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Metal-Organic Frameworks: An Emerging Force in Catalysis
Preface
As one of the most influential porous crystalline materials in the field of materials science in recent years, Metal-Organic Frameworks (MOFs) have expanded their impact from basic chemical research to multiple key sectors such as industrial catalysis, energy conversion and green manufacturing. The awarding of the 2025 Nobel Prize in Chemistry to research related to MOF systems has further confirmed the strategic position of this material system in structural chemistry and applied science. The core advantages of MOFs stem from their regular three-dimensional framework structures constructed by metal nodes and organic ligands, which endow MOFs with ultra-high specific surface area, precisely tunable pore size, abundant functionalization pathways, and programmable regulation of reaction environments at the molecular scale. These unique properties make MOFs representative of a new generation of designable catalytic materials.
1 Brief Introduction to MOF Materials and Their Structures
As illustrated in Figure 2, the metal nodes of MOFs are typically transition metal ions, while the Organic Linkers are mostly nitrogen- or oxygen-containing multidentate ligands (e.g., carboxylic acid and imidazole compounds). This modular assembly approach allows researchers to precisely regulate the physicochemical properties of materials through the rational selection of building units. Compared with traditional porous materials such as zeolites and activated carbon, MOFs exhibit distinct advantages: ① Their specific surface area can reach up to thousands of square meters per gram, far exceeding that of most traditional materials; ② The pore size can be precisely adjusted within the range of 0.5 to 10 nm; ③ Various functional groups can be introduced onto the pore surface via post-synthetic modification, creating an ideal environment for specific catalytic reactions.
2 Unique Advantages of MOF Catalysts
The distinctive structural and chemical properties of MOFs make them highly attractive heterogeneous catalysts for industrial applications, capable of catalyzing oxidation, hydrogenation, polymerization and other reactions. In catalytic applications, the remarkable features of MOF materials are reflected in the following aspects:
Designable Active Sites
By introducing specific functional groups (e.g., -NH₂, -SO₃H, -COOH) into organic ligands or constructing unsaturated coordination sites on metal nodes, active centers with specific acid-base or redox properties can be created. Studies have shown that amino-functionalized Uio-66-NH₂ exhibits excellent performance in CO₂ capture and conversion, while sulfonic acid-functionalized MOFs demonstrate outstanding acid catalytic activity [1].
Space Confinement Effect
The regular pore channels of MOFs can provide a unique microenvironment for catalytic reactions, improving reaction selectivity through steric hindrance and mass transfer limitations. For example, immobilizing Ir(III) polypyridine complexes in the pores of UiO-67 can effectively suppress side reactions common in homogeneous catalysis, significantly enhancing the selectivity of styrene trifluoroethylation reaction [2].
Multifunctional Synergistic Catalysis
MOFs can integrate multiple active sites simultaneously to achieve synergistic catalysis. A bifunctional MOF catalyst reported by Zhou et al., which possesses both Lewis acid and base sites, achieves nearly 100% conversion rate in the cycloaddition reaction of CO₂ and epoxides [3].
The chemical tunability and structural flexibility of MOF materials not only enable them to address catalytic challenges in various fields, but also allow for the optimization of their own stability, selectivity and recyclability.
3 Application Progress in Energy and Environmental Fields
With their unique designability, MOFs have become key catalysts for solving energy challenges. Through the precise selection of metal nodes and organic ligands, MOF materials with high specific surface area, ideal pore size and active sites can be directionally synthesized. This "tailor-made" advantage enables MOFs to perform prominently in processes such as photo/electrocatalytic water splitting, carbon cycle (CO₂ conversion and utilization) and clean energy conversion, providing a new path for the development of a new generation of efficient and green energy technologies.
CO₂ Conversion and Utilization
MOFs show great potential in CO₂ capture and conversion. Catalysts such as Ru@MIL-101 exhibit high activity and stability in CO₂ methanation reaction, providing a new approach for the resource utilization of greenhouse gases. Studies have indicated that at a reaction temperature of 225°C, such catalysts can maintain a CH₄ selectivity of over 99% [4].
Photo/Electrocatalytic Water Splitting
MOF-based composites such as MnCdS/ZnS-VZn display excellent performance in visible-light-driven water splitting for hydrogen production. Experimental data show that the optimal catalyst achieves a hydrogen production rate of 394.4 μmol·h⁻¹·g⁻¹, which is significantly higher than that of many traditional semiconductor catalysts [5].
Biomass Conversion
MOF-derived catalysts have made important progress in the field of biomass refining. The NiMo@NC catalyst achieves a conversion rate of 99.36% in the hydrodeoxygenation of lauric acid, and maintains 95% activity after multiple cycles, showing good prospects for industrial application [6].
4 Development and Challenges of MOFs
The main challenge faced by early MOF materials was insufficient chemical and thermal stability. In recent years, the stability of materials has been significantly improved by constructing frameworks with high-valence metal ions (e.g., Zr⁴⁺, Ti⁴⁺, Fe³⁺) and rigid ligands. Meanwhile, technology companies capable of customized mass synthesis of MOFs, such as Guangdong Carbon Language Advanced Materials Co., Ltd., have emerged. The Zr-based MOFs developed by the company can maintain structural integrity in aqueous and acidic environments, greatly expanding their application scope.
At the same time, large-scale production remains the main bottleneck for the commercial application of MOFs. The traditional solvothermal method has disadvantages such as high energy consumption, long cycle time and large usage of organic solvents. Guangdong Carbon Language Advanced Materials Co., Ltd. has largely addressed these challenges by adopting emerging technologies such as mechanochemical method, continuous flow synthesis and spray drying, providing a feasible path for the industrial production of MOFs. With the continuous innovation of synthesis methods and the deepening understanding of material structures, MOF-based catalysts are moving towards multifunctionalization, intellectualization and practicalization. Future research will focus on improving the long-term stability of materials under actual reaction conditions, designing intelligent catalytic systems with stimulus responsiveness, and exploring the application potential of MOFs in emerging fields such as electrocatalysis and photocatalysis.
The development of MOF materials represents a significant progress in materials science from structural design to functional realization, providing new solutions for addressing major challenges in energy and environmental fields. With the deepening of basic research and the advancement of engineering technology, MOF-based catalysts are expected to play a more important role in green chemistry and sustainable development.