Europium insertion into MgAl hydrotalcite-like compound to promote the photocatalytic oxidation of nitrogen oxides.

Easy synthesis of efficient, non-toxic photocatalysts is a target to expand their potential applications. In this research, the role of Eu3+ doping in the non-toxic, affordable, and easily prepared MgAl hydrotalcite-like compounds (HTlcs) was explored in order to prepare visible light semiconductors. Eu doped MgAl-HTlcs (MA-xEu) samples were prepared using a simple coprecipitation method (water, room temperature and atmospheric pressure) and europium was successfully incorporated into MgAl HTlc frameworks at various concentrations, with x (Eu3+/M3+ percentage) ranging from 2 to 15. Due to the higher ionic radius and lower polarizability of Eu3+ cation, its presence in the metal hydroxide layer induces slight structural distortions, which eventually affect the growth of the particles. The specific surface area also increases with the Eu content. Moreover, the presence of Eu3+ 4f energy levels in the electronic structure enables the absorption of visible light in the doped MA-xEu samples and contributes to efficient electron-hole separation. The microstructural and electronic changes induced by the insertion of Eu enable the preparation of visible light MgAl-based HTlcs photocatalysts for air purification purposes. Specifically, the optimal HTlc photocatalyst showed improved NOx removal efficiency, ∼ 51% (UV-Vis) and 39% (visible light irradiation, 420 nm), with excellent selectivity (> 96 %), stability (> 7 h), and enhanced release of •O2- radicals. Such results demonstrate a simple way to design photocatalytic HTlcs suitable for air purification technologies.

An application of hierarchical MgAl hydrotalcite in the highly efficient treatment of oilfield macromolecular contaminants.

In this work, salicylic acid (SA) was used to induce the self-assembly of octadecyl trimethyl ammonium chloride (OTAC), a cationic surfactant, into three-dimensional wormlike micelle aggregates. These aggregates act as a soft template for hierarchical MgAl hydrotalcite (LDH) to create a multi-level pore structure adsorption material. Scanning electron microscopy characterization showed that the surface of the hierarchical hydrotalcite exhibited a dense layered structure, unlike the monolayer structure of ordinary hydrotalcite. Furthermore, the hierarchical MgAl-LDH possesses a significantly larger specific surface area (113.94 m2/g) and wide pore size distribution ranging more extensively from 2 to 80 nm, which significantly has an impressive adsorption effect on sulfonated lignite (SL), with a maximum adsorption capacity of 192.7 mg/g at pH = 7. Extensive research has been conducted on the adsorption mechanism of hierarchical MgAl-LDH, attributing it to surface adsorption due to the unique multi-level structure of the adsorbent. After two cycles of regeneration experiments, the adsorption capacity of the adsorbent remained at a high level of 179.1 mg/g, demonstrating the excellent renewability of hierarchical MgAl-LDH. Moreover, the hierarchical hydrotalcite showed high adsorption capacity in the adsorption of sulfonated lignite, which was attributed to its larger specific surface area and superior pore structure to expose more active sites.

Modification of Hydrotalcite Loading Tannic Acid with Organic Silane and Application in Anticorrosive Epoxy Coating.

Metal corrosion is a challenge for the world with heavy impacts on the economy. Study on the development of effectiveness anticorrosion additives is a promising strategery for the protection industry. This research focuses on the modification of hydrotalcite Mg-Al (HT) loading tannic acid (TA) with 3-(trimethoxy silyl) propyl methacrylate organo-silane (TMSPM) for applicating as an anti-corrosion additive for epoxy coating on the steel substrate. The suitable ratio of HT and modifiers was investigated and the suitable content of modified HT in epoxy matrix was found based on mechanical properties of the epoxy-based coating. The characteristics of modified HT were assessed through infrared (IR) spectroscopy, X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), thermal gravimetry analysis (TGA), water contact angle (WCA), dynamic light scattering (DLS). Detailly, HT-TA3-S3 shows good stability in distilled water when HT/TA was modified with TMSPM which makes Zeta potential decreases significantly. Besides, SEM analysis presented HT-TA-S has a cylindrical shape about of 500 nm. Moreover, the crystallite size of HT/TA after being modified by TMSPM decreases sharply. All of these prove successfully synthesize HT loading TA with modified TMSPM. Water contact angle (WCA) decreases in case of loading TA and increases in case of modifying with TMSPM (WCA changed from HT (116.3°) to HT-TA (102.4°) and HT-TA-S (120.1°) which indicates the increased hydrophobicity of the sample. The obtained results showed HT/TA was modified successfully with TMSPM. The modification affected the size distribution and surface properties of HT nanoparticles while it did not impact on the crystal structure of HT. After incorporating modified HT/TA into the epoxy coating, the adhesion of coating to steel substrate was improved significantly. Consequently, the adhesion of epoxy/3 wt. % modified HT/TA coating was increased 3 times as compared to epoxy neat (from 0.76 MPa to 2.77 MPa). In addition, the relative hardness and gloss retention of epoxy/3 wt. % modified HT/TA coating reached the maximum values as compared to the others. Owing to salt spraying results, the epoxy/3 wt. % modified HT/TA exhibited an excellent anticorrosion ability for the steel substrate. All the above results show the potential of HT nanoparticles loading TA modified with TMSPM as anticorrosive additives for protective coatings on steel substrates.

Efficient adsorption of rhodamine B using synthesized Mg-Al hydrotalcite/ sodium carboxymethylcellulose/ sodium alginate hydrogel spheres: Performance and mechanistic analysis.

In this study, the sodium dodecyl sulfate intercalated modified magnesium-aluminum hydrotalcite/sodium alginate/sodium carboxymethylcellulose (modified LDHs/SA/CMC) composite gel spheres were synthesized and their efficacies in adsorbing the cationic dye rhodamine B (RhB) from aqueous solutions were evaluated. The effects of adsorption time, pH and temperature on the adsorption of RhB by spheres were investigated. Remarkably, the modified LDHs/SA/CMC gel spheres achieved adsorption equilibrium after 600 min at 25 °C, and the removal rate of RhB at 60 mg/L reached 91.49 % with the maximum adsorption capacity of 59.64 mg/g. The gel spheres maintained over 80 % efficacy across four adsorption cycles. Kinetic and isotherm analyses revealed that the adsorption of RhB conformed to the secondary kinetic model and the Langmuir isotherm, indicating a spontaneous and exothermic nature of the adsorption process. The adsorption mechanisms of modified LDHs/SA/CMC gel spheres on RhB dyes include electrostatic adsorption, hydrogen bonding and hydrophobic interactions. In conclusion, modified LDHs/SA/CMC gel sphere is a green, simple, recyclable and efficient adsorbent, which is expected to be widely used for the treatment of cationic dye wastewater.

Synthesis of layered double hydroxides: Investigating the impact of stirring conditions and reactor design parameters.

The synthesis by coprecipitation of Layered Double Hydroxides (LDHs) is governed by the stages of nucleation and crystal growth associated with the efficiency of the mixing and dispersion process of the reagents. Mixing efficiency is related to process variables, such as agitation speed, type of impeller and baffles presence, among others. In this context, this work proposes an analysis of these variables in a batch reactor, using a 23 factorial design employing the factors: acceleration speed (200 and 1000 rpm), mixing time (2 and 18 h) and presence or absence of baffles. The results were evaluated quantitatively (amount of LDH produced, time and amount of base for the formation of LDHs to begin) and qualitatively (mixing aspects, sedimentation ad grinding). The significant factors affecting the amount of LDH produced (51.94-80.81 g) were agitation speed and aging time. These factors were also correlated with the structural characteristics of the materials produced, such as crystallinity, crystallite size (70.99-174.79 nm), surface area (69.81-97.62 m2/g), pore volume (0.28-0.59 cm3/g), and pore diameter (11.40-34.66 nm). LDHs produced at higher agitation rates (1000 rpm) and longer aging times (18 h) yielded higher quantities of materials (80.81 g) with improved structural characteristics. The study highlights the importance of systematically exploring the synergistic effect between process variables, emphasizing the research potential in this area.

Optimizing Green Synthesis of Hydrotalcite - Silver Nanoparticles using Syzygium Nervosum based Reducing Agent.

Hydrotalcite-silver (HT-Ag) nanoparticles have been involved in various daily crucial applications, such as antibacterial, photocatalytic, adsorption, etc. There are many approaches to synthesizing silver nanoparticles (AgNPs) decorated on hydrotalcite (HT) surface and the most used approach is using a strong reducing agent. Thus, affordable but effective "green" reducing agents - Syzygium nervosum leaf extract, are taken into account in this work to solve several issues related to chemical reducing agents. This work aimed to assess the effect of Syzygium nervosum leaf extract as a reducing agent for green synthesis of AgNPs on HT through an optimizing process using response surface methodology (RSM) and the Box-Benken model. The optimal conditions for the synthesis of AgNPs on HT include a reaction time of 6.15 hours, a reaction temperature of 50 °C, and the ratio of diluted Syzygium nervosum leaf extract to reduce AgNO3 of 50.37 mL/mg. Under the optimal conditions, the yield of the reduction reaction reached 77.54 %, close to the theoretical value of 76.97 %. The optimization model was suitable for the experiment data. Besides, the morphology, density, and characteristics of AgNPs on the surface of HT layers have been determined by using Ultraviolet-visible spectroscopy, Field emission scanning electron microscopy (FESEM), High-resolution transmission electron microscopy (HR-TEM), selected area diffraction, X-ray diffraction, Dynamic light scattering (DLS), Infrared (IR) spectroscopy, Fluorescence emission spectroscopy (FE), Brunauer-Emmett-Teller (BET) methods. The spherical AgNPs were synthesized successfully on the surface of HT with the average particle size of 13.0±1.1 nm. Interestingly, HT-Ag hybrid materials can inhibit strongly the growth of E. coli, S. aureus as well as two antibiotic resistance bacterial strains, P. stutzeri B27, and antibiotic resistance E. coli. Especially, the antibacterial activity quantification and durability of the HT-Ag hybrid materials were also tested. Overall, the HT-Ag hybrid materials are very promising for application in material science and biomedicine fields.

Phenolic Monoterpenes Conversion of Conobea scoparioides Essential Oil by Hydrotalcite Synthesized from Blast-Furnace Slag.

Conobea scoparioides (Plantaginaceae) is an herbaceous plant known as "pataqueira" that grows wild in seasonally wet areas of the Amazon region. It is used for aromatic baths and anti-protozoan remedies by the Brazilian Amazon native people. The main volatile compounds identified in the essential oil of "Pataqueira" were the phenolic monoterpenes thymol and thymol methyl ether and their precursors, the monoterpene hydrocarbons α-phellandrene and p-cymene. A hydrotalcite synthesized from blast-furnace slag exhibited a 3:2 (Mg/Al) molar ratio, and this layered double hydroxide (LDH) was evaluated as a catalyst in converting the main monoterpenes of the "Pataqueira" oil. This action significantly increased the thymol content, from 41% to 95%, associated with the percentual reduction in other main components, such as thymol methyl ether, α-phellandrene, and p-cymene. The LDH reaction showed a strong tendency towards producing hydroxylated derivatives, and its behavior was similar to the hypothetical plant biosynthetic pathway, which leads to the production of the monoterpenes of "Pataqueira" oil. Thymol and its derivatives are potent antiseptics applied in pharmaceutical and hygienic products as antibacterial, antifungal, and antioxidant properties, among others. The present work reports a natural source with a high thymol content in aromatic plants from the Amazon, with evident economic value.

Application of cobalt-cerium-iron ternary layered double hydroxide for extraction of perfluorooctane sulfonate followed by HPLC-MS/MS analysis.

Herein, Ce-doped CoFe layered double hydroxide (LDH), noted as CoCeFe ternary LDH, was prepared using the co-precipitation route. Prosperous synthesis of CoFe LDH and successful partial replacement of iron cations with cerium cations in CoCeFe ternary LDH were confirmed by X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and elemental dot-mapping images. Nanosheet morphology was recognized for both CoFe LDH and CoCeFe ternary LDH from scanning electron microscopy and transmission electron microscopy micrographs. In the following, a dispersive solid phase extraction (DSPE) method was developed using the synthesized CoCeFe ternary LDH as a sorbent for extracting perfluorooctanesulfonic acid (PFOS) from wastewater samples. For the selective analysis of PFOS, high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) in multiple reaction monitoring mode was used. Analytical parameters such as the limit of detection equal to 0.02 µg/L, with a linear range of 0.05-300 µg/L, the limit of quantification equal to 0.05 µg/L, and an enrichment factor equal to 23.3 were achieved for PFOS at the optimized condition (sorbent: 5 mg of CoCeFe ternary LDH, eluent type and volume: 150 µL mobile phase, pH: 3, adsorption time: 3 min, and desorption time: 5 min). The developed strategy for the analysis of PFOS was tested in real wastewater samples, including copper mine and petrochemical wastewater. The amount of analytes in real samples was calculated using the standard addition method, and good relative recovery in the range of 86%-105% was obtained. The main novelty of this research is the application of CoCeFe ternary LDH to extract the PFOS from wastewater using the DSPE method for determination by HPLC-MS/MS.

Integrated study of antiretroviral drug adsorption onto calcined layered double hydroxide clay: experimental and computational analysis.

This study focused on the efficacy of a calcined layered double hydroxide (CLDH) clay in adsorbing two antiretroviral drugs (ARVDs), namely efavirenz (EFV) and nevirapine (NVP), from wastewater. The clay was synthesized using the co-precipitation method, followed by subsequent calcination in a muffle furnace at 500 °C for 4 h. The neat and calcined clay samples were subjected to various characterization techniques to elucidate their physical and chemical properties. Response surface modelling (RSM) was used to evaluate the interactions between the solution's initial pH, adsorbent loading, reaction temperature, and initial pollutant concentration. Additionally, the adsorption kinetics, thermodynamics, and reusability of the adsorbent were evaluated. The results demonstrated that NVP exhibited a faster adsorption rate than EFV, with both reaching equilibrium within 20-24 h. The pseudo-second order (PSO) model provided a good fit for the kinetics data. Thermodynamics analysis revealed that the adsorption process was spontaneous and exothermic, predominantly governed by physisorption interactions. The adsorption isotherms followed the Freundlich model, and the maximum adsorption capacities for EFV and NVP were established to be 2.73 mg/g and 2.93 mg/g, respectively. Evaluation of the adsorption mechanism through computational analysis demonstrated that both NVP and EFV formed stable complexes with CLDH, with NVP exhibiting a higher affinity. The associated adsorption energies were established to be -731.78 kcal/mol for NVP and -512.6 kcal/mol for EFV. Visualized non-covalent interaction (NCI) graphs indicated that hydrogen bonding played a significant role in ARVDs-CLDH interactions, further emphasizing physisorption as the dominant adsorption mechanism.

Sequential hydrotalcite precipitation, microbial sulfate reduction and in situ hydrogen sulfide removal for neutral mine drainage treatment.

This study proposed and examined a new process flowsheet for treating neutral mine drainage (NMD) from an open-pit gold mine. The process consisted of three sequential stages: (1) in situ hydrotalcite (HT) precipitation; (2) low-cost carbon substrate driven microbial sulfate reduction; and (3) ferrosol reactive barrier for removing biogenic dissolved hydrogen sulfide (H2S). For concept validation, laboratory-scale columns were established and operated for a 140-days period with key process performance parameters regularly measured. At the end, solids recovered from various depths of the ferrosol column were analysed for elemental composition and mineral phases. Prokaryotic microbial communities in various process locations were characterised using 16S rRNA gene sequencing. Results showed that the Stage 1 HT-treatment substantially removed a range of elements (As, B, Ba, Ca, F, Zn, Si, and U) in the NMD, but not nitrate or sulfate. The Stage 2 sulfate reducing bioreactor (SRB) packed with 70 % (v/v) Eucalyptus woodchip, 1 % (w/v) ground (<1 mm) dried Typha biomass, and 10 % (w/v) NMD-pond sediment facilitated complete nitrate removal and stable sulfate removal of ca. 50 % (50 g-SO4 m-3 d-1), with an average H2S generation rate of 10 g-H2S m-3d-1. The H2S-removal performance of the Stage 3 ferrosol column was compared with a synthetic amorphous Fe-oxyhydroxide-amended sand control column. Although both columns facilitated excellent (95-100 %) H2S removal, the control column only enabled a further ca. 10 % sulfate reduction, giving an overall sulfate removal of 56 %. In contrast, the ferrosol enabled an extra 99.9 % sulfate reduction in the SRB effluent, leading to a near complete sulfate removal. Overall, the process successfully eliminated a range of metal/metalloid contaminants, nitrate, sulfate (2500 mg-SO4 L-1 in the NMD to <10 mg-SO4 L-1 in the final effluent) and H2S (>95 % removal). Further optimisation is required to minimise release of ferrous iron from the ferrosol barrier into the final effluent.

Unlocking high-performance HCl adsorption at elevated temperatures: the synthesis and characterization of robust Ca-Mg-Al mixed oxides.

The presence of HCl and SO2 gas imposes limitations on syngas utilization obtained from household waste in a wide range of applications. The hydrotalcite-like compounds (HTLs) have been proved that could remove HCl efficiency. However, the research on impact of synthesis conditions of HTLs and SO2 on HCl removal was limited. In this study, a range of Ca-Mg-Al mixed oxide sorbents was synthesized by calcining HTLs, with variations in crystallization temperature, solution pH, and the Ca/Mg molar ratio. These sorbents were examined for their effectiveness in removing HCl at medium-high temperatures under diverse conditions. The adsorption performance of selected sorbents for the removal of HCl, SO2, and HCl-SO2 mixed gas at temperature of 350 °C, 450 °C, and 550 °C, respectively, was evaluated using thermogravimetric analysis (TGA). It was observed that the HTL synthesis parameters significantly influenced the HCl adsorption capacity of Ca-Mg-Al mixed oxides. Notably, HTLs synthesized at 60 °C, a solution pH of 10-11, and a Ca/Mg ratio of 4 exhibited superior crystallinity and optimal adsorption characteristics. For individual HCl and SO2 removal, temperature had a minor effect on HCl adsorption but significantly impacted SO2 adsorption rates. At temperatures above 550 °C, SO2 removal efficiency substantially decreased. When exposed to a mixed gas, the Ca-Mg-Al mixed oxides could efficiently remove both HCl and SO2 at temperatures below 550 °C, with HCl dominating the adsorption process at higher temperatures. This dual-action capability is attributed to several mechanisms through which HTL sorbents interacted with HCl, including pore filling, ion exchange, and cation exchange. Initially, HCl absorbed onto specific sites created by water and CO2 removal due to the surface's polarity. Subsequently, HCl reacted with CaCO3 and CaO formed during HTL decomposition.

Impact of inhibitor loaded with pigments content on properties of inorganic zinc rich coatings.

In order to overcome the poor dispersion of traditional inorganic zinc-rich coating, addressing the sedimentation and the agglomeration caused by high zinc powder content and improve the anti-corrosion performance of coatings. In this paper, the molybdate intercalated hydrotalcite flake zinc layer double hydroxide (ZnAl-NO3-/LDH) was synthesized by hydrothermal synthesis method at first, and the KH560 modified the Mo/LDH flake zinc powder was further obtained by ion exchange method. The results show that the samples have a layered structure of hydrotalcite with good crystal structure through X-ray diffraction (XRD) and Fourier transform infrared (FT-IR), and the molybdate corrosion inhibiting ions inserted successfully into the interlayer structure of hydrotalcite. Meanwhile, different contents of pigments and fillers were added into the inorganic zinc-rich coatings. It was found that the Nyquist radius of curvature and modulus value of the coating were the largest with a pigment and filler content of 40 %, the maximum corrosion potential was -0.017V, and the minimum corrosion current density was 3.377 × 10-7 A-cm-2. The result indicates that the coating has the best corrosion resistance with 40 % pigment content, which has good application prospects in the fields of cross-sea bridges, natural gas and oil pipelines et al.

Mesoporous-Layered Double Oxide/MCM-41 Composite with Enhanced Catalytic Performance for Cyclopentanone Aldol Condensation.

Layered double oxides are widely employed in catalyzing the aldol condensation for producing biofuels, but its selectivity and stability need to be further improved. Herein, a novel MCM-41-supported Mg-Al-layered double oxide (LDO/MCM-41) was prepared via the in situ integration of a sol-gel process and coprecipitation, followed by calcination. This composite was first employed to catalyze the self-condensation of cyclopentanone for producing high-density cycloalkane precursors. LDO/MCM-41 possessed large specific surface area, uniform pore size distribution, abundant medium basic sites and Bronsted acid sites. Compared with the bulk LDO, LDO/MCM-41 exhibited a higher selectivity for C10 and C15 oxygenates at 150 °C (93.4% vs. 84.6%). The selectivity for C15 was especially enhanced on LDO/MCM-41, which was three times greater than that on LDO. The stability test showed that naked LDO with stronger basic strength had a rapid initial activity, while it suffered an obvious deactivation due to its poor carbon balance. LDO/MCM-41 with lower basic strength had an enhanced stability even with a lower initial activity. Under the optimum conditions (50% LDO loading, 170 °C, 7 h), the cyclopentanone conversion on LDO/MCM-41 reached 77.8%, with a 60% yield of C10 and 15.2% yield of C15.

Preparation of Steel-Slag-Based Hydrotalcite and Its Adsorption Properties on Cl- and SO42.

Large amounts of chloride ions (Cl-) and sulfate ions (SO42-) are present in salt-washing wastewater, making it unsuitable for direct release. Adsorption can be used to eliminate Cl- and SO42- from salt-washing wastewater, and hydrotalcite is an excellent adsorbent with high adsorption properties for these ions because of a layered bimetallic hydroxide structure. The selective extraction of various metals, such as calcium, magnesium, aluminum, and iron, from steel slag via acid leaching facilitates the utilization of steel slag in the preparation of hydrotalcite. In this study, the leaching mechanism of metal in steel slag was investigated using steel slag as a raw material and acetic acid as the reaction medium. The study obtained the optimal leaching mechanism for preparing hydrotalcite. Hydrotalcite was synthesized from the steel slag leaching solution by hydrothermal synthesis, and its structure was characterized. The adsorption performance of Cl- and SO42- in salt-washing wastewater was investigated by solution adsorption experiments. The removal rates of Cl- and SO42- in salt-washing wastewater reached 12.8% and 38.0%, respectively. After multiple adsorption cycles, the removal rates increased to 98.0% for Cl- and 96.4% for SO42-.

Ni-Based Hydrotalcite (HT)-Derived Cu Catalysts for Catalytic Conversion of Bioethanol to Butanol.

Catalytic conversion of biomass-derived ethanol into n-butanol through Guerbet coupling reaction has become one of the key reactions in biomass valorization, thus attracting significant attention recently. Herein, a series of supported Cu catalysts derived from Ni-based hydrotalcite (HT) were prepared and performed in the continuous catalytic conversion of ethanol into butanol. Among the prepared catalysts, Cu/NiAlOx shows the best performance in terms of butanol selectivity and catalyst stability, with a sustained ethanol conversion of ~35% and butanol selectivity of 25% in a time-on-stream (TOS) of 110 h at 280 °C. While for the Cu/NiFeOx and Cu/NiCoOx, obvious catalyst deactivation and/or low butanol selectivity were obtained. Extensive characterization studies of the fresh and spent catalysts, i.e., X-ray diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Hydrogen temperature-programmed reduction (H2-TPR), reveal that the catalysts' deactivation is mainly caused by the support deconstruction during catalysis, which is highly dependent on the reducibility. Additionally, an appropriate acid-base property is pivotal for enhancing the product selectivity, which is beneficial for the key process of aldol-condensation to produce butanol.

Photo- and Thermocatalytic CO2 Methanation: A Comparison of Ni/Al2O3 and Ni-Ce Hydrotalcite-Derived Materials under UV and Visible Light.

Catalysts derived from Ni/Al/Mg/Ce hydrotalcite were prepared via a co-precipitation method, varying the Ce/Al atomic ratio. All of the catalytic systems thus prepared were tested for CO2 methanation under dark and photocatalytic conditions (visible and ultraviolet) under continuous flow with the light intensity set to 2.4 W cm-2. The substitution of Al by Ce formed a solid solution, generating oxygen vacancies and Ce3+/Ce4+ ions that helped shift the dissociation of CO2 towards the production of CH4, thus enhancing the activity of methanation, especially at lower temperatures (<523 K) and with visible light at temperatures where other catalysts were inactive. Additionally, for comparison purposes, Ni/Al2O3-based catalysts prepared via wetness impregnation were synthesized with different Ni loadings. Analytical techniques were used for the characterization of the systems. The best results in terms of activity were as follows: Hydrotalcite with Ce promoter > Hydrotalcite without Ce promoter > 25Ni/Al2O3 > 13Ni/Al2O3. Hydrotalcite, with a Ce/Al atomic ratio of 0.22 and a Ni content of 23 wt%, produced 7.74 mmol CH4 min-1·gcat at 473 K under visible light. Moreover, this catalyst exhibited stable photocatalytic activity during a 24 h reaction time with a CO2 conversion rate of 65% and CH4 selectivity of >98% at 523 K. This photocatalytic Sabatier enhancement achieved activity at lower temperatures than those reported in previous publications.

Layered double hydroxides and their tailored hybrids/composites: Progressive trends for delivery of natural/synthetic-drug/cosmetic biomolecules.

Layered double hydroxides (LDHs) are well-known and important class of hydrotalcite-type anionic clays (HTs) materials that are cost-effective with additional advantages of facile synthesis, composition, tenability, and reusability. These convincing characteristics are liable for their applications in various fields related to energy, environment, catalysis, biomedical, and biotechnology. HTs/LDHs are generally synthesized from low cost abundantly available chemical precursors through the aqueous synthetic pathways under mild reaction conditions. These materials can be termed green materials based on their non-toxic nature, availability of precursors, facile and low-cost production using aqueous medium conditions with less hazardous effluents. Diverse and fascinating characteristics have been attributed to HTs/LDHs like anion exchange ability, surface basicity, biocompatibility, controlled release of the anion specific area, porosity, easy surface modification, and pH dependent biodegradability. Hence, HTs/LDHs and their modified and/or functionalized nanohybrids/nanocomposites are reported as the potential drug delivery carriers with a capability to stabilize the susceptible bioactive molecules, may enhance the solubility of poorly soluble drugs along with controlled drug/bioactive molecule release and delivery. These clay and bioactive hybrid materials have good biocompatibility, less cytotoxicity, and better site-targeting with improved cellular uptake than that of free parent biomolecules. These lamellar solids of micro/nanostructure are compatible, host-guest materials and able to fabricate with drugs/cosmeceutical/bio- or synthetic polymers without any change in their molecular structure and reactivity along with improvement in their stabilities. Other important features are facile synthesis, basicity, high stability with easy storage, and efficient administration with low bio-toxicity. This study enlightens the applications of HTs/LDHs along with their hybrids/composites in the field of drug/cosmeceutical/gene delivery systems of natural/synthetic biomolecules.

Highly Selective and Stable Cu Catalysts Based on Ni-Al Catalytic Systems for Bioethanol Upgrading to n-Butanol.

The catalytic upgrading of ethanol into butanol through the Guerbet coupling reaction has received increasing attention recently due to the sufficient supply of bioethanol and the versatile applications of butanol. In this work, four different supported Cu catalysts, i.e., Cu/Al2O3, Cu/NiO, Cu/Ni3AlOx, and Cu/Ni1AlOx (Ni2+/Al3+ molar ratios of 3 and 1), were applied to investigate the catalytic performances for ethanol conversion. From the results, Ni-containing catalysts exhibit better reactivity; Al-containing catalysts exhibit better stability; but in terms of ethanol conversion, butanol selectivity, and catalyst stability, a corporative effect between Ni-Al catalytic systems can be clearly observed. Combined characterizations such as XRD, TEM, XPS, H2-TPR, and CO2/NH3-TPD were applied to analyze the properties of different catalysts. Based on the results, Cu species provide the active sites for ethanol dehydrogenation/hydrogenation, and the support derived from Ni-Al-LDH supplies appropriate acid-base sites for the aldol condensation, contributing to the high butanol selectivity. In addition, catalysts with strong reducibility (i.e., Cu/NiO) may be easily deconstructed during catalysis, leading to fast deactivation of the catalysts in the Guerbet coupling process.

Chemical Recycling of PET Using Catalysts from Layered Double Hydroxides: Effect of Synthesis Method and Mg-Fe Biocompatible Metals.

The chemical recycling of poly(ethylene terephthalate) (PET) residues was performed via glycolysis with ethylene glycol (EG) over Mg-Fe and Mg-Al oxide catalysts derived from layered double hydroxides. Catalysts prepared using the high supersaturation method (h.s.c.) presented a higher surface area and larger particles, but this represented less PET conversion than those prepared by the low supersaturation method (l.s.c.). This difference was attributed to the smaller mass transfer limitations inside the (l.s.c.) catalysts. An artificial neural network model well fitted the PET conversion and bis(2-hydroxyethyl) terephthalate (BHET) yield. The influence of Fe in place of Al resulted in a higher PET conversion of the Mg-Fe-h.s.c. catalyst (~95.8%) than of Mg-Al-h.s.c. (~63%). Mg-Fe catalysts could be reused four to five times with final conversions of up to 97% with reaction conditions of EG: PET = 5:1 and catalyst: PET = 0.5%. These results confirm the Mg-Fe oxides as a biocompatible novel catalyst for the chemical recycling of PET residues to obtain non-toxic BHET for further polymerization, and use in food and beverage packaging.

UV- and visible-light photocatalysis using Ni-Co bimetallic and monometallic hydrotalcite-like materials for enhanced CO2 methanation in sabatier reaction.

The CO2 catalytic reduction activities of four different Co-modified Ni-based catalysts derived from hydrotalcite-like materials (HTCs) prepared by co-precipitation method were investigated under thermal and photocatalytic conditions. All catalysts were tested from 473 to 723 K at 10 bar (abs). The light intensity for photocatalytic reactions was 2.4 W cm-2. The samples were characterized to determine the effect of morphological and physicochemical properties of mono-bimetallic active phases on their methanation activity. The activity toward CO2 methanation followed the next order: Ni > Co-Ni > Co. For the monometallic Ni catalyst an increase of a 72% was achieved in the photo-catalytic activity under UV and vis light irradiation at temperatures lower by > 100 K than those in a conventional reaction. Co-modified Ni based hydrotalcite catalysts performed with stability and no deactivation for the 16 h studied under visible light for methanation at 523 K due to the presence of basic sites.