Heterogeneous Catalytic System Research Articles

Heteroatom‐Containing Zeolites as Solid Lewis Acid Catalysts for the Cycloaddition of CO2 to Epoxides

AbstractThe catalytic cycloaddition of CO2 to epoxides to produce valuable cyclic carbonates represents a simple and promising strategy for CO2 utilization, circumventing the ineffective CO2 reduction process. Despite current progresses, there remains an impending demand for highly‐active, cost‐effective and stable catalysts especially the ideal heterogeneous catalytic systems. Herein, we report the preparation of heteroatom‐containing zeolites through a two‐step process comprising of framework dealumination and subsequent heteroatom incorporation, and their catalytic applications in CO2 cycloaddition to epoxides. Characterization results reveal the successful incorporation of heteroatoms into framework to derive Lewis acidic M‐Beta zeolites (M = Ti, Zr or Hf). The as‐prepared M‐Beta Lewis acids show remarkable performance in the model reaction of CO2 cycloaddition to propylene oxide with the assistance of potassium iodide under solvent‐free conditions. The reaction parameters have been optimized employing Ti‐Beta catalyst and the substrate scope has been investigated. Finally, the impact of Lewis acidity on the cycloaddition reaction is discussed and the actual bifunctional Ti‐Beta/KI catalyst system is proposed, which is of important significance for the understanding of CO2 catalytic cycloaddition to epoxides.

Bypassing halide immobilization with cooperative polymers for the cycloaddition of atmospheric CO2 to epoxides

Atom-economic syntheses of cyclic organic carbonates by cycloaddition of CO2 to epoxides has risen to prominence among various approaches for CO2 fixation. In current literature, there is a general lack of recyclable fully heterogeneous organocatalytic systems which are active under mild conditions (T≤60 °C, atmospheric pressure), and that do not involve elaborated synthetic steps for the synthesis of monomers or the coimmobilization of active sites such as hydrogen bond donors (HBDs) and halide nucleophiles. From the standpoint of cost reduction and sustainability, it is also highly desirable to obtain the catalytic materials from biobased sources, especially waste materials. To address such gaps in the literature, we disclose in this work that a lignin derivative (phenolated lignin, PL) can be used as HBD in cooperation with readily available ionic polymers to form recyclable heterogeneous catalytic systems able to carry out the target cycloaddition reaction under atmospheric pressure at 60 °C. Such an unprecedented approach allows the upcycling of readily available biobased materials for the mild synthesis of cyclic carbonates from CO2 and bypasses the need for elaborated synthetic procedures for the synthesis of coimmobilized HBD-halide systems. PL/QPBAE (quaternized polyaminoester) emerged among various PL/ionic polymer pairs as the most active and efficient catalyst. Such a result was justified through a spectroscopic and analytical investigation as an effect of the ability of PL and QPBAE to closely interact and disperse in the reaction medium, and of the higher flexibility of QPBAE compared to other ionic polymers such as quaternized polyvinylpyridine. The resulting catalytic pair could be used as an efficient recyclable system for the cycloaddition of CO2 to several epoxides under atmospheric conditions with a catalytic performance that compared very well to that of more sophisticated oil-based state-of-the-art polymeric organocatalysts for the same reaction.

Catalytic merits of Ni0.6Zn0.4Fe2O4/f-MWCNTS–CS–Asp/Ni2+ for tailoring 1H-benzo [4,5] imidazo [1,2-b] [1,2,4]triazepine motifs through green domino strategy

The magnetic nano catalyst mediated synthesis of heterocycles is one of the most fascinating fields of chemistry due to its proven applicability in high-efficiency, eco-friendly and recyclable heterogeneous catalytic system. In order to design a novel Ni0.6Zn0.4Fe2O4/f-MWCNTs–CS–Asp/Ni2+ magnetic heterogeneous catalyst, Ni0.6Zn0.4Fe2O4-decorated multi walled CNTs were modified with crosslinked chitosan with l-aspartic acid entrapped Ni2+ nanoparticles. This nano catalyst showed significant catalytic activity in the synthesis of biologically potent novel seven membered heterocycles embracing fused 1H-benzo [4,5]imidazo [1,21,2-b][1,2,4]triazepine skeleton. Owing to its interesting structure and being an important pharmacophore fragment, it was endeavored to exploit its synthesis. For the first time considering an exquisite and accomplishable access to construct (Kaur et al., 2021; Jiang et al., 2006; Stern, 1980) [1,2,4]triazepine framework. In addition, the structures of synthesized heterocycles and morphology of nano catalyst were corroborated on the basis of various spectroscopical and microscopical techniques. Furthermore, employing ultrasonication as energy source in the synthesis of magnetic nano catalyst employing 3R's (reduce, recycle and reuse), mild reaction conditions with appreciable yield along with no consumption and production of hazardous chemicals put it under the umbrella of green and sustainable approach.

Oxygen vacancy engineering in ZnO/ZrO2 composite catalysts for highly enhanced hydrogen production by methanol steam reforming

The ZnO/ZrO2 binary catalyst system has been an emerging and promising catalyst for efficient production of H2 through methanol steam reforming (MSR). Herein, ZrO2 supports with different crystalline phases were prepared by the oxygen vacancy engineering strategy of Li doping, and then ZnO/ZrO2 catalysts were prepared by the isovolumic impregnation method. The different quantities of doped Li have been found to have a significant impact on dominant crystal phase of ZrO2 supports, which dictates the interaction between ZnO and ZrO2 and the number of oxygen vacancies. In comparison with ZnO/ZrO2-20Li and ZnO/ZrO2-40Li catalysts with predominate tetragonal and monoclinic crystal phase, ZnO/ZrO2-3Li with a mixed crystalline phase exhibits higher catalytic activity for methanol conversion (XCH3OH) and CO selectivity (SCO). Complete methanol conversion of the best performing ZnO/ZrO2-3Li catalyst was observed at a very low CO selectivity of 3.1 % at 375 ℃. The XRD, UV, and XPS characterization results indicate that the strong interaction between ZrO2 and ZnO leads to the appearance of large amount of oxygen vacancies at the ZnO/ZrO2 interface, which greatly improves the performance of the catalyst. ZnO/ZrO2 catalyst showed remarkable stability without obvious deactivation after 32 hours of continuous testing. This work highlights the effectiveness of oxygen vacancy engineering of the ZnO/ZrO2 catalysts for applications in methanol steam reforming and other heterogeneous catalytic systems.

Synergy of alloy and ligand for CO2 hydrogenation to formic acid on PdAu/HPC-AP

Formic acid (FA) is of great significance given its extensive applications in various industrial fields. At present, methanol carbonylation is the main industrial production process of FA. However, this process uses two kinds of raw materials from fossil fuels and emits a large amount of CO2. Alternatively, converting CO2 into FA can not only achieve the production of value-added chemicals but also effectively address environmental issues caused by CO2 emission. To improve the low reactivity of CO2, homogeneous and heterogeneous catalytic systems have been widely evaluated, among which heterogeneous catalytic systems are attracting ever-increasing attention owing to their great industrialization prospects. However, some of these heterogeneous catalysts suffer from low catalytic performance. Herein, PdAu alloy nanoparticles anchored on amine-functionalized hierarchical porous carbon (PdAu/HPC-AP) were constructed to drive efficient converting of CO2 into FA. Characterization and testing results demonstrated that the introduced Au atoms caused lattice distortion and charge redistribution on the surface of the bimetallic catalyst, facilitating the adsorption and activation of reaction molecules. Furthermore, the modification of HPC with an appropriate amount of amine ligands was found important to the chemical adsorption of CO2 and the dispersion of PdAu NPs. The Pd60Au40/HPC-AP catalyst with the optimum synergy of alloy and ligand demonstrated excellent activity for the target reaction with a TOF value of 486 h–1 at 100 °C. Moreover, it can even catalyze the reaction at room temperature with a TOF value of 13 h–1.

Recent Advances in Heterogeneously Catalyzed Acceptorless Dehydrogenation of Alcohols to Carbonyl Derivatives and N-heterocyclic Compounds

Oxidation of alcohols in an oxidant-free condition, commonly known as the acceptorless dehydrogenation (AD) reaction, has recently emerged as one of the widely used processes in synthetic organic chemistry. Alcohol acts as an excellent chemical precursor that produces a variety of dehydrogenated value-added products such as carbonyls, acids, acetals, and several coupling products, followed by the concomitant evolution of molecular hydrogen gas. AD reaction of alcohol, therefore, can be considered as a vital reaction for the hydrogen economy using alcohols as a liquid hydrogen carrier. Over the past decade, the growing importance of AD reactions has set the way for the continuous development of various homogeneous and heterogeneous catalytic systems. With the advantage of reusability and recyclability, heterogeneous catalysts have now become more promising and significant in the catalytic domain. This review aims to make an overview of the transition metal-based heterogeneous catalytic system of acceptorless alcohol dehydrogenation reaction reported till December, 2023.

Ultra-efficient peroxymonosulfate utilization and trichloroethylene degradation in heterogeneous catalytic system guided by sheet-like Cu2MnO4 nanoparticles: The role of Cu(III)–O species and free radicals

Synthesizing cubic spinel Cu2MnO4 with nanosheet structure (SCMO) aimed to construct a “non-radical-mediated radical-oxidative reaction”, for increasing PMS utilization efficiency, and solving the defects of SO4•− and •OH through indirect PMS activation by electron transfer process. Compared with box-like Cu2MnO4 (11.1%, 0.0035 min−1) and ordinary Cu2MnO4 nanoparticles (21.3%, 0.0070 min−1), SCMO/PMS showed excellent trichloroethylene removal (98.8%, 0.1577 min−1). The pivotal role of Cu(III) was determined based on EPR analysis, quenching experiments, chemical probe experiments, hydrogen temperature-programmed reduction and Raman spectroscopy analysis, in-situ FTIR and Raman analyses. In brief, the interaction between PMS and SCMO could produce surface-bonded reactive complexes and the subsequent breaking of O–O bond in the sub-stable structure allowed the conversion of Cu(II) to Cu(III), which in turn facilitates the generation of •OH and SO4•−. The density functional theory (DFT) calculations provided supporting evidence for the electron donor role of SCMO and the increase of the electron acceptance capacity of PMS. SCMO/PMS system showed good resistance and degradation efficiency to complex composition and combined pollutants in actually contaminated groundwater, respectively. However, the coexistence of high concentrations of arsenic could significantly affect SCMO performance due to their adsorption on –OH groups, which still need in-depth study.

Advancements in the Heterogeneous Catalytic Hydrogenation of Furfural to Downstream Products

AbstractFurfural is a 5‐membered heterocyclic compound derived from biomass and can be converted into various chemicals and biofuels through hydrogenation. Furfural conversion invariably requires the involvement of catalysts. The performance of these catalysts predominantly hinges on the characteristics of the metal active sites, the properties of the support, and the regulation of reaction conditions. Therefore, the selection of metals and supports, the preparation methods of catalysts, as well as the determination of reaction solvents, temperature, pressure, and catalyst dosage are the factors that researchers need to consider. Based on this, this present review focuses on the production process and heterogeneous catalytic system selection of furfural hydrogenation to prepare downstream products since 2018. It provides a brief introduction to the corresponding catalytic reaction mechanisms, focuses on the effects of different metals and supports on catalytic performance, and provides an outlook on this research direction.

A green and moderate approach for the synthesis of methyl formate via dimethoxymethane disproportionation over H-zeolites

Methyl formate (MF) is an important building block in the modern chemical industry, primarily produced through homogeneous carbonylation of methanol under harsh reaction conditions. It is of great interest but remains challenges to develop new heterogeneous catalytic system under mild reaction conditions to replace the homogeneous route. Herein, we report an efficient and green strategy for MF production by dimethoxymethane (DMM) disproportionation over acidic zeolites. Up to nearly100 % DMM conversion and 0.76 g gcat−1 h−1 of MF space time yield (STY) is achieved over H-SSZ-13 under moderate conditions of 0.1 MPa and 393 K. Moreover, H-SSZ-13 shows superior stability during a 100 h continuous test. Combined with multiple characterizations, formaldehyde (FA) has been proved to be a crucial precursor for the formation of MF and the complete mechanism is proposed. This strategy provides a new and feasible approach for continuous large-scale MF production using acidic zeolite as catalyst by heterogeneous catalytic systems.

A General and Highly Versatile Heterogeneous Pd-Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines.

An efficient heterogeneous catalytic system for the oxidative aminocarbonylation of alkynes and amines in the presence of CO/O2 to afford substituted propiolamides has been developed. The active nanocatalyst, [Pd/Mg3Al-LDH]-300(D), is composed by Pd nanoaggregates (2-3 nm average particle size) stabilized over a partially dehydrated [Mg3Al-LDH] matrix. The methodology has resulted widely applicable, being the first catalytic system, either homogeneous or heterogeneous, able to activate not only aliphatic amines but also poorly-nucleophilic aromatic amines. In fact, >60 substituted propiolamides have been synthesized in good to excellent isolated yields through this methodology, being 27 novel compounds. An important characterization effort (XRD, 27Al MAS NMR, TGA, TPD-CO2, BET area, XPS, HAADF-HRSTEM and HRTEM) and optimization of the synthesis conditions of the optimal catalyst has been performed. This study, together with a series of kinetic and mechanistic essays, indicates that the optimal catalyst is composed by Pd(0) species stabilized in a partially dehydrated/dehydroxylated LDH material with a Mg/Al molar ratio of 3 and a small crystallite size. All the experimental data indicates that the in situ formation of [PdI2] active species in the material surface together with the presence of a matrix with the optimal acid/base properties are key aspects of this process.

Copper‐based nanocatalysts toward chemoselective hydrogenation reaction

AbstractCu‐based catalysts are widely used in various heterogeneous catalytic reaction systems, the precise control of their electronic structure is an intrinsic requirement for the rational design of metal catalysts, and it is also an important basis for clarifying their structure‐activity relationships. Changing the electronic structure of Cu‐based catalysts is an important way to improve the catalytic hydrogenation performance of Cu‐based catalysts by controlling the adsorption intensity between the reaction adsorbate and the active center. In this paper, the application of selective hydrogenation of Cu‐based catalysts is reviewed, with a special emphasis on the selective catalytic hydrogenation reduction of p‐nitrostyrene and CO2. This review particularly emphasizes the application of Cu‐based catalysts in the field of selective hydrogenation and discusses the influence of their different properties on selective hydrogenation performance.

Depolymerization of lignin over heterogeneous Co-NC catalyst

Green and atom-economic depolymerization of lignin remains a great challenge due to its complex non-repetitive structure and the inert property for chemo-digestion. A redox-neutral lignin depolymerization system without the use of extra oxidant and/or reductant over a Co-NC catalyst has been developed in this work, providing the first non-noble metal heterogeneous catalytic system for redox-neutral valorization of lignin. Mechanistic studies based on control reactions and deuterium labeling experiments suggest that the reaction proceeds via a metal-catalyzed dehydrogenation of Cα-OH to afford a carbonyl intermediate, followed by Cβ-O bond cleavage (via hydrogenolysis) to afford monophenols and aromatic ketone products. The hydrogen used for the cleavage of the Cβ-O bond originates from the alcohol moiety in the substrate, and the cascade dehydrogenation and hydrogenolysis steps are highly coupled, rendering it an efficient and atom-economic process.

Probabilistic microkinetic modeling: Species balance equations for a catalyst surface containing multiple short-range order parameters to capture spatial correlations.

Adsorbed molecules on a catalyst almost always arrange themselves in a manner that is far from perfectly random, which gives rise to spatial correlations. These correlations are a result of the interactions between the adsorbed species (adspecies) as well as elementary processes such as diffusion and reaction events that shape the adspecies arrangements. Despite their importance, spatial correlations are usually ignored while writing species balance equations for the modeling of heterogeneous catalytic systems. Recently, we have introduced a probabilistic microkinetic modeling (p-MKM) framework that aims at incorporating spatial correlations in the form of a short-ranged order (SRO) parameter into species balance equations. Here, we extend the approach to catalytic systems of higher complexity, namely, longer interactions and multiple species. This is made possible by including multiple pair probabilities in the p-MKM model for the first time. The interplay between different SRO parameters is probed. An important consideration is how many pair probabilities should be included to capture the underlying complexity with sufficient accuracy.

A review of process of methanol carbonylation to produce acetic acid

Acidic corrosion plays a significant part in the compound business, particularly in the production of new substance fiber. As of now, the primary technique for creating acidic corrosive is the carbonylation of methanol utilizing iridium or rhodium organometallic edifices. The delegate techniques and the most recent advancement of methanol carbonylation to deliver acidic corrosion from two parts of homogeneous catalysis and heterogeneous catalysis are explored efficiently. The present homogeneous catalytic method and heterogeneous catalytic synthesis method using two different catalytic systems are introduced, followed in chronological order by the traditional method of producing acetic acid by carbonylation of methanol in the history of the chemical industry. The primary issues with producing acetic acid using conventional techniques are examined, including the product separation and the costly catalyst recovery. These issues can be resolved by developing and perfecting heterogeneous catalytic systems. The benefits and drawbacks of conventional techniques are broken down, the comprehensive summary and critical analysis of previous research provide comprehensive background knowledge, and the future exploration bearing is to work on the heterogeneous synergist framework to accomplish higher selectivity and preservation rate and work on financial proficiency.

A Review on the Development of Polymer Supported Heterogeneous Palladium Materials for Organic Synthesis and Electrochemical Applications

Abstract:: This comprehensive review explores the advancements in catalytic transformation, focusing on the use of heterogeneous catalytic systems with a particular emphasis on polymeric-supported palladium (Pd) complexes. This study explores the limitations associated with conventional homogeneous reagents, emphasizes the transition to eco-friendly catalytic systems, and emphasizes the importance of Pd nanoparticles. These nanoparticles are particularly noteworthy for their distinctive properties, including elevated catalytic activity, making them promising for various applications in organic synthesis. The review thoroughly examines the design and synthesis of heterogeneous catalysts, emphasizing the crucial selection of safe and recyclable supports to augment the longevity and reusability of metallic catalysts. Diverse polymer varieties, including polystyrene (PS), polyethylene (PE), polyacrylate derivatives, polyethylene glycol (PEG), and grafted polymers, are investigated as viable supports for Pd complexes. The authors intricately describe the synthesis techniques for these polymer-supported Pd catalysts and furnish illustrative examples showcasing their effectiveness in organic transformation. This comprehensive review additionally highlights the synthesis of polymer-supported palladium (Pd) materials and discusses their applications in electrochemistry. The focus extends to the electrocatalytic properties of Pdbased polymeric nanomaterials, showcasing their effectiveness in glucose sensing, hydrogen peroxide detection, and the sensing of other biological analytes. Furthermore, the catalytic capabilities of Pd nanoparticles in various electrochemical applications, including wastewater treatment and electrochemical capacitors, are explored. Integrating polymer-supported Pd materials into these electrochemical processes underscores their versatility and potential contributions to advancements in catalysis and electrochemical sensing. Catalytic applications featuring polymer-supported palladium complexes with polymeric ligands in organic synthesis processes use the Sonogashira reaction, Suzuki-Miyaura coupling, Heck reaction, Catalytic asymmetric transformations, etc. The subsequent section of the paper focuses on the creation of polymeric palladium complexes, achieved by the complexation of polymeric ligands with palladium precursors. It delves into noteworthy examples of catalytic processes employing polymer-supported palladium complexes featuring polymeric ligands, emphasizing distinct polymers, such as PS, PE, polyacrylate derivatives, PEG, and grafting polymers. The review concludes by exploring catalytic asymmetric transformations using chiral palladium complexes immobilized on polymer supports and discusses various chiral ligands and their immobilization on polymer supports, emphasizing their application in asymmetric allylic alkylation. The review furnishes a comprehensive summary of recent advancements, challenges, and prospective avenues in catalytic oxidation facilitated by polymer- supported palladium catalysts with electrochemical applications.

Unlocking high-efficiency decontamination by building a novel heterogeneous catalytic reduction system of thiourea dioxide/biochar

Herein, we reported a new contaminant purification paradigm, which enabled highly efficient reductive denitration and dechlorination using a green, stable reducing agent thiourea dioxide (TDO) coupled with biochar (BC) over a wide pH range under anoxic conditions. Specifically, BC acted as both activators and electron shuttles for TDO decomposition to achieve complete anoxic degradation of p-nitrophenol (PNP), p-nitroaniline, 4-chlorophenol and 2,4-dichlorophenol within 2 h. During this process, multiple strongly reducing species (i.e., SO22-, SO2•- and e-/H•) were generated in BC/TDO systems, accounting for 13.3%, 9.7% and 75.5% of PNP removal, respectively. While electron transfer between TDO and H+ or contaminants mediated by BC led to H• generation and contaminant reduction. These processes depended on the electron-accepting capacity and electron-conducting domains of biochar. Significantly, the BC/TDO systems were highly efficient at a pH of 2.0–8.0, especially under acidic conditions, which performed robustly in common natural water constituents.

Solvent Effects on Heterogeneous Catalysis for the Selective Hydrogenation

AbstractSolvent effects add a new dimension for tuning the activity and selectivity of heterogeneous catalytic reactions, which is extensively employed in the hydrogenation of unsaturated compounds with multiple functional groups. In this concept, we briefly summarize recent developments on how the solvent effects affect the catalytic performance from the following aspects: 1) the polarity of the solvent can influence the interaction between the solvent and the reactant or intermediate; 2) the composition of mixed solvent can influence the reactivity of the reactant or intermediate; 3) solvent effect varies with the metal identity and support; 4) the solvent can induce surface modification of the supported catalysts. This summarization will provide insights into the rational development of efficient and selective heterogeneous hydrogenation catalytic system to realize the precise synthesis of desired chemicals.

Enhancing the performance of catalytic membranes for simultaneous degradation of dissolved organic phosphonates and phosphorous recovery: A fit-for-purpose loose nanofiltration design

In this study, we developed a loose nanofiltration catalytic membrane (LNCM) by incorporating nitrogen-doped carbon nanotubes (NCNT) into graphene oxide (GO) membrane (NCNT@GO-M) to activate peroxymonosulfate for efficient phosphonates degradation into phosphate, reducing phosphorus-based pollution and facilitating P recovery. The NCNT@GO-M exhibited superior permeability (76.7 L m−2 h−1 bar−1) due to its expanded pore size (1.60 nm). It integrated nanoconfinement and surface catalysis, improving the availability of surface-bound sulfate radicals for rapid Orth-P generation (kobs, 1.93 s−1), with the kobs being 2.4 times higher than that of the NCNT membrane catalytic system and 2626 times higher than the NCNT@GO heterogeneous catalytic system. The NCNT@GO-M also demonstrated excellent antifouling, self-cleaning, and anti-interference ability, effectively retaining humic acid with a molecular weight exceeding 3.6 kDa (∼62% removal of dissolved organic carbon), making it suitable for real-water applications. The development of LNCM shows great potential for transforming and recovery of the nutrients in wastewater.

Selective Adsorbent Design with Multifunctional Surfaces: Innovating Solutions for Heterogeneous Catalysis in Water.

Heterogeneous catalytic systems with water as the solvent often have the disadvantage of cross-contamination, while concerns about the purification and workup of the aqueous phase after reactions are rare in the lab or industry. In this context, designing and developing the functional selective solid adsorbent and revealing the adsorption mechanism can provide a new strategy and guidelines for constructing supported heterogeneous catalysts to address these issues. Herein, we report the stable composite adsorbent (Fe/ATP@PPy: magnetic Fe3O4/attapulgite with the polypyrrole shell) that features an integrated multifunctional surface, which can effectively tune the selective adsorption processes for Cu2+, Co2+, and Ni2+ ions and nitrobenzene via the cooperative chemisorption/physisorption in an aqueous system. The adsorption experiments showed that Fe/ATP@PPy displayed significantly higher adsorption selectivity for Ni2+ than Cu2+ and Co2+ ions, especially which exhibited an approximate 100.00% removal for both Ni2+ ions and nitrobenzene in the mixture system with a low concentration. Furthermore, combined tracking adsorption of Ni2+ ions and X-ray photoelectron spectroscopy characterization confirmed that the effective adsorption occurs via ion transfer coordination; the pathway was further validated at the molecular level through theoretical modeling. In addition, the selective adsorption mechanism was proposed based on the adsorption experiment, characterization, and the corresponding density functional theory calculation.

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.