Catalytic Reaction Research Articles

Unveiling the potential of Au cocatalysts to induce SPR charges on CuO/CdS system for sunlight driven hydrogen production†

Atmospheric pollution and increasing costs of the fossil fuels have compelled the researchers to explore the alternative sources. The objective of current project is to discover the stable catalysts that can drive water splitting reaction with sunlight. To the purpose, visible light active catalysts i.e. CdS, CuO/CdS, and Au@CuO/CdS have been synthesized and evaluated for hydrogen generation activities. Gold cocatalysts have been employed to enhance the surface stability and catalytic efficiencies. Whereas, CuO/CdS heterojunction have been synthesized to improve charge separation ability. The optical characteristics, structural properties, and morphology of catalysts have been evaluated by UV‒Vis/DRS, XRD, Raman, BET, SEM, AFM, PL and FTIR techniques. Chemical compositions, photocurrent or charge transfer have been verified with XPS, EDX and EIS results. Catalytic reactions were performed in photoreactor (150mL/Pyrex), whereas hydrogen production activities were predicted via online GC-TCD (Shimadzu-2010/Japan). Results depict that catalyst with 0.8% of Au on CuO/CdS exhibit relatively higher activity (i.e. 32.13 mmolg‒1h‒1) than the other catalysts of the series. Higher activities were attributed to the presence of Au cocatalysts. It has been predicted that coexistence of gold develops Schottky junctions that progressively rectify the surface charges (i.e. movement of electrons). Additionally, gold induces the SPR charges and enhances activity of electrons. Schottky junctions formed by Au cocatalysts on CuO/CdS system restrict the charge recombination i.e. back reactions. In this study, various factors like temperature, pH, light intensity and dose of catalysts have been assessed and discussed. On the basis of activities, it has been concluded that work reported herein hold promise to replace the conventional catalysts used for hydrogen energy technologies.

One-step condensation synthesis of di-tertiary ammonium salt protic ionic liquid for efficiently catalytic CO2 cycloaddition reaction under cocatalyst- and solvent-free conditions

A novel protic ionic liquid di-tertiary ammonium bromide ionic liquid (DTAB-IL) was synthesized by one-step condensation at 0 ℃ with 85 % yield. DTAB-IL also exhibited effective catalytic activity for CO2 cycloaddition without cocatalyst and solvent. The catalytic reaction conditions were optimized to 90 ℃, 4 h, 1 MPa, and the yield of propylene carbonate was obtained 96 % with high selectivity 99 %. Under the optimal conditions, DTAB-IL catalyst exhibited good recyclability and universality to various epoxides. Furthermore, temperature influence and kinetic investigation for propylene carbonate synthesis were studied. The activation energy for DTAB-IL catalyzing CO2 cycloaddition reaction was 43.93 kJ/mol, and the reaction was found to follow first-order for propylene oxide. Efficient cycloaddition reaction of CO2 and epoxide was attributed to the activation of epoxide and CO2 by di-tertiary ammonium and epoxide ring-opening by bromide anion in DTAB-IL.

Positive activation entropy of Bacillus circulans xylanase catalyzed ONPX2 hydrolysis: A mechanistic and engineering study

Transition state (TS) stabilization by enzymes greatly accelerates catalytic reactions. For some enzymes, the TS complex has entropy higher than enzyme substrate (ES) complex. But the origin of favorable entropy remains unclear. In this work, we studied the mechanism of Bacillus Circulans xylanase (BCX) 11 catalyzed o-nitrophenyl β-xylobioside (ONPX2) glycoside hydrolysis. The catalytic reaction exhibits a positive activation entropy, and an increase in ionic strength leads to a decrease in entropy without affecting the activation free energy, indicating that the entropy is predominantly influenced by electrostatic forces. Moreover, NMR measurements of electrostatic attractions within the active site demonstrate a positive entropy, aligning with molecular dynamics (MD) simulations showing that electrostatic interactions contribute to the entropic stabilization of the TS complex. These findings suggest that the positive entropy primarily originates from alterations in electrostatic interactions due to the formation of the oxocarbenium ion at C1 in the TS. Differences of electrostatic interactions in ES and TS modify hydrogen bonding of surrounding residues in the active site which causes their side chain dynamics and thus conformational entropy changes. Residues critical for the positive activation entropy are identified. A new BCX mutant with an increased activation entropy and catalytic activity is found.

Effect of peroxydisulfate activated by B-doped NiFe2Ox for degrading contaminants and mitigating nanofiltration membrane fouling in the landfill leachate treatment

Catalytic oxidation pretreatment is a significant focus in the field of membrane fouling control; however, traditional catalytic materials are plagued by limitations in catalytic sites and challenges in recovery. In this study, a novel catalyst, B-doped NiFe2Ox, was prepared with magnetic recovery capabilities and abundant oxygen vacancies to address landfill leachate treatment and mitigate membrane fouling. The results demonstrated the efficient activation of persulfate (PS) by the catalytic sites on B-NiFe2Ox, which significantly degraded the complex organic pollutants like conjugated double bonds and aromatic compounds in landfill leachate. A large amount of humic acid and soluble microbial products in the landfill leachate were efficiently degraded upon contact with sulfate and hydroxyl radicals produced by B-NiFe2Ox/PS, thereby resulting in achieving a chemical oxygen demand removal efficiency of up to 72% and more than a twofold enhancement in filtration flux. Moreover, the characteristics of the fouled layer reveal that the B-NiFe2Ox/PS system facilitated the formation of a porous cake layer, maximizing the retention of functional groups on the NF270 membrane surface. Notably, a minor presence of B-NiFe2Ox is uniformly distributed within the cake layer, indicating the in-situ occurrence of weak catalytic oxidation reactions. This study provides an effective and innovative approach utilizing catalytic oxidation for membrane fouling control.

Decoration of CeO2 nanoparticles on Cu/Co bimetallic oxide and their catalytic performance

We have developed a series of Co-Cu bimetallic oxide nanocatalysts using an environmentally friendly water phase synthesis method, demonstrating significant potential in catalyzing the CO oxidation reaction. The 0.3Co3O4/0.7CuO nano-hybrid, with a feed ratio of 3:7 for Cobalt(II) chloride hexahydrate to Copper(II) chloride dihydrate, exhibited a CO catalytic oxidation T90 approximately 70 °C lower than that of a single transition metal oxide material. Building on this, we enhanced the catalysts by incorporating CeO2 nanoparticles to produce Co3O4/CuO/CeO2 oxide nanocatalysts. By varying the amount of CeO2 nanoparticles added to the 0.3Co3O4/0.7CuO catalyst, we achieved further improvement in the CO oxidation performance. Specifically, the T90 of the CO catalytic oxidation reaction for the 0.3Co3O4/0.7CuO/0.7CeO2 material was approximately 30 °C lower than that of 0.3Co3O40.7CuO. Various characterization methods, such as XRD, EDX, and in situ FT-IR, were employed to investigate the impact of different components on the CO oxidation process and the potential reaction mechanism. The results indicated that the introduction of CeO2 successfully enhanced the activity and stability of the catalysts.

Suppressing cyclic deactivation of magnesium-calcium dual-functional materials via dispersed metal-carbonate interfaces for integrated CO2 capture and conversion

The integrated CO2 capture and utilization employs chemical looping approach for suppressing the equilibrium limitations of traditional gas-solid catalytic reactions, enabling efficient conversion of dilute CO2 into high-value fuels with minimal energy consumption. However, the diminishing cyclic activity of dual-functional materials poses significant challenges to their industrial application. Herein, we tailored a series of magnesium-calcium materials, the influence of coordinated metals on the cyclic performance were quantitatively investigated. Notably, Fe2Ni2Ce2Mg5Ca20CO3 achieves a cumulative CO yield of 121.0 mmol/g over 15 cycles at 650°C, with a maximum CO yield of 8.3 mmol/g per cycle and 99.0% CO selectivity, and its CO2 capture capacity remains stable at 10.6 mmol/g over 37 adsorption/desorption cycles. Experimental results indicate that lattice phase separation is a fundamental mechanism underlying the decline in cyclic activity. The strategic incorporation of transition metal intermediates promotes the formation of dispersed metal-carbonate interfaces, providing surface hydrogenation sites and accelerating the lattice decomposition and reconstruction of CO3* within a dispersed lattice. This modification mitigates the adsorption/catalytic lattice phase separation, boosts metal migration and deoxygenation activity for cyclic nanoparticle construction. The findings offer valuable strategies for designing highly efficient and stable DFMs in CO2 capture and utilization.

Efficient H2 evolution over MoS2-NiS2/g-C3N4 S-scheme photocatalyst with NiS2 as electron mediator

Low-cost transition metal sulfides are commonly utilized as photocatalysts for H2 production owing to their exceptional conductivity and superior specific surface area. In this study, MoS2-NiS2 nanoflowers with multidimensional space structure was obtained through the sulphuration reaction between S2- and NiMoO4 under Kirkendall effect during hydrothermal reaction. Subsequently, MoS2-NiS2 was loaded on the surface of g-C3N4 nanosheets using a solvent self-assembly strategy to form 3D MoS2-NiS2/g-C3N4 heterojunctions. The experimental results demonstrate that the H2 production rate of 20 wt% MoS2-NiS2/g-C3N4 reaches 22153 μmol·g-1·h-1 under a 300 W Xe lamp irradiation, which is 59.5 and 201.4-folds than MoS2-NiS2 and g-C3N4, and surpasses 20 wt% MoS2/g-C3N4 (211 μmol·g-1·h-1) and 20 wt% NiS2/g-C3N4 (6183 μmol·g-1·h-1). The XPS and Superoxide radical capture experiments demonstrate that the charge transfer between MoS2-NiS2 and g-C3N4 follows the S-scheme route, and NiS2 functions as an electron mediator, facilitating the transfer of electrons from MoS2 to g-C3N4 to consume the holes, which enhances the efficiency of H2 evolution reaction on g-C3N4. Furthermore, the S-scheme heterojunction of MoS2-NiS2/g-C3N4 with the multidimensional geometric structure can provide abundant active sites for catalytic reactions, this presents a promising approach for the development of cost-effective and high-performance g-C3N4-based heterojunctions. This work offers distinctive perspectives on the trajectory of renewable H2 energy development.

Promotion effect of nitrogen doping on the low-temperature NH3-SCR of NO over activated carbon: Characterization and mechanism analysis

Heteroatom nitrogen doping in carbon catalysts is recognized an effective strategy for tailoring the properties of carbon catalysts for various flue gas de-NOx applications. However, accurately discerning the active structures after nitrogen doping and elucidating the promotion effect on low-temperature selective catalytic reduction activity remains a formidable challenge under different nitrogen doping preparation conditions. In this study, a series of nitrogen-doped activated carbon catalysts was synthesized through the L16(45) orthogonal array design method, and the degree of influence of various preparation conditions on de-NOx catalytic activities was also assessed. The optimal preparation conditions determined by range analysis were employed to synthesize NOAC-17, achieving the NO conversion of 95% and N2 selectivity of 99% at 300 °C, respectively. Subsequently, various characterization results proved that nitrogen doping induced the formation of abundant basic groups. The imine, amide, amine, and N-6 groups altered the acid-base of the activated carbon surface and increased the adsorption of acidic NOx. The N-5 and N-Q groups enhanced electronic interaction in the carbon matrix and accelerated electron mobility in the catalytic reaction process. Moreover, the N-6 group played multiple roles beyond the aforementioned effect due to its special structure. It also enhanced the accumulation of oxygen vacancies, which were closely associated with further oxidation of adsorbed NO. The lone electron pair in the N-6 group within the activated carbon framework can alter the polarity of the catalyst, thereby exerting a positive influence on the adsorption and activation of NH3. The nitrogen-doped catalyst identified through range analysis of the orthogonal experiment primarily facilitated the NH3-SCR reaction via the E-R mechanism with supplementary contribution from L-H mechanism at low temperatures. The nitrogen doping conditions obtained for the activated carbon catalyst provide valuable insights for the strategic enhancement of its catalytic performance in low-temperature NH3-SCR reactions.

Lattice energy transfer from homo-crystalline substitution for enhanced piezo-photocatalytic CO2 conversion

The rapid recombination of carriers and large activation energy of CO2 compromise the efficiency of CO2 photoreduction. Herein, SrTiO3 (STO) with different molar ratios of La3+ and Al3+ double-site homo-crystalline substitution is prepared by a ball-milling molten salt method. The concentration of Ti3+ and excess oxygen vacancies decrease to improve the catalytic activity. Meanwhile, the double sites act as electron transfer platforms for easy electron transfer from the bulk phase to the surface to foster CO2 photoreduction. Not only that, the energy transfer due to doping-induced lattice distortion can potentially enhance the photocatalytic activity. A piezoelectrically polarized electric field is introduced to further expedite charge transport. As a result, the activity of La, Al-STO piezo-photocatalytic CO2 reduction is improved to 39.17 µmol g-1h−1, which is more than seven times better than that of the pure STO. Furthermore, CO2 adsorbs spontaneously on the catalysts because the thermodynamic energy barrier decreases due to the piezoelectric force, which is verified by density-functional theory calculation. This study reveals the great potential of double-site homo-crystalline substitution of STO pertaining to the charge transport kinetics and thermodynamics of the catalytic reaction in the piezo-photocatalytic CO2 process.

Hydrogenation Reaction Mechanisms on Ni-Doped MoS2 Catalysts: A Density Functional Theory Study of Sulfur Edge Engineering and Coregulated Electronic Effects.

Precise modulation of local interatomic interactions affecting the electronic structure is an important method to control the catalytic activity and reaction pathways. In this study, we focused on the hydrogenation reaction of naphthalene and employed density functional theory calculations to investigate the specific influence of electronic effects triggered by the coregulation of Ni and sulfur edge engineering on the hydrogenation performance of Ni-doped MoS2 at different edge sulfur coverages (Ni-MoS2-X-θs). Our findings reveal that the interaction between Ni and S in the catalyst matrix material modifies the local electronic structure surrounding the sulfur atoms in the active site. Notably, Ni doping facilitates significant electron transfer, altering the charge and the electronic states at the catalyst edge. This, in turn, affects the adsorption capacity and reactivity of the catalyst, thereby reducing the energy barrier of the hydrogenation reaction. Furthermore, we paid particular attention to the modulation of catalytic activity and reaction pathways under the Eley-Rideal (E-R) mechanism. Interestingly, the sulfur coverage exhibited a nonlinear relationship with the adsorption and activation properties of the probe molecule. Typically, changes in the Mo edge sulfur coverage probability of Ni-MoS2-X-θs have a greater impact on the activation properties. Through comprehensive studies, we demonstrated that both compositional and structural factors must be considered when tailoring the catalytic performance. Importantly, adjusting the ratio of marginal sulfur atoms to metal atoms to 1:1 can effectively enhance the catalytic activity. This study provides valuable insights into the electronic effects regulating the hydrogenation reaction activity of MoS2-based catalysts. It also opens the way for the rational design of novel hydrogenation catalysts, offering a new strategy for optimizing the catalytic performance.

Development of a Master Equation-Based Microkinetic Model to Investigate Gas Phase Cluster Reactions Across a Wide Pressure and Temperature Range.

Small gas-phase metal clusters serve as model systems for complex catalytic reactions, enabling the exploration of the impacts of the size, doping, charge state and other factors under clean conditions. Although the mechanisms of reactions involving metal clusters are known in many cases, they are not always sufficient to interpret the experimental results, as those can be strongly influenced by the chemical kinetics under specific conditions. Therefore, our objective here is to develop a model that utilizes quantum chemical computations to comprehend and predict the precise kinetics of gas-phase cluster reactions, particularly under low-pressure conditions. In this study, we demonstrate that master equation simulations, utilizing reaction paths computed through quantum chemistry, can effectively elucidate the findings of previous experiments. Furthermore, these simulations can accurately predict the kinetics spanning from low-pressure conditions (typically observed in gas-phase cluster experiments) to atmospheric or higher pressures (typical for catalytic experiments). The models are tested for simple elementary steps (Cu4+H2). We highlight the importance of the reaction mechanism simplification in Cu4 ++H2 and provide an interpretation for the previously observed product branching in Pt++CH4.

μ-nitrido diiron phthalocyanines: Electron-withdrawing vs electron-donating substituent effect on oxidation reaction catalysis

μ-nitrido diiron phthalocyanines: Electron-withdrawing vs electron-donating substituent effect on oxidation reaction catalysis

Boosting Catalytic Hydrogen Transfer Cascade Reactions via Tandem Catalyst Design by Coupling Co Single Atoms with Adjacent Co Clusters

Boosting Catalytic Hydrogen Transfer Cascade Reactions via Tandem Catalyst Design by Coupling Co Single Atoms with Adjacent Co Clusters

Elucidating Confinement and Microenvironment of Ru Clusters Stably Confined in MFI Zeolite for Efficient Propane Oxidation.

Achieving active and stable heterogeneous catalysts by encapsulating noble metal species within zeolites is highly promising for high utilization and cost efficiency in thermal and environmental catalytic reactions. Ru considered an economical noble metal alternative with comparable performance, faces great challenges within MFI-type microporous zeolites due to its high cohesive energy and mobility. Herein, an innovative strategy was explored coupling hydrothermal in situ ligand protection with stepwise calcination in a flowing atmosphere to embed ultrasmall Ru clusters anchored at K+-healed silanol sites (≡Si-Ruδ+-O-K complexes) within 10-membered ring sinusoidal channels of MFI. Comprehensive experiments and theoretical calculations unveiled that the interplay between confined Ru clusters and MFI induces local strain in MFI, creating a unique catalytic microenvironment around the Ru clusters. This synergy exhibits superior alkane deep oxidation, performance owing to the confined Ru clusters and the MFI microenvironment collectively pre-activate C3H8 and O2, facilitate the cleavage of C-H and C-C bonds at low temperatures. Notably, the stable geometric and electronic properties of confined Ru show exceptional thermal stability up to 1000 °C, rivaling fresh catalysts. These findings shed vital methodological and mechanistic insights for developing efficacious heterogeneous catalysts for thermal catalysis.

Elucidating Confinement and Microenvironment of Ru Clusters Stably Confined in MFI Zeolite for Efficient Propane Oxidation

Achieving active and stable heterogeneous catalysts by encapsulating noble metal species within zeolites is highly promising for high utilization and cost efficiency in thermal and environmental catalytic reactions. Ru considered an economical noble metal alternative with comparable performance, faces great challenges within MFI‐type microporous zeolites due to its high cohesive energy and mobility. Herein, an innovative strategy was explored coupling hydrothermal in situ ligand protection with stepwise calcination in a flowing atmosphere to embed ultrasmall Ru clusters anchored at K+‐healed silanol sites (≡Si–Ruδ+‐O‐K complexes) within 10‐membered ring sinusoidal channels of MFI. Comprehensive experiments and theoretical calculations unveiled that the interplay between confined Ru clusters and MFI induces local strain in MFI, creating a unique catalytic microenvironment around the Ru clusters. This synergy exhibits superior alkane deep oxidation, performance owing to the confined Ru clusters and the MFI microenvironment collectively pre‐activate C3H8 and O2, facilitate the cleavage of C‐H and C‐C bonds at low temperatures. Notably, the stable geometric and electronic properties of confined Ru show exceptional thermal stability up to 1000 °C, rivaling fresh catalysts. These findings shed vital methodological and mechanistic insights for developing efficacious heterogeneous catalysts for thermal catalysis.

Recent Catalytic Applications of Ferrocene and Ferrocenium Cations in the Syntheses of Organic Compounds

Ferrocene and its oxidized counterpart, the ferrocenium cation, represent a fascinating class of organometallic compounds with broad utility across various fields, including organic synthesis, pharmaceuticals, and materials science. Over the years, ferrocene, ferrocenium cations, and their derivatives have also gained prominence for their versatility in catalytic processes. This review article offers an overview of the research of the last decade into ferrocene- and ferrocenium-based catalysis. Key developments are highlighted in catalytic oxidation, cross-coupling, polymerization reactions, and redox-switchable catalysis, as well as the application of ferrocenium cations as Lewis acid catalysts.

Conversion of Waste Tecoma Leaves into Heteroatom Doped Graphitic Carbon via a One-Step Chemical Activation Method for the Catalytic Oxygen Reduction Reaction and Supercapacitor Application

Conversion of Waste Tecoma Leaves into Heteroatom Doped Graphitic Carbon via a One-Step Chemical Activation Method for the Catalytic Oxygen Reduction Reaction and Supercapacitor Application

Fully Conjugated Microporous Polymers as Metal-Free Heterogeneous Photocatalysts for Organic Transformations.

Photoactive conjugated microporous polymers (CMPs) have recently received huge attention in photocatalytic organic transformations owing to their adjustable structure and functionality. However, commonly reported CMPs are synthesized through metal catalyzed coupling reactions, which require complicated product separation and result in increased costs. In this study, two sp2 carbon-linked CMPs are constructed by organic base induced Knoevenagel reaction using 2,6-dimethylbenzo[1,2-d:4,5-d']bisoxazole and aromatic polyaldehydes as co-monomers. The new benzobisoxazole-based polymer materials feature fully π-conjugated skeleton with broad visible-light absorption, permanent porosity as well as outstanding stability. Importantly, they can effectively induce many organic reactions such as C-3 thiocyanation of indoles under visible-light illumination and show broad substrate applicability and superior recyclability.

AI-Driven Discovery of Asymmetric Pauson-Khand Reactions: A New Toolbox in a Synthetic Chemist's Treasure.

Enantioselective catalytic reactions have a significant impact on chemical synthesis, and they are important components in an experimental chemist's toolbox. However, development of asymmetric catalysts often relies on the chemical intuition and experience of a synthetic chemist, making the process both time-consuming and resource-intensive. The machine-learning-assisted reaction discovery can serve as a very efficient platform for obtaining high-performing catalysts in a time-economical manner without extensive experimentation. Herein, we report a data-driven and machine learning method for reliably predicting enantiomeric excess (%ee) of 211 asymmetric Pauson-Khand reactions (PKR 1-PKR 211) between a variety of 45 unique 1,6-enyne substrates and 12 unique axially chiral biaryl ligands in the presence of different reaction conditions like varying CO gas pressure, temperature, and solvent polarity. Four different machine learning algorithms have been studied: extreme gradient boosting (XGBoost), random forest (RF), light gradient boosting machine (LGBM), and neural network (NN). A fivefold cross validation method was applied to our k-means SMOTE-augmented data set to obtain the optimized hyperparameters for the training set, and subsequently, these parameters were used in the test data set. In the case of the out-of-box set, the XGBoost method is found to be superior among all four machine learning methods investigated. Our out-of-box samples contain a total of 12 unique asymmetric Pauson-Khand reactions (PKR 212-PKR 223) arising from three new 1,3-benzodioxole-based SEGPHOS catalysts, which were never included in the training set. The XGBoost algorithm shows an impressive root mean square error (RMSE) of 7.06 (±1.11) in predicting %ee. The XGBoost-predicted %ee values match reasonably well with the experimental results. The absolute difference between the experimental and XGBoost-calculated %ee values ranges from 0.9 to 7.6 for the majority of the out-of-box Pauson-Khand reactions. The reactions with fluoro-substituted-SEGPHOS ligand L14 shows smaller deviations from the experimental %ee values compared to the reactions with L13 and L15 catalysts where the benzodioxole units do not have fluorine atoms. Finally, we have discovered a library of 3357 lead reactions with excellent %ee (≥99) by engaging the experimentally unknown combinations of the catalysts, substrates, and reaction conditions. The axially chiral biaryl catalysts and enyne substrates present in the library are synthetically accessible. The ligand space in the library is dominated by the presence of tol-BINAP and the DTBM-OMe-BIPHEP ligands. The substrate space is predominantly occupied by NTs-tethered, O-tethered, NBn-tethered, and C(CO2Me)2-tethered 1,6-enynes that have an H or methyl functional group present in the alkyne unit. Our newly discovered library assists a synthetic chemist to develop a highly enantioselective PKR by starting with a priori knowledge without extensive trial-and-error experimentation.

Basic-functionalized Ionic Porous Organic Polymers: Triple Roles in One for Highly Efficient and Recyclable Carboxylative Cyclization of CO2 under Mild Conditions.

The transformation of carbon dioxide (CO2) into high-value chemicals is a significant step towards achieving the goal of "carbon neutrality". α-methylene cyclic carbonate, as an intermediate for the synthesis of many important organic compounds, is widely employed in industrial productions. In this work, a series of ionic porous organic polymers (IPOPs) with different basic-functionalized anions were successfully synthesized and adjusted to have certain BET surface areas and high contents of ion sites by post-modification. These basic-functionalized IPOPs could exhibit excellent catalytic performance for carboxylative cyclization of CO2 at 30 oC and 1 bar in presence of silver salts, eliminating the use of extra organic bases. In the whole catalytic reaction, the basic-functionalized anions could play triple roles: enriching CO2 for further transformation, activating the hydroxyl groups of substrates to improve the catalytic performance, while coordinating with Ag atom to stabilize and regenerate catalyst. Notably, the catalytic system of DCX-4-Tet/Ag2O exhibited excellent recyclability, and the yield of α-alkylidene cyclic carbonate was well maintained at 99% after 5 cycles. To the best of our knowledge, the catalytic system was the first example of basic-functionalized IPOPs that played multiple roles for highly efficient CO2 cyclization under mild conditions without any extra organic bases.