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In the area of energy storage and conversion, Metal-Organic Frameworks (MOFs) are receiving more and more attention. They combine organic nature with long-range order and low thermal conductivity, giving them qualities to be potentially attractive for thermoelectric applications. To make the framework electrically conductive so far, thermoelectricity in this class of materials requires infiltration by outside conductive guest molecules. In this study, an in-situ polymerization of conductive polyaniline inside the porous structure of MOF-801 was conducted to synthesize PANi@MOF-801 nanocomposites for thermoelectrical applications. The growth of polyaniline chains of different loadings inside the host MOF matrix generally enhanced bulk electrical conductivity by about 6 orders of magnitude, leading to Seebeck coefficient value of -141 µVK -1 and improved thermal stability. The unusual increase in electrical conductivity was attributed to the formation of highly oriented conductive PANi chains inside the MOF pores, besides host-guest physical interaction, while the Seebeck coefficient enhancement was because of the energy filtering effect of the developed structure. Modulating the composition of PANi@MOF-801 composites by varying the aniline: MOF-801 ratio in the synthesis bath from 2:1 and 1:1 to 1:2 leads to a change in the semiconductor properties from p-type semiconductor to n-type. Among the examined composites with n-type semiconducting properties exhibited the highest ZT value, 0.015, and lowest thermal conductivity, 0.24 Wm -1  K -1 . The synthesized composites have better performance than those recently reported for a similar category of thermoelectric materials related to MOF-based composites., (© 2024. The Author(s).)

Here in, we are reporting the effect of the catalyst particle size on the catalytic activity and product selectivity by understanding the strength of the interaction between the active catalyst and the reactants (CO 2 and H 2 ). In this regard, two catalytic systems having different active catalyst particle sizes and support surface areas were synthesized using metal-organic frameworks (MOF) (MIL-100(Fe)) having two crystal size ranges as sacrificial templates. The active catalyst having smaller nanoparticles exhibited greater chemisorption of hydrogen (Fe-H bond), resulting in heightened selectivity for paraffin due to hydrogenation of re-adsorbed olefins. Conversely, larger nanoparticles showed enhanced chemisorption of CO 2 (Fe-C bond), leading to increased selectivity for olefins (O/P = 0.15). Additionally, a reduction in particle size boosts activity from 24% to 38.7% at 340 °C/20 bar. While, higher particle size enhances the selectivity towards C 5+ from 11.1 to 45.6% at (300 °C/10 bar) and 9.6 to 21.3% at (340 °C/20 bar)., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Aims: Hepatocellular Carcinoma (HCC) is renowned as a deadly primary cancer of hepatic origin. Sorafenib is the drug-of-choice for targeted treatment of unresectable end-stage HCC. Unfortunately, great proportion of HCC patients showed intolerance or unresponsiveness to treatment. This study assesses potency of novel ProTide; SH-PAN-19 against N-Nitrosodiethylamine (DEN)-induced HCC in male Wistar rats, compared to Sorafenib., Main Methods: Structural entity of the synthesized compound was substantiated via FT-IR, UV-Vis, 1 H NMR and 13 C NMR spectroscopic analysis. In vitro, SH-PAN-19 cytotoxicity was tested against 3 human cell lines; hepatocellular carcinoma; HepG-2, colorectal carcinoma; HCT-116 and normal fibroblasts; MRC-5. In vivo, therapeutic efficacy of SH-PAN-19 (300 mg/kg b.w./day) against HCC could be revealed and compared to that of Sorafenib (15 mg/kg b.w./day) by evaluating the morphometric, biochemical, histopathological, immunohistochemical and molecular key markers., Key Findings: SH-PAN-19 was relatively safe toward MRC-5 cells (IC 50  = 307.6 μg/mL), highly cytotoxic to HepG-2 cells (IC 50  = 24.9 μg/mL) and prominently hepato-selective (TSI = 12.35). Oral LD 50 of SH-PAN-19 was >3000 mg/kg b.w. DEN-injected rats suffered hepatomegaly, oxidative stress, elevated liver enzymes, hypoalbuminemia, bilirubinemia and skyrocketed AFP plasma titre. SH-PAN-19 alleviated the DEN-induced alterations in apoptotic, angiogenic and inflammatory markers. SH-PAN-19 produced a 2.5-folds increase in Caspase-9 and downregulated VEGFR-2, IL-6, TNF-α, TGFβ-1, MMP-9 and CcnD-1 to levels comparable to that elicited by Sorafenib. SH-PAN-19 resulted in near-complete pathological response versus partial response achieved by Sorafenib., Significance: This research illustrated that SH-PAN-19 is a promising chemotherapeutic agent capable of restoring cellular plasticity and could stop HCC progression., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

The widespread adoption of wearable, movable, and implantable smart devices has sparked the evolution of flexible, miniaturized power supplies. High-resolution inkjet printing of flexible microsupercapacitor (μSC) electrodes is a fast, inexpensive, and waste-free alternative manufacturing technology. In this work, a 2D birnessite-type manganese dioxide (δ-MnO 2 ) water-based ink is used to print 10-25 layers of δ-MnO 2 symmetrically on a preprinted interdigitated cell consisting of 10 layers of electrochemically exfoliated graphene (EEG). The cell with 10 printed layers of δ-MnO 2 achieved the highest specific capacitance, energy density, and power density of 0.44 mF cm -2 , 0.045 μW h cm -2 , and 0.0012 mW cm -2 , respectively. Since inkjet-printing technology supports μSC manufacturing with parallel/series connectivity, four cells were used to study and improve the potential window and capacitance that can be used to construct μSC arrays as power banks. This work provides the first approach for designing an inkjet-printed interdigitated hybrid cell based on δ-MnO 2 @EEG that could be a versatile candidate for the large-scale production of flexible and printable electronic devices for energy storage.

The design of a highly active Fe-supported catalyst with the optimum particle and pore size, dispersion, loading, and stability is essential for obtaining the desired product selectivity. This study employed a solvothermal method to prepare two Fe-MIL-88B metal-organic framework (MOF)-derived catalysts using triethylamine (TEA) or NaOH as deprotonation catalysts. The catalysts were analyzed using X-ray diffraction, N 2 -physisorption, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, H 2 temperature-programed reduction, and thermogravimetric analysis and were evaluated for the Fischer-Tropsch synthesis performance. It was evident that the catalyst preparation in the presence of TEA produces a higher MOF yield and smaller crystal size than those produced using NaOH. The pyrolysis of MOFs yielded catalysts with different Fe particle sizes of 6 and 35 nm for the preparation in the presence of TEA and NaOH, respectively. Also, both types of catalysts exhibited a high Fe loading (50%) and good stability after 100 h reaction time. The smaller particle size TEA catalyst showed higher activity and higher olefin yield, with 94% CO conversion and a higher olefin yield of 24% at a lower reaction temperature of 280 °C and 20 bar at H 2 /CO = 1. Moreover, the smaller particle size TEA catalyst exhibited higher Fe time yield and CH 4 selectivity but with lower chain growth probability (α) and C 5+ selectivity., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Fischer-Tropsch has become an indispensable choice in the gas-to-liquid conversion reactions to produce a wide range of petrochemicals using recently emerging biomass or other types of feedstock such as coal or natural gas. Herein we report the incorporation of novel Cu nanoparticles with two Fischer-Tropsch synthesis (FTS) catalytic systems, Fe/reduced graphene oxide (rGO) and Fe-Mn/rGO, to evaluate their FTS performance and olefin productivity in two types of reactors: slurry-bed reactor (SBR) and fixed-bed reactor (FBR). Four catalysts were compared and investigated, namely Fe, FeCu 7 , FeMn 10 Cu 7 , and FeMn 16 , which were highly dispersed over reduced graphene oxide nanosheets. The catalysts were first characterized by transmission electron microscopy (TEM), nitrogen physisorption, X-ray fluorescence (XRF), X-ray diffraction (XRD), and H-TPR techniques. In the SBR, Cu enhanced olefinity only when used alone in FeCu 7 without Mn promotion. When used with Mn, the olefin yield was not changed, but light olefins decreased slightly at the expense of heavier olefins. In the FBR system, Cu as a reduction promoter improved the catalyst activity. It increased the olefin yield mainly due to increased activity, even if the CO 2 decreased by the action of Cu promoters. The olefinity of the product was improved by Cu promotion but it did not exceed the landmark made by FeMn 16 at 320 °C. The paraffinity was also enhanced by Cu promotion especially in the presence of Mn, indicating a strong synergistic effect. Cu was found to be better than Mn in enhancing the paraffin yield, while Mn is a better olefin yield enhancer. Finally, Cu promotion was found to enhance the selectivity towards light olefins C2-4. This study gives a deep insight into the effect of different highly dispersed FTS catalyst systems on the olefin hydrocarbon productivity and selectivity in two major types of FTS reactors., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Organophosphate-based pesticides, such as diazinon, are among the most toxic organic contaminants to human and environment. Effective removal of diazinon from contaminated water sources is critical. Zirconium Metal-organic frameworks (Zr-MOFs) are promising candidates for the removal of organic contaminants from wastewater. Herein, we report the adequacy of a bio based Zr-MOF named MIP-202 for the removal of diazinon from water. On the other hand, the use of these materials in powder form is not workable, the development of scalable and economical processes and integrative of these materials onto beads is paramount for industrial processes. Hence, it was reported a scalable, bio aqueous solution-based preparation strategy for Bio Zr-MOF beads production. The composite material exposed identical reactivity under the same ambient parameters compared to powdered material in an aqueous solution. These results signify a critical procedure to an integrated strategy for organophosphates removal using bio-based MOFs, which demonstrates high potential for manufacturing applications such as continued removal of organophosphates from wastewater supplies.

Synthesis of rational nanostructure design of hybrid materials including uniformly growing, stable and highly porous structures have received a great deal of attention for many energy storage applications. In this study, the positive electrode of the uniform distribution of NiCo 2 O 4 nanorods anchored on carbon nanofibers has been successfully prepared by in-situ growth under the hydrothermal process. Whereas, the activated multichannel carbon nanofibers (AMCNFs) have been fabricated via electrospinning followed by alkaline activation as the negative electrode. The crystal phase, morphological structure for the proposed electrode materials were characterized by x-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the electrochemical behaviors were investigated using cyclic voltammetry (CV), galvanostatic charge and discharge (GCD) and electrochemical impedance spectroscopy (EIS) measurements. Compared to the neat CNFs and the pristine NiCo 2 O 4 , the NiCo 2 O 4 @CNFs hybrid electrodes showed better electrochemical performance and achieved a high specific capacitance up to 649 F g -1 at a current density of 3 A g -1 . The optimized NiCo 2 O 4 @CNFs//AMCNFs asymmetric device achieved a high energy density of 38.5 Wh kg -1 with a power density of 1.6 kW kg -1 and possessed excellent recyclability with 93.1% capacitance retention over 6000 charging/discharging cycles. Overall, the proposed study introduces a facile strategy for the robust design of hybrid structured as effective nanomaterials based electrode for high-performance electrochemical supercapacitors.

This work aims to develop and characterize a new design of free-standing interconnected carbon nanofiber electrodes for supercapacitor application. The fibers are obtained via carbonization of three components of electrospun nanofiber mats based on a polyacrylonitrile polymer (as a carbon backbone precursor), polyvinylalcohol (as a sacrificial copolymer), and 0-1.0 wt% multi-walled carbon nanotubes. Carbonizing these ternary composites results in fibers with about twice as large in surface area and one order of magnitude higher in electrical conductivity than those obtained by the carbonization of neat polyacrylonitrile and/or binary polyacrylonitrile-0-1.0 wt% carbon nanotube mats. The carbonized polyacrylonitrile-polyvinylalcohol-0.3 wt% carbon nanotube mat reveals the highest surface area and electrical conductivity and best capacitive performance. It exhibits energy and power densities of 27.8 Wh kg -1 and 110.59 kW kg -1 , respectively, and cyclic stability of 95% after 2000 charge-discharge cycles at a charging current of 1.0 Ag -1 . The nanotubes' alignment along the fiber's axis, the formation of fiber-fiber interconnected morphology with more mesopore pollution, and changes in the graphitization degree and defect features of fiber crystallites are the reasons for the observed increase in the electrical conductivity, surface area, and capacitive performance of the carbon fibers. Therefore, the new design represents a potential free-standing carbon nanofiber electrode for future electrochemical double layer capacitor (EDLC) device fabrication.

In this work Polyaniline (PANI) fiber has been synthetized by the interfacial polymerization method. The thermal behavior of graphene - multiwall carbon nanotubes (MWCNs) composite material (C-Mix) blended with PANI fiber was investigated. Graphene was prepared by thermal reduction of the fabricated graphene oxide (GO) using modified Hummers' method. SEM measurement reveals that MWCNTs were well organized within 2D large surface area graphene nano-sheets to form 3D carbon-base hierarchical structure, and PANI was mixed as a binder polymer matrix. Structural measurements confirm the formation of wide area graphene sheets with crumples, wrinkles, and folds around the edges. Transmission electron microscopy (TEM) images agreed with the well distribution of CNTs within graphene nano-sheets. Also, the surface morphology of the synthesized composites has a spherical regular agglomeration of PANI granular structure on wide area graphene nano sheets with CNT embedded. The change in the existed phonon modes of the fabricated nano-composite was analyzed using Raman spectroscopy. Moreover, Seebeck coefficient changes from +132.4 μV/K to -10.3 μV/K after adding carbon-based materials which reflects the reverse of predominate carriers by doping PANI with carbon-based material. It has been noticed that there is an enhancement of thermal conductivity of the fabricated composite with respect to neat polymer. Hence, we propose that 3D carbon structure with PANI construct a stable N-Type thermoelectric material., (Copyright © 2019 Elsevier B.V. All rights reserved.)