Exploring Si-centered phthalocyanine as a single atom catalyst for N2O reduction: a DFT study.

To remove the greenhouse gas N2O from the environment, recently, researchers have taken great interest in single-atom catalysts (SACs). In this study, we investigated various reaction pathways and barrier energies for the N2O reduction process onto Si-coordinated phthalocyanine (Si@PthC) employing density functional theory. The outcomes validate that Si decoration in PthC is energetically stable while the corresponding electronic properties show that the Si atom acts as the reactive site for catalytic activity. The N2O molecule exhibits spontaneous dissociation over the catalyst surface from the O-end with -4.01 eV dissociation energy. Meanwhile, N2O dissociation via the N-end involves chemisorption onto the Si@PthC surface with an adsorption energy (Ead) of -1.16 eV, and the dissociation needs an energy barrier of 0.51 eV. The bond distances and negative adsorption energies (-1.11 and -2.40 eV) evince that CO and O2 species chemisorbed onto the Si@PthC surface. However, these energies are smaller than the N2O dissociation energy, which demonstrates that the presence of CO and O2 molecules cannot interrupt the N2O reduction process. Additionally, the CO + O* → CO2 reaction was executed for catalyst recovery, and the reaction proceeds very quickly on the Si@PthC catalyst, with a very small energy barrier (0.37 eV), indicating the excellent catalytic reactivity of the studied catalyst. These results propose that the designed catalyst can be valuable in the progress of novel noble metal-free catalysts for the elimination of harmful N2O from the environment.

Water/Vapor Assisted Fabrication of Large-Area Superprotonic Conductive Covalent Organic Framework Membranes.

Fabrication of large-area ionic covalent organic framework membranes (iCOMs) remains a grand challenge. Herein, the authors report the liquid water and water vapor-assisted fabrication of large-area superprotonic conductive iCOMs. A mixed monomer solution containing 1,3,5-triformylphloroglucinol (TFP) in 1,4-dioxane and p-diaminobenzenesulfonic acid (DABA) in water is first polymerized to obtain a pristine membrane which subsequently underwent crystallization process in mixed vapors containing water vapor. During the polymerization stage, water played a role of a diluting agent, weakening the Coulombic repulsion between sulfonic acid groups. During the crystallization stage, water vapor played a role of a structure-directing agent to facilitate the formation of highly crystalline, large-area iCOMs. The resulting membranes achieved a proton conductivity value of 0.76 S cm-1 at 90 °C under 100% relative humidity, which is among the highest ever reported. Using liquid water and water vapor as versatile additives open a novel avenue to the fabrication of large-area membranes from covalent organic frameworks and other kinds of crystalline organic framework materials.

The outcome of Newtonian heating on Couette flow of viscoelastic dusty fluid along with the heat transfer in a rotating frame: second law analysis.

The outcome of Newtonian heating on the viscoelastic fluid plays a vital role in daily life applications such as conjugate heat transfer around fins, heat exchanger, solar radiation, petroleum industry, etc. Also, rotation of viscoelastic fluid has various importance in product-making industries and engineering. Viscoelastic dusty fluids and Newtonian heating are applicable in nuclear reactors, gas cooling systems, control temperature of the system and centrifugal separators, etc. Therefore, based on this motivation, the present study presents the Newtonian heating effect on the dusty viscoelastic fluid. Additionally, a free convective heat transfer is taken for Couette flow in a rotating frame along with a uniform applied magnetic field. The dust particles possess complex velocities due to rotation and therefore it is the combination of the primary and secondary velocities. For the specified flow, the entropy generation and Bejan number are also computed. Poincare-Light Hill technique has been used for the solution of the system of partial differential equations. The velocity profile for dust particles and fluid are discussed in this article. The influence of different parameters on the Nusselt number, temperature profile, velocity of fluid and dust particle is discussed thoroughly.

Thermal analysis of different shape nanoparticles on hyperthermia therapy on breast cancer in a porous medium: A fractional model.

Cancer is clearly a major cause of disease and fatality around the world, yet little is known about how it starts and spreads. In this study, a model in mathematical form of breast cancer guided by a system of (ODE'S) ordinary differential equations is studied in depth to examine the thermal effects of various shape nanoparticles on breast cancer hyperthermia therapy in the existence of a porous media with fractional derivative connection, when utilizing microwave radiative heating. The unsteady state is determined precisely using the Laplace transform approach to crop a more decisive examination of temperature dissemination of blood temperature inside the breast tissues. Durbin's and Zakian's techniques are used to find Laplace inversion. Mild temperature hyperthermia is used in the treatment, which promotes cell death by increasing cell nervousness to radiation therapy and flow of blood in tumor. In the graphical findings, we can witness the distinct behavior of hyperthermia therapy on tumor cells by applying various metabolic heat generation rates across various time intervals to attain the optimal therapeutic temperature point. Particularly, we used graphs to visualize the behavior of different Nanoparticles with different shaped during hypothermia therapy. In comparison to other nanoparticles and shapes, it demonstrates that gold nanoparticles with a platelet shape are the best option for improving heat transmission. Which assess of heat transfer up to 16.412%.

Rational Design of Broadly Absorbing Boron Dipyrromethene-Carbazole Dyads for Dye-Sensitized Solar Cells: A DFT Study.

Structure engineering of boron dipyrromethene (BODIPY) organic dye, to increase its light-harvesting efficiency in dye-sensitized solar cells, has been the subject of rigorous research recently. Herein, we report on the rational designing of BODIPY-carbazole (D-π-A-A) dyads using density functional theory (DFT). The structure of BODIPY-carbazole was first modified by substituting an electron-donating -N(CH3)2 group at the electron-rich carbazole moiety, and two electron-accepting -COOH groups at the BODIPY core. The DFT calculations showed a significant lowering of the band gap from 2.9 eV (pristine BODIPY-carbazole dyad) to 1.87 eV (modified BODIPY-carbazole dyad). Further modification was demonstrated by the incorporation of heterocyclic rings such as thiophene (denoted as D1T), furan (D1F), and phosphole (D1P) into BODIPY-carbazole moiety, which red-shifted the light absorption spectra and consequently improved the light-harvesting efficiency of the dyes. The interactions at the dye/semiconductor interface were studied by employing their bridged-bidentate adsorption models over the titanium dioxide (TiO2)38 nanocluster. Results suggested that the electrons can be efficiently injected from the lowest unoccupied molecular orbital (LUMO) of dyes into the conduction band of TiO2. Among the three dyads, D1P exhibited superior photovoltaic performance with a maximum power conversion efficiency of 13.50%, a short-circuit current density (J sc) of 27.2 mA·cm-2, and an open-circuit voltage (V oc) of 731 mV. The structurally configured new D1P dye can be used as a potential alternative photosensitizer for high-performance dye-sensitized solar cells.

Covalent Organic Framework Nanosheets as Reactive Fillers To Fabricate Free-Standing Polyamide Membranes for Efficient Desalination.

Mixed matrix membranes (MMMs) have been increasingly utilized in membrane processes. Covalent organic frameworks (COFs) hold great promise as emergent nanofillers to fabricate high-performance MMMs; however, only few studies about COF materials in MMMs have been reported where COFs are all used as nonreactive fillers. Herein, we propose using -NH2-functionalized COF nanosheets as reactive fillers (rCON) to fabricate MMMs. rCON altered the morphology and chemistry of MMMs by controlling the diffusion rate of piperazine through hydrogen bonding prior to the interfacial polymerization process and inducing the creation of ridges in the MMMs with subsequent increase in surface area (∼24%). rCON was chemically cross-linked to the trimesoyl chloride through amide bonding, subsequently elevating the hydrophilicity (∼35%) and fouling resistance of MMMs. The presence of -NH2 groups elevated the rCON-PA compatibility, ensuring the high rCON loading of 5 wt % in the MMMs without sacrificing salt rejection. Accordingly, the PA-rCON MMMs exhibited a flux of 46.5 L m-2 h-1 bar-1, which is 6.8 times higher than that of the pristine PA membrane, with a high rejection rate of 93.5% for Na2SO4.

Mixed Nanosheet Membranes Assembled from Chemically Grafted Graphene Oxide and Covalent Organic Frameworks for Ultra-high Water Flux.

2D graphene oxide (GO) membranes attract great attention because of their ultrathin thickness and superior molecular sieving ability, but their low flux and instability in aqueous environments are still the major challenges for practical applications. In this study, we designed hybrid nanosheets from chemically grafted GO and covalent organic frameworks (COFs) as building blocks to fabricate mixed nanosheet membranes. The covalent triazine framework (CTF), a triazine-based COF, is exfoliated into nanosheets and then reacted with GO to form the GO-CTF hybrid nanosheets, which are then assembled into GO-CTF mixed nanosheet membranes. The GO-CTF membranes show a layered configuration of ca. 32 nm thickness. The incorporation of CTF nanosheets inappreciably changes the interlayer distance of GO-CTF membranes, ensuring high rejections to organic dyes (>90%); meanwhile, the CTF nanosheets afford extra through-plane channels that significantly shorten the water transport pathway. The GO-CTF membranes exhibit a water flux of 226.3 L m-2 h-1 bar-1, more than 12-fold higher than pure GO membranes. Besides, the strong chemical bonds between GO and COF render the GO-CTF membranes notably enhanced stability. Grafting of porous nanosheets onto nonporous nanosheets to acquire hybrid nanosheets as building blocks opens a new avenue to the fabrication of 2D membranes with promising application potential.

Hydrodesulfurization of dibenzothiophene using Pd-promoted Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts coupled with ionic liquids at ambient operating conditions.

Sulfur compounds in fuel oils are a major source of atmospheric pollution. This study is focused on the hydrodesulfurization (HDS) of dibenzothiophene (DBT) via the coupled application of 0.5 wt% Pd-loaded Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts with ionic liquids (ILs) at ambient temperature (120 °C) and pressure (1 MPa H2). The enhanced HDS activity of the solid catalysts coupled with [BMIM]BF4, [(CH3)4N]Cl, [EMIM]AlCl4, and [(n-C8H17)(C4H9)3P]Br was credited to the synergism between hydrogenation by the former and extractive desulfurization and better H2 transport by the latter, which was confirmed by DFT simulation. The Pd-loaded catalysts ranked highest by activity i.e. Pd-Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Ni-Mo/Al2O3 > Co-Mo/Al2O3. With mild experimental conditions of 1 MPa H2 pressure and 120 °C temperature and an oil : IL ratio of 10 : 3.3, DBT conversion was enhanced from 21% (by blank Ni-Mo/Al2O3) to 70% by Pd-Ni-Mo/Al2O3 coupled with [(n-C8H17)(C4H9)3P]Br. The interaction of polarizable delocalized bonds (in DBT) and van der Waals forces influenced the higher solubility in ILs and hence led to higher DBT conversion. The IL was recycled four times with minimal loss of activity. Fresh and spent catalysts were characterized by FESEM, ICP-MS, EDX, XRD, XPS and BET surface area techniques. GC-MS analysis revealed biphenyl as the major HDS product. This study presents a considerable advance to the classical HDS processes in terms of mild operating conditions, cost-effectiveness, and simplified mechanization, and hence can be envisaged as an alternative approach for fuel oil processing.

Modulation of diorganoyl dichalcogenides reactivity by non-bonded nitrogen interactions.

The study was designed to explore the biochemical influence of non bonding nitrogen interactions (N⋯Se/S) on organochalcogens potency. Approximately five and six times higher thiol peroxidase (TPx) like activity was observed for compound (C)-2 than C-1 and C-3, respectively. C-2 also displayed significantly (p<0.05) higher activity in 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging and deoxyribose degradation assays. All compounds, except C-4 and C-6 significantly inhibited Fe (II) and sodium nitroprusside (SNP) induced thiobarbituric acid reactive species (TBARS) production in rat's brain, liver and kidney preparations with highest activity observed for C-2. The highest C-2 activity was attributed to the presence of non-bonded nitrogen interactions which were absent in C-1 and blocked with butoxycarbonyl (BOC group) in C-3. The same structural activity analogy was extended to organosulfur compounds and it was observed that compound with non-bonding nitrogen interactions, i.e. C-5 has significantly (p<0.05) higher TPx like activity than C-6 and C-4. C-5 at the highest tested concentration significantly (p<0.05) protected against Fe (II) and SNP induced TBARS formation in rat's brain, kidney and liver preparations but did not display activity in DPPH and deoxyribose degradation assays. This study confirms the influence of not only N⋯Se interaction but also for the first time the effect of non bonded N⋯S interactions on organochalcogens potency. C-2 (with the highest activity) was also tested in vivo and was administered at three different doses, i.e. 15, 30 and 50 mg/kg to get an exact idea about its interaction with thiol containing molecules (NPSH) and enzyme α-ALA-D (sulfhydryl containing enzyme). Oxidative stress parameters, i.e. free radical concentration by dichlorofluoreseein (DCF) assay, TBARS, ascorbic acid level, hepatic (ALT and AST) and renal (urea and creatinine) toxicity markers were also estimated to get an insight about its possible toxicological profile. Our data indicates that C-2 has higher TPx and Antioxidant activity and importantly, C2 did not induce toxicity even when tested at relatively high doses, indicating that its pharmacological properties should be further explored in models of diseases associated with oxidative stress.