Characterization of Structural and Surface Properties of Nanocrystalline TiO₂−CeO₂ Mixed Oxides by XRD, XPS, TPR, and TPD

This work focuses on characterizing the structural and surface properties of TiXCe1-XO2 (TiO2−CeO2) mixed oxides using XRD, XPS, BET, H2-TPR, and NH3-TPD techniques. The TiXCe1-XO2 mixed oxides synthesized by the urea coprecipitation method showed unimodal nanoporous structure with pore sizes increasing from 3.7 nm for X = 0.9 to 5.3 nm for X = 0.1. Concomitant with their higher surface area and pore volume, the mixed oxides were nanocrystalline, about 4.0 nm in crystallite size when X = 0.9, and 4.8−5.4 nm when X = 0.1− 0.3, which are significantly smaller than TiO2 and CeO2 single oxides prepared by the same method (8.1 to 8.4 nm). A dominant anatase phase was detected by XRD when X was 0.9 or higher while a cubic fluorite phase was dominant when X was 0.3 or lower. Lattice parameters were changed by incorporating Ce into TiO2, and Ti into CeO2, respectively. This change indicates distortion of structure and was attributed to reduction of Ti4+ to Ti3+, and Ce4+ to Ce3+. XPS (Ce 3d, Ti 2p, O 1s) and H2-TPR revealed that the oxidation state of surface cations decreased, and oxygen deficiency of the surface was significantly enhanced by introducing Ce into TiO2, and Ti into CeO2. The structural and surface modification by introducing Ce into TiO2 increased the reducibility of mixed oxides in H2-TPR. NH3-TPD showed that increasing Ti content in TiXCe1-XO2 enhanced surface acidity. Furthermore, H2O and N2 formation from NH3 was detected by mass spectrometry, which was attributed to the oxidation activity of the TiXCe1-XO2 mixed oxides. The highest NH3 oxidation activity was observed when X = 0.9. The present study clearly established that the structural (crystal phase, crystal size, nanoporosity, pore size) and surface properties (reducibility, oxygen deficiency, acidity, oxidation activity) of the TiXCe1-XO2 mixed oxides can be tailored by controlling their composition by the urea coprecipitation procedure

Adsorption of 2,4,6-trichlorophenol by magnetic mesoporous SiO₂ and the adsorption capacity regeneration by UV photolysis

<p>The adsorption of 2,4,6-trichlorophenol (2,4,6-TCP) on synthesized magnetic mesoporous silica (Fe₃O₄/SiO₂/m-SiO₂, MMS) composites and the regeneration of its adsorption capacity through direct UV photolysis was performed in this work. MMS exhibited good performance in removing 2,4,6-TCP from aqueous solutions. The adsorption ratio of 2,4,6-TCP was determined to be influenced by aquatic pH, dissolved humic acids, ionic strength, temperature, and the loaded adsorbents. The adsorption isotherm fit the Freundlich and Polanyi–Manes model better than the Langmuir model, which indicated that the adsorption of 2,4,6-TCP was more likely a pore-filling process. The calculated adsorbed capacity for 2,4,6-TCP on MMS was 55 mg/g. Direct UV photolysis could decompose the adsorbed 2,4,6-TCP and later regenerate the adsorption capacity of MMS to a certain degree; however, the outer mesoporous silica layer was not UV-persistent, and large parts of the mesoporous silica layer were also shown to be corrupted from the Fe₃O₄/SiO₂ core. Therefore, after long duration UV irradiation, the adsorption of 2,4,6-TCP on regenerated MMS was much lower than on freshly synthesized MMS. These results suggest that the photostability of magnetic core-shell-like nanocomposites should be investigated because parts of the composites might leach into the bulk phase during practical use and cause potential environmental risks, similar to other well-known nanomaterials.</p

Degradable Selenium-Containing Polymers for Low Cytotoxic Antibacterial Materials

Developing biodegradable cationic polymers with high antibacterial efficiency and low cytotoxicity is of great significance in biological applications. Selenium is an essential trace element for the human body, and selenium-containing compounds are promising in various health-related applications. To combine selenium with biodegradability, selenide-functionalized polycaprolactones (PCL) with different hydrophobic substituents were synthesized followed by selenoniumization. The optimal polyselenonium salt showed excellent antibacterial activity with an MBC of 2 μg mL–1 and an MIC of 1 μg mL–1 and exhibited good biocompatibility before and after degradation. In addition, the obtained selenium polymer can be well blended with commercial PCL by electrospinning, and films with good antibacterial activity were prepared. This work enriches the knowledge of selenium derivatives and lays a foundation for follow-up research on selenium cationic polymers in the antimicrobial field

SO₃H-Functionalized Ionic Liquids for Selective Alkylation of <i>p</i>-Cresol with <i>tert</i>-Butanol

The SO3H-functionalized ionic liquids were synthesized by using pyridine and 1,4-butane or 1,3-propane sulfone as the source and characterized by NMR and time-of-flight mass spectrometry. The acidity of the ionic liquids determined by the Hammett method is almost the same as that of a conventional acid, such as H2SO4. The catalytic performance of ionic liquids for the tert-butylation of p-cresol with tert-butanol was evaluated; by using the ionic liquids as catalysts at the optimum reaction conditions, 79% of the p-cresol conversion and 92% of the selectivity to 2-tert-butyl-p-cresol can be obtained. The spent ionic liquid can be recovered and recycled. The possible mechanism for this reaction system was discussed based on the reaction results and the ab initio calculation results

Infrared Study of CO₂ Sorption over “Molecular Basket” Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve

An infrared study has been conducted on CO2 sorption into nanoporous CO2 “molecular basket” sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 °C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO2 sorption capacity at higher temperatures. CO2 sorption/desorption behavior studied by in situ transmission FTIR showed that CO2 is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm−1 with CO2 flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO2 species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO2 exposure time and with raising CO2 sorption temperature. By comparison of the CO2 sorption rate at 25 and 75 °C in terms of differential IR intensities, it was found that CO2 sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO2 is reversible at 75 °C. Comparative IR examination of the CO2 sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO2−amine interaction patterns

Universal Antibacterial Surfaces Fabricated from Quaternary Ammonium Salt-Based PNIPAM Microgels

Because of the excellent film-forming ability of poly­(N-isopropylacrylamide) (PNIPAM) microgel and high-efficient bactericidal property of quaternary ammonium salt (QAS), QAS-based PNIPAM (QAS-PNIPAM) microgels are synthesized and employed to modify the surface of a range of commonly used materials including metal, plastic, and elastomer. Bacterial culture is carried out on such QAS-PNIPAM microgel-modified surfaces to examine the viability of the attached bacteria. It is found that the bactericidal efficiency is nearly 100% on the modified surfaces of all the studied materials. We attribute the high-efficient bactericidal performance of QAS-PNIPAM microgel film to the QAS component rather than the topography of the microgel film itself. In addition, the microgel film is robust and shows great integrity even after culture of the bacteria and repeated rinses, and the cell experiment demonstrates that this microgel film is cyto-compatible. Therefore, such a simple, versatile method of preparing antibacterial films paves the way for future bactericidal applications

Generation of Polarization-Sensitive Modulated Optical Vortices with All-Dielectric Metasurfaces

Optical vortices (OVs) created from helical modes of light have extensive applications in optical manipulation, imaging, and optical communications. Moreover, modulated optical vortices (MOVs) with modified wavefronts could provide new opportunities for fractionating particles and actuating microelectromechanical systems. Traditional devices for generating MOVs include spatial light modulators, spiral phase plates, and so on. However, such bulky devices are difficult to be applied to high-level integrated optical systems. Besides, other MOV generators are typically static and polarization-insensitive. Here, we proposed an all-dielectric metasurface to generate polarization-sensitive MOVs. The intensity patterns of the OVs can be modulated by adding a tangential modulation factor in the phase profile. Independent manipulation of two orthogonal polarizations was adopted via tailoring the geometric parameters of silicon (Si) pillars. We experimentally demonstrated that the metasurface could generate a doughnut and an actinomorphic vortex beams for different polarization inputs. In addition, the intensity pattern of the MOVs can be dynamically tuned by adjusting the polarization angle. This work can benefit optical manipulation and can be further extended to visible and near-infrared bands

Merging Geometric Phase and Plasmon Retardation Phase in Continuously Shaped Metasurfaces for Arbitrary Orbital Angular Momentum Generation

Traditional technologies to generate and manipulate the orbital angular momentum (OAM) suffer from bulky size and do not lend themselves to nanophotonic systems. An ultrathin metasurface based on abrupt phase shift has recently been proposed as an alternative method. Nevertheless, gradient phase was generally approximated by multiple meta-atom/molecules with discrete levels of abrupt phase shift, which not only increases the design and fabrication complexity but also causes difficulties in obtaining simultaneous electrical and optical functionality. Furthermore, a discontinuous phase profile would introduce phase noise to the scattering fields and deteriorate the purity of the OAM beams. Here, we propose a wavefront engineering mechanism by virtue of the spin–orbit interaction in continuously shaped plasmonic metasurfaces, which offers a new approach to generate OAM modes of high purity. Equally important, a method producing arbitrary OAM topological charge, integral and fractional, is demonstrated by merging the plasmon retardation phase with the geometric phase in the proposed continuously shaped metasurfaces. The proposed approach is well supported by full-wave numerical simulations and experimental characterization of the fabricated structure in the visible regime

Physics-data-driven intelligent optimization for large-scale meta-devices

Meta-devices have gained significant attention and have been widely utilized in optical systems for focusing and imaging, owing to their lightweight, high-integration, and exceptional-flexibility capabilities. However, based on the assumption of local phase approximation, traditional design method neglect the local lattice coupling effect between adjacent meta-atoms, thus harming the practical performance of meta-devices. Using physics-driven or data-driven optimization algorithms can effectively solve the aforementioned problems. Nevertheless, both of the methods either involve considerable time costs or require a substantial amount of data sets. Here, we propose a physics-data-driven approach based "intelligent optimizer" that enables us to adaptively modify the sizes of the studied meta-atom according to the sizes of its surrounding ones. Such a scheme allows to mitigate the undesired local lattice coupling effect, and the proposed network model works well on thousands of datasets with a validation loss of 3*10-3. Experimental results show that the 1-mm-diameter metalens designed with the "intelligent optimizer" possesses a relative focusing efficiency of 93.4% (as compared to ideal focusing) and a Strehl ratio of 0.94. In contrast to the previous inverse design method, our method significantly boosts designing efficiency with five orders of magnitude reduction in time. Our design approach may sets a new paradigm for devising large-scale meta-devices

Multistage Anticoagulant Surfaces: A Synergistic Combination of Protein Resistance, Fibrinolysis, and Endothelialization

Anticoagulant surface modification of blood-contacting materials has been shown to be effective in preventing thrombosis and reducing the dose of anticoagulant drugs that patients take. However, commercially available anticoagulant coatings, that is, both bioinert and bioactive coatings, are typically based on a single anticoagulation strategy. This puts the anticoagulation function of the coating at risk of failure during long-term use. Considering the several pathways of the human coagulation system, the synergy of multiple anticoagulation theories may provide separate, targeted effects at different stages of thrombosis. Based on this presumption, in this work, negatively charged poly(sodium p-styrenesulfonate-co-oligo(ethylene glycol) methyl ether methacrylate) and positively charged poly(lysine-co-1-adamantan-1-ylmethyl methacrylate) were synthesized to construct matrix layers on the substrate by electrostatic layer-by-layer self-assembly (LBL). Amino-functionalized β-cyclodextrin (β-CD-PEI) was subsequently immobilized on the surface by host–guest interactions, and heparin was grafted. By adjusting the content of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA), the interactions between modified surfaces and plasma proteins/cells were regulated. This multistage anticoagulant surface exhibits inertness at the initial stage of implantation, resisting nonspecific protein adsorption (POEGMA). When coagulation reactions occur, heparin exerts its active anticoagulant function in a timely manner, blocking the pathway of thrombosis. If thrombus formation is inevitable, lysine can play a fibrinolytic role in dissolving fibrin clots. Finally, during implantation, endothelial cells continue to adhere and proliferate on the surface, forming an endothelial layer, which meets the blood compatibility requirements. This method provides a new approach to construct a multistage anticoagulant surface for blood-contacting materials