Search Results (36)

CO₂ cycloaddition with epoxides offers a sustainable route for CO₂ utilization, yet the simultaneous activation of both substrates remains challenging. Herein, using UiO-66(Zr)-NH₂ (denoted as UZN) as a model system, we illustrate that dual-active sites consisting of unsaturated Zr⁴⁺ centers and amine groups can efficiently accelerate CO₂ fixation with epoxides under visible light. The unique ensemble in UZN optimizes light harvesting, promotes charge carrier separation, and enriches bifunctional active sites for efficient adsorption and activation of epoxides and CO₂. Consequently, UZN exhibits significantly improved CO₂-epoxide cycloaddition performance compared to UiO-66(Zr)-H (denoted as UZH), achieving a PC yield of 99.5%, with a production rate of 9.97 mmol·g⁻¹·h⁻¹. This work establishes a clear coordination–photocatalytic synergy in MOF-based systems and provides fundamental insights and a generalizable strategy for designing advanced catalysts for CO₂ transformation. Full article

This study reports the synthesis and catalytic evaluation of a series of imidazolium-based polymeric ionic liquids (PILs) for the cycloaddition of CO₂ to epichlorohydrin (ECH). The synthesized catalysts include homopolymers, poly(3-hydroxyethyl-1-vinylimidazole chloride) (p[HVIm][Cl]) and poly(3-carboxymethyl-1-vinylimidazole chloride) (p[CMVIm][Cl]), and their block copolymers with polystyrene, synthesized for the first time, pS-b-p[HVIm][Cl] and pS-b-p[CMVIm][Cl]. Structural characterization by NMR, IR spectroscopy, and gel permeation chromatography confirmed the successful synthesis. The block copolymers exhibited a low polydispersity index (PDI 1.1–1.2), which is indicative of homogeneous chain lengths and the propensity to form ordered nanostructures, whereas the homopolymers showed higher PDI (2.4–2.9). Catalytic testing at 90 °C and 1 MPa CO₂ for 4 h revealed a clear activity trend: p[CMVIm][Cl] < p[HVIm][Cl] < pS-b-p[CMVIm][Cl] < pS-b-p[HVIm][Cl], with conversions exceeding 75% for all catalysts and a maximum of 82.69% for pS-b-p[HVIm][Cl]. These results demonstrate that the catalytic performance of PILs is governed by a synergistic interplay between the local chemical functionality of the ionic moiety and the overall polymer architecture. Based on these results, the synthesized polymeric ionic liquids, particularly pS-b-p[HVIm][Cl], demonstrate strong potential for creating multifunctional materials. Their ability to self-assemble into ordered nanostructures with distinct hydrophobic and hydrophilic domains provides a foundational architecture for combined gas separation and catalysis. The observed “micellar catalytic effect”, which enhances local reagent concentration near active sites, could be leveraged in a membrane reactor to simultaneously capture and convert CO₂ directly within the membrane. This integrated “separation–reaction” approach represents a promising strategy for advancing circular carbon economy technologies. Full article

A novel metal–organic framework based on zinc ions, designated as Zn-URJC-12, has been synthesized and applied for the first time in the cycloaddition reaction between carbon dioxide and epoxides. This MOF is constructed from two different organic linkers: 5-aminoisophthalic acid and 4,4′-biphenyldicarboxylic acid. The framework features –NH₂ functional groups coordinated to Zn(II) centers, as confirmed by single-crystal X-ray diffraction analysis. Zn-URJC-12 demonstrates exceptional chemical stability in polar organic solvents, such as methanol, while maintaining thermal stability up to 250 °C. The material exhibits high catalytic efficiency in the cycloaddition of CO₂ with epoxides, achieving yields of 100% and 76% for propylene oxide and allyl glycidyl ether, respectively. Additionally, Zn-URJC-12 maintains its structural integrity and catalytic performance during five successive reaction cycles. These findings underscore Zn-URJC-12 as a promising heterogeneous catalyst for the valorization of CO₂ into cyclic carbonates. Full article

Biochar-based materials have gathered increasing attention as sustainable catalysts for carbon dioxide (CO₂) valorization, offering a green alternative to traditional metal-based systems. Produced from renewable biomass through pyrolysis, biochar possesses key features—such as high surface area, rich porosity and tunable surface chemistry—that make it particularly suited for heterogeneous catalysis. This review highlights recent advances in the use of biochar-derived catalysts for key CO₂ conversion reactions, focusing on cycloaddition to epoxides, dry reforming of methane and catalytic biomass upgrading. Emphasis is given to the role of biochar’s origin and preparation methods, which critically influence its structure, surface functionality and catalytic performance. Feedstocks rich in mineral content or oxygenated groups, for instance, can enhance CO₂ activation and product selectivity. Furthermore, tailored modifications—such as doping with heteroatoms or supporting metal nanoparticles—further boost catalytic activity and stability by tuning acid–base behavior, while maintaining low toxicity and cost-effectiveness. Compared to conventional catalysts, biochar-based systems offer advantages in low cost, recyclability and resistance to deactivation. Challenges remain in standardizing production methods, controlling structural variability, minimizing metal leaching and scaling up. This review presents biochar as a versatile, renewable platform for CO₂ utilization, highlighting the importance of rational design, feedstock selection and functionalization strategies for developing efficient, sustainable catalytic systems, in line with green chemistry and circular economy principles. Full article

A series of novel amine triphenolate iron complexes were synthesized and characterized using UV, IR, elemental analysis, and high-resolution mass spectrometry. These complexes were applied to the ring-opening polymerization (ROP) of cyclohexene oxide (CHO), demonstrating excellent activity (TOF > 11050 h⁻¹) in the absence of a co-catalyst. In addition, complex C1 maintained the dimer in the presence of the reaction substrate CHO, catalyzing the ring-opening polymerization of CHO to PCHO through bimetallic synergy. Furthermore, a two-component system consisting of iron complexes and TBAB displayed the ability to catalyze the reaction of CHO with CO₂, resulting in the formation of cis-cyclic carbonate with high selectivity. Complex C4 exhibited the highest catalytic activity, achieving 80% conversion of CHO at a CHO/C4/TBAB molar ratio of 2000/1/8 and a CO₂ pressure of 3 MPa for 16 h at 100 °C, while maintaining >99% selectivity of cis-cyclic carbonates, which demonstrated good conversion and selectivity. Full article

To achieve the peak of carbon dioxide emission and carbon neutrality, utilizing it as a renewable carbon unit in organic synthesis presents an effective chemical solution for sustainable development. In this study, we report a theoretical investigation into the reaction mechanism and the regiodivergence of the Ni-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO₂ by using DFT calculations. The reaction mechanisms can be classified into two types: one is related to the oxidative coupling of the C≡C moiety with CO₂, and the other is related to the oxidative coupling of the two C≡C moieties of diyne. In each type, two possible paths were proposed depending upon the positions of the substituents (H and silyl). Our calculation results indicate that the oxidative coupling of the C≡C moiety and CO₂ favors the positions of H-substituent, while the oxidative coupling of the two C≡C moieties is beneficial for inserting CO₂ at the positions of silyl-substituent. The regiodivergence is controlled by substrate chain-length and ligand in the different reaction mechanisms. Full article

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). Full article

This article describes the use of microwave irradiation in the synthesis of bis(cyclo carbonate) compounds (BCCs) in bulk (without solvent) from carbon dioxide capture using an epoxidized compound—a commercial epoxy resin—and compares this process to the conventional method. CO₂ cycloaddition to epoxides is an ecological and efficient method for the formation of bis(cyclic carbonates). Moreover, the introduction of gas into the reaction mixture was carried out at atmospheric pressure with a controlled flow rate, which is advantageous from an economic point of view. Progressive structural changes and the presence of characteristic chemical groups were monitored using attenuated total reflectance infrared spectroscopy with Fourier transform. The obtained crude products were purified to obtain three fractions, which were subjected to detailed structural analysis using FT-IR and ¹³CNMR. The formation of the main product with two cyclic carbonates was confirmed. The presence of monomers, dimers and trimers in individual fractions as well as their thermal stability were determined, and the molecular masses in individual fractions were determined using gel permeation chromatography (GPC). Full article

In this study, we report the design, synthesis, and catalytic application of the novel nitrogen-rich Zn(II) MOF [Zn₂(μ₃-1κN,2κN′,3κO-HL)₂(DMF)₂]_n·nH₂O (HL²⁻ = 4-((4-(1H-tetrazol-5-yl)phenyl)carbamoyl)benzoate), denoted as ZnMOF, for the efficient conversion of carbon dioxide (CO₂) to cyclic carbonates via cycloaddition with epoxides. It was synthesised from a tetrazole appended amide-functionalised pro-ligand (H₃L) and Zn(NO₃)₂·6H₂O under hydrothermal conditions. The synthesised material was characterised namely by elemental analysis, infrared spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. The catalytic potential of ZnMOF was investigated in the CO₂ cycloaddition reaction with various epoxides, with conversions ranging from 17% to 99%. The catalyst retained its activity across multiple reaction cycles, demonstrating its stability and reusability. The influence of co-catalysts on the reaction was explored, with tetrabutylammonium bromide (TBABr) emerging as the most effective one. A plausible reaction mechanism is proposed. Full article

Development of an effective catalytic system for the cycloaddition of carbon dioxide to epoxides for the preparation of cyclic carbonates under mild conditions is of great importance. Herein, a mixture of zinc iodide, metal chlorides, and strong organic bases is demonstrated to be a useful catalytic system that works at room temperature under atmospheric pressure. The most efficient combination, zinc iodide-niobium chloride-7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (1.2-0.3-3.0 mol%), gave styrene carbonate (95%) from styrene oxide and CO₂ (balloon) at 25 °C for 24 h. Another combination, zinc iodide-zinc chloride-1,8-diazabicyclo[5.4.0]undec-7-ene (1.2-0.8-4.0 mol%), kept the catalytic activity for the preparation of propylene carbonate until the fourth run. Therefore, the reaction system was operationally simple, highly efficient, and proceeded under ambient conditions. The catalyst is composed of readily available reagents and is reusable. Thus, the method presented is a powerful tool for utilizing CO₂ as the starting material for the production of valuable chemicals. Full article

Much effort has been devoted to the development of efficient heterogeneous catalysts for the conversion of carbon dioxide (CO₂) into high-value chemicals. Generally, the cycloaddition of CO₂ to epoxides is considered a green and atom-economic reaction for the production of cyclic carbonates. Based on this, three kinds of silicon-based catalysts modified using zinc(Ⅱ) 2-bromoacetic (Si-ZnBA-n, n = 1, 2, 3) were facilely synthesized and employed for the chemical fixation of CO₂ to epoxides with the use of potassium iodide (KI). A series of characterization techniques were used to characterize the textual structures and physicochemical properties of Si-ZnBA-n. The synergistic effects of Zn, –NH_2, –OH and the nucleophilic group guaranteed the catalytic activity of Si-ZnBA-n. Si-ZnBA-1 exhibited the best catalytic activity among Si-ZnBA-n because Si-ZnBA-1 possessed the highest Zn content. Additionally, the effects of the reaction conditions (temperature, pressure, time and catalyst loadings) were also discussed. The propylene carbonate (PC) yield could reach 97% under 130 °C, 2 MPa, for 5 h without the employment of organic solvent, and its selectivity was 99%. In addition, the recycling property of Si-ZnBA-1/KI was also investigated, and the catalytic system exhibited good cycle performance. Meanwhile, the catalyst showed outstanding versatility for CO₂ application to various epoxides, and a possibly synergistic reaction mechanism was proposed. Finally, a dynamic model was developed to discuss the activation energy of the CO₂ cycloaddition reaction over the Si-ZnBA-1 catalyst. Full article

A diversity-oriented synthesis (DOS) of two new polyheterocyclic compounds was performed via an Ugi-Zhu/cascade (N-acylation/aza Diels-Alder cycloaddition/decarboxylation/dehydration)/click strategy, both step-by-step to optimize all involved experimental stages, and in one pot manner to evaluate the scope and sustainability of this polyheterocyclic-focused synthetic strategy. In both ways, the yields were excellent, considering the high number of bonds formed with release of only one carbon dioxide and two molecules of water. The Ugi-Zhu reaction was carried out using the 4-formylbenzonitrile as orthogonal reagent, where the formyl group was first transformed into the pyrrolo[3,4-b]pyridin-5-one core, and then the remaining nitrile group was further converted into two different nitrogen-containing polyheterocycles, both via click-type cycloadditions. The first one used sodium azide to obtain the corresponding 5-substituted-1H-tetrazolyl-pyrrolo[3,4-b]pyridin-5-one, and the second one with dicyandiamide to synthesize the 2,4-diamino-1,3,5-triazine-pyrrolo[3,4-b]pyridin-5-one. Both synthesized compounds may be used for further in vitro and in silico studies because they contain more than two heterocyclic moieties of high interest in medicinal chemistry, as well as in optics due to their high π-conjugation. Full article

CO₂, as a cheap and abundant renewable C1 resource, can be used to synthesize high value-added chemicals. In this paper, a series of bifunctional metallic niobium complexes were synthesized and their structures were characterized by IR, NMR and elemental analysis. All of these complexes have been proved to be efficient catalysts for the coupling reaction of CO₂ and epoxides to obtain cyclic carbonates under solvent- and co-catalyst-free conditions. By using CO₂ and propylene oxide as a model reaction, the optimal reaction conditions were systematically screened as: 100 °C, 1 MPa, 2 h, ratio of catalyst to alkylene oxide 1:100. Under the optimal reaction conditions, the bifunctional niobium catalysts can efficiently catalyze the coupling reaction with high yield and excellent selectivity (maximum yield of >99% at high pressure and 96.8% at atmospheric pressure). Moreover, this series of catalysts can also catalyze the coupling reaction at atmospheric pressure and most of them showed high conversion of epoxide. The catalysts have good substrate suitability and are also applicable to a variety of epoxides including diepoxides and good catalytic performances were achieved for producing the corresponding cyclic carbonates in most cases. Furthermore, the catalysts can be easily recovered by simple filtration and reused for at least five times without obvious loss of catalytic activity and selectivity. Kinetic studies were carried out preliminarily for the bifunctional niobium complexes with different halogen ions (3a(Cl⁻), 3b(Br⁻), 3c(I⁻)) and the formation activation energies (E_a) of cyclic carbonates were obtained. The order of apparent activation energy E_a is 3a (96.2 kJ/mol) > 3b (68.2 kJ/mol) > 3c (37.4 kJ/mol). Finally, a possible reaction mechanism is proposed. Full article

Surface engineering of conventional catalysts using polymeric coating has been extensively explored for producing hybrid catalytic material with enhanced activity, high mechanical and thermal stability, enhanced productivity, and selectivity of the desired product. The present review discusses in detail the state-of-the-art knowledge on surface modification of catalysts, namely photocatalysts, electrocatalysts, catalysts for photoelectrochemical reactions, and catalysts for other types of reactions, such as hydrodesulfurization, carbon dioxide cycloaddition, and noble metal-catalyzed oxidation/reduction reactions. The various techniques employed for the polymer coating of catalysts are discussed and the role of polymers in enhancing the catalytic activity is critically analyzed. The review further discusses the applications of biodegradable and biocompatible natural polysaccharide-based polymers, namely, chitosan and polydopamine as prospective coating material. Full article

The development and application of new organoboron reagents as Lewis acids in synthesis and metal-free catalysis have dramatically expanded over the past 20 years. In this context, we will show the recent uses of the simple and relatively weak Lewis acid BPh₃—discovered 100 years ago—as a metal-free catalyst for various organic transformations. The first part will highlight catalytic applications in polymer synthesis such as the copolymerization of epoxides with CO₂, isocyanate, and organic anhydrides to various polycarbonate copolymers and controlled diblock copolymers as well as alternating polyurethanes. This is followed by a discussion of BPh₃ as a Lewis acid component in the frustrated Lewis pair (FLP) mediated cleavage of hydrogen and hydrogenation catalysis. In addition, BPh₃-catalyzed reductive N-methylations and C-methylations with CO₂ and silane to value-added organic products will be covered as well along with BPh₃-catalyzed cycloadditions and insertion reactions. Collectively, this mini-review showcases the underexplored potential of commercially available BPh₃ in metal-free catalysis. Full article