Heterogeneous Catalyst Research Articles

Synergistic removal of malachite green and Cr(Ⅵ) using ethylenediamine disuccinic acid functionalized silica gel

As common industrial raw materials, malachite green (MG) and Cr(Ⅵ) generally coexist in waste liquids discharged from the paper printing, leather, and textile industries, causing serious harm to humans and the environment. Therefore, developing an effective method for the synergistic removal of MG and Cr(Ⅵ) from aquatic environments is of great research value. In this work, the non-homogeneous Fenton-like catalysts, namely, EDDS-Silica and EDDS-Co2+-Silica were successfully prepared using ethylenediamine disuccinic acid (EDDS) and silica gel (Silica) as raw materials, and a non-homogeneous Fenton-like catalytic method was developed for the efficient and synergistic removal of MG and Cr(Ⅵ) from wastewater. EDDS-Silica and EDDS-Co2+-Silica were analyzed using Fourier infrared spectroscopy and X-ray photoelectron spectroscopy to determine their structural composition and elemental contents. The catalytic degradation and removal effects of these materials in an MG single-waste system were also investigated. The results demonstrated that the incorporation of both materials can overcome the limitation of the conventional Fenton reaction, which is its applicability to acidic environments only. Moreover, EDDS-Co2+-Silica showed better degradation effects on MG than EDDS-Silica. Quantitative calculations based on density functional theory were used to predict the optimal coordination forms between Co2+and EDDS-Silica as well as the MG structure. The lowest unoccupied and highest occupied molecular orbitals of the catalysts were then used to predict the active sites on which MG tends to capture or release electrons during the degradation reaction. The optimal conditions for the synergistic removal of MG and Cr(Ⅵ) from a binary system using EDDS-Co2+-Silica were further investigated under different influencing factors. The results showed that EDDS-Co2+-Silica still had excellent catalytic effect on the degradation rate of MG in the range of pH 3-7, and the optimal conditions were as follows: solution pH, 7; degradation time, 1 h; temperature, 25 ℃; H2O2 concentration, 20 mmol/L; and the initial mass concentration of Cr(Ⅵ), 25 mg/L. Under the above conditions, the degradation rate was increased from 87.25% to 96.67% compared with that in the MG monosystem. Obvious enhancements in degradation effect and efficiency confirmed that the incorporation of EDDS-Co2+-Silica was favorable for the synergistic removal of MG and Cr(Ⅵ) in the binary system. Strongly oxidizing Cr(Ⅵ) can participate in the Fenton reaction, thus promoting MG degradation over a wide pH range. Thus, a positive synergistic effect exists between MG and Cr(Ⅵ). Considering that a large number of metal ions remained in the solution after the degradation reaction, EDDS-Silica was added to the degradation solution, and adsorption experiments were performed for 4 h at 30 ℃to adsorb and remove Cr and Fe via the strong chelating property of EDDS. The total residual mass concentrations of Cr and Fe were 4.96 and 1.02 mg/L, respectively, which meet national emission standards. These findings indicate that EDDS-Silica has good effects on the removal of residual metal ions after the nonhomogeneous Fenton reaction. As heterogeneous Fenton-like catalysts, the aminopolycarboxylic acid-modified materials proposed in this study can simultaneously promote the Fenton reaction and remove residual metal ions, thereby effectively removing MG and Cr(Ⅵ) from the binary system while ensuring that the content of residual metal ions in the system meets environmental emission standards. This study has broad application prospects in dye degradation and heavy-metal-ion wastewater treatment, and provides a reference value and theoretical basis for the development of other similar ligand-modified materials.

Enhanced dye degradation using MIL-53(Fe)-Modified kraft lignin as a heterogeneous Fenton catalyst

MIL-53(Fe), a metal–organic framework (MOF), is capable of degrading harmful organic contaminants, but it has relatively low Fenton catalytic efficiency. To enhance the degradation performance of MIL-53(Fe), we synthesized MIL-53(Fe)-MKL by incorporating modified kraft lignin (MKL) into pristine MIL-53(Fe). The as-prepared composite demonstrated Fenton activity, degrading 97 % of methylene blue (MB) within 50 min. Compared to pristine MIL-53(Fe) (which achieved 62.4 % MB degradation), the MIL-53(Fe)-MKL composite showed a 34.6 % improvement in MB degradation under identical reaction conditions. The incorporated MKL promotes Fe2+ regeneration from Fe3+ in the Fenton process, activating H2O2 to produce OH radicals, which were identified through scavenging experiments and chemical dosimetry with ESR analysis. The MIL-53(Fe)-MKL composite was reused for at least five cycles without a significant decrease in catalytic efficiency. This reported catalyst takes advantage of both MKL and MIL-53(Fe) to enhance catalytic activity, providing a basis for developing innovative catalysts for organic pollutant degradation.

Anchoring Frustrated Lewis Pair Active Sites on Copper Nanoclusters for Regioselective Hydrogenation.

In recent years, the concept of Frustrated Lewis Pairs (FLPs), which consist of a combination of Lewis acid (LA) and Lewis base (LB) active sites arranged in a suitable geometric configuration, has been widely utilized in homogeneous catalytic reactions. This concept has also been extended to solid supports such as zeolites, metal oxide surfaces, and metal/covalent organic frameworks, resulting in a diverse range of heterogeneous FLP catalysts that have demonstrated notable efficiency and recyclability in activating small molecules. This study presents the successful immobilization of FLP active sites onto the surface of ligand-stabilized copper nanoclusters with atomic precision, leading to the development of copper nanocluster FLP catalysts characterized by high reactivity, stability, and selectivity. Specifically, thiol ligands containing 2-methoxyl groups were strategically designed to stabilize the surface of [Cu34S7(RS)18(PPh3)4]2+ (where RSH = 2-methoxybenzenethiol), facilitating the formation of FLPs between the surface copper atoms (LA) and ligand oxygen atoms (LB). Experimental and theoretical investigations have demonstrated that these FLPs on the cluster surface can efficiently activate H2 through a heterolytic pathway, resulting in superior catalytic performance in the hydrogenation of alkenes under mild conditions. Notably, the intricate yet precise surface coordination structures of the cluster, reminiscent of enzyme catalysts, enable the hydrogenation process to proceed with nearly 100% selectivity. This research offers valuable insights into the design of FLP catalysts with enhanced activity and selectivity by leveraging surface/interface coordination chemistry of ligand-stabilized atomically precise metal nanoclusters.

Acidity and stability of Nb(V) active sites doped in SBA-15 and ZrSBA-15: A DFT study

Mesoporous silicas are of great interest in heterogeneous catalysis due to the structural characteristics of their pores and the adjustable catalytic properties that arise from incorporating heteroatoms. The substitution of Zr and Nb into SBA-15 introduces active sites into the material, rendering it a potential catalyst for acid catalysis reactions. However, discussions regarding the acid properties and metal-support interactions in amorphous silicas functionalized with metals are limited in computational chemistry. This study aims to determine the acid strength and charge transfer effects between Zr(IV) and Nb(V) species in mesoporous silica by proposing a representative SBA-15 cluster of type 5–6. Density Functional Theory (DFT) simulations were conducted using the B3LYP/6-31G(d,p)/def2TZVP levels. The model successfully replicated trends from larger clusters, demonstrating that the more grafted onto the silica structure (i.e. have more Si-O-M bonds), the greater the acid strength of the active site. Additionally, it was found that ZrSBA-15 structures are more stable than NbSBA-15 and possess higher acid strength, a trend supported by experimental observations. The results also suggest that Nb(V) species are more effectively stabilized in ZrSBA-15 than SBA-15, likely due to the presence of Zr(IV) centers in ZrSBA-15. This research contribute to a better understanding of how the support affects the stabilization of active phases, paving the way for the rational design of silica-based heterogeneous catalysts.

The surface chemistry of cuprous oxide

The chemical and electronic properties of copper combined with its large natural abundance lend this material to impact a wide range of technological applications, including heterogeneous catalysis. The reactivity of copper in its Cu1+oxidation state makes this specific configuration relevant in various chemical reactions, but the facile redox properties of copper make the isolation of individual states for fundamental studies difficult. Here we review three Cu2O model systems used to study the interaction of Cu1+ with small molecules making use of surface science techniques: Cu2O/Cu(111), thin polycrystalline Cu2O films on Cu foil, and bulk Cu2O crystals. Advantages and disadvantages of each system are discussed and exemplified through case studies of chemical adsorption and reactivity studies.

Selective recovery of platinum from spent catalysts to fabricate platinum/amorphous manganese oxide/corrugated silica carrier for formaldehyde removal

The efficient recovery and reutilization of spent Pt catalysts have two huge challenges in the metallurgical and chemical industries. Herein, platinum was selectively retrieved from spent Pt/γ-Al2O3 catalysts by a microwave-assisted aqua regia digestion strategy, and the as-obtained platinum extract was utilized to prepare a novel Pt/amorphous MnOx/corrugated silica carrier (Pt/MnOx/CSC) catalyst for formaldehyde removal. To decrease consumption of toxic aqua regia, the γ-Al2O3 in the spent catalysts was converted to chemically stabile α-Al2O3 via high-temperature calcination. The high Pt leaching efficiency of 98.31% was achieved at a digestion temperature of 110oC and aqua regia concentration of 40vol%. However, the high leaching temperatures and aqua regia concentrations caused the part dissolution of α-Al2O3, and thus decreased the Pt leaching efficiency. The CSC in the Pt/MnOx/CSC catalysts served as a support, while both the Pt nanoparticles and amorphous MnOx microspheres acted as active catalysts. The synergistical effects between the Pt and amorphous MnOx endowed the composite catalysts with excellent catalytic activity, and the HCHO removal efficiency reached 100% even after five cycle tests. On the one hand, the nanostructured MnOx microspheres provided great surface areas and rich oxygen vacancies for heterogeneous catalysis. On the other hand, the Pt nanoparticles not only enhanced the low-temperature reducibilities of MnOx, but also decreased the apparent activation energies of HCHO catalytic oxidation. This work provided a new strategy for the selective recovery of platinum from spent catalysts and the reutilization of Pt-based catalysts for the HCHO thermal catalytic oxidation.

PdMoPtCoNi High Entropy Nanoalloy with d Electron Self-Complementation-Induced Multisite Synergistic Effect for Efficient Nanozyme Catalysis.

Engineering multimetallic nanocatalysts with the entropy-mediated strategy to reduce reaction activation energy is regarded as an innovative and effective approach to facilitate efficient heterogeneous catalysis. Accordingly, conformational entropy-driven high-entropy alloys (HEAs) are emerging as a promising candidate to settle the catalytic efficiency limitations of nanozymes, attributed to their versatile active site compositions and synergistic effects. As proof of the high-entropy nanozymes (HEzymes) concept, elaborate PdMoPtCoNi HEA nanowires (NWs) with abundant active sites and tuned electronic structures, exhibiting peroxidase-mimicking activity comparable to that of natural horseradish peroxidase are reported. Density functional theory calculations demonstrate that the enhanced electron abundance of HEA NWs near the Fermi level (EF) is facilitated via the self-complementation effect among the diverse transition metal sites, thereby boosting the electron transfer efficiency at the catalytic interface through the cocktail effect. Subsequently, the HEzymes are integrated with a portable electronic device that utilizes Internet of Things-driven signal conversion and wireless transmission functions for point-of-care diagnosis to validate their applicability in digital biosensing of urinary biomarkers. The proposed HEzymes underscore significant potential in enhancing nanozymes catalysis through tunable electronic structures and synergistic effects, paving the way for reformative advancements in nano-bio analysis.

Efficiently Catalyzing Xylose to Furfural by Synthesizing Solid Acid Catalysts from Lignocellulosic Residues

AbstractThe utilization of biomass as a carbon source for the synthesis of renewable solid acid catalysts (SA) has emerged as a prominent research direction in the field of heterogeneous catalysis. Based on the challenges associated with reusing residues from lignocellulosic biorefining, the biomass‐based SA (BCSA) were prepared using poplar sawdust (PS), hydrothermally pretreated PS (PPS), and the residue of PPS's enzymatic hydrolysis (ER). The characterization revealed that all three types of BCSA were loaded with catalytic groups, and the BCSA synthesized using ER rich in lignin components exhibited a highly efficient catalytic structure. Furthermore, the catalysis of a 20 g/L xylose solution with BCSA‐ER as SA also achieved the highest furfural yield (89.3%) and furfural selectivity (90.3%). The findings of this study suggested that lignin holds significant potential as a carbon carrier for SA, thereby offering a viable solution for utilizing by‐products from lignocellulosic biorefining.

Asymmetric Microenvironment Tailoring Strategies of Atomically Dispersed Dual-Site Catalysts for Oxygen Reduction and CO2 Reduction Reactions.

Dual-atom catalysts (DACs) with atomically dispersed dual-sites, as an extension of single-atom catalysts (SACs), have recently become a new hot topic in heterogeneous catalysis due to their maximized atom efficiency and dual-site diverse synergy, because the synergistic diversity of dual-sites achieved by asymmetric microenvironment tailoring can efficiently boost the catalytic activity by optimizing the electronic structure of DACs. Here, this work first summarizes the frequently-used experimental synthesis and characterization methods of DACs. Then, four synergistic catalytic mechanisms (cascade mechanism, assistance mechanism, co-adsorption mechanism and bifunction mechanism) and four key modulating methods (active site asymmetric strategy, transverse/axial-modification engineering, distance engineering and strain engineering) are elaborated comprehensively. The emphasis is placed on the effects of asymmetric microenvironment of DACs on oxygen/carbon dioxide reduction reaction. Finally, some perspectives and outlooks are also addressed. In short, the review summarizes a useful asymmetric microenvironment tailoring strategy to speed up synthesis of high-performance electrocatalysts for different reactions.

Electron-withdrawing effect of polyoxometalates in Cu(I)-based metal–organic frameworks for enhanced azide-alkyne “click” reaction

Boosting the nucleophilicity of Cu(I) sites is an essential strategy to enhance the efficiency of Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In this work, a Lindquist-type polyoxometalate (POM)-based metal–organic framework, [CuI4(W6O19)2(L)]·2H2O (NEAU-1), was synthesized via an in-situ solvothermal method. Single-crystal X-ray diffraction results reveal that NEAU-1 exhibits a sandwich structure, with POMs intercalated between the two-dimensional layers formed by resorcin[4]arene ligands and Cu(I) ions. NEAU-1 possesses abundant Cu(I) active sites and high chemical stability, making it an effective heterogeneous catalyst for the CuAAC reaction. More importantly, the presence of POMs effectively reduces the electron cloud density around Cu(I) sites, significantly lowering the energy barrier for the formation of copper-acetylide compounds and facilitating subsequent nucleophilic reactions. The synergistic catalytic effect of POMs and Cu(I) can achieve a conversion rate of over 99 % for benzyl azide and phenylacetylene within 40 min. This work presents a sustainable molecular-level strategy to enhance the activity of the CuAAC reaction.

Facile fabrication of Cu/kaolin nanocomposite as highly efficient heterogeneous catalyst for 4-nitrophenol reduction in aqueous solution

Hazardous organic pollutants in industrial wastewaters are becoming a major global challenge that threatens life on earth and particularly poses a serious health risk to human beings. 4-Nitrophenol (4-NP) is a highly hazardous organic contaminant that has been extensively utilized across multiple industries, and their wastewater disposal into water streams leads to a higher accumulation of 4-NP. It is therefore important for both academia and industry to make catalysts that are cheap, very effective, good for the environment, easy to recover, and can be used more than once for reducing 4-NP in normal conditions. This paper reports the synthesis, characterization, and application of Cu/kaolin nanocomposite (NC) as an efficient heterogeneous catalyst for decomposing 4-NP, a model organic molecule. The catalyst was synthesized by incorporating a copper precursor into layered kaolin clay and directly reducing the metal precursor using sodium borohydride (NaBH4). The morphology, structure, surface property, and interaction of the resulting Cu/kaolin NC were characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron spectroscopy/energy-dispersive X-ray spectroscopy, selected area electron diffraction, X-ray diffraction, and N2 adsorption/desorption, and the results clearly demonstrated the growth of copper nanoparticles on the kaolin surface. It was discovered that the Cu nanoparticles (NPs) on the kaolin surface had a crystallite size of about 23.6 nm. The significance of Cu NPs and the high catalytic activity of the synthesized Cu/kaolin NC toward 4-NP reduction by NaBH4 were evaluated by the catalytic reduction experiments. Among the different nanocomposites synthesized, 30-Cu/kaolin showed the highest catalytic activity for 4-NP reduction, with a reduction efficiency of over 99 % within 4 min with a pseudo-first-order rate constant, kapp, of 1.23 min−1. Furthermore, the reusability test indicated that Cu/kaolin NC can be reused for up to six runs efficiently without significant decrease in its catalytic performance, indicating the nanocomposite has excellent stability and great potential applications in industrial and agricultural wastewater treatment.

Sulfur-doped CuCo2O4 as a PMS activator: The synergy of oxygen defects and strong Lewis acid sites in boosting the elimination of ciprofloxacin

Herein, the synthesis of sulfur-modified CuCo2O4 (S-CuCo2O4) nanoparticles as a heterogeneous catalyst for peroxymonosulfate (PMS) activation was reported. The S-CuCo2O4 maintained the spinel structure and exhibited rich oxygen vacancies. Also, the presence of S atoms enlarged the specific surface area and created strong Lewis acid sites that both enhanced the adsorption ability toward PMS and CIP. Compared to the corresponding S-doped single oxides and CuCo2O4, the S-CuCo2O4 with the designed molar ratio of S and metal ions to be 10%, i.e., CCS-10, significantly improved the catalytic activity, indicating the synergism between Cu-O-Co bonds, the oxygen vacancies, and the Lewis acid sites. Under the optimal conditions of 0.1g.L-1 CCS-10 dosage, 0.2g.L-1 PMS, and natural pH, the CCS-10/PMS system could remove approximately 87% of CIP and 70% of TOC within 20min at a four-time higher rate than that of the pristine catalyst. This system showed the highest performance in the pH range from weak acidic to weak basic (pH 5.5 - pH 8.5). CCS10/PMS also displayed considerable efficiency in degrading various pollutants belonging to different categories (methylene blue (MB), carbamazepine (CBZ), bisphenol A (BPA), and sulfamethoxazole (SMX)). SO4•–, •OH, O2•–, and 1O2 active species were found to be responsible for CIP elimination. Finally, the PMS residual concentration was recorded to be 0.01g.L-1 after the reaction. Overall, this study could contribute a possible strategy to enhance the heterogeneous catalysts for the removal of organic pollutants.

Boosting charge separation and active sites exposure by hollow S-scheme MoSe2/Fe2O3 heterojunction for enhanced photocatalytic peroxymonosulfate activation towards ciprofloxacin removal

Regulating the properties of heterogeneous catalyst for efficient peroxymonosulfate (PMS) activation to pollutants degradation remains a challenge in photo-assisted Fenton-like reaction (PF) system. In this study, the novel S-scheme MoSe2/Fe2O3 (H-FMS) heterojunction with hollow nanostructure was successfully developed as visible-light-driven PMS activator for removal of ciprofloxacin (CIP). The prepared H-FMS catalyst in PMS/H-FMS/light system exhibits outstanding photocatalytic performance for CIP degradation, achieving 95.92 % removal of 5 mg/L CIP in 30 min with 0.5 mM PMS. The construction of S-scheme heterojunction provides photoinduced carriers with longer lifetime and higher redox abilities, thus sufficient photogenerated carriers are supplied to directly activate PMS. Simultaneously, the hollow nanostructure possessing multiple light reflection and scattering behaviors further facilitates the utilization of visible light. More importantly, high concentration of photoinduced electrons with high reduction ability in MoSe2 is conducive to continuous exposure of Mo4+ active sites for PMS activation through cycling between transition metal valence states. Overall, effectively separated electron-hole pairs and continuously exposed transition metal active sites both contribute to efficient activation of PMS as well as multi-path generation of ROS, leading to significant improvement in CIP degradation. The results of quenching experiment, electron spin resonance (ESR) technology, liquid chromatography-mass spectrometry (LC-MS) and density functional theory (DFT) calculation confirm that both free radicals (SO4∙-, •OH and O2∙-) and non radicals (1O2 and h+) attack the active sites of CIP possessing high Fukui index, thus contributing to CIP degradation. This work would provide a novel insight for future development and application of photocatalytic PMS activation catalysts in water remediation.

Thermally Stable Oxide-Capsulated Metal Nanoparticles Structure for Strong Metal-Support Interaction via Ultrafast Laser Plasmonic Nanowelding.

Strong metal-support interaction (SMSI) has drawn much attention in heterogeneous catalysts due to its stable and excellent catalytic efficiency. However, construction of high-performance oxide-capsulated metal nanostructures meets great challenge in materials thermodynamic compatibility. In this work, dynamically controlled formation of oxide-capsulated metal nanoparticles (NPs) structures is demonstrated by ultrafast laser plasmonic nanowelding. Under the strong localized electromagnetic field interaction, metal (Au) NPs are dragged by an optical force toward oxide NPs (TiO2). Intense energy is simultaneously injected into this heterojunction area, where TiO2 is precisely ablated. With the embedding of metal into oxide, optical force on Au gradually turned from attractive to repulsive due to the varied metal-dielectric environment. Meanwhile, local ablated oxides are redeposited on Au NP. Upon the whole coverage of metal NP, the implantation behavior of metal NP is stopped, resulting in a controlled metal-oxide eccentric structure with capsulated oxide layer thickness ≈0.72-1.30nm. These oxide-capsulated metal NPs structures can preserve their configurations even after thermal annealing in air at 600°C for 10min. This ultrafast laser plasmonic nanowelding can also extend to oxide-capsulated metal nanostructure fabrication with broad materials combinations (e.g., Au/ZnO, Au/MgO, etc.), which shows great potential in designing/constructing nanoscale high-performance catalysts.

Porous fluorine-cerium nanosheets anchored with FeOOH quantum dots for synergistic enhanced visible-light-driven photo-Fenton degradation of phenol

The utilization of two-dimensional (2D) materials to construct heterogeneous catalysts provides opportunities for environmental remediation, while the incorporation of porous structures can further enhance catalytic performance. In this work, a porous 2D FeOOH/fluorine-cerium (F-Ce) nanosheet composite was designed and synthesized by a simple impregnation-precipitation method. The unique 2D porous structure of F-Ce promoted the high dispersion of FeOOH quantum dots (QDs) (∼1.4 nm) and their tight integration to form S-scheme heterojunctions. This structure offered a greater number of active sites, and significantly improved the capacity of light absorption and the separation and migration efficiency of photogenerated carriers, thus improving catalytic activity. This catalyst achieved a phenol removal rate of 98.1 % within 20 min during the photo-Fenton reaction, which significantly surpasses pure FeOOH (32.9 %) and F-Ce (21.7 %) alone. In particular, the optimized 14FeOOH/F-Ce catalyst achieved more than 95.0 % degradation efficiency within a remarkably short period of 5 min. Mott Schottky and in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) studies demonstrated that the S-scheme charge transfer mechanism of this heterojunction synergistically enhanced the catalytic activity of the Fenton-like reaction. This study provides valuable insights for designing efficient 2D porous heterojunction catalysts for visible-light-driven Fenton applications.

Unveiling Heterogeneous Catalytic Potential of Distinctly Coordinated Polymers Toward Henry and Morita‐Baylis‐Hillman Reactions

AbstractThree 1D coordination polymers (CPs), {[CuL2(H2O)] ⋅ (H2O)3}n (1) {[CoL2(H2O)2] ⋅ (H2O)}n (2) and {[NiL2(H2O)] ⋅ (H2O)3}n (3), (L1=N‐nicotinoylglycinato) have been synthesized by adopting a solvothermal reaction strategy and characterized through several spectral techniques i. e., elemental analyses, FT‐IR, TGA, EDX, DSC, AAS, and PXRD. X‐ray single crystal analysis revealed the 5‐, 6‐ and 7‐coordinated structures respectively for CPs 1, 2 and 3 wherein, L1 connects the metal ions in a bridging mode. The CPs entail H‐bonding, π–π stacking along with other non‐covalent interactions and expand into 3D supramolecular networks. Further, FESEM and HRTEM provided morphological insight for 1–3 and aid in obtaining interplanar spacings. CPs 1–3 possessing distinct coordination numbers and good thermal stability have been subjected to catalysis after optimization and notably, these serve as efficient, easy to work up, and reusable porous heterogeneous catalysts for Henry and Morita‐Baylis‐Hillman (MBH) reactions with reasonably good yields (97–93 %). Remarkably, catalyzed by 1–3 can be reused at least seven times for the Henry reaction and six times for the MBH reaction, retaining their catalytic efficiency. Relative catalytic efficacy toward the Henry and MBH reactions follows the order 1>2>3. Present findings are based on a rational approach of varying coordination number (5, 6 and 7) and metal ions [Cu(II), Co(II) and Ni(II)] respectively in 1–3 having structural evidence and examine their catalytic performances for typical Henry and MBH reactions.

An efficient catalytic method for the Suzuki reaction and oxidation of sulfides by using novel magnetic nanoparticles (SnFe2O4) as a reusable catalyst

In this study, we focused on the deposition of copper nanoparticles onto Cinchonine-functionalized SnFe2O4 magnetic nanoparticles. This environmentally friendly heterogeneous catalyst was thoroughly analyzed using a variety of techniques including SEM, EDS, TGA, TEM, VSM, XRD, ICP, XPS and FT-IR. In addition, it demonstrated outstanding performance as a catalyst for Suzuki reactions and the oxidation of sulfides in environmentally sustainable conditions. The catalyst could be effortlessly separated from the mixture and reused for up to four cycles without any decrease in its catalytic efficacy. This method provides the advantages of a simple procedure, high yields of products, convenient handling, environmentally friendly conditions, and short reaction times.

A multi-modal high pressure and high temperature reaction cell for combined x-ray spectroscopy, scattering, and imaging.

A free-standing and compact reaction cell for combined in situ/operando x-ray spectroscopy, scattering, and imaging measurements at high pressures and high temperatures is described. The cell permits measurements under realistic operating conditions (up to 50bar and 1000°C), under static and flow conditions (up to 100 ml/min), over a wide range of hard x-ray energies, variable detection modes (transmission, fluorescence, and scattering), and at all angles of rotation. An operando XAS, x-ray fluorescence, x-ray computed tomography, and x-ray diffraction computed tomography case study on the reduction of a heterogeneous catalyst is presented to illustrate the performance of the reaction cell.

Encapsulation of Cu/Fe3O4 With RT‐COF‐1 for Improved Stability in Water–Gas Shift Reaction

AbstractStability is crucial for the practical application of heterogeneous catalysts, particularly in industrial processes, where catalyst deactivation often occurs due to factors such as sintering, poisoning, and active site degradation. This study investigates the effectiveness of utilizing covalent organic frameworks (COFs), specifically RT‐COF‐1, to enhance the stability of Cu/Fe3O4 catalysts in harsh water–gas shift (WGS) reaction environments. By encapsulating Cu/Fe3O4 with trace RT‐COF‐1, we aimed to preserve the structural integrity and active interfaces between the metal components during catalytic reactions. Characterization techniques, including X‐ray photoelectron spectroscopy, nitrogen sorption, and high‐angle annular dark‐field scanning transmission electron microscopy, confirmed the successful COF coating and its role in preventing particle aggregation and maintaining active site structures over extended catalytic tests. Notably, Cu/Fe3O4@COF demonstrated significantly enhanced stability during a continuous 24‐h WGS test compared to uncoated catalysts, which exhibited rapid deactivation. Mechanistic insights indicated that COF coating reduced the number of active sites while preserving the overall morphology of the catalyst, contributing to its robust performance. Ultimately, this work highlights the potential of COF encapsulation as an effective strategy for enhancing the durability and efficacy of multifunctional catalysts in challenging reaction conditions.

Novel and reusable magnetic MOF nanocomposite coupled ionic liquid- promoted efficient chemical fixation of CO2 into α-alkylidene cyclic carbonates

Carbon dioxide as a C1 building block to synthesize α-alkylidene cyclic carbonates is an environmental and sustainable approach. In this work, we designed and synthesized a type of multifunctional magnetic MOF nanocomposite catalysts, which could realize the carboxylic cyclization of CO2 and propargylic alcohols into α-alkylidene cyclic carbonates under solvent-free conditions. Among all the prepared nanocomposites, the MnFe2O4@SiO2@Cu-MOF nanocomposite is the best in catalytic activity combined with the tetrabutylphosphonium acetate ([Bu4P]OAc) ionic liquid cocatalyst. The catalytic system MnFe2O4@SiO2@Cu-MOF/[Bu4P]OAc displayed excellent performance in catalyzing the carboxylic cyclization of CO2 and different propargylic alcohols, and a series of α-alkylidene cyclic carbonates were obtained in high to excellent yields (88 ∼ 98 %) under mild reaction conditions (0.2 MPa, 35 °C). In addition, the two-component catalytic system had high stability and reusability, and can be easily separated and reused up to six consecutive cycles without considerable decrease in catalytic activity. Moreover, using the ionic liquid [Bu4P]OAc as the cocatalyst, the nanocomposite had good substrate adaptability for the catalytic carboxylic cyclization, which opens interesting prospects for the development of new magnetic MOF nanocomposites as efficient heterogeneous catalysts for the chemical transformation of CO2 into value-added chemicals.