Mo-BiVO₄/Ca-BiVO₄ Homojunction Nanostructure-Based Inverse Opals for Photoelectrocatalytic Pharmaceutical Degradation under Visible Light

Homojunction engineering has emerged as a potent strategy to evade interfacial stability issues and improve the efficiency of nanostructured metal oxide photocatalysts, though rarely combined with the enhanced light capture ability of three-dimensional macroporous photonic crystal structures. Herein, the formation of nanoscale n-n+ homojunctions between different Mo- and Ca-doped BiVO4 nanocrystals in the skeleton of photonic band gap (PBG) engineered inverse opals is introduced as an advanced approach to simultaneously promote visible light harvesting, electron transport, and charge separation of BiVO4 nanomaterials for the photoelectrocatalytic degradation of pharmaceutical contaminants of emerging concern. Controlled deposition of BiVO4 inverse opal films with tailored PBGs was combined with compositional tuning by Mo- and Ca-doping for slow-photon-assisted visible-light-activated (VLA) photocatalysis. The introduction of shallow dopant states in the Mo-, Ca-doped BiVO4 nanoparticles with relatively weak structural distortions but significantly different donor concentrations resulted in a broad distribution of type-II homojunctions in the nanocrystalline inverse opal walls. Comparative photoelectrochemical evaluation showed that nanostructured homojunction Mo-BiVO4/Ca-BiVO4 photonic films largely outperformed their individual constituents in both photocurrent generation and the VLA photocatalytic degradation rate. Moreover, they exhibited markedly improved performance in the photoelectrocatalytic degradation of tetracycline and ciprofloxacin broad-spectrum antibiotics as well as salicylic acid under visible light, validating their application potential in VLA water remediation by pharmaceutical micropollutants

A study on natural clinoptilolite for CO₂/N₂ gas separation

<p>Based on its low cost and low water adsorption capacity, compared to synthetic zeolites (A-type, X-type and Y-type), natural, untreated clinoptilolite was examined as a potential adsorbent for a separation process targeting on removal of CO₂ from flue gas. Taking into consideration typical flue gas composition and temperature, adsorptive properties of binary CO₂/N₂ mixtures were tested in the temperature range of 268 to 403 K and compared with literature data. The results showed that CO₂ concentration, total pressure, and temperature strongly affect selectivity and working capacity, restricting the conditions under which the material could be used as an efficient adsorbent.</p

Ionic Liquid-Modified Porous Materials for Gas Separation and Heterogeneous Catalysis

This work examines important physicochemical and thermophysical properties of ultrathin ionic liquid (IL) layers under confinement into the pore structure of siliceous supports and brings significant advances toward understanding the effects of these properties on the gas separation and catalytic performance of the developed supported ionic liquid phase (SILP) and solid catalysts with ionic liquid layers (SCILL). SILPs were developed by making use of functionalized and nonfunctionalized ILs, such as 1-(silylpropyl)-3-methyl-imidazolium hexafluorophosphate and 1-butyl-3-methyl-imidazolium hexafluorophosphate ILs, whereas the SCILL was prepared by effectively dispersing gold nanoparticles (AuNPs) onto the IL layers inside the open pores of the SILP. The information derived from the gas absorption/diffusivity and heterogeneous catalysis experiments was exemplified in relation to the liquid crystalline ordering and orientation of the IL molecules, investigated by X-ray diffraction (XRD) and modulated differential scanning calorimetry (MDSC). The extent of pore blocking was elucidated with small angle neutron scattering (SANS) and was proven to be a decisive factor for the gas separation efficiency of the SILPs. CO₂/CO separation values above 50 were obtained in cases where liquid crystalline ordering of the IL layers and extended pore blocking had occurred. The presence of the IL layer in the developed SCILL assisted the formation of ultrasmall (2–3 nm) and well-stabilized AuNPs. The low-temperature CO oxidation efficiency was 22%. The catalytic experiments showed an additional functionality of the IL, acting as an “in-situ trap” that abstracts the product (CO₂) from the reaction site and improves yield

CO₂ Capture by Novel Supported Ionic Liquid Phase Systems Consisting of Silica Nanoparticles Encapsulating Amine-Functionalized Ionic Liquids

We report novel supported ionic liquid (IL) phase systems, described as “inverse” SILPs, consisting of micron size IL droplets within an envelope of silica nanoparticles. These novel IL-in-air powders, produced by an easily scalable phase inversion process, are stable up to 60 °C and 30 bar and are proposed as a means to confront the major drawbacks of conventional SILPs for gas separation. SILPs are usually formed by filling the channels of nanoporous materials with the IL phase. In case the core space of the pores remains open, such conventional SILPs exhibit lack of gas absorption specificity, while complete pore filling leads to diffusivity that is very low compared to that for corresponding bulk ILs; the latter drop is largely due to the high tortuosity of the pore network of the support. The inverse SILPs prepared in this work exhibited promising CO2/N2 separation performance that had reached the value of 20 at absorption equilibrium and enhanced CO2 absorption capacity of 1.5–3 mmol g–1 at 1 bar and 40 °C. Moreover, the CO2 absorption kinetics were very fast compared to conventional SILP systems and to simultaneous N2 absorption; the CO2/N2 selectivity at the short times of the transient stage of absorption had reached values in excess of 200

Co-assembled MoS₂–TiO₂ Inverse Opal Photocatalysts for Visible Light-Activated Pharmaceutical Photodegradation

Heterostructured photocatalytic materials in the form of photonic crystals have been attracting attention for their unique light harvesting ability that can be ideally combined with judicious compositional modifications toward the development of visible light-activated (VLA) photonic catalysts, though practical environmental applications, such as the degradation of pharmaceutical emerging contaminants, have been rarely reported. Herein, heterostructured MoS2–TiO2 inverse opal films are introduced as highly active immobilized photocatalysts for the VLA degradation of tetracycline and ciprofloxacin broad-spectrum antibiotics as well as salicylic acid. A single-step co-assembly method was implemented for the challenging incorporation of MoS2 nanosheets into the nanocrystalline inverse opal walls. Compositional tuning and photonic band gap engineering of the MoS2–TiO2 photonic films showed that integration of low amounts of MoS2 nanosheets in the inverse opal framework maintains intact the periodic macropore structure and enhances the available surface area, resulting in efficient VLA antibiotic degradation far beyond the performance of benchmark TiO2 films. The combination of broadband MoS2 visible light absorption and photonic-assisted light trapping together with the enhanced charge separation that enables the generation of reactive oxygen species via firm interfacial coupling between MoS2 nanosheets and TiO2 nanoparticles is concluded as a competent approach for pharmaceutical abatement in water bodies

CO₂ Capture Efficiency, Corrosion Properties, and Ecotoxicity Evaluation of Amine Solutions Involving Newly Synthesized Ionic Liquids

The CO₂ capture efficiency of nine newly synthesized ionic liquids (ILs), both in their pure states as well as in binary and ternary systems with water and amines, was investigated. The study encompassed ILs with fluorinated and tricyanomethanide anions as well as ILs that interact chemically with CO₂ such as those with amino acid and acetate anions. Compared to amines, some of the novel ILs exhibited a majority of important advantages for CO₂ capture such as enhanced chemical and thermal stabilities and negligible vapor pressure; the previous features counterbalance the disadvantages of lower CO₂ absorption capacity and rate, making these ILs promising CO₂ absorbents that could partially or totally replace amines in industrial scale processes. In addition to their ability to capture CO₂, important issues including corrosivity and ecotoxicity were also examined. A thorough investigation of the capture efficiency and corrosion properties of several solvent formulations proved that some of the new ILs encourage future commercial-scale applications for appropriate conditions. ILs with a tricyanomethanide anion confirmed a beneficial effect of water addition on the CO₂ absorption rate (ca. 10-fold) and capacity (ca. 4-fold) and high efficiency for corrosion inhibition, in contrast with the negative effect of water on the CO₂ absorption capacity of ILs with the acetate anion. ILs with a fluorinated anion showed high corrosivity and an almost neutral effect of water on their efficiency as CO₂ absorbents. ILs having amino acid anions presented a reduced toxicity and high potential to completely replace amines in solutions with water but, in parallel, showed thermal instability and degradation during CO₂ capture. Tricyanomethanide anion-based ILs had a beneficial effect on the capture efficiency, toxicity, and corrosiveness of the standard amine solutions. As a consolidated output, we propose solvent formulations containing the tricyanomethanide anion-based ILs and less than 10 vol % of primary or secondary amines. These solvents exhibited the same CO₂ capture performance as the 20−25 vol % standard amine solutions. The synergetic mechanisms in the capture efficiency, induced by the presence of the examined ILs, were elucidated, and the results obtained can be used as guidance for the design and development of new ILs for more efficient CO₂ capture