Silane Moiety Research Articles

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles.

A commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid-state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub-surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster-type energy transfer from excited sub-surface Ti3+ centers.

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles

AbstractA commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid‐state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub‐surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster‐type energy transfer from excited sub‐surface Ti3+ centers.

Ruthenium(II) complexes containing PEGylated N-heterocyclic carbene ligands for tunning biocompatibility in the fight against cancer

A synthetic procedure was designed for the preparation and characterization of Ag and Ru complexes containing NHC ligands functionalized with PEG fragments. Stability studies were conducted to gain insight of the species in water and other solvents like DMSO, or with reagents like imidazole as representative group for histidine amino acid. The presence of Cl atoms instead of H in the 4,5 positions of the N-heterocyclic carbene afforded higher water stability. The complexes containing PEG units must be considered inactive as anticancer agents. To enhance the anticancer activity of PEG-containing complexes, the balance between hydrophilicity and hydrophobicity was adjusted using a silane moiety, and an anionic carbosilane dendrimer as a lipophilic carrier.

Functionalization of Ti3C2 MXene with Diethylenetriamine for a Column-Based Solid-Phase Extraction of Heavy Metals.

Transition metal carbides, nitrides, and carbonitrides, known as MXenes, are attracting attention for their potential application in trace detection of heavy metals. This study presents diethylenetriamine-functionalized Ti3C2 MXene for trace detection of cadmium and lead ions. Functionalization of Ti3C2 significantly improves the adsorption properties of MXenes by replacing native functional groups with silane moieties that contain three amine groups, offering higher affinity for heavy metals. We demonstrate the efficacy of this material as a solid-phase extractor in column-based solid-phase extraction for heavy metal analysis in various food samples. Diethylenetriamine-functionalized Ti3C2 coupled with the flame atomic absorption spectrometer exhibits exceptional analytical performance. While maintaining a robust stability for 15 adsorption-desorption cycles, the proposed method shows detection limits of 0.09 ng mL-1 for cadmium and 1.7 ng mL-1 for lead, with a linear dynamic range of 0.3-50 ng mL-1 for cadmium and 5-90 ng mL-1 for lead, and relative recoveries of 97.50-101.05 and 98.65-100.80% for cadmium and lead ions, respectively. Additionally, relative standard deviations and enrichment factors were calculated as 0.60-4.70% and 42.3 for cadmium ions and 0.65-1.24% and 44.2 for lead ions.

Comparative Study of Bis-Schiff Case Containing Conjugated Oligomers Based on Phosphate and Silane Moieties: Investigation of Photophysical and Thermal Properties.

Oligo(azomethine)s bearing phosphate and silane moieties were the subject of an investigation within this study. The initial stage involved the synthesis of two Schiff base monomers, denoted as SCH-1 and SCH-2 (SCHs), each possessing a pair of hydroxyl functional groups. This was achieved through a loss of water between the aldehyde and diamine precursors. Subsequently, the Schiff base entities were subjected to oligomerization through HCl-mediated elimination due to the interaction between the hydroxyl groups of the Schiff bases and the chlorine moieties of dichlorodiethylsilane (Si) or phenyl dichlorophosphate (P). This procedure yielded distinct P-oligo(azomethine) (P1-P, P2-P) and Si-oligo(azomethine) (P1-Si and P2-Si) structures corresponding to each precursor. The molecular structures of the synthesized Schiff base monomers and oligo(azomethine)s were elucidated employing Fourier transform infrared, 1H NMR, and 13C NMR techniques. Thermal properties of the resulting products were assessed by utilizing thermogravimetric analysis (TG-DTG/DTA and DSC) techniques. Scanning electron microscopy (SEM) was employed to acquire high-resolution images and detailed surface information on the samples. Additionally, X-ray diffraction was employed to analyze the phase properties of the solid samples. Furthermore, the optical band gap (E g) values of the resulting P-oligo(azomethine)s and Si-oligo(azomethine)s were determined utilizing UV-vis spectrophotometer. The relatively low band gap values exhibited by the synthesized oligo(azomethine)s were indicative of their potential suitability as semiconductive materials in the realm of electronic and optoelectronic device fabrication. Photoluminescence (PL) measurements disclosed a green emission profile upon excitation by blue light. The oligo(azomethine)s incorporating methoxy groups demonstrated a red shift in comparison to their counterparts with methyl groups. Remarkably, no discernible fluctuations in fluorescence were observed over a 3600 s interval under consistent conditions. This observation underscored the inherent stability of the PL emission across the spectral range of exciting light. Thermal analyses unveiled high thermal stability of the synthesized oligo(azomethine)s, sustaining their structural integrity up to 220 °C. The char % of P-oligo(azomethine)s and Si-oligo(azomethine)s were observed to fall within the range of 29.45-55.47% at 1000 °C. SEM images revealed the absence of pores on the surface of P2-Si, which exhibited the highest limiting oxygen index and thermal heat release index (T HRI) values.

Nanoclay protonation and silane functionalization to enhance mechanical and fracture performance of epoxy nanocomposites

AbstractNanoclay is considered to be one of the best fillers for reinforcement in structural polymer composites because of its low cost, easy availability, and ability to improve mechanical, thermal, corrosion resistance, barrier properties and nonflammability in corresponding nanocomposites. Pristine nanoclay is hydrophilic and therefore needs surface modification to make it compatible for uniform dispersion with polymer matrix. In the present work, montmorillonite nanoclay was protonated for generating more hydroxyl groups to facilitate silane functionalization and is reinforced to prepare epoxy nanocomposites with a varying content of 0.5 to 20 wt%. Studies are also conducted to investigate the effect of silanization of unprotonated nanoclay on epoxy nanocomposites. Interestingly, uniform highly exfoliated reduced‐size nanoclay platelets are obtained for functionalized protonated nanoclay. This behavior is attributed to the increase in the d‐spacing between the interlayers of the nanoclay during protonation and silanization. Tensile performances are found best with 0.5 wt% of silanized clay with an improvement of ~50%, ~84% and ~177% in strength, modulus and absorbed failure energy compared to neat epoxy. Although flexural and fracture performance are found highest with 2 wt% of silanized protonated clay with an improvement of ~57.5% in flexural strength and a remarkable ~241% and ~964% enhancement in fracture toughness and fracture energy compared to neat epoxy. The toughening mechanism investigation endorses the improvement in interfacial adhesion of the protonated silanized nanoclay that enhances the properties of the interfacial region, which significantly enhances the resistance for in‐panne crack propagation in epoxy nanocomposites.Highlights Synthesized silanized and silanized protonated montmorillonite clay. Protonation facilitated silane moiety attachment onto nanoclay. Maximum improvement of flexural strength by ~57.5% for ESPrC2. KIC and GIC were highest showing ~1.74 MPam1/2 and ~830.28 J/m2 for ESPrC2. Enhanced interfacial adhesion due to SPrC with the epoxy matrix.

Milled graphitic nanoparticle toughened epoxy composites via increased resistance to in-plane crack propagation

Fascinating features of 2D-based carbon materials like graphene have drawn increasing attention to fulfill the desire to enhance the fracture toughness of epoxy composites. However, challenges remain to improve their dispersibility in polymers and increase interaction ability. Thus, work is needed to synthesize alternative cost-effective 2D carbon nanofillers capable of delivering consistent performance as a reinforcer to monitor the fracture toughness of the epoxy composites. The present study demonstrates transforming graphite to ball-milled graphite (BMG) via an effective high-energy wet ball milling process. Herein a noteworthy size reduction is achieved for the BMG ranging from ∼217 to 227 nm. Microscopic investigation spotted an exfoliated 3D networked graphite nanosheet with nanopores. These BMGs were functionalized to attach amine-based silane moieties and were incorporated into the epoxy network. Consequently, even at higher loading levels, they showed their astonishing capability to enhance the crack far field resistance of nanocomposite resulting in significantly improved fracture toughness and energy to ∼2.31 MPa m1/2 and ∼11.30 kJ/m2, respectively. Improvement is ascribed to the better dispersing ability of BMG, which provides a consistent strong interfacial interaction with the epoxy network to modulate material resistance to fracture. Such environmentally friendly nanofillers must be industrially acceptable for synthesizing durable epoxy nanocomposite systems and can be utilized to prepare structural composites.

Fluorinated Silane-Modified Filtroporation Devices Enable Gene Knockout in Human Hematopoietic Stem and Progenitor Cells.

Intracellular delivery technologies that are cost-effective, non-cytotoxic, efficient, and cargo-agnostic are needed to enable the manufacturing of cell-based therapies as well as gene manipulation for research applications. Current technologies capable of delivering large cargoes, such as plasmids and CRISPR-Cas9 ribonucleoproteins (RNPs), are plagued with high costs and/or cytotoxicity and often require substantial specialized equipment and reagents, which may not be available in resource-limited settings. Here, we report an intracellular delivery technology that can be assembled from materials available in most research laboratories, thus democratizing access to intracellular delivery for researchers and clinicians in low-resource areas of the world. These filtroporation devices permeabilize cells by pulling them through the pores of a cell culture insert by the application of vacuum available in biosafety cabinets. In a format that costs less than $10 in materials per experiment, we demonstrate the delivery of fluorescently labeled dextran, expression plasmids, and RNPs for gene knockout to Jurkat cells and human CD34+ hematopoietic stem and progenitor cell populations with delivery efficiencies of up to 40% for RNP knockout and viabilities of >80%. We show that functionalizing the surfaces of the filters with fluorinated silane moieties further enhances the delivery efficiency. These devices are capable of processing 500,000 to 4 million cells per experiment, and when combined with a 3D-printed vacuum application chamber, this throughput can be straightforwardly increased 6-12-fold in parallel experiments.

Synthesis and characterization of a novel thermally stable silane-based host material for blue phosphorescent organic light-emitting diodes

We report a novel thermally stable host material, namely, bis[3-(2-indolo[3,2,1-jk]carbazolyl)phenyl)diphenylsilane (Si-IDCz), for use in blue phosphorescent organic light-emitting diodes (PhOLEDs). Here, Si-IDCz exhibits a high glass transition temperature (Tg) of 151 °C as it contains a thermally stable silane moiety. Additionally, the rigid silicon core within Si-IDCz effectively suppresses molecular interactions, resulting in a wide bandgap and high triplet energy. Here, we used Si-IDCz as the single host for the blue PhOLEDs. The blue PhOLED with the single-host Si-IDCz exhibited an external quantum efficiency (EQE) of over 15%; an EQE of over 11% was maintained at a high luminance of 5000 cd/m2 owing to the high thermal stability of the Si-IDCz. Furthermore, an improved EQE of more than 20% was achieved by introducing a mixed-host system to enhance the photoluminescence quantum yield; the efficiency roll-off was reduced as well.

The Mechanical Properties Relationship of Radiation-Cured Nanocomposites Based on Acrylates and Cationic Polymerized Epoxies and the Composition of Silane-Modified Tungsten Disulfide Nanoparticles.

The effect of semiconducting tungsten disulfide (WS2) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1-4 nm) on the NPs' surface having a thickness of 1-4 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345-385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS2 NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS2 NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin's mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS2 NPs.

Multi-treatments based on polydimethylsiloxane and metal-organic framework wrapped with graphene oxide for achieving long-term corrosion and fouling protection: experimental and density functional theory aspects

In this study, ZIF-8 metal–organic framework decorated on surface of graphene oxide nanosheets and functionalized with silane moieties (F-GO@MOF) is employed to enhance the anti-corrosion, anti-bacterial, and anti-fouling properties of epoxy coatings modified with polydimethylsiloxane (epoxy-PDMS). The epoxy-PDMS/F-GO@MOF sample has revealed super-hydrophobic behavior with least water contact angle changes (Δθ ≈ 5° while Δθ ≈ 17° is recorded for epoxy-PDMS sample) during 20 days of immersion, twice pull-off adhesion strength (6.8 MPa compared to 3.7 MPa for epoxy-PDMS coating), and significantly higher impedance modulus (8.82 × 108 Ω·cm2 which is 3 times more than the epoxy-PDMS sample) during 60 days of immersion in NaCl electrolyte. The anti-bacterial test against Pseudomonas sp. and anti-fouling monitoring in Qingdao port have shown that fewer bacteria and marine organisms are attached on the epoxy-PDMS/F-GO@MOF coating, respectively, indicating advanced fouling and bacterial resistance of the nanocomposite sample. Based on the theoretical studies by density functional theory (DFT) method, the binding of the components in the GO@MOF complex is notably large which could inhibit the penetration of corrosive agents toward the steel substrate. In addition, the stabilization of the GO@MOF nanohybrid is mainly controlled through van der Waals (vdW) forces.

Hybrid Ligand Polymerization for Weakly Confined Lead Halide Perovskite Quantum Dots

Rational ligand passivation is essential to achieve a higher performance of weakly confined lead halide perovskite quantum dots (PQDs) via a mechanism of surface chemistry and/or microstrain. In situ passivation with 3-mercaptopropyltrimethoxysilane (MPTMS) produces CsPbBr3 PQDs with an enhanced photoluminescence quantum yield (PLQY, ΦPL) of up to 99%; meanwhile, charge transport of the PQD film can be enhanced by one order of magnitude. Herein, we examine the effect of the molecular structure of MPTMS as the ligand exchange agent in comparison to octanethiol. Both thiol ligands promote crystal growth of PQDs, inhibit nonradiative recombination, and cause blue-shifted PL, while the silane moiety of MPTMS manipulates surface chemistry and outperforms owing to its unique cross-linking chemistry characterized by FTIR vibrations at 908 and 1641 cm-1. Emergence of the diagnostic vibrations is ascribed to hybrid ligand polymerization arising from the silyl tail group that confers the advantages of narrower size dispersion, lower shell thickness, more static surface binding, and higher moisture resistance. In contrast, the superior electrical property of the thiol-passivated PQDs is mostly determined by the covalent S-Pb bonding on the interface.

Starch-Directed Synthesis of Worm-Shaped Silica Microtubes

Many strategies have been adopted to prepare silica materials with highly controlled structures, typically using sol-gel chemistry. Frequently, the alkoxysilanes used in sol-gel chemistry are based on monoalcohols, e.g., Si(OEt)4. The structural control over silica synthesis achieved by these precursors is highly sensitive to pH and solvency. Alkoxysilanes derived from the sugar alcohol glycerol (diglycerylsilane) react more slowly and with much less sensitivity to pH. We report that, in the presence of cooled aqueous starch solutions, glyceroxysilanes undergo transesterification with the sugars on starch, leading to (hollow) microtubules resembling worms of about 400 nm in diameter. The tubes arise from the pre-assembly of starch bundles, which occurs only well below room temperature. It is straightforward to treat the first-formed starch/silica composite with the enzyme amylase to, in a programmed fashion, increasingly expose porosity, including the worm morphology, while washing away untethered silica and digested starch to leave an open, highly porous materials. Sintering at 600 °C completely removes the starch silane moieties.

Investigation of a novel approach to the core of stemofoline: enantioselective construction of a bicyclic intermediate with three contiguous chiral centers

<p indent="0mm">The enantioselective synthesis of a bicyclic intermediate containing three contiguous chiral centers for a novel approach to the core of stemofoline is described. A (<italic>S</italic>)-malimide derivative developed in this laboratory was used as the chiral building block. The latter was converted in three steps (<italic>N</italic>-deprotection, a Mitsunobu reaction, and a cross-olefin metathesis) into another malimide with the <italic>N</italic>-substituent bearing a nucleophilic allylic silane moiety. The Grignard reagent addition took place regioselectively at the C-2 carbonyl to yield a hemiaminal. The key intramolecular aza-Sakurai reaction was promoted by trifluoroboron etherate, which led to the desired cyclization in good to excellent combined yields. Four diastereomers were formed from this reaction, whose stereochemistries were determined by NOESY technique. The latter revealed that the major diastereomer (obtained in 35% yield) possessed the correct stereochemistries required for the total synthesis of natural enantiomer of stemofoline. A regioselective Wacker oxidation resulted in the formation of the title compound along with a minor regioisomer (an aldehyde) in a ratio of 18: 1 (combined yield: 50%).

Wettability Alteration to Reduce Water Blockage in Low-Permeability Sandstone Reservoirs

This study is a continuation of our previous work, which focused on a near-wellbore water blockage alleviation by applying a thermally cured silane-functionalized benzoxazine to modify rock wettability. In this new analysis, we have demonstrated that the resin can be applied in low-permeability sandstones (approximately 15 mD as opposed to 100 to 200 mD in the previous study) to change the rock surface wettability from water-wet to intermediate gas-wet. We have also demonstrated that curing temperatures as low as 125 °C (as opposed to 180 °C in our previous study) can significantly change wettability, indicating surface functionalization through the silane moiety and ring-opening polymerization of the benzoxazine moiety. In drainage core flooding experiments at 2.5 wt.% resin loading, compared to untreated samples, brine recovery increments of 6.3 to 6.9% were obtained for curing temperatures of 125 to 180 °C, respectively. A maximum 20% increment in the end-point relative gas permeability was achieved at a curing temperature of 180 °C. A coupled experimental and numerical study, conducted at core and wellbore scales, demonstrates the potential effectiveness of our chemical treatment in improving gas productivity at the field scale. Reservoir simulations indicate a 2.9 to 10.6% improvement in gas deliverability for a treatment radius of 4 to 16 m, respectively.

Green composites from vanillin-based benzoxazine and silane surface modified chopped carbon fibers

By following the rules of green chemistry, a novel composite is developed from a renewable and ecofriendly resource, namely, vanillin. The latter was used as a phenolic precursor for the microwave synthesis of a bio-based benzoxazine resin (Va-BZ). Afterward, high-performance green composites were developed by reinforcing Va-BZ with various amounts of chopped silane surface modified carbon fibers (CFs). The chemical structure of the Va-BZ monomers was confirmed by 1H NMR and Fourier transform infrared spectroscopy. The grafting of the silane moiety on the CF surface was assessed by FTIR and TGA analyses. The autocatalytic ring opening polymerization of the Va-BZ monomers was confirmed by DSC analysis. The mechanical performances of the developed green composites were studied by flexural and tensile investigations. The findings suggested that the maximum amount of 20 wt. CFs afforded the best results, with flexural and tensile strengths of 450 and 462 MPa, respectively. The SEM was used to study the fractured tensile surfaces and elucidated the toughening mechanism. Meanwhile, the TGA showed that the introduction of the CFs markedly improved the thermal stability of the benzoxazine matrix. Overall, this study confirmed that greener approaches can also result in high-performance composites satisfying the needs of exigent applications.

Mechanical and thermal properties of fully green composites from vanillin-based benzoxazine and silane surface modified chopped basalt fibers

By following the rules of green chemistry, a novel composite is developed from a renewable and ecofriendly resource, namely the vanillin. The latter was used as a phenolic precursor for the microwave synthesis of a bio-based benzoxazine resin (Va-BZ). Afterwards, high performance green composites were developed by reinforcing the Va-BZ with various amounts of chopped silane surface modified basalt fibers (BFs). The chemical structure of the Va-BZ monomers was confirmed by 1H NMR and FTIR spectroscopy. The grafting of the silane moiety on the BFs surface was assessed by FTIR and TGA analyses. The autocatalytic ring opening polymerization of the Va-BZ monomers was confirmed by DSC analysis. The mechanical performances of the developed green composites were studied by flexural and tensile investigations. The findings suggested that the maximum amount of 20 wt. BFs afforded the best results, with flexural and tensile strengths of 447 and 460 MPa, respectively. The SEM was used to study the fractured tensile surfaces and elucidated the toughening mechanism. Meanwhile, the TGA showed that the introduction of the BFs markedly improved the thermal stability of the benzoxazine matrix. Finally, the gamma rays shielding effectiveness was studied and revealed the highly benefic role of the BFs. For instance, a 1 cm thick Va-BZ polymer only showed a 6% gamma rays screening ratio, the latter was improved to 18.4% for the composite made of 20 wt.% of treated BFs. Overall, this study confirmed that greener approaches can also result in high performance composite satisfying the needs of exigent applications.

Aqueous bifunctionalization of cellulose nanocrystals through amino and alkyl silylation: functionalization, characterization, and performance of nanocrystals in quartz microflotation

Surface modifications of cellulose nanomaterials can be used to tailor their surface charge and hydrophilicity-hydrophobicity characteristics. Additionally, it can facilitate the selective interaction of nanocelluloses with other solid particles to further expand their applicability in different fields. For instance, cellulose nanocrystals (CNC) with amphiphilic features are potential green alternatives in mineral processing such as particle flotation. In the present study, aqueous, one- and two-step silylation of CNCs with amino and alkyl silanes was considered to create a novel bifunctionalized CNCs that contained both positively charged amino silane moieties and hydrophobic alkyl chains. Especially, the effects of reaction conditions and different reaction routes on the silylation were investigated, and the electric surface potential and hydrophobicity of CNCs were determined. The bifunctionalization conducted by the simultaneous addition of an amino silane and alkyl silane led to a high reaction efficiency, and the grafting amount was notably higher than that obtained with the sequential reactions with individual reagents. After the functionalization, the hydrophobicity of the CNCs was strongly altered, leading to water contact angles of up to 135° on CNC films. However, the silylation with amino silanes slightly affected the ζ-potential of the functionalized CNCs. Due to the relatively low ζ-potential, the interaction and orthokinetic attachment of CNCs onto quartz surfaces were insufficient, resulting in a limited flotation recovery in microflotation using a Hallimond tube.

Flexible Nano-TiO2 Sheets Exhibiting Excellent Photocatalytic and Photovoltaic Properties by Controlled Silane Functionalization-Exploring the New Prospects of Wastewater Treatment and Flexible DSSCs.

TiO2 nanoparticles surface-modified with silane moieties, which can be directly coated on a flexible substrate without the requirement of any binder materials and postsintering processes, are synthesized and characterized using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller, X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, time-correlated single-photon counting, and transmission electron microscopy. The viability of the prepared surface-modified TiO2 (M-TiO2) sheets as a catalyst for the photo-induced degradation of a model dye, methylene blue, was checked using UV–visible absorption spectroscopy. The data suggest that, compared to unmodified TiO2, M-TiO2 sheets facilitate better dye-degradation, which leads to a remarkable photocatalytic activity that results in more than 95% degradation of the dye in the first 10 min and more than 99% of the degradation in the first 50 min of the photocatalytic experiments. We also demonstrate that M-TiO2 can be recycled with negligible reduction in photocatalytic activity. Further, the photovoltaic properties of the developed M-TiO2 sheets were assessed using UV–visible absorption spectroscopy, electrochemical impedance spectroscopy (EIS), and photochronoamperometry. Dye-sensitized solar cells (DSSC) fabricated using M-TiO2 as the photoanode exhibited a photoconversion efficiency of 4.1% under direct sunlight. These experiments suggested that M-TiO2 sheets show enhanced photovoltaic properties compared to unmodified TiO2 sheets, and that, when N-719 dye is incorporated, the dye–TiO2 interaction is more favorable for M-TiO2 than bare TiO2. The simple solution processing method demonstrated in this paper rendered a highly flexible photoanode made of M-TiO2 with superior charge-separation efficiency to an electrode made of bare TiO2. We propose that our findings on the photovoltaic properties of M-TiO2 open up arenas of further improvement and a wide scope for the large-scale production of flexible DSSCs on plastic substrates at room temperature in a cost-effective way.

Sustainable biofuel production from non-edible oils utilizing modified montmorillonite based porous clay heterostructures

ABSTRACT Surface modification was performed for montmorillonite clay by grafting phenyl triethoxy silane moiety followed by sulfonation to obtain the heterogeneous acidic catalyst. The prepared catalyst was recognized using numerous analytical procedures. FTIR spectra inspected the functional groups of the original clay and gave an insight view on the sulfonated clay. XRD provided information on sulfonation of original clay by the shifting of signals at 2θ at 18.5°, 26.55°, and 61.89° peaks to 17.8° (003), 25.5° (003). TPD profile showed the presence of different acidic sites on the surfaces of the studied compounds identified as weak, moderate, and strong types; further, the sulfonation step generated high intensity of the strong acidic sites on the clay surface. Surface area analysis showed that the introduction of sulfonate moieties within the clay framework crowded the pores and decreased their effective area and volume to 66.31 m2/g and 0.11 cm3/g. TGA identification indicated that the introduction of sulfonate groups within the clay framework increased its thermal stability by up to 600°C, due to the hydrogen bonding between the hydroxyl groups of clay and sulfonate groups. The analyses pointed out the successful grafting and sulfonation on the clay. The prepared catalyst was employed during catalytic conversion of used cooking oil and Jatropha oil into their corresponding biofuels. B10 blends of Jatropha oil and used cooking oil by petroleum Jet A-1 have exhibited densities at 0.8037 and 0.8040 g/cm3, while flashpoints were 46°C and 46°C, also the freeze points were also identical at −54 oC. The yield % of Jatropha oil and used cook oil biofuels using the optimum catalyst ratio (0.8% by weight) were 95% and 86%. The biofuels and their blend specifications were measured and compared using the fossil diesel Jet A-1.