Alkoxide Catalyst Research Articles

Organic-Inorganic Hybrid Perovskite for Ferroelectric Catalysis.

Organic-inorganic hybrid perovskite ferroelectric has gained significant attention for its structural flexibility and diversity. They can directly utilize metal nodes and organic groups as active sites in catalysis. Additionally, their ferroelectric polarization occurs around these active sites, significantly enhancing catalytic activity and demonstrating immense potential for applications. However, their catalytic applications remain underexplored. This work marks the first utilization of the molecular perovskite ferroelectric [3,3-difluorocyclobutylammonium]2CuCl4 (Cu-DFCBA) as a catalyst for alkane oxidation. Under ultrasonic stimulation, it achieved a remarkable turnover number as high as 2402. Compared to inorganic ferroelectrics like lithium niobate (LiNbO3), the molecular ferroelectric exhibited a 1200-fold increase in catalytic activity. This highlights Cu-DFCBA's robust ferroelectric properties and underscores the vast potential of molecular ferroelectrics in catalysis, guiding future system designs.

Transesterification catalyst strength as observed by solution-based oxygen-17 nuclear magnetic resonance spectroscopy

Natural abundance oxygen-17 nuclear magnetic resonance spectroscopy (17O-NMR) was applied to study homogeneous transesterification catalysts for fatty acid methyl ester production. Alkoxide catalysts were made with selected permutations of lithium, sodium, magnesium, and potassium hydroxides with ethanol, methanol, isopropanol, and glycerol. Pilot scale transesterification reactions of Canola oil were completed and the 17O-NMR spectra were collected from the reaction products. The alkoxide solutions showed the downfield shifts relative to the reagent alcohol, in a linear relationship with the concentration of catalyst ion. The electron deshielding of the oxygen of the alkoxide catalyst is observed directly by 17O-NMR, and the fastest catalyst has the largest downfield (high frequency) shift. This effect is most pronounced in potassium methoxide and less pronounced for less polar solvents such as isopropanol.

Synthesis and catalytic activity of single-site group V alkoxide complexes for the ring-opening polymerization of ε-caprolactone.

The synthesis, characterization, and ring-opening polymerization (ROP) activity of a family of niobium and tantalum alkoxide catalysts was studied. The final catalysts are made in a two-step synthesis, first by reacting the desired homoleptic metal ethoxide with a phenolketoimine ligand to form a series of synthetic intermediates, followed by reaction with catechol to produce a catalytic platform with a single ethoxide initiator. By using two separate ligands, the electronic properties of the catalyst can be tuned, and the molecular weight of the polymer can be increased. It was found that synthetic intermediates adopted a mer geometry both in solution and in the solid state. This mer geometry was retained for the final catechol derivatives, however in one case, where catechol was substituted for 3-methoxycatechol, the molecule adopted a highly distorted fac geometry. Catalytic ROP activity of the synthetic intermediates and final catechol derivatives with ε-caprolactone was studied through a kinetic analysis. In all seven cases studied the reactions proceeded through the expected coordination-insertion mechanism, following pseudo first-order kinetics and increasing in Mn linearly vs. conversion. The single-initiator catechol derivatives increased the Mn by three times compared to that of the three-initiator synthetic intermediates with little decrease in the overall reaction rate. Both the nature of the ligand and metal were found to impact the rate of reaction in these systems. By switching from an electron donating ligand to an electron withdrawing ligand, the rate was found to nearly double. Tantalum species were faster than their niobium counterparts by ∼3 times in the synthetic intermediates and ∼1.5 times in the catechol derivatives. This observed periodicity supports recent literature findings in this area.

Markovnikov-Selective Cobalt-Catalyzed Wacker-Type Oxidation of Styrenes into Ketones under Ambient Conditions Enabled by Hydrogen Bonding.

The replacement of palladium catalysts for Wacker-type oxidation of olefins into ketones by first-row transition metals is a relevant approach for searching more sustainable protocols. Besides highly sophisticated iron catalysts, all the other first-row transition metal complexes have only led to poor activities and selectivities. Herein, we show that the cobalt-tetraphenylporphyrin complex is a competent catalyst for the aerobic oxidation of styrenes into ketones with silanes as the hydrogen sources. Remarkably, under room temperature and air atmosphere, the reactions were exceedingly fast (up to 10 minutes) with a low catalyst loading (1 mol %) while keeping an excellent chemo- and Markovnikov-selectivity (up to 99 % of ketone). Unprecedently high TOF (864 h-1 ) and TON (5,800) were reached for the oxidation of aromatic olefins under these benign conditions. Mechanistic studies suggest a reaction mechanism similar to the Mukaiyama-type hydration of olefins with a change in the last fundamental step, which controls the chemoselectivity, thanks to a unique hydrogen bonding network between the ethanol solvent and the cobalt peroxo intermediate.

Connecting 16- with 4-Membered Rings: Ring-Opening Polymerization of Bio-Based ω-Pentadecalactone with Amino-Alkoxy-Bis(phenolate) Yttrium Initiators and Copolymerization with β-Butyrolactone

Ring-opening polymerization (ROP) of bio-based lactones is an effective way to overcome limited fossil resources. The 16-membered, musk-derived ω-pentadecalactone (PDL) occurs naturally as an ω-hydroxy fatty acid. As PDL is considered a macrolactone, controlled ROP of this transoid lactone is mostly obtained via enzymatic routes. Herein, amino-alkoxy-bis(phenolate) yttrium amido and alkoxide catalysts are reported for controlled metal-catalyzed ROP of PDL. PDL polymerizations are conducted at elevated temperatures from 60 to 100 °C to produce poly(ω-pentadecalactone) (PPDL) with number-average molecular weights of up to 134.5 kg mol−1 and moderate polydispersities (1.5 to 2.1). Utilizing isopropanol as a chain transfer agent (CTA) lead to higher initiator efficiencies and low polydispersities while still showing full monomer conversions with molar masses tunable by the amount of CTA. Block copolymerizations of PDL are performed via sequential addition. Four-membered, cisoid, and rather reluctant, racemic β-butyrolactone (BBL), which can be synthesized from carbon dioxide, is chosen as the second block. After determining that PDL has a lower coordination strength to the yttrium center and has to be added as the first monomer, successful connection between PPDL and poly(3-hydroxybutyrate) (PHB) blocks is shown via SEC and DOSY NMR spectroscopy. Different ratios of PDL and BBL are chosen to obtain PPDL-b-PHB polymers with different block length and molar masses. Powder X-ray diffraction measurements and DSC measurements prove the preservation of crystallinity in the block copolymers.

Copolymerization of polyethylene terephthalate and polycaprolactone using catalytic transesterification

A random copolymer between polyethylene terephthalate (PET) and polycaprolactone (PCL) is formed using catalytic transesterification in the melt. The copolymer, poly[(ET)2-co-(CL)2], has a backbone structure similar to that of polybutylene adipate terephthalate (PBAT) and could replace it at a lower cost, while simultaneously managing waste PET. Theoretically, a biodegradable copolymer is achieved when only two consecutive ET blocks remain. This degree of transesterification requires an active catalyst, capable of selective transesterification while limiting undesired chain scission. 1H NMR spectroscopy revealed that titanium alkoxide catalysts were the most effective for rapid transesterification, leading to di-blocks of both ET and CL units. It was found that the random copolymer could only be produced by catalysts containing both highly acidic metal ions and highly basic, small linear ligands. These observations led to the proposal that catalytic transesterification is likely to occur via an insertion-coordination mechanism. Increasing catalyst loading from 0.35 to 1.1 parts per hundred when using Ti(OBu)4 significantly accelerates transesterification, but a plateau is reached at about 0.85. Pleasingly, a reaction time of 2 min was sufficient for the reaction to be complete, suggesting reactive extrusion could be feasible. DSC thermograms of Ti(OEt)4 and Ti(OBu)4 catalysed blends have no observable recrystallization and melting peaks along with a sharp glass transition temperature suggesting the copolymer was highly amorphous with no unreacted homopolymers. Gel permeation chromatography of THF soluble blends revealed that a high extent of transesterification led to a decrease in chain length such that the Mn was reduced from about 68000 (PCL) to 13000–20000 (copolymer), suggesting that there is a need to use a minimum amount of catalyst to avoid excessive chain scission. The results demonstrate a proof-of-concept that transesterification of PET with PCL is possible to a high extent and that the reaction proceeds via an insertion-coordination mechanism. The results will inspire future research towards repurposing waste PET on extrusion scales and the creation of other biodegradable polyester materials using waste polymers.

Synthesis and characterization of N4-donor Schiff base copper(II) immobilized on superparamagnetic Fe3O4@SiO2 and its use as a recyclable catalyst for oxidation of alkenes, alcohols, and determination of antibacterial activity

N4-donor Schiff base copper(II) nanoparticles were easily prepared through surface modification of silica-coated magnetite nanoparticles (Fe3O4@SiO2) with pyrrole 2-carbaldehyde Schiff base and a subsequent reaction with Cu(CH3COO)2.H2O in ethanolic solution. This nanocatalyst was characterized using thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and magnetization. Efficient oxidation of alkenes and alcohols was carried out over the Schiff base copper(II) nanoparticles. Catalytic tests showed that the catalyst was particularly effective for the oxidation of α-methyl styrene, norbornene, benzyl alcohol, and benzohydrol. The results showed that acetophenone, 2-norbornanone, benzoic acid, and benzophenone with selectivity values of 88, 100, 100, and 100, respectively, were obtained. The heterogeneous catalyst of N4-donor Schiff base copper(II) offers advantages such as ease of product separation, catalyst recycling, and ease of preparation. Antibacterial tests against two gram-positive and two gram-negative bacterial species found that the bacteria stopped growing in the catalyst medium.

One-step highly selective catalytic oxidation of cyclohexane to KA-oil over functional CeMn0.5Co0.5Ox composite oxide: Synergistic effects between Mn and Co species with different valences and metal ion ratios

Presently, one-step highly selective oxidation of cyclohexane to KA-oil, which is a crucial organic chemical intermediate for the production of ε-caprolactam and adipic acid, is still a tremendous challenge. In this work, the functional CeMn0.5Co0.5Ox composite oxide catalysts were successfully prepared by glycine-nitrate combustion method. The results showed that 93.0% of selectivity to KA-oil with 4.6% of cyclohexane conversion was achieved over CeMn0.5Co0.5Ox under the optimal reaction conditions. The experimental and characterization results showed that the excellent catalytic performance of CeMn0.5Co0.5Ox is attributed to the synergistic effects between Mn and Co species with different valences and metal ion ratios, which efficiently promote the directional decomposition or reduction of cyclohexyl hydroperoxide (CHHP) intermediate to KA-oil. The density functional theory (DFT) calculations further confirmed the synergistic catalysis of CeMn0.5Co0.5Ox in the selective oxidation. This work affords the new insights into the design of efficient catalyst for the selective oxidation of alkanes.

Cobalt ferrite magnetic nanoceramics as an efficient nanocatalyst for the oxidation of olefins in the presence of molecular O2 as an environmentally safe oxidant

Selective oxidation of olefins using catalysts with unique structural and compositional characteristics, high cost‐efficiency, and optimal catalytic performance is still one of the ongoing tasks. In the present study, we synthesized cobalt ferrite (CoFe2O4) magnetic nanoceramics by the sol–gel process as a feasible and effective technique for synthesizing high purity, homogeneous, and crystalline nanoceramics. The nanoceramics were characterized by different analyses such as FT‐IR, XRD, DLS, SEM, XPS, and VSM to investigate their size, morphology, crystallinity, and magnetic properties. Then, the obtained nanoceramics were applied as an environmentally clean catalyst for the oxidation of various olefins to the corresponding epoxides in the presence of molecular O2 and at ambient conditions. The results showed that the CoFe2O4 nanoceramic could act as an efficient catalyst for converting olefins to the corresponding products with excellent yields. To further study the catalytic activity, the effects of some parameters, including catalyst concentration, temperature, time, and solvent, on the oxidation reactions were also studied. In addition, the heterogeneous CoFe2O4 catalyst has advantages such as high selectivity, facile recovery, and reusability of catalyst without a significant decrease in catalytic activity. Finally, our results showed that the catalytic performance of these nanoceramics is among the best reported catalysts for olefin oxidation.

Mn(III) Schiff base complexes containing crown ether rings immobilized onto MCM-41 matrix as heterogeneous catalysts for oxidation of alkenes

Six catalysts MnL1–MnL6, containing two crown ether rings and their analogs supported on the MCM-41 heterogeneous substrate (MnL1@MCM41-MnL5@MCM41) were synthesized and characterized. A mixture of molecular oxygen, as an oxidant, and these catalysts were used for the epoxidation of styrene. As a general result, the supported catalysts showed better performance compared with the unsupported analogs. On the other hand, the supported species, in addition to recyclability, did not require an axial base and reducing agent.

An Advanced Characterization Toolbox for Selective Olefin Oxidation Catalysts

AbstractThe selective oxidation of propylene and isobutene form a central cornerstone in chemical industry, typically catalysed by bismuth molybdate based multicomponent systems. Over the past decades, a detailed knowledge has been gained on the mechanism by theoretical and experimental studies including in situ and operando characterization techniques, using simplified model catalysts. These have provided excellent insight, but in industrially applied selective oxidation typically multi‐component catalysts are used, leading to higher activity and selectivity. New concepts and characterization methods allow now studies of the more complex multicomponent catalysts covering the various length and time scales and potentially providing new insights into the dynamics and cooperation during catalysis. Starting with an overview of past concepts and milestones, we report on latest developments and future trends in the field of selective oxidation of lower olefins. Thereby we focus both on conventional spectroscopic and advanced characterisation methods and discuss the importance of integral and spatially‐resolved approaches. We conclude that fundamental understanding of such complex oxidation reactions requires combined and interdisciplinary research, now possible with the new characterization tools, data analysis schemes and reactor modelling approaches. This allows bridging the various complexity scales.

Synthesis of UiO-66-Sal-Cu(OH)2 by a Simple and Novel Method: MOF-Based Metal Thin Film as a Heterogeneous Catalyst for Olefin Oxidation

Metal-organic frameworks (MOFs), particularly UiO-66-NH2, are employed as a catalyst in many industrial catalyst applications. As converting catalysts into thin film significantly increases their catalytic properties for the epoxidation of olefins, we report a general approach to synthesizing MOF thin films (UiO-66-Sal-Cu(OH)2). Using the postsynthesis method (PSM), UiO-66-NH2 was functionalized with salicylaldehyde and entrapped on copper hydroxide nanoparticle surfaces using a modern strategy (MOF thin film). We used field-emission scanning electron microscopy (FE-SEM), EDX (energy-dispersive X-ray analysis), XRD (X-ray diffraction), FT-IR (Fourier transform infrared), BET (Brunauer-Emmett-Teller), TGA (thermogravimetric analysis), XPS (X-ray photoelectron spectroscopy), and ICP-MS (inductively coupled plasma mass spectrometry) to determine the structure and morphology of the synthesized UiO-66-Sal-Cu(OH)2. The oxidation of cyclooctene by the UiO-66-Sal-Cu(OH)2 thin film was studied. Due to its advantages, such as being environmentally friendly (base metal-loaded catalyst, room temperature, solvent-free reaction), reusability, and high yield, this compound can be an appropriate catalyst for the oxidation of olefins.

Highly Efficient Oxidation of Propane at Low Temperature over a Pt-Based Catalyst by Optimization Support.

Pt-based catalysts have attracted widespread attention in environmental protection applications, especially in the catalytic destruction of light alkane pollutants. However, developing a satisfying platinum catalyst with high activity, excellent water-resistance, and practical suitability for hydrocarbon combustion at low temperature is challenging. In this study, the Pt catalyst supported on the selected Nb2O5 oxide exhibited an efficient catalytic activity in propane oxidation and exceeded that of most catalysts reported in the literature. More importantly, the Pt/Nb2O5 catalyst maintained excellent activity and durability even after high-temperature aging at 700 °C and under harsh working conditions, such as a certain degree of moisture, high space velocity, and composite pollutants. The excellent performance of the Pt/Nb2O5 catalyst was attributed to the abundant metallic Pt species stabilized on the surface of Nb2O5, which prompted the C-H bond dissociation ability as the rate-determining step. Furthermore, propane was initially activated via oxidehydrogenation and followed the acrylate species path as a more efficient propane oxidation path on the Pt/Nb2O5 surface. Overall, Pt/Nb2O5 can be considered a promising catalyst for the catalytic oxidation of alkanes from industrial sources and could provide inspiration for designing superb catalysts for the oxidation of light alkanes.

Manganese(II) coordination compounds of thiazole-hydrazone based NNN-donor ligands: Synthesis, characterization and catalytic activity

The reaction of Mn(OAc)2·4H2O with (E)-2-(2-(pyridin-2-ylmethylene)hydrazinyl)benzo[d]thiazole (HL1) and (E)-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)benzo[d]thiazole (HL2), in methanol resulted in the formation of [Mn(L1)2]∙2CH3OH (1) and [Mn(L2)2] (2) as neutral mononuclear Mn(II) coordination compounds. These compounds were characterized by spectroscopic methods and their molecular structures were determined by single crystal X-ray diffraction analysis. In these compounds, the ligands are coordinated to the Mn(II) core via the nitrogen atoms of thiazole ring, pyridine ring and imine moiety and act as tridentate mononegative NNN-donor ligand. The manganese(II) coordination compounds were also used as catalyst for olefin oxidation in the presence of tert-butylhydroperoxide (TBHP) or H2O2 as oxidant. Under similar experimental conditions with equal loading of Mn(II) coordination compounds, the presence of TBHP resulted in higher oxidation conversion than H2O2.

Investigating the Ring-Opening Polymerization Activity of Niobium and Tantalum Ethoxides Supported by Phenoxyimine Ligands.

A variety of metal catalysts from around the periodic table have been studied for the ring-opening polymerization (ROP) of cyclic esters. Within this field, group V catalysts have been rarely explored. To better understand the effect the choice of metal and ligand has on ROP activity, a series of 10 niobium and tantalum alkoxide catalysts, supported by a range of phenoxyimine ligands, were synthesized. The electronics and steric bulk of the ligands were varied on the phenoxy group (tBu, Cl, and OMe) and the imine group (Ph; 2,6-diMePh; 2,6-diiPrPh; and 2,4,6-tritBuPh) to probe their effect on the catalyst structure and activity. Catalysts were characterized with 1D, 2D, and variable-temperature NMR techniques to determine their structure in solution. Single crystal X-ray diffraction studies were conducted to establish their solid-state structure. The 10 catalysts are pseudo-octahedral, and each shows ligand coordination through phenoxy-oxygen and imine-nitrogen (O,N). In the case of the o-vanillin ligand set, however, evidence was found for O,O-coordination of the ligand when the steric encumbrance of the imine-nitrogen was increased. Each catalyst was active for the ring-opening polymerization of both rac-lactide (LA) and ε-caprolactone (CL) in the absence of solvent at 140 °C. In the case of CL, the catalysts supported by chloro-containing ligands showed the most polymerization control based on final polymer molecular weight and dispersity. Ligand trends were less clear for the polymerization of LA, though in all cases the catalysts were more controlled than the parent homoleptic alkoxide [M(OEt)5; M = Nb or Ta]. The most promising catalyst in the family was tested for copolymerization activity of LA and CL in one pot. Copolymerization of the two monomers was successful and yielded random poly(caprolactone-co-lactide).

SNS ligand-assisted catalyst activation in Zn-catalysed carbonyl hydroboration.

Ligands that include Lewis acid/base functionality have extensive applications in bifunctional catalysis using first row metals. In this work, zinc bis(amido), bis(thiolate) and amido-thiolate SNS complexes were prepared and compared as precatalysts for carbonyl hydroboration using pinacolborane. Mechanistic studies revealed two different ligand-assisted precatalyst activation pathways, both leading to an active and robust zinc alkoxide catalyst. This work furthers our understanding of metal-ligand cooperation in first-row metal catalysis.

Titanium ONN-(phenolate) Alkoxide Complexes: Unique Reaction Kinetics for Ring-Opening Polymerization of Cyclic Esters.

The synthesis, characterization, and polymerization kinetics of four new titanium ONN-(phenolate) alkoxide catalysts were studied. Each catalyst is fluxional at room temperature, suggesting the ligand amine arm may be labile, but adopts a fac geometry in solution at low temperature (223 K) and in the solid state. All catalysts are active for the ring-opening polymerization of both ε-caprolactone (CL) and rac-lactide (LA). GPC analysis indicates that the well-known coordination-insertion mechanism is being followed. However, whereas the typical first-order dependence on monomer concentration is observed in CL, an unexpected zeroth-order dependence is observed with LA. This suggests that, in the case of LA, catalyst saturation occurs and a Michaelis-Menten model can be used to explain the kinetics. An initial mechanism is discussed within this model that proposes CL polymerization proceeds by a 7-coordinate intermediate, whereas LA polymerization adopts a 6-coordinate intermediate, facilitated by the ligand amine arm. Attempts to isolate catalyst-monomer intermediates are ongoing.

A novel o-vanillin Fe(III) complex catalytically active in C-H oxidation: exploring the magnetic exchange interactions and spectroscopic properties with different DFT functionals.

The novel complex [FeIIICl(L)2(H2O)] (1) was synthesized by interaction of iron(III) chloride with ethanol solution of o-vanillin (HL) and characterized by IR, UV/Vis spectroscopy, thermogravimetry and single crystal X-ray diffraction analysis. The molecules of 1 in the solid state are joined into supramolecular dimeric units, where a set of strong hydrogen bonds predefines the structure of the dimer according to the "key-lock" principle. From the Hirshfield surface analysis the contribution of π⋯π stacking to the overall stabilization of the dimer was found to be negligible. Broken symmetry DFT calculations suggested the presence of long-range antiferromagnetic interactions (J = -0.12 cm-1 for H = -JS1S2 formalism) occurring through the Fe-O⋯O-Fe pathway, as evidenced by the studies of the model dimers where the water molecules were substituted by acetonitrile and acetone ones. The benchmark studies using a set of literature examples and various DFT functionals revealed the hybrid-GGA B3LYP as the best one for prediction of FeIII⋯FeIII antiferromagnetic exchange couplings of small magnitude. Magnetic susceptibility measurements confirmed antiferromagnetic coupling between the metal atoms in 1 with a coupling constant of -0.35 cm-1. Catalytic studies demonstrated that 1 acts as an efficient catalyst in the oxidation of cyclohexane with hydrogen peroxide in the presence of nitric acid promoter and under mild conditions (yield up to 37% based on the substrate), while tert-butylhydroperoxide (TBHP) and m-chloroperoxybenzoic acid (m-CPBA) as oxidants exhibit less efficiency. Combined UV/TDDFT studies evidence the structural rearrangement of 1 in acetonitrile with the formation of [FeIIICl(L)2(CH3CN)] species. The TDDFT benchmark using nine common DFT functionals and two model compounds (o-vanillin and [FeIII(H2O)6]3+ ion) support the hybrid meta-GGA M06-2X functional as the one most correctly predicting the excited state structure for the Fe(III) complexes, under the conditions studied.

Circular dichroism spectroscopy of catalyst preequilibrium in asymmetric autocatalysis of pyrimidyl alkanol.

Mechanistic understanding of the asymmetric autocatalysis of pyrimidyl alkanol is a highly attractive and challenging topic due to its unique feature of amplification of enantiomeric excess. Circular dichroism spectroscopic analysis of this reaction allows monitoring of the structual changes of possible catalyst precursors in the solution state and shows characteristic temperature and solvent dependence. TD-DFT calculations suggest that these spectral changes are induced by a dimer-tetramer equilibrium of zinc alkoxides.

Bimetallic‐organic Frameworks CoMo‐ZIF‐67: An Efficient and Stable Catalyst for Selective Oxidation of Alkenes

AbstractDeveloping catalysts for the selective oxidation of alkenes with environment‐friendly, unique structural characteristics, high economic benefit and better catalytic performance is important. Herein, we employed ZIF‐67 as the sacrificial template to synthesize bimetallic‐organic frameworks CoxMo100‐x‐ZIF nanocages by a facile dissolution‐regrowth strategy. The Co51.8Mo48.2‐ZIF catalyst was tested under various experimental parameters for the selective oxidation of cyclooctene to screen the optimal reaction conditions. Under the optimal reaction conditions, Co51.8Mo48.2‐ZIF nanocages exhibited a high cyclooctene conversion of 99.3 % and a selectivity of 99.0 % to epoxy cyclooctane. Furthermore, Co51.8Mo48.2‐ZIF nanocages can maintain their catalytic performance after reused five catalytic cycles. This bimetallic catalyst could also be used for the epoxidation of a wide range of alkenes, such as hexene or cyclohexene. In addition, the kinetic studies were conducted, and a reasonable reaction mechanism was proposed based on density functional theory calculations. The outstanding catalytic performance of CoxMo100‐x‐ZIF nanocages can be attributed to the cooperativity between Co and Mo sites and the hollow structure with high surface areas.