the employment of PHMB has provided a simple route for the development of highly effective Pd/ZSM-23 catalysts for n -alkane hydroisomerization.

One-pot hydroprocessing of vegetable oils to the corresponding fatty alcohols or long-chain alkanes is highly demanded. In this work, we present results on the hydroconversion of sunflower oil in a batch stirred reactor using either CuZn oxide catalysts with different Cu/Zn ratios prepared by the calcination of hydroxycarbonate precursors or bifunctional catalysts prepared by mixing the CuZn oxides with a commercial HBEA zeolite. The characteristics of the CuZn samples were determined by N2 adsorption, N2O chemisorption, and XRD analysis. The influence of CuZn catalysts composition, reaction temperature (210-270 degrees C), hydrogen pressure (6.0-14.0 MPa), and catalyst loading on the conversion of sunflower oil was investigated. Under optimized conditions of 250 degrees C and 10 MPa H2, a nearly 89 % octadecanol yield was obtained after 3 h of sunflower oil hydroconversion using a catalyst with the Cu/Zn atomic ratio of 1. This Cu1Zn catalyst also confirmed its high stability in the production of fatty alcohols without any loss in activity after its reuse in three consecutive reaction cycles. The addition of HBEA to the Cu1Zn catalyst under the same reaction conditions led to the formation of hydrocarbons. It allowed concluding that metallic Cu species in the bifunctional catalysts were active sites for the hydrogenolysis of triglycerides to fatty alcohols and double bonds hydrogenation, while the acidic sites of HBEA were responsible for the dehydration of the produced alcohols affording hydrocarbons. As a result, n-octadecane with the yield of 65 % and a mixture of C18 alkenes and isoalkanes with the yield of 18 % were produced over the CuZn-HBEA catalyst under the same reaction conditions. It was shown that the addition of Pd to HBEA led to an increase in sunflower conversion from 90 % to 97 %.