Abstract Metal–organic framework (MOF)-derived pyrolytic materials retain the pristine MOF advantages—high porosity and large surface area—while offering markedly improved stability, making them promising enzyme immobilization carriers. Their pore sizes can be rationally tuned via prepyrolysis modification, in situ activation, or postpyrolysis treatment, thereby enabling the tailored immobilization of bulky enzymes such as lipases. This review is the first to systematically address the use of pyrolyzed MOFs for enzyme immobilization, filling a gap in the literature. We compare derivatives from N-containing, O-containing, and N/O-containing ligands, revealing that N/O-type ligands excel in accommodating large enzymes. Pyrolysis mechanisms under inert, oxidative, reducing, and H2O atmospheres are summarized, linking each atmosphere to material properties. A dedicated section consolidates pore-enlargement strategies—a critical yet underexplored aspect. Finally, we demonstrate the potential of these materials to enhance enzyme stability, activity, and reusability in biocatalysis and biosensing, providing both a practical design guide and broader insights for catalysis, energy storage, and environmental applications.

Enzyme immobilization on solid supports enhances stability and reusability, yet nanoscale carriers such as metal-organic frameworks (MOFs) still face challenges in efficient recovery. While pyrolysis can magnetize Fe-MOFs, conventional methods often compromise either enzyme activity or structural integrity. This study presents a rational two-step oxidation-reduction (O-R) pyrolysis strategy to convert Meso-MIL-88A into a magnetically recyclable, mesoporous biocatalyst support (O-R500). Unlike one-step carbonization, which generates enzyme-incompatible Fe3O4, or carbonization-oxidation routes that collapse the framework, our approach first transforms the MOF into a robust α-Fe2O3 template while preserving its morphology. Citric acid then acts as a mild, slow-releasing reductant, selectively producing a γ-Fe2O3-rich phase without damaging the mesostructure. The resulting O-R500 exhibits well-defined mesopores (∼13 nm), sufficient magnetization (16 emu/g) for rapid separation, and a biocompatible surface that maintains the native conformation of immobilized Candida antarctica lipase B (CalB). In the synthesis of phosphatidyl EPA/DHA, CalB@O-R500 achieved 84.5% incorporation and retained 90.3% activity over five cycles, outperforming nonmagnetic counterparts. This work not only provides a high-performance magnetic biocatalyst but also establishes a generalizable design principle for converting Fe-MOFs into structured, biocompatible, and functionally integrated carriers.

Metal-organic frameworks (MOFs) with tunable porosity are promising carriers for enzyme immobilization, but their practical application is limited by structural instability and difficult recovery. We previously developed an oxidation-reduction (O-R) pyrolysis strategy for mesoporous MIL-88 A, yielding a magnetic carrier (O-R-Meso) with excellent lipase immobilization and recyclable catalysis. Herein, we verify the applicability of this O-R pathway for Fe-based MIL-88 A with tailored pore structures (micro-, meso-, macroporous) by extending it to microporous C-MIL-88 A and macroporous SOM-MIL-88 A. The O-R derivatives (O-RC, O-R-Meso and O-R-SOM) retained the original morphology and pore channel integrity, with improved specific surface area and sufficient magnetization (13-23 emu/g) for magnetic separation. Notably, after O-R pyrolysis, MIL-88 A with various pore sizes essentially maintained or even enhanced the specific activity of immobilized lipase (Candida antarctica lipase B, CalB), successfully deriving into magnetic carriers with enhanced catalytic efficiency and recyclability. This superiority originates from the preserved pore structure and biocompatible γ-Fe2O3 surface of the O-R derivatives, which effectively retain the native conformation of CalB. Besides, this work systematically compares the secondary structure of free and immobilized CalB on MOF-derived carriers with distinct pore architectures, providing direct structural evidence for the superior enzyme-carrier compatibility of mesoporous materials. In the transesterification synthesis of phosphatidyl EPA/DHA, CalB@O-R-Meso showed the highest EPA/DHA total incorporation, prominent sn-1 positional selectivity, and optimal reusability, outperforming CalB@O-R-C and CalB@O-R-SOM. Furthermore, kinetic studies on the CalB@O-R-Meso-catalyzed system confirmed a Ping-Pong BiBi mechanism and revealed competitive product inhibition by phosphatidyl EPA/DHA (Ki = 29.8 mM) with negligible internal mass transfer resistance (η ≈ 1). This work establishes a O-R pyrolysis strategy for tunable porosity Fe-MOFs, clarifies pore size-dependent enzyme -carrier compatibility, and provides a fundamental kinetic basis for phosphatidyl EPA/DHA synthesis.

Trimethylene carbonate (TMC) is an innovative modifier for polylactic acid and a promising biodegradable polymer monomer with broad application potential. However, industrial production of TMC faces challenges such as high catalyst costs, safety issues, and environmental impacts. Enzymatic catalysis offers a potential alternative, but its low product yields have hindered progress. In this study, we introduce a novel synthesis route for TMC using bio-based 1,3-propanediol (1,3-PDO) and dimethyl carbonate (DMC) as substrates. This process involves lipase-catalyzed formation of the intermediate 3-hydroxypropyl methyl carbonate (P1), which is then cyclized to produce TMC. Notably, the by-product, C,C'-1,3-propanediyl C,C'-dimethyl ester (P2), reacts with 1,3-PDO to regenerate P1, further enhancing the overall TMC yield. The mechanism exploration reveals that 1,3-PDO acts as both a reactant and an acid catalyst, initiating a nucleophilic substitution reaction on P2 to produce P1. Under optimized conditions, we achieved a total TMC yield of 88%, the highest reported to date.This study provides a novel green synthesis route for TMC that holds great promise for industrial application, given its safer conditions and competitive yields.

The production of biodiesel from single-cell oils (SCOs) utilizing industrial wastes as feedstock presents an economically viable approach. To date, studies have rarely reported the utilization of vinasse combined with industrial glycerol for the production of SCO. This study aimed to assess the performance of a Rhodotorula toruloides strain in vinasse from ethanol distilleries supplemented with pure/raw glycerol as an affordable carbon feedstock for SCO production. Several critical factors, including the C/N ratio, the impact of impurities in the crude glycerol, the proper nitrogen source, and the effects of the vinasse compositions, were evaluated. The results showed that the incorporation of urea and raw glycerol increased the lipid content to 51.8 ± 1.6% and the lipid productivity to 0.034 ± 0.001 g L−1h−1. Elevated biomass (42.5 g L−1) and lipid (11.0 g L−1) concentrations indicated that impurities in the raw glycerol positively affected the growth and lipid accumulation of this strain. Notably, supplementing raw glycerol to the vinasse led to a 16.1% increase in biomass concentration and a 25.7% rise in lipid content, significantly enhancing lipid productivity by 59.6%. The fatty acid profile predominantly featured unsaturated fatty acids (96.8%), including high percentages of stearic acid (41.8 ± 2.6%), palmitic acid (21.8 ± 1.5%), and oleic acid (18.3 ± 1.4%), aligning with the standards for vegetable-oil-based biodiesel manufacture. Fed-batch strategies using pulse-feeding turned out to be less effective than the constant-flow feeding strategy with vinasse supplemented with raw glycerol, which achieved a higher lipid productivity of 0.30 g L−1h−1.

1,3-dioleoyl-2-palmitoylglycerol (OPO) and 1-oleoyl-2-palmitoyl-3-linoleoylglycerol (OPL) are two essential types of human milk fat substitutes (HMFS). Their unique fatty acid composition and distribution play a significant role in promoting infant health, making the reaction conversion and acyl migration critical factors for developing efficient preparation methods. Promoting the conversion of the substrate while simultaneously inhibiting acyl migration is crucial for obtaining the desired HMFS products. In this study, we comparatively investigated enzymatic acidolysis and transesterification for HMFS production and revealed enzymatic kinetics as well as acyl migration mechanism during the process. Acyl migration was observed through the lipase-catalyzed mechanism, and the associated free energy changes were analyzed using density functional theory (DFT). The presence of long-chain fatty acids in the synthesis system resulted in intermediates with higher relative free energy during acyl migration. Based on these findings, we propose a novel synthesis strategy consisting of multi-step transesterification and dry fractionation, leveraging the differences in freezing points to minimize acyl migration. The resulting OPO product contains 90.42% oleic acid specifically at the sn-1,3 positions, highlighting its potential application in infant formulas. This study presents a systematic investigation of the kinetics and mechanisms involved in lipase-mediated HMFS production, providing valuable insights for rational synthesis approaches.

Mesoporous MIL-88A (Meso-MIL-88A) shows significant potential as an effective carrier for immobilizing large molecules such as lipases. This study investigates Meso-MIL-88A immobilized lipase for the catalysis of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) incorporation into soybean phosphatidylcholine. Phosphatidyl-EPA and phosphatidyl-DHA are known for their superior health benefits and have garnered significant global attention. Firstly, we developed a novel and green water-washing strategy to synthesize Meso-MIL-88A, demonstrating its significant potential as an effective carrier for immobilizing large molecules such as lipases. Nitrogen adsorption/desorption and XPS analyses revealed that water as the eluent yielded larger average pore diameters and lower sulfur residue content compared to ethanol. This optimized Meso-MIL-88A carrier was used to immobilize Candida antarctica lipase B (CalB@Meso-MIL-88A), which was applied to the production of phosphatidyl-EPA and phosphatidyl-DHA. The immobilized CalB@Meso-MIL-88A exhibited exceptional catalytic efficiency, achieving an unprecedented sn-1 positional incorporation rate of 86.8% (44.2% EPA, 42.7% DHA) with 90% EPA/DHA-ethyl ester (EE) donors, while 97% DHA-EE resulted in a record-high 90.1% DHA incorporation at the sn-1 position. Kinetic studies and molecular docking simulations indicated a higher substrate affinity for DHA-EE, attributed to enhanced transfer efficiency of EPA/DHA-EE in organic solvent system. This study presents the first demonstration of the potential of Meso-MIL-88A for industrial lipase immobilization via this optimized route, offering an eco-friendly and highly efficient catalytic application for nutraceutical synthesis.

Single-crystalline ordered macro-microporous CuBTC shows excellent mass transfer performance and has high fatty acid stability, making it highly promising as an enzyme immobilization carrier. However, its practical application is severely limited by its poor water stability. To address this challenge, we introduced a ligand, 1,2,3-benzotriazole (BTA), known for its hydrophobicity and strong coordination with copper. A series of CuBTC-derived dual-ligand SOM-MOFs (SOM-MIXs) was successfully synthesized with enhanced hydrophobicity and improved water stability. The CuBTC-derived SOM-MIXs demonstrated superior performance for lipase immobilization, resulting in a maximum increase of 66.9% in specific activity. To address the limitation that excessive addition of 1,2,3-benzotriazole does not further enhance the hydrophobicity of the carrier and may lead to structural damage, a sol-gel method was employed to coat the SOM-MIX with highly hydrophobic PDMS, leading to a further increase of 139.1% in the specific activity. The resulting immobilized lipase exhibited excellent catalytic performance and remarkable reusability, with 90.09% activity retention after five cycles in the synthesis process of 1-oleoyl-2-palmitoyl-3-linoleoylglycerol (OPL) by acidolysis. This work highlights the potential of SOM-MIX@PDMS and provides valuable insights into the rational design and postmodification of metal-organic frameworks (MOFs) for enzyme immobilization in diverse applications.

MIL-88A, a metal-organic framework (MOF), has significant promise for lipase immobilization due to its robust acid and water tolerance coupled with cost-effectiveness. Nonetheless, enhancing the dimensional compatibility of carrier with lipase and substrate is imperative for its broader application. In this study, we innovatively synthesized mesoporous MIL-88A (Meso-MIL-88A) with a fairly wide pore distribution around 10 nm using a soft-template method followed by a citrate dissociation strategy. The adsorption isotherm of Meso-MIL-88A conformed to the Langmuir model, exhibiting a notable increase in the adsorption capacity of lipase ET 2.0 compared to common MIL-88A (C-MIL-88A), attributed to the augmented external specific surface area (59 to 19 m2/g). Moreover, the immobilized lipase on Meso-MIL-88A showcased superior specific activity and enzyme activity recovery in contrast to C-MIL-88A, owing to enhanced structural preservation of lipase protein and reduced mass transfer resistance. Greater stability towards pH and temperature and better dynamic performance of immobilized lipase compared to free lipases exhibited the great advantages of Meso-MIL-88A as immobilized carrier. Notably, in the synthesis of phosphatidyl DHA (docosahexaenoic acid), immobilized CalB (Candida antarctica lipase B) on Meso-MIL-88A exhibited a 41.89 % incorporation of DHA into PC (phosphatidylcholine) within 48 h and an 82.60 % recovery after five batches of use. SEM observations confirmed the sustained integrity of the immobilized lipase structure post-recycling, underscoring the good stability of Meso-MIL-88A in the catalysis system. This study unveils the substantial potential of Meso-MIL-88A in lipase immobilization and offers a facile approach to tailoring the pore size of MOFs for practical application system.

Single-crystalline ordered macro-microporous CuBTC (SOM-CuBTC) is a promising carrier for lipase immobilization due to enhanced mass transfer and stability toward fatty acids. However, the low yield per mass of the template during the preparation process and the water instability of the SOM-CuBTC carrier have posed significant limitations on its practical applications. In this study, we addressed these challenges by introducing a novel dual-solvent system consisting of dimethyl sulfoxide (DMSO) and ethanol to obtain a stable precursor solution with a concentration approximately 10 times higher than that in previous literature, yielding 21.4 mg of SOM-CuBTC per gram of the polystyrene template. However, the decomposition of SOM-CuBTC in an aqueous system of lipase immobilization was observed. We explored chemical vapor deposition and sol-gel methods for hydrophobic modification on SOM-CuBTC. SOM-CuBTC coated by hydrophobic polydimethylsiloxane (PDMS) via the sol-gel method possessed excellent chemical stability and exhibited great potential for lipase immobilization with a significant increase by 98.7% in the specific activity. The obtained immobilized lipase not only showed improved thermal stability and pH tolerance but also displayed excellent catalytic performance in the synthesis process of 1-oleoyl-2-palmitoyl-3-linoleoylglycerol (OPL) by acidolysis. This work reveals the great potential of SOM-CuBTC and provides new insights into the rational design of metal-organic frameworks for enzyme immobilization in extensive applications.

Biodiesel yield prediction is vital for optimizing process efficiency, minimizing costs, and maintaining product quality. Traditional methods are labor-intensive, costly, and lack real-time capabilities, leading to inefficiencies in operations. Data-driven soft sensors offer real-time prediction but require extensive, high-quality datasets, posing practical challenges. To address these limitations, this study proposes a hybrid soft sensor model that integrates mechanistic and data-driven approaches. Mechanistic models were utilized to generate computational data via MATLAB (R), reducing the reliance on costly laboratory experiments. A comprehensive dataset (n =1500) comprising seven input variables-catalyst type, feedstock type, temperature, reaction time, free fatty acid (FFA) content, water content, and methanol-to-oil ratio-along with one output variable (biodiesel yield) was developed. This dataset was used to train various machine learning algorithms, with the artificial neural network (ANN) model demonstrating the highest predictive accuracy, achieving an R2 (goodness of fit) of 0.998 and root mean square error (RMSE) of 0.303. Hyperparameter tuning further enhanced the model's performance, reducing RMSE and the mean absolute error (MAE) by 63 % and 61.7 %, respectively. By combining mechanistic and data-driven techniques, this hybrid model effectively overcomes the limitations of traditional and purely data-driven methods, providing a cost-effective and efficient solution for biodiesel yield prediction and data generation.

Metal-organic frameworks (MOFs) have gained significant scientific interest due to their wide-ranging applications across various disciplines. Precisely controlling the crystal size of MOFs plays a pivotal role in enhancing their performance for practical applications. Nevertheless, achieving the rational synthesis of MOFs with desired size distributions remains a formidable challenge. In this research, we elucidate the crystallization mechanism of MOFs and propose an enlightening approach to systematically synthesize MOFs with diverse size distributions. Using MIL-88A as a case study, we uncover its crystallization mechanism characterized as oriented assembling and Ostwald ripening. Our investigation reveals that the ratio of the assembling rate to the ripening rate, denoted as VA/VR, exerts a profound influence on the resulting size distribution of MOFs. Specifically, higher VA/VR values yield both larger average sizes and increased standard deviation in the size distribution. We introduce VA/VR as the size variation factor and demonstrate its efficacy as a guiding principle for tailoring the synthesis of MIL-88A with distinct size distributions. Furthermore, we showcase the versatility of the size variation factor VA/VR by applying it successfully to the controlled synthesis of other MOFs, including MOF-14 and HKUST-1. These findings offer profound insights into the fundamental principles governing MOFs crystallization, paving the way for more effective and precise synthesis methodologies.

Macroporous metal-organic frameworks (MOFs) exhibit immense promise as carriers for immobilizing macromolecules, notably lipases. Nevertheless, their minute particle dimensions pose challenges in the recycling process, thereby significantly constraining their widespread practical utilization. To address this limitation, this study explores the potential of incorporating magnetic substances during the carbonization process, especially focusing on the use of magnetically carbonized Macro-MIL-88A for lipase immobilization and biodiesel production. The effects of different carbonation temperatures on macroporous MIL-88A and microporous MIL-88A were investigated. Our findings revealed that the carbonization temperature influenced the preservation of the 3D structure and the generation of magnetite. Carbonized Macro-MIL-88A (Macro-Fe3O4-C) at 500 degrees C exhibited superior specific activity and enhanced activity recovery. Lipase immobilized on Macro-Fe3O4-C (Macro-Fe3O4-C-TLL) demonstrated higher methanol tolerance during the biodiesel production process compared to Micro-Fe3O4-C. The reduced reusability of Macro-Fe3O4-C-TLL was attributed to the adsorption of the by-product glycerol. We further investigated pre- and posthydrophobic modifications on Macro-Fe3O4-C and found that post-PDMS modification maintained both high enzyme loading and good reusability of the immobilized lipase during biodiesel production. This study presents a promising method to enhance the reusability of immobilized large molecules by incorporating magnetite via a straightforward carbonization process.

The urgent need to address greenhouse gas (GHG) emissions underscores the significance of biodiesel as a key liquid biofuel. Compared to chemical biodiesel production, enzymatic technology offers a more sustainable alternative. This article presents a comparative study between a two-step enzymatic biodiesel production technology, already successfully industrialized, and conventional chemical technologies utilizing soybean oil (SBO) and waste cooking oil (WCO) as feedstock, respectively. The economic analysis demonstrates significant cost savings with the enzymatic process resulting in reductions of 16.33% and 36.54% for SBO and WCO, respectively. Enzymatic technology also exhibits substantial reductions in energy consumption, with a decrease of 86.8% and 60.2% for SBO and WCO, respectively. LCA findings indicate that enzymatic technology diminishes environmental impacts and GHG emissions are less than 78.86% and 63.05% for SBO and WCO, respectively. This study provides crucial insights for decision-makers, marking a significant paradigm shift in biodiesel production.

Diversifying waste cooking oil (WCO)-based biodiesel production towards epoxy fatty acid methyl esters (EFAMEs) offers a double gain, boosting revenue channels in the biodiesel sector and driving the development of sustainable phthalate plasticizer alternatives. This study explored the techno-economic feasibility of co-derived biodiesel and EFAMEs from WCO using a three-step process involving enzymatic transesterification, urea complexation, and performic acid epoxidation. The result shows that a plant processing 61,300 tonnes/year of WCO, may produce similar to 27,770 tonnes/year of biodiesel and similar to 30,180 tonnes/year of EFAMEs, with a total heating duty of 1,124 kW and annual electricity consumption of 34.9 million kWh. The initial capital investment of the plant in China amounts to 136.8 MM CNY, with an annual manufacturing cost of 460 MM CNY in 2022. Technoeconomic evaluation demonstrats a net present value (NPV) of 421.9 MM CNY at a 10 % discount rate, an internal rate of return (IRR) of 37.69 %, and discounted payback period of 2.37 years. The break-even point (BEP) is estimated at an annual sales volume of total products of 27,101 tonnes/year, including 12,790, 11,769, 2,542, and 2,390 tonnes/year of epoxy plasticizers, biodiesel, glycerol, and polymeric grease, respectively, collectively utilizing 42.38 % of the processing capacity. Monte Carlo simulation indicates minimal risk of the project, with probabilities of 98.5 % for IRR > 10 % and 97.8 % for a positive NPV. This study affirms the economic viability of co-producing biodiesel and EFAMEs from WCO for industrial application.

Despite the excellent properties of single-crystalline ordered macro-microporous MOFs (SOM-MOFs) compared to conventional MOFs, their further development has been hindered by the lack of versatile and high-yielding preparation protocols. This study introduces an innovative universal fabrication method that can easily solve the two major challenges of precursor stabilization and crystallization modulation, enabling the efficient synthesis of various SOM-MOFs with high yields. Notably, our approach has successfully yielded SOM-MIL-88A, a novel MOF showcasing exceptional stability in both water and acidic solutions, a remarkable achievement unprecedented in prior SOM-MOF research. SOM-MIL-88A has demonstrated exponentially improved performance over conventional MIL-88A in adsorption, catalysis, immobilized enzymes, and composite biosensing. Furthermore, our versatile protocol has been successfully applied to synthesize SOM-HKUST-1 and SOM-ZIF-8, resulting in significantly improved yields (increase by about 10-fold and 2-fold, respectively, compared to the previously reported protocol). This groundbreaking achievement marks a pivotal advancement in the preparation of diverse SOM-MOFs with tailored properties, presenting exciting prospects for future research on MOFs.

Metal–organic framework materials (MOFs) and their derivatives are considered ideal immobilization carrier materials because of their large specific surface area, high porosity and excellent structural designability. Among them, ZIF-8 has great potential for immobilization of enzymes due to mild synthesis conditions, and good biocompatibility. However, conventional ZIF-8 crystals have poor separation and recovery efficiency due to their small pore size and poor acid stability, greatly limiting their application in enzyme immobilization and further application. Although the carbonization of ZIF-8 by pyrolysis has been shown to be one of the approaches that can enhance its chemical stability, this still does not effectively solve the problem of the difficulty of recycling. Herein, we developed a strategy of pre-carbonization immersion (immersion in aqueous FeSO4 solution before carbonization) to synthesize ordered macroporous ZIF-8-derived carbon materials with stable ferromagnetism (denoted as CZ-x-M-y, where x denotes the carbonization temperature and y denotes the concentration of the impregnated FeSO4 solution) and used them to immobilize lipases for biodiesel production. XRD analysis showed that the magnetic properties in the materials came from Fe3C species. We found that the magnetic carbon materials obtained by carbonization at 600 °C showed the best immobilization effect, where CZ-600-M-0.3 (using 0.3 mol·L−1 FeSO4 aqueous solution to soak ZIF-8 and carbonized at 600 °C) had the highest enzyme loading of 183.04 mg·g−1, which was 49.7% higher than that of the non-magnetic CZ-600. In addition, CZ-600-M-0.5 maintained the highest enzyme activity, which was 81.9% of the initial activity, after five batches of reuse. The stable magnetic support materials reported in this study have promising potential for the industrial application of immobilized lipase.

•ZIF-8 derived N-doped macroporous carbon was achieved through pyrolysis.•The evolution of N species during the pyrolysis of ZIF-8 was presented.•The doping of pyrrolic N species contributed to enhance substrate’s reactivity.

MOF-derived carbon has extraordinary advantages including highly ordered morphology inherited from MOFs and improved chemical stability arising from its carbon nature, which may be a promising immobilized enzyme carrier. Herein, we prepared two MOF-derived carbon materials of different structures for the immobilization of lipase from Eversa (R) Transform 2.0 and systematically evaluated their application potential in biodiesel production system. Compared with C-C (derived from conventional microporous ZIF-8), 3DOM-C (derived from 3D ordered macro-microporous ZIF-8) exhibited superior immobilization performance with an 145.1% increase in enzyme loading and an 130.2% increase in activity. Moreover, lipase immobilized on 3DOM-C (3DOM-C@TLL) showed better catalytic performance than C-C@TLL, with faster conversion rate in lipase-mediated biodiesel production. Remarkably, the higher surface hydrophobicity of the 3DOM-C@TLL was proved to be the key factor in its improved catalytic performance. Meanwhile, we found that the affinity between immobilized enzyme molecules and water significantly weakened the hydrophobicity of C-C@TLL and 3DOM-C@TLL, which could be of adverse effect on their application in biodiesel production. To enhance the hydrophobicity of immobilized lipase biocatalyst, a facile post-immobilization hydrophobic modification strategy was proposed by coating the 3DOM-C@TLL with polydimethylsiloxane (PDMS). The as obtained super hydrophobic 3DOM-C@TLL@PDMS biocatalyst showed excellent catalytic performance in biodiesel production, with a much higher initial reaction rate, which was 3.3 folds of that catalyzed by C-C@TLL, and 1.8 folds of that catalyzed by 3DOM-C@TLL. This work shed light on the great potential of constructing MOF-derived hierarchically ordered porous carbon for enzyme immobilization in extensive practical applications.