CO2-Free Ethylene Oxide Production via Liquid-Phase Epoxidation with Fe2O3/MSM Catalyst.

In this study, we present an approach for ethylene oxide (EO) production that addresses environmental concerns by eliminating greenhouse gas emissions. Our catalyst, Fe2O3/MSM, was synthesized using a hydrothermal method, incorporating Fe2O3 nanoparticles into a well-structured mesoporous silica matrix (MSM). We selected peracetic acid as the oxidant, enabling CO2-free EO production while yielding valuable by-products such as acetic acid, monoethylene glycol, and diethylene glycol. X-ray diffraction (XRD), X- ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analyses confirmed the heteroatom structure of the catalysts and porosity, while Transmission electron microscopy (TEM) analysis provided insights into its morphology. Then, the synthesized catalyst was used in the liquid-phase epoxidation of ethylene for EO production. Our systematic experiments involved varying critical parameters such as temperature, ethylene to oxidant ratio, catalyst dosage, and solvent to optimize EO selectivity and ethylene conversion. The results of this study demonstrated an 80.2 % ethylene conversion to EO with an EO selectivity of 87.6 %. The production process yielded valuable by-products without CO2 emissions, highlighting its environmental friendliness.

Correction: Development of a chromium oxide loaded mesoporous silica as an efficient catalyst for carbon dioxide-free production of ethylene oxide.

[This corrects the article DOI: 10.1039/D3RA05858A.].

Controlled dynamic variation of interfacial electronic and optical properties of lithium intercalated ZrO2/MoS2 vdW heterostructure.

Efficient strategies for modifying the characteristics of van der Waals (vdW) layered materials in a precise and reversible mode remain challenging. Our suggested method for customization entails the implementation of layer-sliding and intercalation. In this work, a norm-conserving approach within the context of density functional theory has been used to examine the electronic and optical properties of two-dimensional (2D) van der Waals heterostructure (vdWHS), which is modeled by using 2D zirconium dioxide (1T-ZrO2) and molybdenum disulfide (1T-MoS2) monolayers of similar phase. Both contributing monolayers have similar lattice structures, with a minimum lattice mismatch of 0.83 %, and have corrugation on both sides that can successfully retain foreign species at the vdW-gap. In the next step, interfacial engineering through Li-intercalation and layer-sliding was employed to modify physical properties of the vdWHS. It is the worth mentioning that a narrow bandgap of 0.102 eV (0.22 eV) has been observed in the unintercalated ZrO2/MoS2 vdWHS when employing PW-LDA (hybrid-functional). Li-intercalation and sliding process significantly influenced the electronic properties of the studied vdWHS. Furthermore, un-slided and fully-slided Li-intercalated vdWHS exhibit an increase in the vdW-gap by 3.78 % and 27.14 %, respectively, as compared to unintercalated vdWHS. To further understand the electrical behaviour at the interface of contributing monolayers, a comparative study has also been made for the variation in the planar average charge density difference, charge transfer, and interface dipole moment for unintercalated and intercalated vdWHS. In the unintercalated vdWHS, the calculated values of ΔQ and µ(z) provide evidence of significant charge transfer from 1T-ZrO2 to 1T-MoS2 before sliding, whereas in the fully-slided vdWHS, there is 80.11 % more charge transfer from 1T-MoS2 to 1T-ZrO2. Li-intercalation increases the magnitude of ΔQ (by 90.27 %) near 1T-MoS2, indicating a sufficient quantity of charge transfer from the 1T-MoS2 monolayer. The results of the anisotropic analysis show that the calculated in-plane and out-of-plane components of the real and imaginary parts of the dielectric function differ significantly. The optical absorption and energy losses of Li-intercalated vdWHS experience a substantial decrease of about 90 % and 50 %, respectively, as compared to unintercalated vdWHS. Our employed method promotes the notion that interfacial engineering through simultaneous layer-sliding and intercalation approach can be used to regulate and modify the physical properties of 2D insulator/metal based vdWHS.

Development of a chromium oxide loaded mesoporous silica as an efficient catalyst for carbon dioxide-free production of ethylene oxide.

Ethylene oxide (EO) is a significant raw material used in many commodities for consumers, particularly ethoxylates, polymers, and certain other glycol derivatives. We synthesized a catalyst by incorporation of chromium oxide into a mesoporous silica material (Cr/MSM) via the hydrothermal method, an effective catalyst for partial ethylene oxidation for producing carbon dioxide (CO2) free EO. Subsequently, XRD, BET, XPS, and TEM were used to analyse the structural characteristics of the Cr/MSM catalyst. The catalytic performance of the synthesized catalyst was assessed in the liquid-phase epoxidation (LPE) of ethylene, utilizing peracetic acid (PAA) as an oxidant. This approach not only circumvented the generation of CO2 but also mitigated the risk of metal leaching. Confirmation of the successful production of EO was achieved through GC chromatography, where the presence of a peak with a retention time (RT) of 8.91 minutes served as conclusive evidence. We systematically explored a range of reaction parameters, including temperature, catalyst concentration, the molar ratio of ethylene to PAA, and solvent effect. This comprehensive investigation aimed to fine-tune the reaction conditions, ultimately improving ethylene conversion and enhancing the selectivity of the catalyst for EO production. This approach can effectively resolve the issues of greenhouse gas emissions and metal leaching that had been associated with previously reported catalysts.

Bismuth-Rich Co/Ni Bimetallic Metal-Organic Frameworks as Photocatalysts toward Efficient Removal of Organic Contaminants under Environmental Conditions.

Active photocatalysts with an efficiency of 99% were prepared for the degradation of the industrial dye, methylene blue (MB), under visible light irradiation. These photocatalysts comprised Co/Ni-metal-organic frameworks (MOFs), to which bismuth oxyiodide (BiOI) was added as a filler to prepare Co/Ni-MOF@BiOI composites. The composites exhibited remarkable photocatalytic degradation of MB in aqueous solutions. The effects of various parameters, including the pH, reaction time, catalyst dose, and MB concentration, on the photocatalytic activity of the prepared catalysts were also evaluated. We believe that these composites are promising photocatalysts for the removal of MB from aqueous solutions under visible light.

Correction: CO2 free production of ethylene oxide via liquid phase epoxidation of ethylene using niobium oxide incorporated mesoporous silica material as the catalyst.

[This corrects the article DOI: 10.1039/D2RA07240H.].

CO2 free production of ethylene oxide via liquid phase epoxidation of ethylene using niobium oxide incorporated mesoporous silica material as the catalyst.

Ethylene Oxide (EO) is an essential raw material used in various consumer products like different glycol derivatives, ethoxylates, and polymers. We hydrothermally synthesize niobium oxide incorporated with mesoporous silica material (Nb/MSM), an efficient catalyst for CO2 free-ethylene oxide (EO) production via partial oxidation of ethylene. The structural properties of Nb/MSM catalysts were characterized using XRD, TEM, and N2 adsorption-desorption. The catalytic activity of synthesized materials in liquid phase epoxidation (LPE) of ethylene was evaluated in the presence of peracetic acid (PAA) as an oxidant to avoid the production of CO2 and also minimize metal leaching. GC chromatography was used to investigate the successful production of EO, and a peak with a retention time (RT) of 9.01 min served as confirmation. Various reaction parameters viz. temperature, catalyst concentration, ethylene to PAA molar ratio, and solvent effect were investigated in order to optimize the reaction conditions for enhancing the ethylene conversion and selectivity for EO production. By this approach, the challenges of greenhouse gas production and metal leaching were addressed which were associated with previously reported catalysts.

Photocatalytic degradation of industrial dye using hybrid filler impregnated poly-sulfone membrane and optimizing the catalytic performance using Box-Behnken design.

Mixed Matrix Membranes have gained significant attention over the past few years due to their diverse applications, unique hybrid inorganic filler and polymeric properties. In this article, the impregnation of nano-hybrid filler (polyoxometalates (∼POMs) encapsulated into the metal-organic framework (MOF) âˆ¼ PMOF) on the polysulfone membrane (∼PSF) was done, resulting in a mix matrix membrane (∼PMOF@PSF). The developed structure was characterized by Fourier transform infrared (FT-IR), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopes (TEM). The results confirmed that the nano-hybrid filler was successfully fabricated on the surface of PSF. Different loading ratios of nano-hybrid filler (5%, 10%, 20%, 30%, and 40%) were used for impregnation. The study's objective was to enhance catalytic performance using optimization curves designed using a three-level Box-Behnken Design (BBD) simulation. The photodegradation of Methylene Blue (∼MB) was studied against PMOF@PSF30% and was found to perform optimally when the concentration of catalyst, time of degradation, and temperature were 0.05-0.15 gm, 40-120 min, and 30-70 °C respectively. These experiments were replicated 15 times, and obtained results were further processed using a two-quadratic polynomial model to develop response surface methodology (RSM), which allowed for a functional relationship between the decolorization and experimental parameters. The optimal performance of the reaction mixture was calculated to be 0.15 gm for concentration, 70 °C for temperature, with an 80 min reaction time. Under these optimal conditions, the predicted decolorization of MB was 98.09%. Regression analysis with R2 > 0.99 verified the fit of experimental results with predicted values. The PMOF@PSF PSF30% demonstrated excellent reusability as its dye degradation properties were significantly unaffected after ten cycles.

Oligoimide-Mediated Graphene Oxide-Epoxy Nanocomposites with Enhanced Thermal Conductivity and Mechanical Properties.

The current study reports the preparation of thermally conductive polymeric nanocomposites. For this purpose, two epoxy-based nanocomposites were prepared by dispersing a different type of functionalized graphene oxide (GO) nanofiller in each series. Both these GO nanofillers were functionalized by covalently bonding oligoimide chains on their surfaces. In one series, these oligoimide chains were prepared by reaction of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with a diamine 4,4'-methylenedianiline (MDA). While in the other case, BTDA was reacted with N,N'-[((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(4,1-phenylene)]bis(4-aminobenzamide) (BDM) to mount oligoimide chains on the surface of GO. Both types of oligoimide chains have amino groups as chain-end functional groups. These modified GO nanofillers were added to the epoxy matrices separately to prepare their respective nanocomposites (MDA-B-GO-epoxy nanocomposites and BDM-B-GO-epoxy nanocomposites). The chain-end amino groups of oligoimide chains reacted with the epoxy ring developing a covalent bonding between oligoimide chains of GO and the epoxy matrix. Moreover, these oligoimide chains prevented the agglomeration of GO by acting as spacer groups leading to the uniform dispersion of GO in the epoxy matrix. Various analytical techniques were used to examine the attachment of oligoimide chains to the GO surface, and to examine the morphology, curing potential, mechanical strength, thermal stability, and thermal conductivity of the prepared nanocomposites. We demonstrated that the thermal conductivity of MDA-B-GO-epoxy nanocomposites increased by 52% and an increase of 56% was observed in BDM-B-GO-epoxy nanocomposites. Similarly, a significant improvement was observed in the mechanical strength and thermal stability of both types of nanocomposites.

Fabrication of Guided Tissue Regeneration Membrane Using Lignin-Mediated ZnO Nanoparticles in Biopolymer Matrix for Antimicrobial Activity.

Periodontal disease is a common complication, and conventional periodontal surgery can lead to severe bleeding. Different membranes have been used for periodontal treatment with limitations, such as improper biodegradation, poor mechanical property, and no effective hemostatic property. Guided tissue regeneration (GTR) membranes favoring periodontal regeneration were prepared to overcome these shortcomings. The mucilage of the chia seed was extracted and utilized to prepare the guided tissue regeneration (GTR) membrane. Lignin having antibacterial properties was used to synthesize lignin-mediated ZnO nanoparticles (∼Lignin@ZnO) followed by characterization with analytical techniques like Fourier-transform infrared spectroscopy (FTIR), UV-visible spectroscopy, and scanning electron microscope (SEM). To fabricate the GTR membrane, extracted mucilage, Lignin@ZnO, and polyvinyl alcohol (PVA) were mixed in different ratios to obtain a thin film. The fabricated GTR membrane was evaluated using a dynamic fatigue analyzer for mechanical properties. Appropriate degradation rates were approved by degradability analysis in water for different intervals of time. The fabricated GTR membrane showed excellent antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacterial species.

4-quinolin-8-yloxy Linked Triphenylamine Based Polyimides: Blue Light Emissive and Potential Hole-Transport Materials.

A series of fluorescent donor- acceptor (D-A) alternating copolyimides (P1, P2, P3 and P4) with 4-quinolin-8-yloxy linked triphenylamine main polymer chain have been synthesized by conventional polycondensation. All the synthesized co-polyimides were characterized by elemental, gel permeation chromatography and FTIR spectral analysis. These newly prepared PIs possess HOMO energy levels in range of - 4.74 to - 4.78 eV and have medium optical band gaps. The photoluminescence spectral analysis revealed blue to violet emission with appreciable efficiency with lower onset oxidation potentials suitable for the facile hole injection materials. All the photophysical and electrochemical properties were also explored in context of effect of the pendant 4- quinolin-8-yloxy, indicating suitable combination of donor (TPA) on one hand and imide and pendant as acceptor on both ends.Graphical Abstract.

4-Nitro-phenyl 2-chloro-benzoate.

The aromatic rings in the title compound, C13H8ClNO4, enclose a dihedral angle of 39.53 (3)°. The nitro group is almost coplanar with the ring to which it is attached [dihedral angle = 4.31 (1)°]. In the crystal, mol-ecules are connected by C-H⋯O hydrogen bonds into chains running along [001].

4-Pheneth-oxy-aniline hemihydrate.

The crystal structure of the title compound, C(14)H(15)NO·0.5H(2)O, features N-H⋯O and O-H⋯N hydrogen bonds between the amino group and water molecule of crystallization, which generate a chain along the c axis. The water mol-ecule lies on a twofold rotation axis. A C-H⋯π inter-action is observed between the phenyl and aniline rings. The angle between the mean planes of the phenyl rings is 72.51 (7)°.

1,10-Bis(4-nitro-phen-oxy)deca-ne.

The title compound, C(22)H(28)N(2)O(6), crystallizes with four half-mol-ecules in the asymmetric unit: each mol-ecule is located about a crystallographic inversion centre. The central methyl-ene groups of two mol-ecules are disordered over two sets of equally occupied sites. The crystal packing is characterized by sheets of mol-ecules parallel to (14).

4-(4-Nitro-phenoxy)biphen-yl.

The two phenyl rings of the biphenyl unit of the title compound, C(18)H(13)NO(3), are almost coplanar [dihedral angle 6.70 (9)°]. The nitro-phenyl ring, on the other hand, is significantly twisted out of the plane of the these two rings, making dihedral angles of 68.83 (4)° with the middle ring and 62.86 (4)° with the end ring. The nitro group is twisted by 12.1 (2)° out of the plane of the phenyl ring to which it is attached.