Sustainable waste management and recycling of Zn–Al layered double hydroxide after adsorption of levofloxacin as a safe anti-inflammatory nanomaterial

Inorganic nano-layered double hydroxide (LDH) materials are used in the catalytic field, and have demonstrated great applicability in the pharmacological fields. In the current study, we report Zn–Al LDH as an adsorbent for levofloxacin (levo). The physical and chemical properties of the prepared material before and after adsorption were monitored using X-ray diffraction, Fourier-transform infrared (FT-IR) spectroscopic analysis, energy dispersive X-ray spectroscopy (EDX), Brunauer–Emmett–Teller (BET) surface area measurements, high-resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM). Density functional theory (DFT) calculations for levo and its protonated species were studied at the B3LYP/6-311G (d,p) level of theory. The removal percentage of levo was 73.5%. The adsorption isotherm was investigated using nine different models at pH 9, where the obtained correlation coefficients (R²) using the Redlich–Peterson and Toth models were 0.977. The thermodynamic parameters ΔS°, ΔG° and ΔH° were estimated and discussed in detail. Also, to support the adsorption research field, the applicability of the formed waste after the adsorption of levo onto Zn–Al LDH was investigated for medical purposes. The toxicity of levo in both normal and nanocomposite form was studied. Neither toxicological symptoms nor harmless effects were exhibited throughout the in vivo study. The oral anti-inflammatory activity, tested using 6% formalin to produce edema in the footpad, was manifested as a significant increase of 37% in the anti-inflammatory effect of the Zn–Al LDH/levo nanocomposite compared to levo in its normal form.

Zn-Al LDH was synthesized using the co-precipitation method, characterized and used as an efficient adsorbent for the removal of levofloxacin. The safety and toxicity of the administered Zn-AL LDH/levo as a safe anti-inflammatory material.     

Acid–base sites synergistic catalysis over Mg–Zr–Al mixed metal oxide toward synthesis of diethyl carbonate

In heterogeneous catalysis processes, development of high-performance acid–base sites synergistic catalysis has drawn increasing attention. In this work, we prepared Mg/Zr/Al mixed metal oxides (denoted as Mg₂Zr_xAl_1−x–MMO) derived from Mg–Zr–Al layered double hydroxides (LDHs) precursors. Their catalytic performance toward the synthesis of diethyl carbonate (DEC) from urea and ethanol was studied in detail, and the highest catalytic activity was obtained over the Mg₂Zr_0.53Al_0.47MMO catalyst (DEC yield: 37.6%). By establishing correlation between the catalytic performance and Lewis acid–base sites measured by NH₃-TPD and CO₂-TPD, it is found that both weak acid site and medium strength base site contribute to the overall yield of DEC, which demonstrates an acid–base synergistic catalysis in this reaction. In addition, in situ Fourier transform infrared spectroscopy (in situ FTIR) measurements reveal that the Lewis base site activates ethanol to give ethoxide species; while Lewis acid site facilitates the activated adsorption of urea and the intermediate ethyl carbamate (EC). Therefore, this work provides an effective method for the preparation of tunable acid–base catalysts based on LDHs precursor approach, which can be potentially used in cooperative acid–base catalysis reaction.

Mg/Zr/Al mixed metal oxides were prepared via a facile phase transformation process of hydrotalcite precursors, which showed acid–base sites synergistic catalytic performance toward the synthesis of diethyl carbonate from ethanol and urea.     

Tuning the structural properties of cadmium–aluminum layered double hydroxide for enhanced photocatalytic dye degradation

The distinctive layered structure, chemical stability and tunability of layered double hydroxides (LDHs) have led to extensive investigations in various areas of photocatalysis, including photocatalytic water splitting, carbon dioxide photoreduction, and degradation of organic pollutants. Here, a series of visible light active cadmium–aluminum layered double hydroxides (CdAl LDHs) with various Cd²⁺ : Al³⁺ ratios is synthesized via the reaction-diffusion framework (RDF) leading thereby to a hierarchal spherical structure of the LDH. The aim of this study is to develop an optimal CdAl LDH photocatalyst that is activated by solar light irradiation and tested for methylene blue (MB) degradation. The structural and physicochemical properties of the synthesized materials are determined by several imaging and spectroscopic techniques. The photocatalytic study reveals a strong dependence of the photocatalytic activity of the CdAl LDH on the cationic ratio with an optimal performance at a ratio Cd²⁺ : Al³⁺ equal to 3 : 1. A mechanism is proposed whereby the activity is ascribed to the formation of intermediate reactive oxidative species (ROS) during the photodegradation reactions and scrutinised by invoking different ROS quenchers and corroborated by density functional theory (DFT) calculations.

Hierarchical structures of Cd Al LDH of various cationic ratios of Cd : Al are successfully synthesized via the reaction diffusion framework. The obtained microspheres are investigated for the photocatalytic degradation of methylene blue.     

Correction: Sustainable waste management and recycling of Zn–Al layered double hydroxide after adsorption of levofloxacin as a safe anti-inflammatory nanomaterial

Correction for ‘Sustainable waste management and recycling of Zn–Al layered double hydroxide after adsorption of levofloxacin as a safe anti-inflammatory nanomaterial’ by Samar M. Mahgoub et al., RSC Adv., 2020, 10, 27633–27651. DOI: 10.1039/D0RA04898D.

The authors regret that, in the originally published version of this article, the name of the author Fatma I. Abo El-Ela was incorrectly displayed as Fatma L. Abo El-Ela. The correct author list is displayed above.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Effect of unmelted lime on the element distribution behavior on a CaO–SiO2–MgO–Al2O3–FeO–CaF2(–Cr2O3) slag

In this study, a CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂(–Cr₂O₃) slag was chosen according to the compositions of the stainless steel slag for industrial production, and a CaO block was added to the molten slag after the synthetic slag was fully melted. The influences of unmelted lime on the distribution of elements and the structure of product layers at the lime/slag boundary, particularly the existing state of chromium oxide in the chromium-bearing stainless steel slag, were deeply discussed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and FactSage 7.1. The experiment results indicated that when the unmelted lime existed in the CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂ slag system, two product layers of periclase (MgO) and dicalcium silicate (Ca₂SiO₄) at the boundary of the CaO block were formed. However, when the CaO block was added in the CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂–Cr₂O₃ stainless steel slag, besides MgO and Ca₂SiO₄ product layers, needle-shaped calcium chromite (CaCr₂O₄) was also precipitated around the CaO block. Moreover, a small amount of Cr dissolved in the periclase phase. Eh–pH diagrams showed that the CaCr₂O₄ and MgO phase unstably existed in a weak acid aqueous solution. Therefore, the existence of unmelted lime in the stainless steel slag could enhance the leachability of chromium.

The effect of unmelted lime on the distribution of elements and structure of product layers in CaO–SiO₂–MgO–Al₂O₃–FeO–CaF₂(–Cr₂O₂) stainless steel slag and the action of unmelted lime phase mechanism in experimental slags was conducted.     

Diatomite/Cu/Al layered double hydroxide hybrid composites for polyethylene degradation

A diatomite/Cu/Al layered double hydroxide hybrid composite (DI-LDH) was synthesized using the hydrothermal method. The synthesized DI-LDH composites were characterized via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and the Brunauer–Emmett–Teller (BET) method. Polyethylene degradation over DI-LDH was studied in a batch reactor. DI-LDH showed layered structures, indicating that the diatomite/Cu/Al double hydroxide hybrid was successfully synthesized. A significant decrease in the degradation temperature and the released amounts of CO and CO₂ was observed in the DI-LDH catalytic degradation reaction, which indicated that DI-LDH was helpful for the polyethylene degradation reaction. The X-ray photoelectron spectroscopy (XPS) results suggested that the reaction of Cu²⁺ → Cu⁺ occurred in polyethylene catalytic pyrolysis, which resulted in the decrease in the released CO amount. DI-LDH may be a potential environmental catalyst that can be applied to treat LDPE waste.

DI-LDH that can reduce the pyrolysis temperature of LDPE and the release of carbon monoxide (CO) and carbon dioxide (CO₂).     

Synthesis of a novel magnetic Caragana korshinskii biochar/Mg–Al layered double hydroxide composite and its strong adsorption of phosphate in aqueous solutions

Phosphate pollution of aquatic ecosystems is of great concern and requires the development of high-performance materials for effective pollution treatment. To realize efficient phosphate removal from aqueous solution, an easily separable magnetic (Fe₃O₄) Caragana korshinskii biochar/Mg–Al layered double hydroxide composite (denoted as FCB/MAC) was synthesized via two-step electro-assisted modification for the first time. Subsequently, the physical and chemical properties of FCB/MAC were characterized. Furthermore, the sorption mechanism for phosphate removal was investigated in detail. The results indicated that Fe₃O₄ and the Mg–Al layered double hydroxide were successfully embedded in the biochar matrix. Moreover, FCB/MAC exhibited a high phosphate adsorption capacity and excellent magnetic properties for easy recovery. The maximum phosphate sorption capacity of FCB/MAC was 252.88 mg g⁻¹, which is much higher than the capacities of most magnetic phosphate adsorbents. In addition, the adsorption kinetics and isotherms indicated that phosphate adsorption by FCB/MAC was controlled by the pseudo-second-order kinetic model and the Langmuir–Freundlich isotherm model. The phosphate adsorption mechanism involves anion exchange, electrostatic attraction, and ligand exchange. After five adsorption–desorption cycles, the phosphate adsorption capacity of FCB/MAC was 25.71 mg g⁻¹ with 51.43% removal efficiency and high recyclability. Thus, the composite prepared in this study is a promising adsorbent for phosphate removal from aqueous solution, and this work provides an excellent reference for constructing novel biochar-based phosphate adsorbents.

This study describes an optimized two-step electro-assisted modification process for the preparation of biochar modified with Fe₃O₄ and Mg–Al layered double hydroxide.     

Electrochemical oxidation of boron-doped nickel–iron layered double hydroxide for facile charge transfer in oxygen evolution electrocatalysts

The oxygen evolution reaction (OER) is the key reaction in water splitting systems, but compared with the hydrogen evolution reaction (HER), the OER exhibits slow reaction kinetics. In this work, boron doping into nickel–iron layered double hydroxide (NiFe LDH) was evaluated for the enhancement of OER electrocatalytic activity. To fabricate boron-doped NiFe LDH (B:NiFe LDH), gaseous boronization, a gas–solid reaction between boron gas and NiFe LDH, was conducted at a relatively low temperature. Subsequently, catalyst activation was performed through electrochemical oxidation for maximization of boron doping and improved OER performance. As a result, it was possible to obtain a remarkably reduced overpotential of 229 mV at 10 mA cm⁻² compared to that of pristine NiFe LDH (315 mV) due to the effect of facile charge-transfer resistance by boron doping and improved active sites by electrochemical oxidation.

An electrochemically oxidized boron-doped NiFe LDH electrocatalyst was prepared and the electrocatalyst showed improved water oxidation performance.     

SILP materials based on TiO2–SiO2 and TiO2–SiO2/lignin supports as new catalytic materials for hydrosilylation reaction – synthesis,physicochemical characterization and catalysis

The oxide system TiO₂–SiO₂ as well as a TiO₂–SiO₂/lignin system have been obtained by the sol–gel synthesis method and applied as supports in Supported Ionic Liquid Phase (SILP) materials. In total 24 SILP systems were obtained with ionic liquids containing imidazolium, pyridinium, phosphonium or sulfonic cations and bis(trifluoromethylsulfonyl)imide or methylsulfate anions, and homogeneous complexes of rhodium or platinum as the active phase. The supports and catalytic materials were subjected to thorough characterization by elemental analysis, XRD, SEM-EDX, IR, and TGA, and their particle size distribution and porous properties were assessed. The new SILP materials were used in hydrosilylation of 1-octene with 1,1,1,3,5,5,5-heptamethyltrisiloxane. The effectiveness of hydrosilylation reaction catalyzed by the obtained SILP materials for the polar and nonpolar reagents was assessed. All the catalytically active materials were proved to be easy to isolate and reuse, and the best SILP systems have been shown to be active in 10 or more subsequent catalytic cycles.

24 new easily isolated and reusable Pt-SILP and Rh-SILP materials with TiO₂–SiO₂ and TiO₂–SiO₂/lignin supports, with improved durability and stability, as effective catalysts for hydrosilylation reactions.     

Preparation and application of layered double hydroxide nanosheets

Layered double hydroxides (LDH) with unique structure and excellent properties have been widely studied in recent years. LDH have found widespread applications in catalysts, polymer/LDH nanocomposites, anion exchange materials, supercapacitors, and fire retardants. The exfoliated LDH ultrathin nanosheets with a thickness of a few atomic layers enable a series of new opportunities in both fundamental research and applications. In this review, we mainly summarize the LDH exfoliation methods developed in recent years, the recent developments for the direct synthesis of LDH single-layer nanosheets, and the applications of LDH nanosheets in catalyzing oxygen evolution reactions, crosslinkers, supercapacitors and delivery carriers.

Layered double hydroxides (LDHs) with unique structure and excellent properties have been widely studied in recent years.     

Auxiliary-directed etherification of sp2 C–H bonds under heterogeneous metal–organic framework catalysis: synthesis of ethenzamide

An efficient protocol for 8-aminoquinoline assisted alkoxylation and phenoxylation of sp² C–H bonds under heterogeneous catalysis was developed. The optimal conditions employed Cu-MOF-74 (20%), K₂CO₃ base, pyridine ligand or dimethyl formamide solvent, and O₂ oxidant at 80 °C or 100 °C for 24 hours. Cu-MOF-74 revealed remarkably higher activity when compared with other previously commonly used Cu-MOFs in cross coupling reactions, supported copper catalysts, and homogeneous copper salts. The reaction scope with respect to coupling partners included a wide range of various substrates. Interestingly, the developed conditions are applicable for the synthesis of high-profile relevant biological agents from easily accessible starting materials. Furthermore, a leaching test confirmed the reaction heterogeneity and the catalyst was reused and recycled at least 8 times with trivial degradation in activity.

An efficient protocol for 8-aminoquinoline assisted alkoxylation and phenoxylation of sp² C–H bonds under heterogeneous catalysis was developed.     

A class of novel luminescent layered double hydroxide nanotubes

Herein, we report a class of novel lanthanide-doped self-supported layered double hydroxide (LDH) nanotubes featuring a combination of micro- and mesoporosity. The synthesis of the nanotubes has been achieved by a soft-templating strategy. Incorporation of La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺ or Tb³⁺ in the LDHs assisted the self-assembly of the double hydroxide layers onto the surface of Pluronic P-123 worm-like micelles, enabling the formation of the nanotubes. Removal of the micellar template provides accessibility to the mesopores, yielding a network of hollow cylindrical nanotubes with internal diameter of about 10 nm. An antenna molecule (benzene-1,3,5-tricarboxylate, BTC) is hosted in their 1-nanometre-wide micropores. Upon UV excitation, the nanotubes emit light in a set of wavelengths ranging from the ultraviolet to the infrared.

The incorporation of triply charged lanthanides in layered double hydroxides (LDHs) enables the curvature of the LDH sheets, unlocking the possibility of using a soft templating strategy to produce a class of luminescent, hierarchical LDH nanotubes.     

Bifunctional acid–base mesoporous silica@aqueous miscible organic-layered double hydroxides

A facile method for the synthesis of a series of mesoporous silica nanoporous (MSN) aqueous miscible organic layered double hydroxide core@shell nanocomposites using MCM-41, Al-MCM-41, SBA-15, and MCM-48 as the core is reported. These materials exhibit hierarchical morphologies with high surface areas and good porosity. Chemically, these materials offer controllable bifunctional basicity and acidity.

Core@shell materials which exhibit hierarchical morphology with ultra high surface area and controllable pore size and structure have been synthesised.     

层状双氢氧化物在生物工程应用中的研究进展

背景:层状双氢氧化物是一种具有良好的生物相容性和降解性的无机纳米材料,目前已有多种药物成功与其形成插层复合体,并且取得了预期的结果.目的:综述层状双氢氧化物在生物工程领域的研究与应用.方法:通过计算机检索2003/2010的文献为主,学校图书馆检索为辅.中文检索词为"纳米技术,药物载体,层状双氢氧化物,基因,基因治疗,生物传感器,靶向给药",英文检索词为"nanotechnology,drug carrier,layered double hydroxide,gene,gene therapy,biosensor,targeting drug delivery".纳入与层状双氢氧化物应用于生物工程领域相关的文献,例如作为药物载体、基因载体以及在生物传感器等方面的应用.排除关于层状双氢氧化物物理化学性质的研究文献.结果与结论:化学性质不稳定、毒副作用大的药物(包括基因)与层状双氢氧化物的插层复合体不仅能够控释,还能提高药物的稳定性.因此,层状双氢氧化物是一类极具有发展潜力的"绿色"载体材料.但是,目前关于层状双氢氧化物在生物工程中的研究应用仅限于实验室阶段,研究人员需为其应用于临床付出更大的努力.     

A modified random network model for P2O5–Na2O–Al2O3–SiO2 glass studied by molecular dynamics simulations

We investigated the short- and medium-range structural features of sodium aluminosilicate glasses with various P₂O₅ (0–7 mol%) content and Al/Na ratios ranging from 0.667 to 2.000 by using molecular dynamics simulations. The local environment evolution of network former cations (Si, Al, P) and the extent of clustering behavior of modifiers (Na⁺) is determined through pair distribution function (PDF), total correlation function (TDF), coordination number (CN), Q_xⁿ distribution and oxygen speciation analysis. We show that Al–O–P and Si–O–Al linkage is preferred over other connections as compared to a random model and that Si–O–Si linkage is promoted by the P₂O₅ addition, which is related to structural heterogeneity and generates well-separated silicon-rich and aluminum–phosphorus-rich regions. Meanwhile, due to the relatively high propensity of Al to both Si and P, heterogeneity can be partly overcome with high Al content. A small amount of Si–O–P linkages have been detected at the interface of separated regions. Clustering of Na⁺ is also observed and intensified with the addition of P₂O₅. Based on the simulated structural information, a modified random network model for P₂O₅-bearing sodium aluminosilicate glass has been proposed, which could be useful to optimize the mobility of sodium ions and design novel functional glass compositions.

(A) A modified structural model proposed for P₂O₅-bearing sodium aluminosilicate glasses. (B) Degree of preferred connection (DPC) of different T–O–T network linkage for LAP, MAP and HAP glass compositions with various P₂O₅ content.     

A recyclable heterogeneous–homogeneous–heterogeneous NiO/AlOOH catalysis system for hydrocarboxylation of acetylene to acrylic acid

Concerns about the high-valued utilization of coal- and natural gas-based acetylene has provided particular impetus for exploration of acrylic acid (AA) production via one-step hydrocarboxylation reaction. Motivated by simple recovery, recycling and reuse of the catalyst, we report a high-performance NiO/AlOOH catalyst with AA space-time-yield of 412 g_AA g_cat.⁻¹ h⁻¹, obtainable by a simple incipient wetness impregnation method. Detailed kinetic and controlled experiments confirmed that nickel species on such a solid catalyst provide a heterogeneous–homogeneous–heterogeneous catalytic cycle where the chelates formed between CO and leached nickel act as the active species. The thorough recovery of leached nickel species improves the catalyst stability greatly. These preliminary findings indicate further prospects for new heterogeneous catalyst design in traditional homogeneous catalytic systems.

The heterogeneous–homogeneous–heterogeneous catalytic cycle during the hydrocarboxylation of acetylene to acrylic acid over a NiO/AlOOH catalyst.     

Cu(ii) Schiff base complex intercalated into layered double hydroxide for selective oxidation of ethylbenzene under solvent-free conditions

A new heterogeneous catalyst was prepared by intercalation of NNOO donor Cu(ii) Schiff base complex derived from 2-hydroxy-1-naphthaldehyde and 4-amino benzoic acid into Zn–Al layered double hydroxide {LDH-[NAPABA–Cu(ii)]}. Synthesized catalyst was characterized by Inductively coupled plasma atomic emission spectroscopy, energy dispersive X-ray analysis, scanning electron microscopy, X-ray diffraction, Transmission electron microscopy, BET surface area, Fourier transform infrared spectroscopy, thermo-gravimetric analysis, electron paramagnetic resonance spectroscopy and diffuse reflectance UV-visible spectroscopy. The catalytic performance of LDH-[NAPABA–Cu(ii)] was studied for the liquid phase solvent-free oxidation of ethylbenzene at 393 K, using tert-butylhydroperoxide as an oxidant. In oxidation reaction ethylbenzene was oxidized to acetophenone, benzaldehyde and benzoic acid. The major product was acetophenone. A maximum, 80.54% conversion of ethylbenzene was observed after 7 hours. The catalyst was recycled seven times without significant loss of catalytic activity.

A heterogeneous catalytic system, LDH-[NAPABA–Cu(ii)]/TBHP gave maximum 80.54% conversion and 99.60% selectivity for acetophenone in oxidation of ethylbenzene and catalyst can be reused for seven cycles.     

Solid base catalysts derived from Ca–Al–X (X = F−, Cl− and Br−) layered double hydroxides for methanolysis of propylene carbonate

The Ca–Al and Ca–Al–X (X = F⁻, Cl⁻ and Br⁻) catalysts were prepared via thermal decomposition of Ca–Al layered double hydroxides (LDHs), and tested for methanolysis of propylene carbonate (PC) to produce dimethyl carbonate (DMC). The catalytic performance of these catalysts increased in the order of Ca–Al–Br⁻ < Ca–Al < Ca–Al–Cl⁻ < Ca–Al–F⁻, which was consistent with the strong basicity of these materials. The recyclability test results showed that the addition of Al and halogens (F⁻, Cl⁻ and Br⁻) not only stabilized the CaO but also improved the recyclability of the catalysts. Particularly, the Ca–Al–F⁻ catalyst exerted the highest stability after 10 recycles. These catalysts have an important value for the exploitation of DMC synthesis by transesterification of PC with methanol.

The CA-F⁻ catalyst modified with Al³⁺ and F⁻ was highly active and recyclable for dimethyl carbonate synthesis.     

Effect of carbon on the co-presence of metallic tungsten as a nucleation agent and Eu2+ in glass: crystallization of CaO–Al2O3–SiO2 glass probed with Eu2+ luminescence

This study demonstrated simple redox control in glasses by improving the method used to added glass raw materials. Specifically, the effect of carbon on the co-presence of metallic tungsten (W) particles as nucleation agents and Eu²⁺ ions in CaO–Al₂O₃–SiO₂ (CAS) glass was investigated via their crystallization to form CAS glass-ceramics (GCs). In this study, the glass specimens were prepared by mixing glass cullet containing metallic W particles and Eu²⁺ ions, respectively, with a glass batch containing carbon. Whereas the glass specimen was yellowish because of the presence of Eu²⁺ when carbon was not added during the remelting process, the glass specimen prepared with carbon was black because of the presence of metallic W particles. In addition, this specimen displayed the 470 nm emission band in its fluorescence spectrum recorded under 393 nm excitation, which was attributed to the presence of Eu²⁺. According to the fluorescence and transmission spectra, the glass specimen showed a darker coloration and more intense 470 nm emission band compared with the specimen prepared by the conventional melting method that included a remelting process. These results indicated that metallic W and Eu²⁺ were reduced with greater efficiency by the melting method that involved mixing the glass cullet and batch. In addition, the heat-treated glass specimen prepared by the aforementioned mixing method contained a greater amount of metastable CaAl₂Si₂O₈ with increasing heat treatment time as revealed by X-ray diffraction analysis and scanning electron microscopy observation. The intensity of the 470 nm emission band decreased with increasing intensity of the band at 420 nm because of the incorporation of Eu²⁺ into the crystalline phase, and the increase in intensity of the 420 nm band was lineally proportional to the volume fraction of the crystallized glass specimens. The results therefore indicated that the co-presence of metallic W particles as nucleation agents and Eu²⁺ as a probe for tracking the crystallization process was achieved by the addition of carbon during the remelting process of mixed cullet containing W and Eu²⁺ through crystallization of the CAS glass. The results thus demonstrate the importance of improving the method used to added glass raw materials.

Effect of carbon on the co-presence of metallic tungsten (W) as nucleation agents and Eu²⁺ ions as a probe for tracking crystallization in CaO–Al₂O₃–SiO₂ (CAS) glass was demonstrated by efficient reduction method of Eu²⁺ and metallic W.     

Reactive adsorption desulfurization of NiO and Ni0 over NiO/ZnO–Al2O3–SiO2 adsorbents: role of hydrogen pretreatment

Reactive adsorption desulfurization (RADS) of Fluidized Catalytically Cracked (FCC) gasoline on reduced and unreduced NiO/ZnO–Al₂O₃–SiO₂ adsorbents was studied. Various characterizations such as powder X-ray diffraction (XRD), H₂-temperature-programmed reduction (H₂-TPR), the H₂/O₂ pulse titration (HOPT), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are used to evaluate the effects of hydrogen pretreatment of the adsorbents. XRD and HOPT results indicate that NiO is hard to be reduced to Ni⁰ under the conditions of RADS. H₂-TPR shows that NiO might be reduced to Ni⁰ at the temperature of 598 °C, much higher than the temperature of RADS. The Ni 2p_3/2 spectrum of Ni⁰ is not observed for the reduced adsorbent, but the main peak of Ni 2p_3/2 of NiS is found for the spent adsorbent. The unreduced NiO/ZnO–Al₂O₃–SiO₂ adsorbent performs a better desulfurization than the reduced adsorbent at the beginning of desulfurization process. NiO and Ni⁰ are assumed as the main active components and present a good desulfurization ability in RADS. Finally, a change in the RADS mechanism is presented and discussed.

A possible reaction mechanism of desulfurization on NiO/ZnO–Al₂O₃–SiO₂ is discussed.