Abstract:

The synergistic enhancement of catalytic activity and selectivity constitutes a critical challenge in modern heterogeneous catalysis， which directly influences target product yield， reaction energy efficiency， and process economics. Molecular imprinting technology （MIT） has demonstrated exceptional potential in overcoming this limitation by enabling the rational design of molecularly imprinted catalysts （MICs） with high activity， superior selectivity， and favorable thermal stability. These advanced catalysts combine biomimetic recognition with heterogeneous catalysis， wherein precisely engineered imprinted cavities integrate two key structural features， including catalytically active sites with tailored electronic properties and molecular imprinting cavities with specific structure. These imprinted cavities endow MIC exhibit exceptional molecular recognition capabilities， enabling selective binding to substrates， intermediates， and products via reversible covalent bonds， electrostatic interactions， hydrogen bonding， and other noncovalent forces. This precise recognition facilitates the mediation of specific reaction pathways， ensuring high-selectivity synthesis of target compounds. The preparation of MIC typically involves three sequential steps： template molecule assembly， template configuration fixation， and template molecule elution. In the template assembly stage， reversible interactions are commonly employed to drive the self-assembly of template molecules （target-structured molecules） with functional monomers， forming stable imprinted complexes. For template configuration fixation， cross-linking polymerization or surface engineering techniques are predominantly utilized to immobilize the assembled structure， ensuring the preservation of cavity geometry after template removal. Subsequent elution of the template molecules generates imprinted cavities on the MIC surface. By optimizing template assembly methodologies and fixation strategies based on application-specific requirements， both the cavity structure and catalytic binding modes can be precisely modulated， thereby enhancing catalytic activity and selectivity for tailored catalyst design. Additionally， the introduction of precious metals （e.g.， Rh， Ru， Au， Ag） and non-precious metals （e.g.， Fe） as catalytic active sites further augments MIC performance. Despite the promising application potential of MICs in chemical synthesis， their preparation and characterization remain challenged by several key limitations， like the sub-nanostructured imprinted cavities hindering detailed structural elucidation of binding sites， template molecules encapsulation within the polymer matrix during cross-linking resulting in incomplete elution， quantitative analysis of metal species in polymer-based MICs lacking standardized methodologies. To address these challenges and guide design of high-performance MICs， researchers have integrated advanced characterization techniques to comprehensively evaluate MIC structure， including morphology， elemental composition， active site distribution， chemical bonding information， and metal coordination environments. Currently， MICs exhibit tremendous application potential in the synthesis of various fine chemical products， but related review articles focusing on MIC are relatively scarce. This review focuses on the applications of MIT in thermal catalysis， systematically discussing its fundamental principles， theoretical foundations， and historical development. Next， various typical synthetic strategies for MICs， including bulk， suspension， precipitation， and surface imprinting polymerization are summarized. Then series of key characterization methods， such as Fourier transform infrared spectroscopy （FT-IR）， elemental analysis （EA）， and high-resolution mass spectrometry （HRMS） are described to analyze the structure of MICs. Moreover， different types of MICs （noble metal， non-noble metal， and metal free MICs） are used in catalytic reactions， including hydrolysis， oxidation， reduction， coupling， and polymerization. In addition， the photo-/electrocatalysis， artificial enzyme design， sensing， and adsorption/separation are also discussed as emerging applications of MIT. Finally， the research challenges and future directions are proposed in this field.

Key words: molecular imprinting technology, molecularly imprinted catalyst, catalytic reaction, research progress