Aluminium-Based Metal-Organic Framework Nano Cuboids and Nanoflakes with Embedded Gold Nanoparticles for Carbon Dioxide Fixation with Epoxides into Cyclic Esters.

The fixation of carbon dioxide with epoxides is one of the most attractive methods for the green utilisation of this greenhouse gas and leads to many valuable chemicals. This process is characterised by 100% atom efficiency; however, an efficient catalyst is required to achieve satisfactory yields. Metal-organic frameworks (MOFs) are recognised as being extremely promising for this purpose. Nevertheless, many of the proposed catalysts are based on ions of rare elements or elements not entirely safe for the environment; this is notable with commercially unavailable ligands. In an effort to develop novel catalysts for CO2 fixation on an industrial scale, we propose novel MOFs, which consist of aluminium ions coordinated with commercially available 1,4-naphthalene dicarboxylic acid (Al@NDC) and their nanocomposites with gold nanoparticles entrapped inside their structure (AlAu@NDC). Due to the application of 4-amino triazole and 5-amino tetrazole as crystallization mediators, the morphology of the synthesised materials can be modified. The introduction of gold nanoparticles (AuNPs) into the structure of the synthesised Al-based MOFs causes the change in morphology from nano cuboids to nanoflakes, simultaneously decreasing their porosity. However, the homogeneity of the nanostructures in the system is preserved. All synthesised MOF materials are highly crystalline, and the simulation of PXRD patterns suggests the same tetragonal crystallographic system for all fabricated nanomaterials. The fabricated materials are proven to be highly efficient catalysts for carbon dioxide cycloaddition with a series of model epoxides: epichlorohydrin; glycidol; styrene oxide; and propylene oxide. Applying the synthesised catalysts enables the reactions to be performed under mild conditions (90 °C; 1 MPa CO2) within a short time and with high conversion and yield (90% conversion of glycidol towards glycerol carbonate with 89% product yield within 2 h). The developed nanocatalysts can be easily separated from the reaction mixture and reused several times (both conversion and yield do not change after five cycles). The excellent performance of the fabricated catalytic materials might be explained by their high microporosity (from 421 m2 g-1 to 735 m2 g-1); many catalytic centres in the structure exhibit Lewis acids' behaviour, increased capacity for CO2 adsorption, and high stability. The presence of AuNPs in the synthesised nanocatalysts (0.8% w/w) enables the reaction to be performed with a higher yield within a shorter time; this is especially important for less-active epoxides such as propylene oxide (two times higher yield was obtained using a nanocomposite, in comparison with Al-MOF without nanoparticles).

Catalytic Strategies for the Cycloaddition of CO2 to Epoxides in Aqueous Media to Enhance the Activity and Recyclability of Molecular Organocatalysts.

The cycloaddition of CO2 to epoxides to afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling of CO2. One of the main focuses of the current research in this area is the discovery of readily available, sustainable, and inexpensive catalysts, and of catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant in the cycloaddition process, is progressively emerging as a helpful reaction component. On the one hand, it serves as an inexpensive hydrogen bond donor (HBD) to enhance the performance of ionic compounds; on the other hand, aqueous media allow the development of diverse catalytic protocols that can boost catalytic performance or ease the recycling of molecular catalysts. An overview of the advances in the use of aqueous and biphasic aqueous systems for the cycloaddition of CO2 to epoxides is provided in this work along with recommendations for possible future developments.

2-Benzamide Tellurenyl Iodides: Synthesis and Their Catalytic Role in CO2 Mitigation.

Benzamide-derived organochalcogens (chalcogen=S, Se, and Te) have shown promising interest in biological and synthetic chemistry. Ebselen molecule derived from benzamide moiety is the most studied organoselenium. However, its heavier congener organotellurium is under-explored. Here, an efficient copper-catalyzed atom economical synthetic method has been developed to synthesize 2-phenyl-benzamide tellurenyl iodides by inserting a tellurium atom into carbon-iodine bond of 2-iodobenzamides in one pot with 78-95 % yields. Further, the Lewis acidic nature of Te center and Lewis basic nature of nitrogen of the synthesized 2-Iodo-N-(quinolin-8-yl)benzamide tellurenyl iodides enabled them as pre-catalyst for the activation of epoxide with CO2 at 1 atm for the preparation of cyclic carbonates with TOF and TON values of 1447 h-1 and 4343, respectively, under solvent-free conditions. In addition, 2-iodo-N-(quinolin-8-yl)benzamide tellurenyl iodides have also been used as pre-catalyst for activating anilines and CO2 to form a variety of 1,3-diaryl ureas up to 95 % yield. The mechanistic investigation for CO2 mitigation is done by 125 Te NMR and HRMS studies. It seems that the reaction proceeds via formation of catalytically active Te-N heterocycle, an ebtellur intermediate which is isolated and structurally characterized.

Efficiency in Carbon Dioxide Fixation into Cyclic Carbonates: Operating Bifunctional Polyhydroxylated Pyridinium Organocatalysts in Segmented Flow Conditions.

Novel polyhydroxylated ammonium, imidazolium, and pyridinium salt organocatalysts were prepared through N-alkylation sequences using glycidol as the key precursor. The most active pyridinium iodide catalyst effectively promoted the carbonation of a set of terminal epoxides (80 to >95% yields) at a low catalyst loading (5 mol%), ambient pressure of CO2, and moderate temperature (75 °C) in batch operations, also demonstrating high recyclability and simple downstream separation from the reaction mixture. Moving from batch to segmented flow conditions with the operation of thermostated (75 °C) and pressurized (8.5 atm) home-made reactors significantly reduced the process time (from hours to seconds), increasing the process productivity up to 20.1 mmol(product) h-1 mmol(cat)-1, a value ~17 times higher than that in batch mode.

Bicyclic Guanidine Promoted Mechanistically Divergent Depolymerization and Recycling of a Biobased Polycarbonate.

We here report the organocatalytic and temperature-controlled depolymerization of biobased poly(limonene carbonate) providing access to its trans-configured cyclic carbonate as the major product. The base TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) offers a unique opportunity to break down polycarbonates via end-group activation or main chain scission pathways as supported by various controls and computational analysis. These energetically competitive processes represent an unprecedented divergent approach to polycarbonate recycling. The trans limonene carbonate can be converted back to its polycarbonate via ring-opening polymerization using the same organocatalyst in the presence of an alcohol initiator, offering thus a potential circular and practical route for polycarbonate recycling.

Exploiting the Use of the Decarboxylative S-Alkylation Reaction to Produce Self-Blowing, Recyclable Polycarbonate Foams.

Polymeric foams are widely used in many industrial applications due to their light weight and superior thermal, mechanical, and optical properties. Currently, increasing research efforts is being directed towards the development of greener foam formulations that circumvent the use of isocyanates/blowing agents that are commonly used in the production of foam materials. Here, a straightforward, one-pot method is presented to prepare self-blown polycarbonate (PC) foams by exploiting the (decarboxylative) S-alkylation reaction for in situ generation of the blowing agent (CO2 ). The concomitant formation of a reactive alcohol intermediate promotes a cascade ring-opening polymerization of the cyclic carbonates to yield a cross-linked polymer network. It is shown that these hydroxyl-functionalized polycarbonate-based foams can be easily recycled into films through thermal compression molding. Furthermore, it is demonstrated that complete hydrolytic degradation of the foams is possible, thus offering the potential for zero-waste materials. This straightforward and versatile process broadens the scope of isocyanate-free, self-foaming materials, opening a new pathway for next-generation environmentally friendly foams.

Intermetallic Copper-Based Electride Catalyst with High Activity for C-H Oxidation and Cycloaddition of CO2 into Epoxides.

Inorganic electrides have been proved to be efficient hosts for incorporating transition metals, which can effectively act as active sites giving an outstanding catalytic performance. Here, it is demonstrated that a reusable and recyclable (for more than 7 times) copper-based intermetallic electride catalyst (LaCu0.67 Si1.33 ), in which the Cu sites activated by anionic electrons with low-work function are uniformly dispersed in the lattice framework, shows vast potential for the selective C-H oxidation of industrially important hydrocarbons and cycloaddition of CO2 with epoxide. This leads to the production of value-added cyclic carbonates under mild reaction conditions. Importantly, the LaCu0.67 Si1.33 catalyst enables much higher turnover frequencies for the C-H oxidation (up to 25 276 h-1 ) and cycloaddition of CO2 into epoxide (up to 800 000 h-1 ), thus exceeding most nonnoble as well as noble metal catalysts. Density functional theory investigations have revealed that the LaCu0.67 Si1.33 catalyst is involved in the conversion of N-hydroxyphthalimide (NHPI) into the phthalimido-N-oxyl (PINO), which then triggers selective abstraction of an H atom from ethylbenzene for the generation of a radical susceptible to further oxygenation in the presence of O2 .

Uniform Core-Shell Microspheres of SiO2@MOF for CO2 Cycloaddition Reactions.

A SiO2@MOF core-shell microsphere for environmentally friendly applications was introduced in this study. Several types of metal-organic framework core-shell microspheres were successfully synthesized. To achieve high stability and favorable catalytic performance, modification and coating methods were necessary for optimization. The improved SiO2@MOF core-shell microspheres were used in the cycloaddition reaction of carbon dioxide and propylene oxide. Dispersion ability was enhanced by the addition of core-shell microspheres, which also produced high catalytic activity. Accompanied with tetrabutylammonium bromide as a co-catalyst, SiO2@ZIF-67 had a maximum conversion of 97%, and the results revealed that SiO2@ZIF-67 could be used for 5 reaction cycles while maintaining high catalytic performance. This recycling catalyst was also reacted with a series of terminal epoxides to form corresponding cyclic carbonates with high conversion rates, indicating that SiO2@MOF core-shell microspheres exhibit promise in the field of catalysis.

Facile Construction of Carboxyl-Functionalized Ionic Polymer towards Synergistic Catalytic Cycloaddition of Carbon Dioxide into Cyclic Carbonates.

The development of bifunctional ionic polymers as heterogeneous catalysts for effective, cocatalyst- and metal-free cycloaddition of carbon dioxide into cyclic carbonates has attracted increasing attention. However, facile fabrication of such polymers having high numbers of ionic active sites, suitable types of hydrogen bond donors (HBDs), and controlled spatial positions of dual active sites remains a challenging task. Herein, imidazolium-based ionic polymers with hydroxyl/carboxyl groups and high ionic density were facilely prepared by a one-pot quaternization reaction. Catalytic evaluation demonstrated that the presence of HBDs (hydroxyl or carboxyl) could enhance the catalytic activities of ionic polymers significantly toward the CO2 cycloaddition reaction. Among the prepared catalysts, carboxyl-functionalized ionic polymer (PIMBr-COOH) displayed the highest catalytic activity (94% yield) in the benchmark cycloaddition reaction of CO2 and epichlorohydrin, which was higher than hydroxyl-functionalized ionic polymer (PIMBr-OH, 76% yield), and far exceeded ionic polymer without HBDs groups (PIMBr, 54% yield). Furthermore, PIMBr-COOH demonstrated good recyclability and wide substrate tolerance. Under ambient CO2 pressure, a number of epoxides were smoothly cycloadded into cyclic carbonates. Additionally, density functional theory (DFT) calculation verified the formation of strong hydrogen bonds between epoxide and the HBDs of ionic polymers. Furthermore, a possible mechanism was proposed based on the synergistic effect between carboxyl and Br- functionalities. Thus, a facile, one-pot synthetic strategy for the construction of bifunctional ionic polymers was developed for CO2 fixation.

Efficient imidazolium ionic liquid as a tri-functional robust catalyst for chemical fixation of CO2 into cyclic carbonates.

The recent increase in CO2 levels has had an extensive impact on the environment; hence an effective catalyst for chemical CO2 fixation into value-added products is demanded. This work demonstrates a simple approach towards the chemical fixation of CO2 to cyclic carbonates without solvent, metal and additives using one-pot synthesized tri-functional-imidazolium bromide ionic liquid. Herein, synthesized tri-functional-imidazolium-based ionic liquids, namely 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium bromide ([VIMEtOH][Br] (24 and 72 h)), 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium hydroxyl ([VIMEtOH][OH]) and poly 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium bromide (poly [VIMEtOH][Br]), were used for the comprehensive investigation of chemical fixation of CO2 into cyclic carbonates and their physiochemical properties. In case of [VIMEtOH][Br] ionic liquid, it displayed time-dependent synthesis dissolution in the reaction system. This study found that [VIMEtOH][Br]-72 ionic liquid is not dissolved in the reaction system. The effect on the catalytic efficiency of the presence of functional groups in ionic liquids such as N-vinyl (-CC-N), acidic proton of imidazolium (-C (2)-H) and hydroxyl (-OH) along with bromide anion and the reaction conditions are systematically investigated. For CO2 fixation, 99.6% conversion of propylene oxide with an excellent selectivity of propylene carbonate (≥99%) over [VIMEtOH][Br]-72 catalyst (at 120 °C, 2 MPa, 2 h) was observed without co-catalyst, metal and solvent. Also, it demonstrated an excellent wide substrates scope of epoxide and all reactions were performed on gram-scalable, which are potential prospects for industrial use.

Immobilization of Ionic Liquid on a Covalent Organic Framework for Effectively Catalyzing Cycloaddition of CO2 to Epoxides.

Transforming CO2 into value-added chemicals has been an important subject in recent years. The development of a novel heterogeneous catalyst for highly effective CO2 conversion still remains a great challenge. As an emerging class of porous organic polymers, covalent organic frameworks (COFs) have exhibited superior potential as catalysts for various chemical reactions, due to their unique structure and properties. In this study, a layered two-dimensional (2D) COF, IM4F-Py-COF, was prepared through a three-component condensation reaction. Benzimidazole moiety, as an ionic liquid precursor, was integrated onto the skeleton of the COF using a benzimidazole-containing building unit. Ionization of the benzimidazole framework was then achieved through quaternization with 1-bromobutane to produce an ionic liquid-immobilized COF, i.e., BMIM4F-Py-COF. The resulting ionic COF shows excellent catalytic activity in promoting the chemical fixation of CO2 via reaction with epoxides under solvent-free and co-catalyst-free conditions. High porosity, the one-dimensional (1D) open-channel structure of the COF and the high catalytic activity of ionic liquid may contribute to the excellent catalytic performance. Moreover, the COF catalyst could be reused at least five times without significant loss of its catalytic activity.

Valorization of CO2 through the Synthesis of Cyclic Carbonates Catalyzed by ZIFs.

One way to exploit CO2 is to use it as a feedstock for the production of cyclic carbonates via its reaction with organic epoxides. As far as we know, there is still no heterogeneous catalyst that accelerates the reaction in a selective, efficient and industrially usable way. Cobalt and zinc-based zeolitic imidazole frameworks (ZIFs) have been explored as heterogeneous catalysts for this reaction. In particular, we have prepared ZIF-8 and ZIF-67 catalysts, which have been modified by partial replacement of 2-methylimidazole by 1,2,4-triazole, in order to introduce uncoordinated nitrogen groups with the metal. The catalysts have shown very good catalytic performance, within the best of the heterogeneous catalysts tested in the cycloaddition of CO2 with epichlorohydrin. The catalytic activity is due ultimately to defects on the outer surface of the crystal, and varies in the order of ZIF-67-m > ZIF-67 > ZiF-8-m = ZIF-8. Notably, reactions take place under mild reaction conditions and without the use of co-catalysts.

Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO2 with the Corresponding Epoxides.

Functionalized aluminosilicate materials were studied as catalysts for the conversion of different cyclic carbonates to the corresponding epoxides by the addition of CO2. Aluminum was incorporated in the mesostructured SBA-15 silica network. Thereafter, functionalization with imidazolium chloride or magnesium oxide was performed on the Al_SBA-15 supports. The isomorphic substitution of Si with Al and the resulting acidity of the supports were investigated via 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and NH3 adsorption microcalorimetry. The Al content and the amount of MgO were quantified via inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. The anchoring of the imidazolium salt was assessed by 29Si and 13C MAS NMR spectroscopy and quantified by combustion chemical analysis. Textural and structural properties of supports and catalysts were studied by N2 physisorption and X-ray diffraction (XRD). The functionalized systems were then tested as catalysts for the conversion of CO2 and epoxides to cyclic carbonates in a batch reactor at 100 or 125 °C, with an initial CO2 pressure (at room temperature) of 25 bar. Whereas the activity of the MgO/xAl_SBA-15 systems was moderate for the conversion of glycidol to the corresponding cyclic carbonate, the Al_SBA-15-supported imidazolium chloride catalysts gave excellent results over different epoxides (conversion of glycidol, epichlorohydrin, and styrene oxide up to 89%, 78%, and 18%, respectively). Reusability tests were also performed. Even when some deactivation from one run to the other was observed, a comparison with the literature showed the Al-containing imidazolium systems to be promising catalysts. The fully heterogeneous nature of the present catalysts, where the inorganic support on which the imidazolium species are immobilized also contains the Lewis acid sites, gives them a further advantage with respect to most of the catalytic systems reported in the literature so far.

Deep Eutectic Solvents as Catalysts for Cyclic Carbonates Synthesis from CO2 and Epoxides.

In recent years, the chemical industry has put emphasis on designing or modifying chemical processes that would increasingly meet the requirements of the adopted proecological sustainable development strategy and the principles of green chemistry. The development of cyclic carbonate synthesis from CO2 and epoxides undoubtedly follows this trend. First, it represents a significant improvement over the older glycol phosgenation method. Second, it uses renewable and naturally abundant carbon dioxide as a raw material. Third, the process is most often solvent-free. However, due to the low reactivity of carbon dioxide, the process of synthesising cyclic carbonates requires the use of a catalyst. The efforts of researchers are mainly focused on the search for new, effective catalysts that will enable this reaction to be carried out under mild conditions with high efficiency and selectivity. Recently, deep eutectic solvents (DES) have become the subject of interest as potential effective, cheap, and biodegradable catalysts for this process. The work presents an up-to-date overview of the method of cyclic carbonate synthesis from CO2 and epoxides with the use of DES as catalysts.

Nitrene-Mediated C-H Oxygenation: Catalytic Enantioselective Formation of Five-Membered Cyclic Organic Carbonates.

The synthesis of non-racemic 5-membered cyclic carbonates from abundant alcohols is reported. Conversion of the alcohol into an azanyl carbonate is followed by a chiral-at-ruthenium catalyzed cyclization to provide chiral cyclic carbonates in yields of up to 95 % and with up to 99 % ee. This new synthetic method is proposed to proceed through a nitrene-mediated intramolecular C(sp3 )-H oxygenation which includes an unusual 1,7-hydrogen atom transfer within a ruthenium nitrene intermediate. The method is applicable to the synthesis of non-racemic chiral mono-, di- and trisubstituted cyclic alkylene carbonates.

A Novel Catalytic Route to Polymerizable Bicyclic Cyclic Carbonate Monomers from Carbon Dioxide.

A new catalytic route has been developed for the coupling of epoxides and CO2 affording polymerizable six-membered bicyclic carbonates. Cyclic epoxides equipped with a ß-positioned OH group can be transformed into structurally diverse bicyclic cyclic carbonates in good yields and with high selectivity. Key to the chemo-selectivity is the difference between the reactivity of syn- and anti-configured epoxy alcohols, with the latter leading to six-membered ring carbonate formation in the presence of a binary AlIII aminotriphenolate complex/DIPEA catalyst. X-ray analyses show that the conversion of the syn-configured substrate evolves via a standard double inversion pathway providing a five-membered carbonate product, whereas the anti-isomer allows for activation of the oxirane unit of the substrate opposite to the pendent alcohol. The potential use of these bicyclic products is shown in ring-opening polymerization offering access to rigid polycarbonates with improved thermal resistance.

Pd/Cu Dual-Catalyzed Asymmetric Synthesis of Highly Functional All-Carbon Quaternary Stereocenters from Vinyl Carbonates.

The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp3 )-C(sp3 ) bond formation reactions is reported. The key substrate, a vinyl cyclic carbonate, is activated to provide concomitantly both the requisite nucleophile (by formal umpolung) and electrophile reaction partner preceding the asymmetric cross-coupling process. A wide screening of reaction conditions, additives and catalyst precursors afforded a protocol that gave access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er's) of up to 90 : 10.

Azo-Functionalized Zirconium-Based Metal-Organic Polyhedron as an Efficient Catalyst for CO2 Fixation with Epoxides.

Chemical fixation of CO2 as C1 source at ambient temperature and low pressure is an energy-saving way to make use of the green-house gas, but it still remains a challenge since efficient catalyst with high catalytic active sites is required. Here, a novel monoclinic azo-functionalized Zr-based metal-organic polyhedron (Zr-AZDA) has been prepared and applied in CO2 fixation with epoxides. The inherent azo groups not only endow Zr-AZDA with good solubilization, but also act as basic sites to enrich CO2 showing efficient synergistic catalysis as confirmed by TPD-CO2 analysis. XPS results demonstrate that the Zr active sites in Zr-AZDA possess suitable Lewis acidity, which satisfies both substrates activation and products desorption. DFT calculation indicates the energy barrier of the rate-determining step in CO2 cycloaddition could be reduced remarkably (by ca. 60.9 %) in the presence of Zr-AZDA, which may rationalize the mild and efficient reaction condition employed (80 °C and 1 atm of CO2 ). The work provides an effective multi-functional cooperative method for improvement of CO2 cycloaddition.

Water-Borne Isocyanate-Free Polyurethane Hydrogels with Adaptable Functionality and Behavior.

Polyurethane hydrogels are attractive materials finding multiple applications in various sectors of prime importance; however, they are still prepared by the toxic isocyanate chemistry. Herein the facile and direct preparation in water at room temperature of a large palette of anionic, cationic, or neutral polyurethane hydrogels by a non-isocyanate route from readily available diamines and new hydrosoluble polymers bearing cyclic carbonates is reported. The latter are synthesized by free radical polymerization of glycerin carbonated methacrylate with water-soluble comonomers. The hydrogel formation is studied at different pH and its influence on the gel time and storage modulus is investigated. Reinforced hydrogels are also constructed by adding CaCl2 to the formulation that in-situ generates CaCO3 particles. Thermoresponsive hydrogels are also prepared from new thermoresponsive cyclic carbonate bearing polymers. This work demonstrates that a multitude of non-isocyanate polyurethane hydrogels are easily accessible under mild conditions without any catalyst, opening new perspectives in the field.

Synergetic effect of ZnCo2O4/inorganic salt as a sustainable catalyst system for CO2 utilization.

Currently, it is essential to consider the rapidly increasing emission of CO2 into the atmosphere, causing major environmental issues such as climate change and global warming. In this work, we have developed the binary catalyst system (ZnCo2O4/inorganic salt) for chemical fixation of CO2 with epoxides into cyclic carbonates without solvent, and all reactions were performed on a large scale using a 100 ml batch reactor. Two mesoporous catalysts of ZnCo2O4 with different architecture, such as flakes (ZnCo-F) and spheres (ZnCo-S) were synthesized and utilized as a heterogeneous catalyst for cycloaddition reaction. The bifunctional property of catalysts is mainly attributed to strong acidic and basic properties confirmed by TPD (NH3 & CO2) analysis. The ZnCo-F catalyst exhibited excellent conversion of propylene oxide (99.9%) with good corresponding selectivity of propylene carbonate (≥99%) in the presence of inorganic salt (KI) at 120 °C, 2 MPa, 3 h. In addition, ZnCo-F catalyst demonstrated good catalytic applicability towards the various substrates scope of the epoxide. Furthermore, the catalytic properties were examined by evaluating the reaction parameter such as catalyst loading, pressure, temperature and time. The proposed catalyst exhibited good reusability for cycloaddition reaction without significant change in its catalytic activity and proposed a possible reaction mechanism for chemical fixation of CO2 with epoxide into cyclic carbonate over ZnCo-F/KI.