Recyclable Catalyst Research Articles

Recycling of Homogeneous Catalysts─Basic Principles, Industrial Practice, and Guidelines for Experiments and Evaluation

Recycling of Homogeneous Catalysts─Basic Principles, Industrial Practice, and Guidelines for Experiments and Evaluation

Chitosan-derived carbon sphere with self-activating behavior for stable oxygen reduction reaction in acid and alkaline media

Utilizing shrimp waste-derived Chitosan as biomass source, we developed metal-free nitrogen and sulfur-doped porous carbon (NSPC) with a high specific surface area of 609.53 m2/g as a remarkable electrocatalyst for oxygen reduction reaction (ORR), surpassing benchmark Pt/C with half-wave (0.8574 V) and onset (0.9573 V) potentials in alkaline (0.1 M KOH) media. Besides high electrocatalytic activity, NSPC-800 showed excellent methanol tolerance ability and significantly low hydrogen peroxide yields (H2O2) of 5 % and 8 % in 0.1 M KOH and 0.5 M H2SO4, which is comparably lower than the previously reported chitosan based non-precious catalysts. Interestingly NSPC-800 displays robust stability in 0.1 M KOH electrolyte, improving the current retention rate from 89.17 % to 95.18 % over an increased operation period, evidencing its self-activating characteristics. This self-activating stability is also mirrored in 0.5 M H2SO4 where both fresh and recycled (after 5000 CV cyles) NSPC-800 catalysts retained more than half of their initial current. Additionally, to identify the nature of the active sites, the ORR measurements were correlated with ex-situ spectroscopy for post-stability of fresh and recycled NSPC-800 catalysts revealed dynamic reconfiguration of nitrogen, sulfur, and oxygen active sites evidenced compared to the pre-stability elemental surface, indicating an adaptive response of the catalyst to the harsh operating environment. In the future, our biomass-derived NSPC-800 will pave the way to develop cost-effective and highly efficient catalysts from waste to energy devices promising a twin-goal approach, contributing to the circular economy and sustainable development goals.

Regioselective hydroformylation of propene catalysed by rhodium-zeolite.

Hydroformylation is an industrial process for the production of aldehydes from alkenes1,2. Regioselective hydroformylation of propene to high-value n-butanal is particularly important, owing to a wide range of bulk applications of n-butanal in the manufacture of various necessities in human daily life3. Supported rhodium (Rh) hydroformylation catalysts, which often excel in catalyst recyclability, ease of separation and adaptability for continuous-flow processes, have been greatly exploited4. Nonetheless, they usually consist of rotationally flexible and sterically unconstrained Rh hydride dicarbonyl centres, only affording limited regioselectivity to n-butanal5-8. Here we show that proper encapsulation of Rh species comprising Rh(I)-gem-dicarbonyl centres within a MEL zeolite framework allows the breaking of the above model. The optimized catalyst exhibits more than99% regioselectivity to n-butanal and more than99% selectivity to aldehydes at a product formation turnover frequency (TOF) of 6,500 h-1, surpassing the performance of all heterogeneous and most homogeneous catalysts developed so far. Our comprehensive studies show that the zeolite framework can act as a scaffold to steer the reaction pathway of the intermediates confined in the space between the zeolite framework and Rh centres towards the exclusive formation of n-butanal.

A efficient, regioselective and solvent free synthesis of 5,9-dihydropyrimido[4,5-e][1,2,4]triazolo[1,5-a]pyrimidine-6,8(4H,7H)-diones derivatives in presence nanocatalyst sulfuric acid grafted with silica-3-aminotriazol

In this research, SO3H-functionalized Silica grafted 3-amino triazol has been prepared and identified through FT-IR, XRD, EDX, Fe-SEM, and TGA spectra. 3-chloropropyltriethoxysilane was first reacted with silica nanoparticles and then treated with 3-amino-1H-1,2,4-triazoles and grafted finally with chlorosulfonic acid to prepare SiO2@(CH2)3-AT/SO3H (SNPS-AT/SO3H). Afterward, the catalytic efficiency has been investigated as a homogeneous and recyclable catalyst for the solvent-free synthesis of 5,9-dihydropyrimido[4,5-e][1,2,4]triazolo[1,5-a]pyrimidine-6,8(4H,7H)-diones by the one-pot multi-component reaction of aromatic aldehydes with 3-amino-1H-1,2,4-triazoles and 1,3-dimethyl barbituric acid under thermal (100 °C) conditions.

Modified nano magnetic Fe2O3-MgO as a high active multifunctional heterogeneous catalyst for environmentally beneficial carbon–carbon synthesis

In this study, novel nanomagnetic catalysts, namely Fe2O3-MgO@choline formate (Ch. F.) and Fe2O3-MgO@choline cyanide (Ch. CN), were synthesized through immobilizing choline-based ion liquids to magnetic support via a simple and cost-effective methodology. FT-IR, TGA, FE-SEM, VSM, EDS, BET, and XRD techniques were employed to assess and characterize these organic–inorganic compounds. Following the successful preparation of nanoparticles, the catalysts were utilized in Knoevenagel and benzoin condensations. Fe2O3-MgO@Ch.F. exhibited exceptional activity in Knoevenagel condensation under solvent-free conditions at room temperature, achieving high yields (91–98%) in a short timeframe. Similarly, Fe2O3-MgO@Ch.CN demonstrated remarkable activity in benzoin condensation under environmentally friendly solvent conditions, yielding higher isolated yields (76–88%). Furthermore, these magnetically recyclable multifunctional catalysts displayed the ability to be reused up to five times without a significant loss in efficiency. Additionally, the heterogeneity of this nanocatalyst was investigated using the hot filtration technique. The findings indicated that the reaction primarily occurs via a heterogeneous pathway.

Palladium anchored to BisPyP@bilayer-SiO2@NMP organic–inorganic hybrid as an efficient and recoverable novel nanocatalyst in suzuki and stille C–C coupling reactions

The palladium anchored to BisPyP@bilayer-SiO2@NMP organic–inorganic hybrid was employed as an effective and recyclable organometallic catalyst in Suzuki and Stille C–C coupling reactions. The structure of this magnetic nanocatalyst was determined using various techniques such as SEM, TEM, FT-IR, EDS, ICP-OES, VSM, N2 adsorption–desorption isotherms, XRD, and TGA. In both of the mentioned coupling paths, the yields of the products were very favorable and ranged from 90 to 98%. Also, they had significant features compared to previous reports, such as very short reaction time (5–15 and 7–20 min respectively in the Suzuki and Stille reactions), easy work-up, broad substrate scope, ease of separation of the catalyst using a magnet, suitable reproducibility of the catalyst in 6 runs, heterogeneous nature of the catalyst and not washing it during consecutive runs with confirmation of hot filtration and ICP-OES methods.

Polymerizable deep eutectic solvents: Convenient reactive dispersion media for the preparation of novel multi-walled carbon nanotubes-based functional materials

A new straightforward and green approach for the covalent functionalization of multi-walled carbon nanotubes (MWCNTs) was developed. This carbon nanostructure was efficiently derivatized by polymerizing proper deep eutectic monomers (DEM), a subclass of deep eutectic solvents (DES), based on a series of mono- and bis-vinyl imidazolium salts endowed with different functional groups (–OH, –NH2, –NH3+Br–) in the side chain or in the spacer. Herein, DEM systems played a triple role as convenient dispersion media for MWCNTs, efficient reactive systems, and also as structure-directing agents for the radical-initiated polymerization process onto the surface of MWCNTs. In addition, the new methodology allowed obtaining highly functionalized hybrid materials, as shown by thermogravimetric analyses, in short reaction times (<1h). Transmission electron microscopy (TEM) revealed that the polymeric network orderly develops along the surface of the nanotubes, which act as templating agent for both mono- and bis-vinyl imidazolium salts, despite the random nature of the polymerization process for the latter species. This new functionalization strategy of MWCNTs stands out for its environmentally friendly and time-saving nature leading to the formation of materials with significant potential for applications in a plethora of research fields. As a proof of their possible application, we tested these new hybrid materials as recoverable and recyclable catalysts for the conversion of CO2 into cyclic carbonates under solvent-free conditions, showing good catalytic performances, even in the absence of additional co-catalysts.

Microwave-Induced Chemical Recycling of Colored Polyester Textile Wastes Promoted by Zn[(L)Proline]2, as a Recyclable Homogeneous Catalyst

Microwave-Induced Chemical Recycling of Colored Polyester Textile Wastes Promoted by Zn[(L)Proline]2, as a Recyclable Homogeneous Catalyst

Base-free synthesis of renewable furan-2,5-dicarboxylic acid (FDCA) over an earth-abundant magnetic catalyst

Being a biobased alternative to petroleum-based terephthalic acid (TPA), furan-2,5-dicarboxylic acid (FDCA) requires a low-cost and efficient catalytic system for its commercialization. This study describes FDCA production using whey permeate powder (WPP)-derived 5-(hydroxymethyl)furfural (HMF) in a base-free system over a magnetically recyclable catalyst composed of earth-abundant metals (Mn and Fe). The impact of MnCl2·4 H2O loading on the iron core was studied at different levels and found optimal at the ratio of 1:1. The in-situ oxidation of HMF was carried out using ozone and t-BuOOH as the oxidants in a γ-valerolactone (GVL) -water solvent system. It was observed that the ozone pre-treatment (3 h at room temperature) of HMF increased the FDCA yield from 39.7 % (without ozonation) to 60 % at a reaction condition of 130 °C for 2 h. The concentration profiles for the intermediates formed during HMF to FDCA oxidation i.e., 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), furan-2,5-dicarbaldehyde (DFF), and 5-formyl-2-furancarboxylic acid (FFCA) were analyzed at different reaction temperatures to evaluate the reaction kinetics. The kinetic study revealed that the present solvent-catalytic system favored HMFCA formation over DFF due to the requirement of higher activation energy for the latter. The HMF to FDCA catalytic solvent was tested for WPP, which afforded an overall FDCA yield of 14.6 % at 130 °C in 120 min. In addition, the Mn1Fe1 consisted of mixed phases of Mn3O4, Mn2O3, MnO2, Fe2O3, and Fe3O4 and demonstrated variation in oxidation states for Mn (Mn3+↔Mn2+) and Fe (Fe2+↔Fe3+) species.

Recyclable and dual-functional Ag3PO4/3D graphene aerogel photocatalysts for simultaneous water oxidation and pollutant degradation

Exploiting recyclable and reusable photocatalysts in pollutants elimination and water splitting has drawn extensive research attention for solving the increasing energy and environmental issues. Herein, we designed a high-performance dual functional Ag3PO4/three-dimensional (3D) graphene aerogel (APGA) photocatalyst, in which the 3D GA with extremely lightweight and high mechanical stability served as the support for Ag3PO4 particles, preventing the serious weight loss during the recovery process. Moreover, different from the traditional powder photocatalysts, the application of 3D GA support avoided the secondary contamination caused by the catalyst residue during the reaction. The abundant hydroxyl groups on the surface of porous 3D GA prevented the aggregation of Ag3PO4 particles, forming a close interfacial contact. Profiting from the large number of active sites and high conductivity of 3D GA, the optimized APGA-12 sample showed excellent O2 generation (814.1 μmol·g−1) and synchronous Cr (VI) reduction (87.5 %) efficiency. In addition, the APGA-12 sample also exhibited excellent carbamazepine (CBZ) degradation activity (99 % within 30 min) in the presence of peroxymonosulfate (PMS). Cycling experiments combined with the scaled-up reactions verified the good mechanical and chemical stability of APGA samples. This work provided a promising strategy for solving the problems of catalyst recycling in the field of pollutant degradation and water oxidation.

Chitosan-supported calcium hydroxide hybrid material as new, efficient, and recyclable catalyst for biodiesel production

In this work, a novel supported catalyst was prepared starting from calcium chloride and chitosan flakes using a very mild approach in an aqueous medium without final calcination at high temperatures. The as-prepared catalyst was fully characterized by thermogravimetric analysis (TGA), attenuated total reflectance Fourier transform infrared (ATR-FTIR), and X-ray photoelectron (XPS) spectroscopies, transmission and scanning electron microscopies (TEM, SEM), Energy Dispersive X-ray Spectroscopy (EDS), demonstrating that it consists of calcium hydroxide particles of about 200 nm supported on chitosan micrometric structures. The most crucial parameters in the transesterification process were investigated. A methanol/oil ratio of 6:1, a reaction time of 6 h, and a temperature of 60 °C were found to lead to complete conversion. A reaction on a gram scale using waste oil as a starting material was also tested, and excellent results were achieved. Moreover, the catalyst proved to be very robust, since even after the 10th recycle, the conversion rate remained at around 90 %. Spectroscopic analyses showed minimal leaching of material without modification of chemical composition. The kinetic behavior (activation energy, Ea) of the catalyst was also studied, which resulted in similar outcomes to Ca-based systems present in the literature, but without the need for costly preparations and with superior recycling resistance. An Ea value of 63.25 kJ·mol−1 was found, which agrees with data reported in the literature.

Advances in the Homogeneously Catalyzed Hydrogen Production from Biomass Derived Feedstocks: a Review.

Biomass‐derived feedstocks for hydrogen production are crucial as an alternative to fossil fuel especially in those areas where green electricity and clean water are scarce. In this framework the transformation of simple (formic acid, alcohols) and more complex (polyalcohols, sugars and cellulose) bio‐derivatives in pure hydrogen is recognized as a promising approach. Parallel to great effort in heterogeneous catalysis, milder molecular systems represent a more selective eye for alternative solutions and mechanistic insights. In the present review the introduction summarizes the challenges in the catalytic utilization of biomass‐derived feedstocks, followed by the advances in homogeneously catalyzed hydrogen production from different substrates which will cover formic acid, with oustanding efficiency with noble metals and promising results with earth abundant ones and alcohols and polyalcohols, with particular emphasis to the development of heterogenized systems, ligand assisted catalysts and bi‐catalytic synergistic solutions which allow to avoid base and to promote catalyst stability and recyclability. In the last part, description of hydrogen production from more complex substrates, such as sugars and cellulose, will show the role of molecular complexes in main and side reactions. Critical comments on the reported advances are provided along the whole discussion.

H6P2W18O62·18H2O as a Recyclable Catalyst for Synthesis of Tetrahydrobenzo[b]pyrans

H6P2W18O62·18H2O as a Recyclable Catalyst for Synthesis of Tetrahydrobenzo[b]pyrans

Phosphine-incorporated Metal-Organic Framework for Palladium Catalyzed Heck Coupling Reaction.

As an emerging material with the potential to combine the high efficiency of homogeneous catalysts and high stability and recyclability of heterogeneous catalysts, metal-organic frameworks (MOFs) have been viewed as one of the candidates to produce catalysts of the next generation. Herein, we heterogenized the highly active mono(phosphine)-Pd complex on surface of UiO-66 MOF, as a catalyst for Suzuki and Heck cross coupling reactions. The successful immobilization of these Pd-monophosphine complexes on MOF surface to form UiO-66-PPh2-Pd was characterized and confirmed via comprehensive set of analytical methods. UiO-66-PPh2-Pd showed high activity and selectivity for both Suzuki and Heck Cross Coupling Reactions. This strategy enabled facile access to mono(phosphine) complexes which are challenging to design and require multistep synthesis in homogeneous systems, paving the way for future MOF catalysts applications by similar systems.

Fe3O4@SiO2@CSH+VO3− as a novel recyclable heterogeneous catalyst with core–shell structure for oxidation of sulfides

Iron nanoparticles, with low toxicity and many active sites, are among the materials that not only reduce waste along with green chemistry but also increase the separation power and recover the catalyst from the reaction environment. In this study, first, the surface of iron nanoparticles was silanized, and in the next step, the complex of chitosan HCl.VO3 was placed on the surface of Fe3O4 (Fe3O4@SiO2@CSH+VO3−). This nanocatalyst is a novel, recoverable, and potent nanocatalyst with high selectivity for the oxidation of sulfides to sulfoxides. Various physicochemical techniques such as IR, XRD, TGA, SEM, EDX, mapping, TEM, and VSM were used to affirm the well synthesis of the catalyst. Oxidation of sulfides in the presence of hydrogen peroxide as a green oxidant and in ethanol was catalyzed by the Fe3O4@SiO2@CSH+VO3−. All sulfoxides were achieved with high efficiency and in a short time. The notable privileges of this method include facile and economic catalyst synthesis, proper catalyst durability, great performance, simple catalyst isolation, good recovery capability, at least up to 5 times without an index drop in catalytic power.

Hal-Py-SO3H as a novel and recyclable catalyst for highly efficient synthesis of xanthene and spiropyran derivatives

The aim of this research is to synthesize a new sulfonic acid catalyst based on halloysite nanotubes (Hal-Py-SO3H) and characterize it as a solid acid nanocatalyst by various analytical techniques such as Fourier-Transformed Infrared spectroscopy (FTIR), Thermal gravimetric Analysis (TGA), X-ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Vibrating Energy-Dispersive X-ray analysis (EDX), Transmission electron microscopy (TEM) and X-ray atomic mapping. Furthermore, this new catalyst was evaluated in synthesizing spiropyran derivatives via multicomponent reactions (MCRs) and Xanthen derivatives under environmentally sustainable conditions. The main advantages of this approach include green conditions, excellent yields, quick reaction rates, and ease of preparation. Additionally it was observed that the catalyst exhibited robust stability even after multiple recycling processes, indicating its potential for practical applications in sustainable chemical transformations.

In situ growth of iron incorporated Ni3S2 nanosheet on nickel foam in mediating electron transfer to peroxymonosulfate for pollutant abatement

Catalytic oxidation of organic pollutants is a well-known and effective technique for pollutant abatement. Unfortunately, this method is significantly hindered in practical applications by the low efficiency and difficult recovery of the catalysts in a powdery form. Herein, a three-dimensional (3D) framework of Fe-incorporated Ni3S2 nanosheets in-situ grown on Ni foam (Fe-Ni3S2@NF) was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate (PMS) oxidation of organic compounds in water. A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni3S2 nanosheets on the Ni foam. Fe-Ni3S2@NF possessed outstanding activity and durability in activating PMS, as it effectively facilitated electron transfer from organic pollutants to PMS. Fe-Ni3S2@NF initially supplied electrons to PMS, causing the catalyst to undergo oxidation, and subsequently accepted electrons from organic compounds, returning to its initial state. The introduction of Fe into the Ni3S2 lattice enhanced electrical conductivity, promoting mediated electron transfer between PMS and organic compounds. The 3D conductive Ni foam provided an ideal platform for the nucleation and growth of Fe-Ni3S2, accelerating pollutant abatement due to its porous structure and high conductivity. Furthermore, its monolithic nature simplified the catalyst recycling process. A continuous flow packed-bed reactor by encapsulating Fe-Ni3S2@NF catalyst achieved complete pollutant abatement with continuous operation for 240 h, highlighting its immense potential for practical environmental remediation. This study presents a facile synthesis method for creating a novel type of monolithic catalyst with high activity and durability for decontamination through Fenton-like processes.

Highly Selective Isomerization of Glucose to Fructose through a Biphasic and Recyclable Mimetic Enzyme Catalyst

AbstractDeveloping a biphasic catalyst is of great significance for improving reaction efficiency and its industrial application. Herein a novel biphasic catalyst containing three functional groups of chlorophenol, amino and carboxyl was synthesized and used as mimic glucose isomerase to catalyze the isomerization. The mimic enzyme exhibited excellent catalytic performance for isomerization of glucose to fructose under mild conditions. Temperature and pH of solution showed significant influence on the conversion of glucose and the selectivity of fructose. The yield and selectivity of fructose reached 32.4 % and 91.0 % after reacting 2 h, respectively, at pH 9.5 and 90 °C. The solubility of the catalyst exhibited dual sensitivity to both pH and temperature. The catalyst was in a soluble state during the reaction process and could be precipitated by reducing the pH and temperature of the reaction system. The catalyst could be reused and still maintained good catalytic activity after five consecutive cycles.

Solvent-free conversion of CO2 in carbonates through a sustainable macroporous catalyst

The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO2 capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (1H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br−, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO2 capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.

Unlocking the Potential of Liquid Multiphase Systems for Metal‐Catalysed Reactions

AbstractLiquid multiphase systems (MPS) have gained attention in recent years due to their versatility for catalytic processes. This review article presents a critical discussion of the most recent advances on the utilization of MPS in both homogeneous and heterogeneous metal‐catalysed reactions. Pros and cons of some exemplificative multiphase configurations are highlighted and compared to conventional methods in single liquid solvents. The application of MPS for the implementation of strategies for the upgrading of biobased molecules is also examined with emphasis on process intensification and sustainability including the catalyst/products separation and the in‐situ recycle and reuse of the metal catalysts. These aspects are analyzed with a view on expanding MPS applications and whenever possible, explore scale‐up opportunities.