Minimizing CO2 emissions by photocatalytic CO2 reduction to CH3OH over Li2MnO3/WO3 heterostructures under visible illumination.

Photocatalytic CO2 reduction to valuable fuels has proved to be a favourable process to produce renewable energy and reduce CO2 emissions, which mostly depends on designing effective photocatalysts with the rapid separation rate of charge carriers. In this contribution, mesoporous n-n heterojunction Li2MnO3/WO3 nanocomposites were designed via a simplistic sol-gel process for CO2 reduction utilizing visible illumination (λ > 420 nm). XRD and TEM measurements confirmed the synthesized Li2MnO3/WO3 nanocomposite is a monoclinic structure, and its particle size is 25 ± 5 nm. The obtained Li2MnO3/WO3 exhibited narrower bandgap energy (1.74 eV), larger surface area (212 m2g-1), exceedingly visible absorbing, and lower recombination of electron and hole. The yield of CH3OH was determined about 198, 871, 1140, 1550 and 1570 mmolg-1 for bare WO3 and 5%, 10%, 15% and 20% Li2MnO3/WO3 nanocomposites, respectively. These results evidenced that the 15% Li2MnO3/WO3 photocatalyst exhibited the best reduction ability compared to other nanocomposites. The CO2 reduction over 15% Li2MnO3/WO3 photocatalyst achieved a maximal CO2 conversion with the substantially boosted CH3OH, i.e., 1550 mmolg-1 after 9 h, which was enhanced 7.8 folds great than of WO3 NPs. Mesoporous Li2MnO3/WO3 nanocomposites, in comparison with bare WO3 NPs, created more active sites for facilitating CO2 and had a specific electric field to more effectively separate charge carriers. The Li2MnO3/WO3 photocatalyst has superior photostability during the continuous reduction of CO2 for 45 h with no remarkable decrease. The possible direct S-scheme mechanism for electron transfer over Li2MnO3/WO3 photocatalyst with the enhanced CO2 reduction ability was discussed. The present work demonstrates an avenue for building highly effective heterostructure photocatalysts in solar-energy-induced potential applications.

Favorable Heteroaromatic Thiazole-Based Polyurea Derivatives as Interesting Biologically Active Products.

This research sought to synthesize a new set of heteroaromatic thiazole-based polyurea derivatives with sulfur links in the polymers' main chains, which were denoted by the acronyms PU1-5. Using pyridine as a solvent, a diphenylsulfide-based aminothiazole monomer (M2) was polymerized via solution polycondensation with varied aromatic, aliphatic, and cyclic diisocyanates. Typical characterization methods were used to confirm the structures of the premonomer, monomer, and fully generated polymers. The XRD results revealed that aromatic-based polymers had higher crystallinity than aliphatic and cyclic derivatives. SEM was used to visualize the surfaces of PU1, PU4, and PU5, revealing spongy and porous shapes, shapes resembling wooden planks and sticks, and shapes resembling coral reefs with floral shapes at various magnifications. The polymers demonstrated thermal stability. The numerical results for PDTmax are listed in the following order, ranked from lowest to highest: PU1 < PU2 < PU3 < PU5 < PU4. The FDT values for the aliphatic-based derivatives (PU4 and PU5) were lower than those for the aromatic-based ones (616, 655, and 665 °C). PU3 showed the greatest inhibitory impact against the bacteria and fungi under investigation. In addition, PU4 and PU5 demonstrated antifungal activities that, in contrast with the other products, were on the lower end of the spectrum. Furthermore, the intended polymers were also tested for the presence of the proteins 1KNZ, 1JIJ, and 1IYL, which are frequently utilized as model organisms for E. coli (Gram-negative bacteria), S. aureus (Gram-positive bacteria), and C. albicans (fungal pathogens). This study's findings are consistent with the outcomes of the subjective screening.

Transition Metal-Catalyzed C-H Functionalization Through Electrocatalysis.

Electrochemically promoted transition metal-catalyzed C-H functionalization has emerged as a promising area of research over the last few decades. However, development in this field is still at an early stage compared to traditional functionalization reactions using chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal-catalyzed C-H functionalization. From the standpoint of sustainability, environmental friendliness, and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom-economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal-electrocatalyzed C-H functionalization over the past decade and describes how the unique features of electricity enable metal-catalyzed C-H functionalization in an economic and sustainable way.

Combination Effect of Novel Bimetallic Ag-Ni Nanoparticles with Fluconazole against Candida albicans.

The increasing frequency of antifungal drug resistance among pathogenic yeast "Candida" has posed an immense global threat to the public healthcare sector. The most notable species of Candida causing most fungal infections is Candida albicans. Furthermore, recent research has revealed that transition and noble metal combinations can have synergistic antimicrobial effects. Therefore, a one-pot seedless biogenic synthesis of Ag-Ni bimetallic nanoparticles (Ag-Ni NPs) using Salvia officinalis aqueous leaf extract is described. Various techniques, such as UV-vis, FTIR, XRD, SEM, EDX, and TGA, were used to validate the production of Ag-Ni NPs. The antifungal susceptibility of Ag-Ni NPs alone and in combination with fluconazole (FLZ) was tested against FLZ-resistant C. albicans isolate. Furthermore, the impacts of these NPs on membrane integrity, drug efflux pumps, and biofilms formation were evaluated. The MIC (1.56 µg/mL) and MFC (3.12 µg/mL) results indicated potent antifungal activity of Ag-Ni NPs against FLZ-resistant C. albicans. Upon combination, synergistic interaction was observed between Ag-Ni NPs and FLZ against C. albicans 5112 with a fractional inhibitory concentration index (FICI) value of 0.31. In-depth studies revealed that Ag-Ni NPs at higher concentrations (3.12 µg/mL) have anti-biofilm properties and disrupt membrane integrity, as demonstrated by scanning electron microscopy results. In comparison, morphological transition was halted at lower concentrations (0.78 µg/mL). From the results of efflux pump assay using rhodamine 6G (R6G), it was evident that Ag-Ni NPs blocks the efflux pumps in the FLZ-resistant C. albicans 5112. Targeting biofilms and efflux pumps using novel drugs will be an alternate approach for combatting the threat of multi-drug resistant (MDR) stains of C. albicans. Therefore, this study supports the usage of Ag-Ni NPs to avert infections caused by drug resistant strains of C. albicans.

Mesoporous BiVO4/TiO2 heterojunction: enhanced photoabsorption and photocatalytic ability through promoted charge transfer.

BiVO4 has been constructed into heterojunctions with TiO2 to boost the photocatalytic ability under visible illumination. Here, mesoporous BiVO4/TiO2 nanocomposites have been fabricated by a facile sol-gel approach utilizing nonionic surfactant and addressed for morphological, optical, structural, and degradation of ciprofloxacin (CIP) in water under visible illumination as an antibiotic pollutant model. The TEM images demonstrated that the TiO2 NPs are homogenous in terms of shape and size (15 ± 5 nm). The introduction of BiVO4 into mesoporous TiO2 could effectively enhance the rapid separation efficiency of the photoinduced carriers and optical absorption. The 3%BiVO4/TiO2 photocatalyst possessed the best degradation efficiency (100%) within 60 min which was promoted 20-folds larger than TiO2 NPs (5%). 3%BiVO4/TiO2 nanocomposite exhibited the fastest degradation rate (2.15 × 10-2 min-1), which was 40 times faster than bare TiO2 photocatalyst (0.05 × 10-2 min-1). The enhanced photocatalytic ability originated from superior charge separation characteristics and high solar energy absorption in mesopore structures. The recombination rate and mobility of charge carriers were characterized utilizing photoluminescence (PL) and photoelectrochemical measurements. This work highlights the advantages of mesoporous heterojunction BiVO4/TiO2 nanocomposites for photocatalytic performances and provides a multilateral route to design an effective wide-spectrum response photocatalyst for the development of comparable materials. The photocatalytic mechanism for degradation CIP over BiVO4/TiO2 was discussed in detail..

Synthesis and Characterization of Green ZnO@polynaniline/Bentonite Tripartite Structure (G.Zn@PN/BE) as Adsorbent for As (V) Ions: Integration, Steric, and Energetic Properties.

A green ZnO@polynaniline/bentonite composite (G.Zn@PN/BE) was synthesized as an enhanced adsorbent for As (V) ions. Its adsorption properties were assessed in comparison with the integrated components of bentonite (BE) and polyaniline/bentonite (PN/BE) composites. The G.Zn@PN/BE composite achieved an As (V) retention capacity (213 mg/g) higher than BE (72.7 mg/g) and PN/BE (119.8 mg/g). The enhanced capacity of G.Zn@PN/BE was studied using classic (Langmuir) and advanced equilibrium (monolayer model of one energy) models. Considering the steric properties, the structure of G.Zn@PN/BE demonstrated a higher density of active sites (Nm = 109.8 (20 °C), 108.9 (30 °C), and 67.8 mg/g (40 °C)) than BE and PN/BE. This declared the effect of the integration process in inducing the retention capacity by increasing the quantities of the active sites. The number of adsorbed As (V) ions per site (1.76 up to 2.13) signifies the retention of two or three ions per site by a multi-ionic mechanism. The adsorption energies (from -3.07 to -3.26 kJ/mol) suggested physical retention mechanisms (hydrogen bonding and dipole bonding forces). The adsorption energy, internal energy, and free enthalpy reflected the exothermic, feasible, and spontaneous nature of the retention process. The structure is of significant As (V) uptake capacity in the existence of competitive anions or metal ions.

One-step preparation of RGO/Fe3O4-FeVO4 nanocomposites as highly effective photocatalysts under natural sunlight illumination.

The study used a one-step hydrothermal method to prepare Fe3O4-FeVO4 and xRGO/Fe3O4-FeVO4 nanocomposites. XRD, TEM, EDS, XPS, DRS, and PL techniques were used to examine the structurally and morphologically properties of the prepared samples. The XRD results appeared that the Fe3O4-FeVO4 has a triclinic crystal structure. Under hydrothermal treatment, (GO) was effectively reduced to (RGO) as illustrated by XRD and XPS results. UV-Vis analysis revealed that the addition of RGO enhanced the absorption in the visible region and narrowed the band gap energy. The photoactivities of the prepared samples were evaluated by degrading methylene blue (MB), phenol and brilliant green under sunlight illumination. As indicated by all the nanocomposites, photocatalytic activity was higher than the pure Fe3O4-FeVO4 photocatalyst, and the highest photodegradation efficiency of MB and phenol was shown by the 10%RGO/Fe3O4-FeVO4. In addition, the study examined the mineralization (TOC), photodegradation process, and photocatalytic reaction kinetics of MB and phenol.

Highly Dispersed Pt Nanoparticle-Doped Mesoporous ZnO Photocatalysts for Promoting Photoconversion of CO2 to Methanol.

Photoreduction of CO2 is considered a challenge due to the lack of effective photocatalysts with wide-spectrum absorption, active charge separation dynamically, and CO2 adsorption. Herein, mesoporous Pt/ZnO nanocomposites with different Pt percentages (0.5-2%) have been fabricated using the sol-gel process in the presence of a template for CO2 photoreduction during visible-light exposure. Pt nanoparticles (NPs) deposited onto mesoporous ZnO with a considerable surface area can effectively promote charge mobility. The mesoporous 1.5% Pt/ZnO nanocomposite exhibits an optimal CH3OH yield (668 µmol g-1), which is 18.5-fold larger than that of mesoporous ZnO (36 µmol g-1). The most photoactive material was the 1.5% Pt/ZnO nanocomposite, producing CH3OH of 668 µmol g-1, and the production rate of CH3OH over the 1.5% Pt/ZnO nanocomposite (74.11 µmol g-1 h-1) was increased 20 times in comparison with ZnO NPs (3.72 µmol g-1 h-1). The enhancement of CO2 photoreduction efficiency over Pt/ZnO nanocomposites was attributed to the formation of the heterojunction at the Pt/ZnO interface, promoting a lower resistance to charge transfer and a larger electron transfer to the conduction band. Mesoporous Pt/ZnO nanocomposites offer enhanced accessibility and a larger surface area. Such an unparalleled mesostructure provides a new framework for the construction and design of photoactive materials with high-efficiency photocatalysts.

Synthesis of zeolite/geopolymer composite for enhanced sequestration of phosphate (PO43-) and ammonium (NH4+) ions; equilibrium properties and realistic study.

Zeolite impeded geopolymer (Z/G) was synthesized from natural kaolinite and diatomite. The structure (Z/G) was characterized as an enhanced adsorbent for PO43- and NH4+ ions from aqueous solutions, groundwater, and sewage water. The synthetic Z/G structure exhibits sequestration capacities of 206 mg/g and 140 mg/g for PO43- and NH4+, respectively which are higher values than the recognized results for the geopolymer and other adsorbents in literature. The sequestration reactions of PO43- and NH4+ by Z/G are of Pseudo-Second order kinetic behavior considering both the Chi-squared (χ2) and correlation coefficient (R2) values. The sequestration reactions occur in homogenous and monolayer forms considering their agreement with Langmuir behavior. The Gaussian energies (12.4 kJ/mol (PO43-) and 10.47 kJ/mol (NH4+)) demonstrate the operation of a chemical sequestration mechanism that might be involved zeolitic ion exchange process and chemical complexation. Additionally, these reactions are exothermic processes of spontaneous and favorable properties based on thermodynamic studies. The Z/G structure is of significant affinity for both PO43- and NH4+ even in the existence of other anions as Cl-, HCO3-, SO42-, and NO3-. Finally, the structure used effectively in the purification of groundwater and sewage water from PO43- and NH4+ in addition to nitrate, sulfate, and some metal ions.

Insight into the role of the zeolitization process in enhancing the adsorption performance of kaolinite/diatomite geopolymer for effective retention of Sr (II) ions; batch and column studies.

Diatomite/kaolinite-based geopolymer (GP) was synthesized and incorporated in zeolitization process (Z/GP) to investigate the role of the zeolite phases in inducing its retention capacity of the dissolved Sr (II) ions in water. The retention of Sr (II) ions using Z/GP in comparison with GP was evaluated based on both batch and fixed-bed column studies. In the batch study, the zeolitized geopolymer (Z/GP) shows enhancement in the Sr (II) retention capacity (193.7 mg/g) as compared to the normal geopolymer (102 mg/g). Moreover, the recyclability studies demonstrate higher stability for Z/GP than GP with a retention percentage higher than 90% for five reusing runs. The kinetic and the equilibrium properties of the occurred Sr (II) retention reactions follow the assumption of the Pseudo-Second order model (R2 > 0.96) and Langmuir model (R2 > 0.97), respectively. The Gaussian energies (15.4 kJ/mol (GP) and 11.47 kJ/mol (Z/GP)) related to retention mechanism of chemical type and within the suggested range for the zeolitic ion exchange processes. The Sr (II) retention reactions by GP and Z/GP are of spontaneous and exothermic properties which qualifies the products to be used at low-temperature conditions (20 °C). The column studies also declared higher performance for the Z/GP fixed bed as compared to the normal GP bed considering the total Sr (II) retention percentage (72.9%), treated volume (8 L), saturation time (1620 min), and a maximum capacity of Z/GP particles in the bed (567.6 mg/g).

Intense Visible-Light Absorption in SrRuO3/C3N4 Heterostructures for the Highly Efficient Reduction of Hg(II).

Strontium ruthenium oxide (SrRuO3) is recognized as a metallic itinerant ferromagnet and utilized as a conducting electrode in heterostructure oxides with unforeseen optical characteristics, including remarkably low-reflection and high-absorption visible-light spectrum compared to classical metals. By coupling mesoporous SrRuO3 nanoparticles (NPs) with porous g-C3N4 nanosheets for the first time, we evidence remarkably promoted visible light absorption and superior photocatalytic performances for Hg(II) reduction under illumination with visible light. The photocatalytic performance of g-C3N4 increased upon boosting the SrRuO3 percentage to 1.5%, and this (1.5% SrRuO3/g-C3N4 heterostructure) is considered the optimum condition to obtain a high photocatalytic efficiency of about 100% within 50 min. It was promoted 3.68 and 5.75 times compared to SrRuO3 and g-C3N4, respectively. Also, a Hg(II) reduction rate of 1.5% SrRuO3/g-C3N4 was enhanced3.84- and 6.28-fold than those of pure SrRuO3 NPs and g-C3N4, respectively. Such a high photocatalytic performance over SrRuO3/g-C3N4 photocatalysts was explained by the characteristics of SrRuO3 NPs incorporated on porous g-C3N4 layers, which demonstrate strong absorption of visible light with a narrow band gap, a large photocurrent density of ∼9.07 mA/cm2, well-dispersed and small particle sizes, and cause facile diffusion of HCOOH and Hg(II) ions and electrons. The present work provides a dramatic novel approach to the challenge of constructing visible-light photosensitive photocatalysts for wastewater remediation.

Virus and chlorine adsorption onto guanidine modified cellulose nanofibers using covalent and hydrogen bonding.

Unsafe drinking water leads to millions of human deaths each year, while contaminated wastewater discharges are a significant threat to aquatic life. To relieve the burden of unsafe water, we are in search of an inexpensive material that can adsorb pathogenic viruses from drinking water and adsorb toxic residual chlorine from wastewater. To impart virus and chlorine removal abilities to cellulosic materials, we modified the primary hydroxyl group with a positively charged guanidine group, to yield guanidine modified cellulose derivatives. Microcrystalline cellulose (MC) bearing covalently bonded guanidine hydrochloride (MC-GC) and hydrogen-bonded guanidine hydrochloride (MC-GH) were synthesized, and electrospun into nanofibers after blending with the non-ionogenic polyvinyl alcohol (PVA), to produce large pore sized, high surface area membranes. The MC-GC/PVA and MC-GH/PVA nanofibers were stabilized against water dissolution by crosslinking with glutaraldehyde vapor. The water-stable MC-GC/PVA mats were able to remove more than 4 logs of non-enveloped porcine parvovirus (PPV) and enveloped Sindbis virus and reached 58% of chlorine removal. The MC-GC/PVA nanofibers demonstrated better performance for pathogen removal and dechlorination than MC-GH/PVA nanofibers. This first study of MC-GC/PVA electrospun mats for virus removal shows they are highly effective and merit additional research for virus removal.

Highly selective heteroaromatic sulfur containing polyamides for Hg+2 environmental remediation.

Environmental remediation concerns about pollution and contamination removal from environmental media, such as soil, air, or surface water. Enormous efforts have been applied in metal removal from surface water. In this study, four novel heteroaromatic sulfur-containing polyamides 6a-d carry both types of aliphatic and aromatic species in their polymer backbones as selective adsorbents for Hg+2 metal ion from aqueous solution have been synthesized in considerable amounts. The polycondensation method at low temperature is used as a simple and low coast polymerization technique. This occurred by the interaction of the thiophene-based monomer 5 with different diacid chlorides of both types. Beforehand the polymerization, the structures of monomer 5 were confirmed by spectral and elemental analyses. Also, the structures of the new polymers were investigated by both spectral and elemental analysis; besides their solubility, GPC data, XRD diffraction patterns, thermal analysis, and FE-SEM micrographs. The synthesized polymers were freely soluble in polar protic solvents due to the presence of heteroaromatic sulfur functional groups. Furthermore, the analytical competition of the new polymers has been tested using inductively coupled plasma-optical emission spectrometry (ICP-OES) for its selective extraction across different metal ions. Polymer 6c was the most selective toward Hg+2 and considered as a highly selective adsorbent for Hg+2 environmental remediation among all derivatives and its adsorption detection and efficiency were also investigated. Polymer 6c showed the most effective adsorption quantity on its surface at pH = 1. Moreover, the calculated adsorption isotherm showed a typical isotherm to the Langmuir adsorption type. This showed that the adsorption capacity of polymer 6c for Hg+2 was 47.95 mg g-1. These novel polymers are serving as simple and inexpensive heavy metal ions adsorbent materials from drinking water and wastewater.