Cycloaddition Reaction Of CO2 Research Articles

MIL-101(Cr)/aminoclay nanocomposites for conversion of CO2 into cyclic carbonates.

We present the use of an amine functionalized two-dimensional clay i.e., aminoclay (AC), in the chemistry of a three-dimensional metal-organic framework (MOF) i.e., MIL-101(Cr), to prepare MIL-101(Cr)/AC composites, which are exploited as catalysts for efficient conversion of CO2 gas into cyclic carbonates under ambient reaction conditions. Three different MOF nanocomposites, denoted as MIL-101(Cr)/AC-1, MIL-101(Cr)/AC-2, and MIL-101(Cr)/AC-3, were synthesized by an in situ process by adding different amounts of AC to the precursor solutions of the MIL-101(Cr). The composites were characterized by various techniques such as FT-IR, PXRD, FESEM, EDX, TGA, N2 adsorption, as well as CO2 and NH3-TPD measurements. The composites were exploited as heterogeneous catalysts for CO2 cycloaddition reactions with different epoxides and the catalytic activity was investigated at atmospheric pressure under solvent-free conditions. Among all the materials, MIL-101(Cr)/AC-2 shows the best catalytic efficiency under the optimized conditions and exhibits enhanced efficacy compared to various MIL-101(Cr)-based MOF catalysts, which typically need either high temperature and pressure or a longer reaction time or a combination of all the parameters. The present protocol using MIL-101(Cr)/AC-2 as the heterogeneous catalyst gives 99.9% conversion for all the substrates into the products at atmospheric pressure.

Co(II)-N4 Catalysts for the Coupling of CO2 with Epoxides into Cyclic Carbonates: Catalytic Activity, Computational and Kinetic Studies.

In this study, we synthesized and characterized a series of cobalt(II) complexes bearing linear tetradentate N4 ligands. These Co(II)-N4 complexes proved to be efficient catalysts for the cycloaddition reaction between carbon dioxide and epoxides even at room temperature and 1 bar pressure of carbon dioxide without the need for solvents or cocatalysts. Furthermore, when combined with (triphenylphosphoranylidene)ammonium chloride (PPNCl) as a cocatalyst, the Co-N4 catalysts exhibited an impressive turnover frequency of up to 41,000 h-1 for coupling of epichlorohydrin/CO2. These Co(II)-N4 catalysts were found to have excellent stability and reusability, retaining their catalytic activity after they were recycled seven times. Density functional theory (DFT) calculations provided a comprehensive mechanism for the cycloaddition reaction, indicating that the rate-determining step is the epoxide ring opening, in both the presence and absence of PPNCl. Further kinetic studies allow us to determine the activation parameters (ΔH‡, ΔS‡, and ΔG‡ at 25 °C) of the coupling reaction using the Eyring equation. The Gibbs free activation energy obtained from the kinetic studies was in close agreement with that of the DFT calculations. The substituent effect on the cycloaddition reaction of CO2 with various substituted styrene oxides was also examined for the first time.

Two 2D Metal-Organic Frameworks Based on Purine Carboxylic Acid Ligands for Photocatalytic Oxidation of Sulfides and CO2 Chemical Fixation.

Two two-dimensional (2D) layered metal-organic frameworks (MOFs), namely, {[Yb(L)(H2O)2NO3]·2H2O}n (Yb-MOF) and [Er(L)(H2O)3Cl]n (Er-MOF) (H2L = 5-((6H-purin-6-yl)amino)isophthalic acid), were constructed by a solvothermal method and characterized. The catalytic performance study showed that the Yb-MOF could efficiently catalyze the oxidation of sulfides to sulfoxides under 15 W light-emitting diode (LED) blue light irradiation. Electron paramagnetic resonance spectroscopy and free-radical trapping experiments demonstrated that the photocatalytic reaction process involved •O2-, and the corresponding mechanism was proposed. Moreover, Er-MOF exhibited good catalytic efficiency and excellent substrate tolerance in the cycloaddition reaction of CO2, and the reaction conditions were mild. After 5 cycles, the catalytic activities of two MOFs did not significantly decrease, and the framework structures remained unchanged. Therefore, the Yb-MOF and Er-MOF were considered efficient and stable heterogeneous catalysts.

Imidazole-based organic polymer frameworks as metal- and halogen-free heterogeneous platforms for efficient CO2 cycloaddition

Developing effective metal- and halogen-free heterogeneous catalysts for the CO2 cycloaddition remains a challenge. In this study, novel imidazole-based hyper-crosslinked polymers (HCP-BZ, HCP-BP and HCP-TBZ) with abundant N sites were constructed via a one-pot polymerization, and employed as heterogeneous catalysts for the CO2 cycloaddition reaction. The special skeletal pore structure with abundant hierarchical pore structures and uniformly distributed active sites were demonstrated by various characterization technologies. The optimal HCP-TBZ(16:1) exhibits a good CO2 selective adsorption performance with a CO2 adsorption capacity of 2.23 mmol/g and CO2/N2 adsorption selectivity of 41 at 273 K and 0.1 MPa. Additionally, the resulting catalyst HCP-TBZ(16:1) achieves an excellent catalytic performance with 96 % yield and 99 % selectivity without metal, halogen, cocatalyst and solvent additions (120 °C, 1.0 MPa CO2, 5 h). Moreover, the HCP-TBZ(16:1) also exhibits a satisfactory catalytic activity under the mild conditions (70 °C, 1.0 MPa CO2), and can effectively catalyze the cyclic carbonate preparation from the dilute CO2 (15 %CO2/85 %N2). The comparable catalytic activity and the determined structural stability, reusability and universality make the prepared imidazole-based HCPs a potential heterogeneous catalyst candidate for the CO2 cycloaddition. This study will provide some guidance for developing metal-free and halogen-free CO2 adsorption and conversion platforms.

Facile synthesis of Al-g-C3N4/Bi2S3 with enhanced for CO2 cycloaddition reaction performance

In this paper, a high specific surface area lamellar heterogeneous composite catalyst (MCN) was synthesized for the cycloaddition reaction of CO2 and epoxides. MCN is doped aluminum with high catalytic activity in Bi2S3 and g-C3N4 with photocatalytic activity, and it was prepared by a facile one-step calcination method. This catalyst achieved 88 % and 97 % conversion and selectivity for the cycloaddition reaction of epichlorohydrin and CO2 with no change in yield after five cycles. In addition, the two compositions of Bi2S3 and g-C3N4 in MCN resulted in enhanced light absorption of the catalyst, thus providing some photothermal performance. This paper provides an idea for the design of bifunctional catalysts with Lewis acid-base.

Polymorphism and Its Influence on Catalytic Activities of Lanthanide-Glutamate-Oxalate Coordination Polymers.

To study the relationship between polymorphism and catalytic activities of lanthanide coordination polymers in the cycloaddition reactions of CO2 with epoxides, the monoclinic and triclinic polymorphs of [LnIII(NH3-Glu)(ox)]·2H2O, where LnIII = LaIII (I), PrIII (II), NdIII (III), SmIII (IV), EuIII (V), GdIII (VI), TbIII (VII), and DyIII (VIII), NH3-Glu- = NH3+ containing glutamate, and ox2- = oxalate, were synthesized and characterized. Factors determining polymorphic preference, the discrepancy between the two polymorphic framework structures, potential acidic and basic sites, thermal and chemical stabilities, active surface areas, void volumes, CO2 sorption/desorption isotherms, and temperature-programmed desorption of NH3 and CO2 are comparatively presented. Based on the cycloaddition of CO2 with epichlorohydrin in the presence of tetrabutylammonium bromide under solvent-free conditions and ambient pressure, catalytic activities of the two polymorphs were evaluated, and the relationship between polymorphism and catalytic performances has been established. Better performances of the monoclinic catalysts have been revealed and rationalized. In addition, the scope of monosubstituted epoxides was experimented and the outstanding performance of the monoclinic catalyst in the cycloaddition reaction of CO2 with allyl glycidyl ether under ambient pressure has been disclosed.

Preparation of Magnetic Nano-Catalyst Containing Schiff Base Unit and Its Application in the Chemical Fixation of CO2 into Cyclic Carbonates

The development of a catalyst for the conversion of CO2 and epoxides to the corresponding cyclic carbonates is still a very attractive topic. Magnetic nano-catalysts are widely used in various organic reactions due to their magnetic separation and recycling properties. Here, a magnetic nano-catalyst containing a Schiff base unit was designed, synthesized and used as a heterogeneous catalyst to catalyze CO2 and epoxides to form cyclic carbonates without solvents and co-catalysts. The catalyst was characterized using Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric (TG), VSM, SEM, TEM and BET. The results show that the magnetic nano-catalyst containing the Schiff base unit has a high activity in the solvent-free cycloaddition reaction of CO2 with epoxide under mild conditions, and is easily separated from the reaction mixture driven by external magnetic force. The recovered catalyst maintains a high performance after five cycles.

Poly(ionic liquid)-based aerogels for continuous-flow CO2 upcycling

The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable of capture and conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts for processes at or near atmospheric pressure. PILs industrial application poses challenges due to the low porosity of PIL, the limited batch conversion capacity, and the difficulties in reuse. To overcome these limitations, we herein propose the use of AEROPILs catalysts obtained from the integration of PILs in chitosan-based aerogels. These cost-effective highly porous materials have unique and tuneable porous properties making them not only ideal sustainable CO2 sorbents but also promising heterogeneous catalysts. While AEROPILs show moderate yields for CO2 conversion in batch mode, high catalytic activity was achieved when AEROPILs were used to catalyse the CO2 cycloaddition reaction to epoxides in packed-bed reactors operated under continuous flow. The catalytic activity and stability were maintained over 60 h without activity loss, and high productivity (space-time yield of 21.18 gprod h−1 L−1). This research reveals the pioneering use of AEROPILs to efficiently upcycle CO2 into cyclic carbonate under a continuous flow setup.

Upcycling Waste Biomass–Production of Porous Carbonaceous Supports from Paper Mill Sludge and Application to CO2 Conversion

AbstractThe urgent need for sustainable waste management strategies has led to the exploration of innovative approaches for the valorization of waste. In this study, a method is proposed for carbonizing waste biomass materials, particularly paper mill waste sludges (primary and biological) and knots, to produce porous carbonaceous supports. Through an initial hydrothermal carbonization followed by carbonization with nitrogen flow, porous carbon materials are successfully generated. The findings of this investigation validate the successful generation of effective carbonaceous supports utilizing waste biomass materials. These materials are then evaluated for their effectiveness as porous supports in the ionic liquid‐catalyzed cycloaddition reaction of CO2 to styrene oxide, achieving a remarkable conversion rate of up to 98% and an impressive selectivity exceeding 99%. Additionally, the results underscore the significant impact of the selected IL on the overall conversion process. Overall, this study presents a promising pathway for the valorization of paper mill waste sludge through the production of porous carbon materials with potential applications in catalysis and beyond.

Facet and dual vacancy engineering-boosting BiOBr for enhanced CO2 and epoxide cycloaddition reaction under mild and cocatalyst-free conditions: Double substrate active sites and activated surface bromine ions synergy

Among the many strategies for CO2 resource utilization, the synthetic technology of cyclic carbonates with 100 % atom economy through CO2and epoxide is one of the most industrially viable routes, but its efficiency has been severely hampered by the lack of highly active catalytic sites. Moreover, due to the intrinsic thermodynamic stability and kinetic inertia of CO2 and the higher energy barrier of the ring-opening reaction of epoxides, the heterogeneous catalytic conversion of CO2 highly depends on harsh operating conditions, high temperatures and pressures, and the incorporation of cocatalysts. The development of efficient heterogeneous catalysts for CO2 conversion under cocatalyst-free and mild conditions has always been a challenge. Herein, we have proposed a synergetic strategy of facet and vacancy engineering for the construction of highly efficient heterogeneous catalyst BiO1-xBr1-y-(010) for CO2 cycloaddition, where introducing the OVs-BrVs pairs into typical (010) facets BiOBr with simultaneous surface Lewis acid sites Bi3+ and nucleophilic sites Br−. By combining theoretical calculations and a series of systematic experiments, such as CO2 temperature-programmed desorption, electron paramagnetic resonance and fluorescence probe analysis experiments, the introduced OVs-BrVs pair can not only form Bi3+-Bi(3-x)+ dual active sites on the surface, which activate PO and CO2 respectively to reduce the energy barrier of CO2 insertion, but also activate Br− near BrVs to enhance their nucleophilic attacking ability and reduce the energy barrier of epoxides ring-opening. As a result, the BiO1-xBr1-y-(010) with abundant surface OVs-BrVs pairs showed a high cyclic carbonates conversion of 99 % with 100 % selectivity under cocatalyst-free and mild conditions, far surpassing most heterogeneous catalytic systems. This work provides a completely new strategy to construct high-performance heterogeneous CO2 cycloaddition catalysts through a simple facet and vacancy engineering strategy to overcome the harsh operating conditions limitation and the use of cocatalysts.

The self-assembly of tetranuclear [Gd4] cluster: Magnetic refrigeration and efficient CO2 chemical fixation

In this paper, the self-assembly of Gd3+ ions and ligand 5-chlorine-8-hydroxylquinoline (HL) successfully generated one tetranuclear lanthanide compound [Gd4(µ3-OH)2(L)6(acac)4] (1) (L = 5-chlorine-8-hydroxylquinoline; Hacac = acetylacetone), in which four Gd3+ ions are connected into a [Gd4O2] cluster. Magnetic studies revealed that anti-ferromagnetic interactions between neighbouring Gd3+ ions were observed in 1. In addition, 1 also shows magnetocaloric effect and the −ΔSm value reaches 28.05 J kg−1 K−1 at T = 2.0 K and ΔH = 7 T. Catalytic experiments indicated that 1 and tetra-n-butylammonium bromide (TBAB) could synergistically catalyze the cycloaddition reaction of CO2 and epoxides at relatively mild condition.

Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies.

The crystal structure of the metal-organic framework (MOF), {Mn2(1,4-bdc)2(DMF)2}n (1) (1,4-bdcH2, 1,4-benzenedicarboxylic acid; DMF, N,N-dimethylformamide), is known for a long time; however, its desolvated structure, {Mn2(1,4-bdc)2}n (1'), is not yet known. The first-principles-based computational simulation was used to unveil the structure of 1' that shows the expansion in the framework, leading to pore opening after the removal of coordinated DMF molecules. We have used 1' that contains open metal sites (OMSs) in the structure in cyanosilylation and CO2 cycloaddition reactions and recorded complete conversions in a solventless setup. The pore opening in 1' allows the facile diffusion of small aldehyde molecules into the channels, leading to complete conversion. The reactions with larger aldehydes, 2-naphthaldehyde and 9-anthracenecarboxaldehyde, also show 99.9% conversions, which are the highest reported until date in solventless conditions. The in silico simulations illustrate that larger aldehydes interact with Mn(II) OMSs on the surfaces, enabling a closer interaction and facilitating complete conversions. The catalyst shows high recyclability, exhibiting 99.9% conversions in the successive reaction cycles with negligible change in the structure. Our investigations illustrate that the catalyst 1' is economical, efficient, and robust and allows reactions in a solventless greener setup, and therefore the catalysis with 1' can be regarded as "green catalysis".

Experimental and kinetic evaluation on cobalt Salen conjugated organic polymers for CO2 cycloaddition reactions and iodine vapor adsorption

The fixing reactions of carbon dioxide with epoxides will not only help to ameliorate the problem of global warming, but also facilitate the synthesis of cyclic carbonates that have a multitude of applications. Herein, a new sequence of Salen cobalt complexes adjusted with different counterions and interconnected with pyrene group were synthesized through Friedel–Crafts alkylation, which were served as conjugated organic polymers (SP-COPs) for taking advantage of catalytic CO2 fixation reactions and iodine adsorption. Further characterizations were carried out through FT-IR, UV, TGA, and SEM to comprehend the intact structure, thermal stability, morphology and other physical and chemical properties. All materials exhibited effective catalytic performance, and in particular, SP-COP-1 with co-catalyst of TBAI achieved 96.2% conversion under ultra-mild conditions. The Ea was obtained to be 46.4 kJ·mol−1 by performing kinetic experiments at different temperatures by fitting the experimental data. The performance of iodine vapor adsorbed by these materials at ambient pressure of 75°C reached 2.8 g·g−1, 2.2 g·g−1 and 2.6 g·g−1 respectively, and the adsorption process is describable in terms of pseudo-first-order and pseudo-second-order adsorption kinetics.

Photo-induced CO2 cycloaddition and tetracycline degradation over novel FeOx modified defective graphitic carbon nitride composite

Utilizing sunlight to achieve CO2 conversion and environmental remediation has been a key focus. Herein, “all-in-one” graphitic carbon nitride (g-C3N4) composite-based photocatalysts were synthesized by a simple one-step low-temperature calcination. Lower calcination temperature resulted in defective g-C3N4 enriched in cyano and hydroxyl groups. It was found that by incorporating amorphous FeOX, the resulted FeOX/O-g-C3N4 photocatalyst shows very good performance towards both CO2 cycloaddition reaction and photo-Fenton degradation of tetracycline (TC). It was also found that the photocatalyst shows the highest styrene carbonate yield of 83% (23 mmol g−1 h−1) under ambient conditions, which is 13.8 times higher than that obtained over pure g-C3N4. The photocatalyst also exhibits a 4.7 times faster TC removal rate than that of pure g-C3N4. Systematic characterization and mechanism study demonstrate the role of defects and photo-induced charge carriers.

Two coordination polymers based on imidazopyridine carboxylic acid ligand for efficient catalytic cycloaddition of CO2 with epoxides and cyanosilylation

Two coordination polymers (CPs){[M(L)2(H2O)2]·2H2O}n (M=Co (1) and Mn (2), HL=4-(3H-imidazo[4,5-b]pyridin-2-yl) benzoic acid) have been prepared under hydrothermal method and systematically characterized. The catalytic properties of the two CPs were investigated, the results showed that CP 1 could be used to catalyze CO2 cycloaddition reactions efficiently under eco-friendly, solvent-free conditions. The influencing factors and catalytic mechanism of cycloaddition reaction were discussed. Moreover, CP 2 exhibited catalytic performance for cyanosilylation reaction. The recycling experiments showed that the CPs 1 and 2 could be recovered and reused at least 5 reaction cycles without an obvious decrease of catalytic activity.

One-step synthesis of hydroxyl-functionalized ionic hyper-cross-linked polymers with high surface areas for efficient CO2 capture and fixation

Ionic liquid-based functional materials have attracted significant attention for their distinctive structure in the field of CO2 capture and conversion. In this work, a series of hydroxyl-functionalized ionic hyper-cross-linked polymers are prepared through a one-step Friedel-Crafts reaction involving hypoxanthine (HX) and benzimidazole (BI) as the monomers, along with various halohydrocarbon crosslinking agents. These polymers demonstrate a high specific surface area (558–1480 m2·g−1), well-developed microporous structure, and unique ion sites, enabling them to exhibit remarkable and reversible CO2 adsorption properties. Particularly noteworthy is their CO2 adsorption capacity, which surpasses that of similar ionic polymers documented in the literature, reaching 157.5 mg·g−1 at 273 K and 1 bar. Additionally, these polymers function as recyclable catalysts in the cycloaddition reaction of CO2 and epoxides, enabling the conversion of CO2 into cyclic carbonates with yields of up to 99 % even without a co-catalyst. Mechanism investigation reveals that the introduction of hydroxyl groups in the polymer is the key to improving catalytic activity through a synergistic catalytic effect. This research provides a novel concept for designing ionic functional materials with capabilities in both CO2 adsorption and catalytic activity.

Green conversion of CO2 by N-heterocyclic carbene-CO2 adducts grafted hierarchical porous silica microspheres

The multiphase catalysts DMSNs-Cb-X containing NHC-CO2 adducts were synthesized by soft template method that is, first preparing dendritic multi-model pore silica nanoparticles (DMSNs) with central-radial structure, and then grafting imidazoline functional groups, and finally allowing to react with dimethyl carbonate to graft NHC-CO2 adducts. The investigations had the scope to improve the performance and to elucidate the effect of NHC-CO2 adducts on the CO2 cycloaddition reaction. The optimum catalyst DMSNs-Cb-1 and the optimum reaction conditions (200 mg, 100 °C, 10 h) were obtained via thermogravimetric analysis. CO2 cycloaddition reaction with epoxide DMSNs-Cb-1 can convert CO2 and epoxide to cyclic carbonate at ambient pressure without solvent and co-catalysts (1 bar, 100 °C). The reaction proceeds with high yield and high conversion frequency (TOF = 27.4 h−1). The prepared catalyst is easily recovered and still has high activity after five cycles of experiments. The excellent catalytic performance of the obtained catalyst can be attributed to the synergy of hierarchical porous structure and NHC-CO2 adducts acting as CO2 adsorption sites as well as zwitterionic catalytic sites. This work demonstrates an efficient strategy for green conversion of CO2 into cyclic carbonates.

Fine-tuning covalent organic frameworks for structure-activity correlation via adsorption and catalytic studies

In applications utilizing Covalent Organic Frameworks (COFs) for adsorption, the interplay between crystallinity (vis-à-vis surface area) and active sites still remains ambiguous. To address this, the present study introduces three isoreticular COFs—COP-N18 (covalent organic polymer with short-range order), COF-N18 (COF having long-range order), and COF-N27 (semicrystalline COF with pyridyl heteroatoms)—to explore this duality. Through systematic variations in structural order, pore volume, and pore-wall nitrogen content, we aim to establish a structure–activity relationship (SAR) for these COFs via adsorption and catalysis, using CO2 and I2 as probes. Our investigation highlights the positive influence of crystallinity, surface area, and pore volume in adsorption as well as catalysis. However, the presence of heteroatoms manifests complex behavior in CO2 adsorption and CO2 cycloaddition reactions with epoxides. COF-N18 and COF-N27 showed comparable CO2 uptake capacities at different temperatures (273, 293, and 313 K) and ∼1 bar pressure. Additionally, CO2 cycloaddition reactions were performed with substrates possessing different polarities (epichlorohydrin, 1,2-epoxydodecane) to elucidate the role of COF surface polarity. Further investigation into iodine adsorption was performed to understand the impact of COF structural features on the modes of adsorption and adsorption kinetics. Improvements in COF-crystallinity results in faster average iodine uptake rate at 80% (K80% = 1.79 g/h) by COF-N18. Whereas, heteroatom doping slows down iodine adsorption kinetics (0.35 g/h) by prolonging the adsorption process up to 72 h. Overall, this study advances our understanding of COFs as adsorbents and catalysts, providing key insights into their SAR while emphasizing structural fine-tuning as a key factor for impactful environmental applications.

A Multivariate 2D Metal-Organic Framework with Open Metal Sites for Catalytic CO2 Cycloaddition and Cyanosilylation Reactions.

This work reports the synthesis of a dual functional 2D framework, {[Zn2(4-tpom)2(oxdz)2]·4H2O}n (1), at room temperature, where a bent dicarboxylate, oxdz2- (4,4'-(1,3,4-oxadiazole-2,5-diyl)dibenzoate), and a neutral flexible N-donor linker, 4-tpom (tetrakis(4-pyridyloxymethylene)methane), are utilized. Its single-crystal X-ray analysis indicated a 2-fold interpenetrated 2D framework having tetracoordinated Zn(II) centers and dangling pyridyl groups. Its further characterization was carried out with elemental microanalysis, FTIR spectroscopy, TG analysis, and powder X-ray diffraction. The tetracoordinated Zn(II) centers as active Lewis acidic sites and the N atoms of 4-tpom as Lewis basic sites in 1 are explored for its functioning as a heterogeneous catalyst in two important reactions, (i) cycloaddition of CO2 with various epoxides and (ii) cyanosilylation reaction under solvent-free conditions. We could successfully show the cycloaddition of styrene oxide with CO2 (99% conversion) under balloon pressure with low catalyst (0.2-0.3 mol %) and cocatalyst (0.5-0.75 mol %) loadings, which is otherwise difficult to achieve. It was observed that all the substrates (aromatic and aliphatic), irrespective of their sizes, showed conversion percentage >99%. In the cyanosilylation reaction, a conversion of 96% was obtained with 1.5 mol % of 1 at room temperature for 12 h. This framework emerged as an excellent recyclable catalyst for both the reactions.

Macrocycle-on-COF photocatalyst constructed by in-situ linker exchange for efficient photocatalytic CO2 cycloaddition

Functionalizing macrocycle with gas capture and catalytic ability onto covalent organic frameworks (COFs) can generate hierarchical porous materials with enhanced properties, while the challenge is how to improve full utilization of the active sites and maintain the crystallinity of the parent framework. Herein, we developed a “Macrocycle-on-COF” strategy by partial in-situ linker exchange to gain core-shell hybrids containing hierarchical pores. We demonstrated that the macrocycle-on-COF with functionalized pillar[5]arene have a profound effect on highly CO2 adsorption and abundant active sites. The photoelectrical measurement showed that the macrocycle-on-COF was an excellent photocatalyst with fast photoresponse and superior charge separation efficiency. With the assistance of light, the functionalized OH-P[5]-on-COF achieves efficient photocatalytic CO2 cycloaddition reaction under ambient conditions (20 °C and 1 atm), in which a 99% conversion can be achieved within 3 h and the performance is superior compared to previously reported COFs. This study presents the first example of using COFs as photocatalysts for photocatalytic CO2 cycloaddition reaction under ambient conditions.