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.

The amide bond is a crucial structural motif in numerous bioactive natural products and pharmaceutical compounds. Mono- (MC) and double-aminocarbonylation (DC) are key methodologies for synthesizing aryl amides, including versatile α-ketoamides. However, selectively controlling MC and DC of aryl halides has been a long-standing challenge. Here, we report a previously unknown strategy to fully invert the selectivity from MC to DC in palladium (Pd)-doped indium(III) oxide nanocatalysts by introducing oxygen vacancies (Ov) to modulate the second-beyond coordination spheres (SBCSs) of Pd, and catalysts show excellent activity, selectivity, and reusability for synthesizing diverse amides and α-ketoamides (130 examples). SBCS modulation drives long-range electron transfer to fine-tune electron localization, elongating Pd-O bonds, and weakening their strength to promote the second carbon monoxide adsorption and insertion for the DC pathway.

Perovskite with high temperature stability and tunability is a very promising material for dry reforming of methane (DRM), but its poor resistance to carbon coking severely limits its application. To improve the performance of catalysts in resistance to carbon coking, a common strategy is to construct active alloy structures. Here, we designed a new perovskite-type catalyst Nd0.9Mg0.1Fe0.4Ni0.6O3 by screening lanthanides and alkaline earth metal at the A site of perovskite and controlling the iron-nickel ratio at the B site. This catalyst exhibited excellent activity and good stability in the DRM reaction. The optimized Nd0.9Mg0.1Fe0.4Ni0.6O3 catalyst achieved conversions of CH4 of 93.1% and CO2 of 94.7% at 850 degrees C without diluent gas, and exhibited stable activity for 100 h. The good performance of Nd0.9Mg0.1Fe0.4Ni0.6O3 material can be attributed to the formation of exsolved Fe-Ni alloy nanoparticles with a ratio of 1:1.

The hydroaminocarbonylation of alkenes is one of the most promising methods for economically utilizing carbon monoxide (CO) to form high-value organic molecules. Here, we reported that a dual-atom catalyst named PdYb/CeO2 was prepared by impregnation method for the one step synthesis of amides from CO, alkenes with amines. Compared with Pd/CeO2, PdYb/CeO2 nearly doubled the amide yield. And the latter exhibited improved chemical selectivity and functional group tolerance toward diverse olefin and amine substrates. Characterization indicated that Pd and Yb species were embedded into the CeO2 support in a doped form. The incorporation of Yb optimized the electronic state of Pd through electronic regulation, which enhanced the catalytic activity. Mechanistic analysis revealed that the Lewis acid activated trace water in this system, providing a hydrogen source for the reaction. This heterogeneous catalytic system avoided the separation challenges of traditional homogeneous catalysts and the dependence on corrosive Brønsted acids, offering a strategy for the development of efficient carbonylation.

A series of zinc-acetate-triazolato catalysts (Zn(OAc)ATZ, Zn(OAc)TZ, Zn(OAc)TRZ, ATZ = 3-amino-1,2,4-triazolate, TZ = 1,2,4-triazolate, TRZ = 5-aminotetrazole) were developed for the direct synthesis of alkyl carbamates and corresponding alcohols from ammonia and dialkyl carbonates. Among them, Zn(OAc)ATZ exhibited exceptional catalytic performance due to its high surface area (441.11 m2/g), hierarchical porosity, and appropriate coordination environment. Under optimized conditions, 89% conversion of diethyl carbonate (DEC) with 88% ethyl carbamate (EC) yield could be achieved over Zn(OAc)ATZ at 80°C for 16 h. For dimethyl carbonate (DMC), a remarkable 98% conversion and 97% methyl carbamate (MC) yield were obtained at 30°C within 6 h, while dibutyl carbonate (DBC) required 24 h at 90°C to reach 95% conversion and 93% butyl carbamate (BC) yield. Characterization of XPS and FT-IR revealed that the synergistic interaction between Zn-N bonds and carboxylate groups stabilized the active sites, enabling efficient substrate activation. The catalyst retained >87% activity after three cycles, demonstrating excellent stability in alkaline ammonia environments. This work provides a sustainable and industrially viable strategy for alkyl carbamate synthesis, aligning with green chemistry principles and the "dual-carbon" agenda.

Rational catalyst design and reaction mechanism investigation guided by clarification of relationship between the active sites and elementary reaction steps at molecular level are challenging but essential in heterogeneous catalysis. Here we demonstrate the alteration of active sites on surface-interface by doping Ag-single atoms to Cu-crystal lattice of Cu/Al2O3, tuning the selectivity of CO2 reductive amination from N-methylation to N,N-dimethylation. Characterizations and DFT calculations reveal that active sites for Cu/Al2O3 are interface site of [Cu(I)-O/Cu(0)]inter and surface sites of [Cu]surf while that change to [Ag(I)-O/Cu(0)]inter and [Ag1Cu]surf after doping Ag-single atoms. Three different elementary reaction steps including N-H activation of amines, CO2 hydrogenation and C-N coupling are involved and interface sites are beneficial for N-H activation and surface sites are conducive to CO2 hydrogenation and C-N coupling. Importantly, N-H activation and C-N coupling for N,N-dimethylation are more favorable over [Ag(I)-O/Cu(0)]inter and [Ag1Cu]surf regulating the selectivity, due to the orbitals matching and lower energy barrier. Controlling catalyst selectivity requires linking atomic sites to each reaction step. Adding isolated silver atoms to copper reshapes surface and interface sites, steering carbon dioxide amination from single to double methylation.

A novel ML-driven strategy to accelerate the discovery of high-performance metal catalysts for ethylene glycol diamination.

A cobalt catalyst with high dispersion and supported on N-doped carbon was developed for the amino carbonylation of cyclohexane. This catalyst produced amide yields ranging from 65 to 90% and exhibited high stability over ten cycles. The system is compatible with a wide variety of substrates, making it a sustainable and efficient method for functionalising C(sp3)-H bonds.

Controlling product selectivity in catalysis is fundamental for green synthesis, yet challenging, especially aiming for switchable outcomes between different products within a single catalytic system. This is exemplified in the industrially crucial hydroformylation reaction, where achieving controlled switching between aldehydes and alcohols remains difficult due to the inability of uniform active site to independently govern the hydrogenation and desorption steps of the aldehyde intermediate. Herein, we report CeO2-supported single-atom Rh catalyst, in which triphenylphosphine (PPh3) serves as molecular switch to precisely modulate the chemoselectivity between alcohols and aldehydes in alkene hydroformylation with broad substrate compatibility and excellent stability. The Rh/CeO2 exhibits up to 99% chemoselectivity and 93% yield toward alcohols, while the PPh3-Rh/CeO2 shifts the chemoselectivity to aldehydes with up to 99% with 91% yield. Characterizations and theoretical calculations reveal that the coordination of PPh3 modulates the electronic structure of Rh, increasing the electron density at Rh centers. This electronic modification alters the hydrogenation pathway from oxygen-then-carbon to carbon-then-oxygen, raising the Gibbs free energy barrier for the rate-determining step of aldehyde hydrogenation by 0.26 eV, thereby switching the chemoselectivity to aldehyde. This work establishes ligand-modified single-atom catalysts as a versatile platform for controlling reaction chemoselectivity.

In this work, a porous organic polymer supported Zn catalyst (Zn@PIP-1) complexed with an ionic liquid (IL), zinc halide (ZnX2), and vinyl-functionalized triphenylphosphine (p-3vPPh3) has been synthesized by a one-pot method and used for the capture and conversion of waste carbon dioxide (CO2 19.4%) from flue gases of complex composition into valuable cyclic carbonates. Combined structure characterization studies of Zn@PIP-1 revealed successful integration of multiple sites and excellent structural stability, conferring high activity and stability under mild, additive-free conditions. The catalyst showed good group tolerance and a series of carbonates with different structures were successfully obtained in high yields. In addition, the catalyst was recyclable and could be successively used 5 times without obvious activity loss. We systematically evaluated the catalyst's robustness through rigorous poisoning resistance assessments against major flue gas contaminants. The experimental data revealed exceptional tolerance thresholds: (1) sustained catalytic efficiency (99% yield retention) under extreme oxidative conditions (O2, 53 333 ppm), (2) unimpaired performance at CO concentrations exceeding 33 333 ppm, and (3) 99% product yield maintained in the presence of 51 233 ppm H2O. This work provides some insights into the design of stable polymer catalysts for efficient CO2 transformation.

Carbon dioxide based degradable polycarbonate can be obtained through the copolymerization reaction of carbon dioxide with epoxide in the presence of a catalyst. This polymer has attracted much attention in recent years owing to its environmentally friendly and sustainable characteristics, and excellent material properties. Due to its unique properties, CO2-based polycarbonate has a wide range of applications in many fields such as electronic and electrical parts, automotive parts, medical devices, aerospace equipment, power electronic equipment, and radiation protection products. Therefore, numerous catalytic systems have been explored for the CO2/epoxide copolymerization process, in which zinc catalyst has the longest history and the greatest variety. In this short review, the significant advances in zinc catalysts for the copolymerization transformation of CO2 with epoxide are demonstrated, covering both heterogeneous and homogeneous catalysts. Moreover, both benefits and drawbacks of zinc catalytic system are described, and the outlook for large-scale industrial applicati ons in the future is also represented. 1 Introduction 2 Heterogeneous Zinc Catalysts 3 Homogeneous Zinc Catalysts 4 Overview of Heterogeneous and Homogeneous Zinc Catalysts 5 Conclusion

This study reports the development of a novel amino-functionalized ionic liquid catalyst, namely 1-butyl-3-methylimidazolium amino triazole ([EMIM]ATZ), for the efficient and sustainable synthesis of ethyl methyl carbonate (EMC) via transesterification of dimethyl carbonate (DMC) and ethanol (C2H5OH) at room temperature. Addressing the limitations of conventional catalytic systems that require elevated temperatures (> 75 degrees C), [EMIM]ATZ achieves 62% DMC conversion and 56% EMC yield within 8 h under room temperature (25 degrees C), while conventional ionic liquids ([EMIM]Cl, [EMIM]BF4, [EMIM]PF6 etc.) showed almost no activity at room temperature. The catalyst's superior activity stems from its strong basicity (pH approximate to 9.2) and enhanced CO2 absorption capacity (200 mgg(-1)), which synergistically activate C2H5OH and stabilize reaction intermediates. Structural characterization via FTIR and thermogravimetric analysis (TGA) confirmed the catalyst's thermal stability and recyclability, with no significant degradation observed over five reuse cycles (89% activity retention). In addition, the ionic liquid was also able to catalyze the synthesis of methyl propyl carbonate (PMC) and methyl butyl carbonate (BMC) at room temperature.

Propane dehydrogenation (PDH) has emerged as a promising technology to address the growing demand for propylene. However, Pt-based catalysts face a fundamental challenge in balancing high catalytic activity with long-term stability owing to the restriction of the linear scaling relationship. Herein, we present a breakthrough solution through the development of a europium-modified Pt-based high-entropy intermetallic (HEI) catalyst. The introduction of the rare-earth metal Eu breaks the trade-off relationship by reducing the size of the nanoparticles, thereby exposing more active species and increasing catalytic activity while providing an electron-rich Pt center to facilitate the desorption of propylene. The optimal HEI PtZnInSnEu/SiO2 catalyst enables over 40% propylene yield with sustained catalytic stability during continuous 100 hours of operation at 580 degrees C.

The urgent need for sustainable chemical processes has driven the exploration of carbon dioxide (CO2) and dinitrogen (N2) as abundant, renewable feedstocks for producing value-added chemicals and fuels. This review focuses on the transformation of CO2 and N2, highlighting their significance in green chemistry. We begin by discussing the fundamental principles of green chemistry and the advantages of utilizing CO2 and N2 to mitigate greenhouse gas emissions and reduce reliance on fossil resources. Subsequently, the review examines advanced transformation pathways for CO2 conversion, including electrocatalytic reduction, photocatalytic processes, and thermochemical transformations, evaluating their efficiency and scalability. The reduction of N2 and nitrogen oxides (NOx) to ammonia (NH3) is explored, presenting innovative alternatives to the traditional Haber-Bosch process that offer improved energy efficiency and lower environmental impact. Furthermore, the synthesis of nitrogenous compounds beyond NH3 is discussed, highlighting the versatility of green NH3 in the production of diverse chemicals. A key focus is placed on integrating CO2 and N2 transformations through CN coupling reactions, enabling the direct formation of organic molecules with reduced environmental footprints. The review concludes by identifying current challenges and future directions, emphasizing the potential of catalytic technologies to foster a sustainable and resilient chemical industry.

Direct synthesis of high-value-added chemicals from low-carbon molecules is of great research importance. The C(sp3)-H bonds in alkanes exhibit a high bond dissociation energy and a very low polarity; consequently, achieving highly selective synthesis of esters through alkoxy carbonylation in heterogeneous catalysis is a particularly challenging process. Herein, we describe the immobilization of a single-atom palladium catalyst supported by porous organic polymers for highly selective ester formation in cycloalkane carbonylation, which achieves a selectivity as high as 82% and a benzyl alcohol conversion of up to 96%. Various catalytic characterization methods, including XRD, XPS, TEM, SEM, and FTIR, indicate that palladium species are uniformly distributed in the polymer. This work suggests a promising method for the design of hybrid catalytic systems and offers meaningful insights into the development of bifunctional catalysts for selective alkoxy carbonylation.

Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption, probably lead to improving catalytic performances. Herein, bimetallic Ni3Mo/Al2O3 catalyst was demonstrated and exhibited over 5 times more active than Pt/Al2O3 toward the ethane dehydrogenation (EDH) as well as 2-10 times activity enhancement compared with their monometallic Ni and Mo counterparts and other Ni-based bimetallic nanoparticles. Kinetic studies revealed that the activation energy over Ni3Mo/Al2O3 (111 kJ mol-1) was much lower than that of Ni (157 kJ mol-1) and Mo (171 kJmol-1). DFT calculations showed ethane was adsorbed on the Ni or Mo surface in a more parallel configuration, whereas over Ni3Mo it adopted an inclined configuration. This change promoted ethane adsorption and pre-activation of the C-H bond, thereby benefiting the ethane dehydrogenation process on the Ni3Mo surface. Published by Elsevier B.V. All rights reserved.

Hydroformylation of alkenes constitutes a substantial industrial catalytic process. Tunable synthesis of alcohols and aldehydes by hydroformylation is challenging in heterogeneous catalysis. Here, we describe the encapsulation of single-atom Co catalysts in a porous phosphine polymer for the tunable synthesis of alcohols and aldehydes in olefin hydroformylation. With the polymer encapsulated single atom Co2(CO)8@PPh3-1/10 as the catalyst, almost complete conversion of 1-octene and a selectivity to alcohols of 94% at 170 degrees C while aldehydes with 87% yield was obtained at 140 degrees C, and was eco-friendly with a 100% atomic efficiency reaction and in line with principles of 'green chemistry'. Various catalyst characterization methods including XRD, TEM, HADDF-STEM and in situ FT-IR spectroscopy showed that Co species were homogeneously distributed in the pores of PPh3 and the formation of HCo(CO)x as the catalytically active species was successful. This work provides meaningful insights into the development of non-noble metal heterogeneous catalysts for the selective hydroformylation reaction.

Rhodium-alloyed catalysts with both high activity and stability hold great promise for the hydroformylation of alkenes. Here, we report a rhodium-cobalt alloy assembled on hexagonal boron nitride nanosheets with abundant N vacancies through a simple one-pot impregnated approach (RhCo/dh-BN), in which vacancies promote metal dispersion and alloy formation, and improve the performance of internal heterogeneous hydroformylation reaction. According to FTIR, XRD, BET, TEM and EPR characterization suggest that N vacancies are constructed on boron nitride and RhCo alloy anchors, while XPS and STEM are used to characterize the structural and electronic properties as well as the morphology of the RhCo alloy. RhCo/dh-BN exhibits good catalytic activity over a wide substrate scope for various aliphatic and aromatic alkenes including internal and terminal ones. As an example, for the 2-octene hydroformylation reaction, the nonanal yield is 97% with a TOF of 923 h-1. In addition, the catalyst could be reused up to five times under the same reaction conditions without loss of activity.

Dimethyl carbonate (DMC) is a vital chemical compound with extensive applications, particularly as a solvent in lithium-ion battery electrolytes. In this study, a novel catalyst, 3-amino-1,2,4-triazole calcium [Ca(ATZ)2], was synthesized, characterized, and applied for the efficient synthesis of DMC via the transesterification of ethylene carbonate (EC) and methanol. The catalyst demonstrated exceptional performance, achieving 73% EC conversion and 99% DMC selectivity under mild conditions (25 degrees C, 5 min). A unique feature of Ca(ATZ)2 was its ability to transition from heterogeneous to homogeneous catalysis during the reaction. Initially, the reaction proceeded through heterogeneous catalysis, but as ethylene glycol (EG) was generated, the catalyst partially dissolved in EG, shifting to a homogeneous phase. This dual-phase mechanism significantly enhanced reaction efficiency. The effects of reaction conditions, alcohol structure, and catalyst reusability were systematically investigated, and a plausible catalytic mechanism was proposed. The results highlight the potential of Ca(ATZ)2 as a sustainable and highly efficient catalyst for DMC production, offering a promising route for industrial applications. This work not only advances the field of catalytic chemistry but also contributes to the development of greener and more cost-effective chemical processes.

The indirect conversion of carbon dioxide (CO 2 ) is one of the important pathways to reduce greenhouse effect and achieve CO 2 conversion and utilization. The reaction route from CO 2 with epoxy compounds to produce methanol and ethylene glycol via ethyl carbonate intermediate is attracted widespread attention due to the lower thermodynamic energy barrier and 100% elements utilization in CO 2 . However, the ethyl carbonate hydrogenation to methanol as the part of the route is still limited by excessive metal loading, high H 2 /ethylene carbonate (EC) molar ratios, and insufficient stability. In this study, copper (Cu)‐based catalyst containing surface oxygen vacancy is developed via the sol–gel (SG) method to promote hydrogenation of ethyl carbonate, based on the adsorption of carbonyl groups by oxygen vacancy (O v ). Noted that the optimal catalyst of 8Cu/SiO 2 ‐SG exhibits excellent catalytic performance (99% conversion of ethyl carbonate, 99% yield of ethylene glycol and 96% yields methanol) under moderate conditions and operate stably over 120 h in stability testing. The experimental and characterization results show that the concentration of O v in catalyst is positively correlated with the methanol yield, which suggest that the precise regulation of O v enhances carbonyl adsorption and improve the catalytic performance. This work provides a rational design strategy for efficient hydrogenation catalysts.