Immobilization Of Catalysts Research Articles

Highly Efficient Carbon Dioxide Electroreduction via DNA-Directed Catalyst Immobilization.

Electrochemical reduction of carbon dioxide (CO2) is a promising route to up-convert this industrial byproduct. However, to perform this reaction with a small-molecule catalyst, the catalyst must be proximal to an electrode surface. Efforts to immobilize molecular catalysts on electrodes have been stymied by the need to optimize the immobilization chemistries on a case-by-case basis. Taking inspiration from nature, we applied DNA as a molecular-scale "Velcro" to investigate the tethering of three porphyrin-based catalysts to electrodes. This tethering strategy improved both the stability of the catalysts and their Faradaic efficiencies (FEs). DNA-catalyst conjugates were immobilized on screen-printed carbon and carbon paper electrodes via DNA hybridization with nearly 100% efficiency. Following immobilization, a higher catalyst stability at relevant potentials is observed. Additionally, lower overpotentials are required for the generation of carbon monoxide (CO). Finally, high FE for CO generation was observed with the DNA-immobilized catalysts as compared to the unmodified small-molecule systems, as high as 79.1% FE for CO at -0.95 V vs SHE using a DNA-tethered catalyst. This work demonstrates the potential of DNA "Velcro" as a powerful strategy for catalyst immobilization. Here, we demonstrated improved catalytic characteristics of molecular catalysts for CO2 valorization, but this strategy is anticipated to be generalizable to any reaction that proceeds in aqueous solutions.

Construction of trifloaluminate ionic liquid catalyst on the silica surface dedicated for continuous flow Diels-Alder synthesis

Supported ionic liquid phases (SILP) are efficiently use for the construction of highly active, heterogeneous and recyclable catalysts. In this study, three strategies towards chemical immobilization of trifloaluminate ionic liquid catalyst into microporous/mesoporous silica support were investigated. The order of silica surface modification with trifloaluminate ILs components had crucial influence on the catalytic activity and stability which was tested in the model Diels-Alder reaction between isoprene and maleic anhydride in acetonitrile at room temperature. The best catalytic performance (maleic anhydride conversion > 97% in ten reaction cycles) was achieved for catalyst created through the synthesis of trifloaluminate ionic liquid in the first step with further bounding to the silica surface using 25 wt% of ionic liquid loading. The effective transformation of the Diels-Alder reaction to continuous flow synthesis led to 97% maleic anhydride conversion over 432 h with a TOF of 104.3 h−1 and significantly improved process sustainability.

Covalent Tethering of Cobalt Porphyrins on Phenolic Resins for Electrocatalytic Oxygen Reduction and Evolution Reactions.

Using functionalized supporting materials for the immobilization of molecular catalysts is an appealing strategy to improve the efficiency of molecular electrocatalysis. Herein, we report the covalent tethering of cobalt porphyrins on phenolic resins (PR) for improved electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A cobalt porphyrin bearing an alkyl bromide substituent was covalently tethered on phenolic resins, through the substitution reaction of alkyl bromides with phenolic hydroxyl groups, to afford molecule-engineered phenolic resins (Co-PR). The resulted Co-PR was efficient for electrocatalytic ORR and OER by displaying an ORR half-wave potential of E1/2=0.78 V versus RHE and an OER overpotential of 420 mV to get 10 mA/cm2 current density. We propose that the many residual phenolic hydroxyl groups on PR will surround the tethered Co porphyrin and play critical roles in facilitating proton and electron transfers. Importantly, Co-PR outperformed unmodified PR and PR loaded with Co porphyrins through simple physical adsorption (termed Co@PR). The zinc-air battery assembled using Co-PR displayed a performance comparable to that using Pt/C+Ir/C. This work is significant to present phenolic resins as a functionalized material to support molecular electrocatalysts and demonstrate the strategy to improve molecular electrocatalysis with the use of phenolic resin residues.

Enhancing photocatalytic performance of atom transfer radical addition (ATRA) reactions in water using immobilized 10-Phenylphenothiazine catalysts on mesoporous silica supports

The development of catalysts is crucial for sustainable chemistry, and heterogeneous catalysis, specifically, can be environmentally friendly and recyclable. Catalyst immobilization in materials has been explored, in which mesoporous silica materials have shown outstanding results in catalysis. Photocatalysis has also gained attention, providing solutions for organic synthesis and late-state functionalization, mainly using homogeneous catalysts and organic solvents. The use of aqueous media for photocatalytic reactions is particularly attractive from a sustainability perspective yet can influence reaction chemoselectivity. However, poor solubility of the organic substrates and the catalyst limits photocatalytic methods in water. Mesoporous silicas are water-stable materials suitable for catalytic applications in such media, including photocatalysis. In this work, we demonstrate an atom transfer radical addition (ATRA) reaction in water using immobilized 10-phenylphenothiazine (PTH) catalyst on different mesoporous silica supports, showing improved photocatalytic performance compared to homogeneous conditions and substrate selectivity depending on the hydrophobicity of the alkene.

Catch-and-Release: The Assembly, Immobilization, and Recycling of Redox-Reversible Artificial Metalloenzymes.

Technologies to improve the applicability of artificial metalloenzymes (ArMs) are gaining considerable interest; one such approach is the immobilization of these biohybrid catalysts on support materials to enhance stability and enable their retention, recovery, and reuse. Here, we describe the immobilization of polyhistidine-tagged ArMs that allow the redox-controlled replacement of catalytic cofactors that have lost activity, e.g., due to poisoning or decomposition, on immobilized metal affinity chromatography resins. By using periplasmic siderophore-binding protein scaffolds that originate from thermophilic bacteria (GstCeuE and PthCeuE) in combination with a siderophore-linked imine reduction catalyst, reaction rates were achieved that are about 3.5 times faster than those previously obtained with CjCeuE, the analogous protein of Campylobacter jejuni. Upon immobilization, the GstCeuE-derived ArM showed a decrease in turnover frequency in the reduction of dehydrosalsolidine by 3.4-fold, while retaining enantioselectivity (36%) and showing improved stability that allowed repeat recovery and recycling cycles. Catalytic activity was preserved over the initial four cycles. In subsequent cycles, a gradual reduction of activity was evident. Once the initial activity decreased to around 40% of the initial activity (23rd recycling cycle), the redox-triggered artificial cofactor release permitted the subsequent recharging of the immobilized protein scaffold with fresh, active cofactor, thereby restoring the initial catalytic activity of the immobilized ArM and allowing its reuse for several more cycles. Furthermore, the ArM could be assembled directly from protein present in crude cell extracts, avoiding time-consuming and costly protein purification steps. Overall, this study demonstrates that the immobilization of redox-reversible ArMs facilitates their "catch-and-release" assembly and disassembly and the recycling of their components, improving their potential commercial viability and environmental footprint.

Immobilised Ruthenium Complexes for the Electrooxidation of 5-Hydroxymethylfurfural.

Abundantly available biomass-based platform chemicals, including 5-hydroxymethylfurfural (HMF), are essential stepping stones in steering the chemical industry away from fossil fuels. The efficient catalytic oxidation of HMF to its diacid derivative, 2,5-furandicarboxylic acid (FDCA), is a promising research area with potential applications in the polymer industry. Currently, the most encouraging approaches are based on solid-state catalysts and are often conducted in basic aqueous media, conditions where HMF oxidation competes with its decomposition. Efficient molecular catalysts are practically unknown for this reaction. In this study, we report on the synthesis and electrocatalysis of surface-bound molecular ruthenium complexes for the transformation of HMF to FDCA under acidic conditions. Catalyst immobilisation on mesoporous indium tin oxide electrodes is achieved through the incorporation of phosphonic acid anchoring groups. Screening experiments with HMF and further reaction intermediates revealed the catalytic route and bottlenecks in the catalytic synthesis of FDCA. Utilising these immobilised electrocatalysts, FDCA yields of up to 85 % and faradaic efficiencies of 91 % were achieved, without any indication of substrate decomposition. Surface analysis by X-ray photoelectron spectroscopy (XPS) post-electrocatalysis unveiled the desorption of the catalyst from the electrode surface as a limiting factor in terms of catalytic performance.

Cutinase Immobilization on a Supramolecular Cage Protein Scaffold

Background: Self-assembly of preformed nanoparticles into larger and more complex materials, termed nanoarchitectonics, is an area of great interest as the resulting higher-order architectures can exhibit advanced supramolecular properties important in sensor design, catalysis, and ferromagnetic properties. Objective: The aim of the current investigation is to explore the application of self-assembling protein networks to serve as molecular scaffolds for immobilization of enzyme catalysts. The use of 12 nm ferritin cage proteins to serve as components of these scaffolds would expand the application of these types of multifunctional proteins to the fabrication of advanced biomaterials. Method: Humicola insolens cutinase was immobilized on a supramolecular protein scaffold using bioconjugation to biotinylate the enzyme of interest. The protein-based scaffold consisted of a ferritin- biotin-avidin system, and the interaction of biotin and avidin was used to suspend the enzyme molecules onto this network. Matrix-assisted laser desorption mass spectrometry, scanning electron microscopy, and energy dispersive X-ray spectroscopy were employed to analyze the supramolecular cage protein scaffold at various stages of fabrication. Results: The activities of these scaffold-bound enzymes towards chromogenic esters and polyethylene terephthalate (PET) were analyzed and found to remain active towards both substrates following biotinylation and immobilization. Conclusion: Biotinylated Humicola insolens cutinase enzymes can be immobilized on nanodimensional protein networks composed of avidin and biotinylated horse spleen ferritin and exhibit catalytic activity toward a small substrate, p-nitrophenylbutyrate, as well as an industrial plastic. Selfassembling protein networks may provide new approaches for biomolecular immobilization.

Improvement of the performance of hydrazine fuel cells without immobilization of ink catalysts on the membrane: a new electrocatalyst of mixed metal oxides as cathode and nickel foam-based Ni–Co nanoparticles as anode

Improvement of the performance of hydrazine fuel cells without immobilization of ink catalysts on the membrane: a new electrocatalyst of mixed metal oxides as cathode and nickel foam-based Ni–Co nanoparticles as anode

Tailoring graphitic nitrogen-enriched electrocatalytic membranes for acetaminophen degradation: Mechanistic insights into the site-specific reactive process

The pressing concern of pharmaceuticals and personal care products (PPCPs) in water, particularly with the increased usage of acetaminophen (ACE) during the COVID-19 pandemic, draws attention to the necessity for efficient water treatment. This study introduces tailored electrocatalytic carbon membranes featuring naturally doped nitrogen functionalities for energy-efficient electrochemical water treatment. The introduction of graphitic-N functionality into polyacrylonitrile electrospun fibers can be achieved through carbonization and activation processes, forming a freestanding electrocatalytic carbon membrane (ECM). In addition, in-situ immobilization of TiO2 on the ECM enables a deeper exploration of catalyst’s role in generating reactive oxygen species. As demonstrated, the enriched graphitic N in the membrane contributed to an enhanced electron transfer ability, resulting in extraordinary electrocatalytic activities. Note that graphitic N also served as site-specific active sites for ACE degradation. By utilizing the electrocatalytic carbon membranes, complete degradation of ACE was achieved within 60 min, with an electrical energy per order (EEO) of approximately 0.6 kWh/m3/order. This demonstrates the high degradation efficiency and low energy requirement of the system. Moreover, scavenger experiments demonstrate the significant involvement of O2•–, •OH and 1O2 in ACE degradation. Within the TiO2 decoration, there is a notable enhancement in the contribution of •OH during the degradation process. Overall, this study not only innovates electrocatalytic membrane design and catalyst immobilization but also advances our understanding of site-specific reactive processes in electrified water treatment.

Material-specific binding peptides empower sustainable innovations in plant health, biocatalysis, medicine and microplastic quantification.

Material-binding peptides (MBPs) have emerged as a diverse and innovation-enabling class of peptides in applications such as plant-/human health, immobilization of catalysts, bioactive coatings, accelerated polymer degradation and analytics for micro-/nanoplastics quantification. Progress has been fuelled by recent advancements in protein engineering methodologies and advances in computational and analytical methodologies, which allow the design of, for instance, material-specific MBPs with fine-tuned binding strength for numerous demands in material science applications. A genetic or chemical conjugation of second (biological, chemical or physical property-changing) functionality to MBPs empowers the design of advanced (hybrid) materials, bioactive coatings and analytical tools. In this review, we provide a comprehensive overview comprising naturally occurring MBPs and their function in nature, binding properties of short man-made MBPs (<20 amino acids) mainly obtained from phage-display libraries, and medium-sized binding peptides (20-100 amino acids) that have been reported to bind to metals, polymers or other industrially produced materials. The goal of this review is to provide an in-depth understanding of molecular interactions between materials and material-specific binding peptides, and thereby empower the use of MBPs in material science applications. Protein engineering methodologies and selected examples to tailor MBPs toward applications in agriculture with a focus on plant health, biocatalysis, medicine and environmental monitoring serve as examples of the transformative power of MBPs for various industrial applications. An emphasis will be given to MBPs' role in detecting and quantifying microplastics in high throughput, distinguishing microplastics from other environmental particles, and thereby assisting to close an analytical gap in food safety and monitoring of environmental plastic pollution. In essence, this review aims to provide an overview among researchers from diverse disciplines in respect to material-(specific) binding of MBPs, protein engineering methodologies to tailor their properties to application demands, re-engineering for material science applications using MBPs, and thereby inspire researchers to employ MBPs in their research.

Pivotal role of starch in restoring the photocatalytic performance of chitosan films for eliminating water pollutants.

The photocatalytic performance of chitosan-derived catalytic films deteriorates due to surface area loss during catalyst immobilization. It limits the practical efficacy of these films, despite being a greener and more reusable alternative to powdered catalysts. Herein, we have restored and enhanced the photocatalytic efficiency of chitosan films from 67% to 95% by starch impregnation. The combinatorial impact of the enhanced adsorption due to the unique surface structure of the starch-chitosan surface and cooperative charge separation efficiency of the photocatalyst balance the effect of surface area loss and photocatalytic performance is restored.

Evoking dynamic Fe–Nx active sites through the immobilization of molecular Fe catalysts on N-doped graphene quantum dots for the efficient electroreduction of nitrate to ammonia

Selective and highly active NO3−RR electrocatalysts featuring molecular M–Nx sites derived from the immobilization of Fe ions within N-doped graphene quantum dots.

Fe-Ni porphyrin/mesoporous titania thin film electrodes: a bioinspired nanoarchitecture for photoelectrocatalysis.

Porphyrin and porphyrinoid derivatives have been extensively studied in the assembly of catalysts and sensors, seeking biomimetic and bioinspired activity. In particular, Fe and Ni porphyrins can be used for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by immobilization of these molecular catalysts on semiconductor materials. In this study, we designed a hybrid material containing a crystalline mesoporous TiO2 thin film in which the catalytic centres are Ni-porphyrin (NiP), Fe-porphyrin (FeP), and a NiP/FeP bimetallic system to assess whether the coexistence of both metalloporphyrins improves the OER activity. The obtained photoelectrodes were physicochemically and morphologically characterized through high-resolution FE-SEM images, UV-vis and Raman spectroscopies, cyclic voltammetry, and impedance measurements. The results show a differential behavior of the mono- and bimetallic porphyrin systems, where the Fe(iii) centre in FeP may increase the acidity and lower the reduction potential of the Ni2+/3+ couple when co-deposited with NiP leading to an improved photoelectrochemical water-oxidation performance. We have validated the cooperative effect of both metal complexes within this novel system, where the μ-peroxo-bridged interaction between Fe and Ni is integrated into a supramolecular heterometallic structure of porphyrins.

Pentanuclear iron complex for water oxidation: Spectroscopic analysis of reactive intermediates in solution and catalyst immobilization into the MOF-based photoanode

Photoelectrochemical water splitting can produce green hydrogen for industrial use and CO2-neutral transportation, ensuring the transition from fossil fuels to green, renewable energy sources. The iron-based electrocatalyst [FeII4FeIII(μ-3-O)(μ-L)6]3+ (LH = 3,5-bis(2-pyridyl)pyrazole) (1), discovered in 2016, is one of the fastest molecular water oxidation catalysts (WOC) based on earth-abundant elements. However, its water oxidation reaction (WOR) mechanism has not been yet fully elucidated. Here, we present in situ X-ray spectroscopy and electron paramagnetic resonance (EPR) analysis of electrochemical WOR promoted by (1) in water-acetonitrile solution. We observed transient reactive intermediates during the in situ electrochemical WOR, consistent with a coordination sphere expansion prior to the onset of catalytic current. At a pre-catalytic (∼+1.1 V vs. Ag/AgCl) potential, the distinct g ∼ 2.0 EPR signal assigned to FeIII/FeIV interaction was observed. Prolonged bulk electrolysis at catalytic (∼+1.6 V vs. Ag/AgCl) potential leads to the further oxidation of Fe centers in (1). At the steady state achieved with such electrolysis, the formation of hypervalent FeVO and FeIVO catalytic intermediates was inferred with XANES and EXAFS fitting, detecting a short FeO bond at ∼ 1.6 Å. (1) was embedded into MIL-126 MOF with the formation of a (1)-MIL-126 composite. The latter was tested in photoelectrochemical WOR and demonstrated an increase in electrocatalytic current upon visible light irradiation in acidic (pH = 2) water solution. The presented spectroscopic analysis gives further insight into the catalytic pathways of multinuclear systems and should help the subsequent development of more energy- and cost-effective water-splitting catalysts based on earth-abundant metals. Photoelectrocatalytic activity of (1)-MIL-126 confirms the possibility of creating an assembly of (1) inside a solid support and harnessing solar irradiation towards industrial applications of the catalyst.

Pt(PPh3)4 and Pt(PPh3)4@IL catalyzed hydroboration of ketones

An efficient method for the reduction of various ketones via [Pt(PPh3)4]-catalyzed hydroboration with HBpin has been successfully developed for the first time. The protocol is suitable for symmetrical and unsymmetrical derivatives possessing electron donating or withdrawing functional groups. O-borylated products were easily converted to 2° alcohols via hydrolysis with high isolated yields. According to the low-temperature NMR spectroscopy, a reaction mechanism was proposed. Additionally, effective immobilization of the catalyst in the ionic liquid [BMIM][NTf2] was applied to increase the productivity of the process by carrying out reactions under the repetitive batch mode, obtaining higher TON values and limiting the amount of expensive Pt used. The catalyst stability and almost neglectable leaching were confirmed by ICP-MS analysis of the extracted mixture. A simple separation method via extraction with n-heptane, efficient catalyst immobilization, and the commercial availability of the Pt complex, make this protocol an attractive method for the hydroboration of ketones

Hierarchical porous alumina ceramics as multi-functional support with excellent performance

Hierarchical porous nanostructure alumina ceramics (HP-Al2O3) were prepared through a novel approach involving polymer-assisted freeze-drying and subsequent calcination. The resulting material exhibits interconnected micro-meso-macro pores, distinguishing it from traditional Al2O3 nanoparticles (Al2O3-Nps) prepared without freeze-drying. By manipulating freeze-drying precursors and calcination temperatures, we tailor the morphology and structure of HP-Al2O3. Notably, the HP-Al2O3 demonstrates a remarkable 5.3-fold increase in adsorption efficiency for Congo red compared to Al2O3-Nps, attributed to its significantly larger specific surface area. The HP-Al2O3 is a versatile platform for building multi-functional composites, proved by immobilizing silver nanoparticles (AgNps) and graphitized carbonitride (g-C3N4) through chemical reduction and gas-solid reaction methods, respectively. When employed for the reduction of 4-nitrophenol and the degradation of Rhodamine B, Ag/HP-Al2O3 and g-C3N4/HP-Al2O3 display approximately 2.5 and 2.4 times higher reaction rate constants compared to Ag/Al2O3-Nps and g-C3N4/Al2O3-Nps. This enhanced catalytic performance is attributed to several key factors: the 3D porous framework of the HP-Al2O3 facilitates efficient catalyst immobilization, the microporous and mesoporous nature increases the active site and specific surface area, and the hierarchical porous structure enhances mass diffusion and light capture. Moreover, the self-supporting nature of the HP-Al2O3 simplifies separation and recovery from reaction solutions. With the integration of its hierarchical porous structure and commendable recovery properties, HP-Al2O3 emerges as a promising candidate for various functional applications, particularly in catalysis.

A One‐Pot Three‐In‐One Synthetic Strategy to Immobilize Cobalt Corroles on Carbon Nanotubes for Oxygen Electrocatalysis

AbstractMolecular electrocatalysis requires the immobilization of molecular catalysts on electrode materials for practical uses. Direct adsorption of catalyst molecules on electrode materials is simple, but grafting molecules through chemical bonds can significantly improve electrocatalytic efficiency and durability. However, designing and synthesizing catalyst molecules to simultaneously improve catalytic activities and realize easy grafting on electrodes is challenging. The study herein reports on a one‐pot strategy to graft Co corroles on pyridine‐modified carbon nanotubes (CNTs) for oxygen electrocatalysis. By modifying CNTs with pyridines, the resulting pyridine‐modified CNTs can function as platforms to grab in situ generated Co corroles through the axial pyridine ligation on Co. Such an immobilization strategy combines three effects for the regulation of electrocatalysis, including the axial ligand effect, the electron transfer effect, and the chemical bond effect. The resulting hybrid materials show high efficiency for oxygen electrocatalysis, and the Zn–air battery assembled using these materials displays comparable performance as the Pt/Ir‐based battery. Moreover, the electrocatalytic efficiency of these hybrid materials can be systematically tuned by using different pyridines, highlighting the controllable feature of this strategy. Therefore, this work is significant to present a one‐pot three‐in‐one strategy to immobilize catalyst molecules on CNTs for electrocatalysis.

Polyoxometalate-Modified Amphiphilic Polystyrene-block-poly(2-(dimethylamino)ethyl methacrylate) Membranes for Heterogeneous Glucose to Formic Acid Methyl Ester Oxidation.

Herein, we present a new heterogeneous catalyst active toward glucose to formic acid methyl ester oxidation. The catalyst was fabricated via electrostatic immobilization of the inorganic polyoxometalate HPA-5 catalyst H8[PMo7V5O40] onto the pore surface of amphiphilic block copolymer membranes prepared via non-solvent-induced phase separation (NIPS). The catalyst immobilization was achieved via wet impregnation due to strong coulombic interactions between protonated tertiary amino groups of the polar poly(2-(dimethylamino)ethyl methacrylate) block and the anionic catalyst. Overall, three sets of five consecutive catalytic cycles were performed in an autoclave under 90 °С and 11.5 bar air pressure in methanol, and the corresponding yields of formic acid methyl ester were quantified via head-space gas chromatography. The obtained results demonstrate that the membrane maintains its catalytic activity over multiple cycles, resulting in high to moderate yields in comparison to a homogeneous catalytic system. Nevertheless, presumably due to leaching, the catalytic activity declines over five catalytic cycles. The morphological and chemical changes of the membrane during the prolonged catalysis under harsh conditions were examined in detail using different analytic tools, and it seems that the underlying block copolymer is not affected by the catalytic process.

Turning on Asymmetric Catalysis of Achiral Metal-Organic Frameworks by Imparting Chiral Microenvironment.

The development of heterogeneous asymmetric catalysts has attracted increasing interest in synthetic chemistry but mostly relies on the immobilization of homogeneous chiral catalysts. Herein, a series of chiral metal-organic frameworks (MOFs) have been fabricated by anchoring similar chiral hydroxylated molecules (catalytically inactive) with different lengths onto Zr-oxo clusters in achiral PCN-222(Cu). The resulting chiral MOFs exhibit regulated enantioselectivity up to 83 % ee in the asymmetric ring-opening of cyclohexene oxide. The chiral molecules furnished onto the catalytic Lewis sites in the MOF create multilevel microenvironment, including the hydrogen interaction between the substrate and the chiral -OH group, the steric hindrance endowed by the benzene ring on the chiral molecules, and the proximity between the catalytic sites and chiral molecules confined in the MOF pores, which play crucial roles and synergistically promote chiral catalysis. This work nicely achieves heterogeneous enantioselective catalysis by chiral microenvironment modulation around Lewis acid sites.

Turning on Asymmetric Catalysis of Achiral Metal‐Organic Frameworks by Imparting Chiral Microenvironment

AbstractThe development of heterogeneous asymmetric catalysts has attracted increasing interest in synthetic chemistry but mostly relies on the immobilization of homogeneous chiral catalysts. Herein, a series of chiral metal–organic frameworks (MOFs) have been fabricated by anchoring similar chiral hydroxylated molecules (catalytically inactive) with different lengths onto Zr‐oxo clusters in achiral PCN‐222(Cu). The resulting chiral MOFs exhibit regulated enantioselectivity up to 83 % ee in the asymmetric ring‐opening of cyclohexene oxide. The chiral molecules furnished onto the catalytic Lewis sites in the MOF create multilevel microenvironment, including the hydrogen interaction between the substrate and the chiral −OH group, the steric hindrance endowed by the benzene ring on the chiral molecules, and the proximity between the catalytic sites and chiral molecules confined in the MOF pores, which play crucial roles and synergistically promote chiral catalysis. This work nicely achieves heterogeneous enantioselective catalysis by chiral microenvironment modulation around Lewis acid sites.