Recyclable Heterogeneous Catalyst Research Articles

Addressing polar solvent challenges in the heterogenization of palladium catalysed Hayashi-Miyaura reaction on polymer support

The development of recyclable heterogeneous catalysts for the palladium-catalysed additions of arylboronic acids to nitrostyrenes is investigated in this study. Two strategies, direct copolymerization and post-modification, are explored for immobilizing chiral isoquinoline-oxazoline ligands onto polymer matrices. Various copolymer formulations are prepared, and their catalytic activity, recyclability, and reaction kinetics are evaluated. The incorporation of polar functional groups into the polymer matrix enhances catalytic properties, albeit with a decrease in reaction rate compared to the homogeneous system. Post-modification using a polystyrene-polyethylene glycol (PS-PEG) support shows promise, resulting in a moderate decrease in reaction rate and satisfactory performance over multiple reaction cycles. The findings provide valuable insights into the immobilization of chiral ligands and highlight the advantages and limitations of different polymer compositions. These results contribute to the development of advanced catalytic systems for the synthesis of biologically relevant compounds.

Pyromellitic acid grafted to cross-linked LDH by dendritic units: An efficient and recyclable heterogeneous catalyst for green synthesis of 2,3-dihydro quinazoline and dihydropyrimidinones derivatives

In this work, using layered double hydroxide (LDH) inorganic substrate, melamine as binding agent and dendrimer G1 and also pyromellitic acid (PMA) organic catalytic agent a heterogeneous acid catalyst was designed and prepared. After that, the prepared organic-inorganic catalyst was evaluated by various identification techniques such as FTIR, EDX, XRD, TGA, FESEM, and BET, and the results showed that the desired structure was successfully prepared. Also, in order to investigate the efficiency of the LDH@Me-PMA nanocatalyst as an efficient and heterogeneous catalyst, it was used for green and one-pot synthesis of 2,3-dihydro quinazoline and 3,4-dihydropyrimidinone-2-(1H)-ones derivatives. The use of LDH@Me-PMA catalyst led to the synthesis of the desired derivatives with higher efficiency and shorter reaction time than previously reported works. In addition, the prepared LDH@Me-PMA acid catalyst has the ability to be recycled and reused for 5 consecutive periods and has high stability, which is well consistent with the principles of green chemistry.

Water-Compatible and Recyclable Heterogeneous SABRE Catalyst for NMR Signal Amplification.

A water-compatible and recyclable catalyst for nuclear magnetic resonance (NMR) hyperpolarization via signal amplification by reversible exchange (SABRE) was developed. The [Ir(COD)(IMes)Cl] catalyst was attached to a polymeric resin of bis(2-pyridyl)amine (heterogeneous SABRE catalyst, HET-SABRE catalyst), and it amplified the 1H NMR signal of pyridine up to (-) 4455-fold (43.2%) at 1.4 T in methanol and (-) 50-fold (0.5%) in water. These are the highest amplification factors ever reported among HET-SABRE catalysts and for the first time in aqueous media. Moreover, the HET-SABRE catalyst demonstrated recyclability by retaining its activity in water after more than three uses. This newly designed polymeric resin-based heterogeneous catalyst shows great promise for NMR signal amplification for biomedical NMR and MRI applications in the future.

Solvent-Free Synthesis of 1, 4 Dihydropyridines Derivatives via Hantzsch Reaction Employing MgFe2O4 MNPs: An Efficient and Recyclable Heterogeneous Catalyst

Solvent-Free Synthesis of 1, 4 Dihydropyridines Derivatives via Hantzsch Reaction Employing MgFe2O4 MNPs: An Efficient and Recyclable Heterogeneous Catalyst

Highly Functionalized SWCNTs with a Dopamine Derivative as a Support for Pd Nanoparticles: A Recyclable Catalyst for the Reduction of Nitro Compounds and the Heck Reaction.

Single-walled carbon nanotubes (SWCNTs) were functionalized with a dopamine derivative in which the amine group was converted to azide (dopamine azide). The direct reaction of SWCNTs and dopamine azide in o-dichlorobenzene at high temperature (160 °C) led to very highly functionalized CNTs (≈60 wt%). Surprisingly, despite this high degree of functionalization, Raman spectroscopy detected a low disruption of the π-network of the carbonaceous support. This finding was justified by the rehybridization from sp3 to sp2 of the sidewall carbon atoms of CNTs involved in the functionalization process. Further characterization by means of different techniques such as X-ray photoelectron spectroscopy (XPS) analysis and transmission electron microscopy (TEM) allowed to shed some light on the chemical composition and morphology of the obtained material. Moreover, the estimation of the total content of phenolic units and their reducing potential after CNTs functionalization was also assessed using Folin and Ciocalteu and 2,2-diphenyl-1-picryl hydrazide (DPPH) assays. The functionalization of CNTs was exploited to immobilize palladium(II) species that were subsequently reduced with NaBH4 leading to the formation of Pd nanoparticles (NPs). The so obtained hybrid material was used as a recyclable heterogeneous catalyst for the reduction of nitro compounds and the Heck reaction.

An artificial intelligence approach to model and optimize biodiesel production from used cooking oil using CaO incorporated zeolite catalyst

The current work investigated the possibility of employing chicken eggshell-zeolite composite as a cheap and recyclable heterogeneous catalyst for used cooking oil (UCO) conversion into its corresponding methyl ester (UCOME) via methanolysis process. Various catalysts were formulated by loading eggshell on the zeolite and calcined at different temperatures to obtain CaO incorporated zeolite (CaO-Zel) catalyst. The catalyst sample calcined at 800 °C for 4 h (CaO-Zel-800) exhibited best activity for methanolysis process and was analyzed using various techniques, including BET, surface basicity, TPD-CO2, TGA/DTA, SEM, XRD and FTIR. The transesterification process was modeled using artificial intelligence approach viz. artificial neural network (ANN) and adaptive neuro-fuzzy inference system (ANFIS) while optimization of the operating variables (temperature, catalyst loading, time and molar ratio) was performed by interfacing the developed models with ant colony optimization (ACO) algorithm. The closeness of coefficient of determination (R2) to unity and low mean square error (MSE) indicated that the methanolysis of UCO was adequately described by the developed models with ANFIS model (R2 = 0.9997 and MSE = 0.1271) superior to ANN model (R2 = 0.9953 and MSE = 2.0762). The highest UCOME yield of 99.45 ± 0.51 wt% was achieved with ANFIS-ACO under the condition; reaction temperature (72.97 °C), methanol/UCO molar ratio (7.14:1), reaction time (131.97 min) and catalyst dosage (5.39 wt%). The results of the sensitivity analysis revealed that all the operating variables influence UCOME yield, and none could be discarded. The CaO-Zel-800 catalyst was reused for five consecutive reaction cycles, and its activity only decreased by about 12%.

Ru-bentonite catalyzed green Knoevenagel condensation of substituted benzaldehydes with ethyl cyanoacetate

The full-text of the article will be published in the English version of the journal "Catalysis in Industry" No. 1, 2024.To develop Ru-incorporated bentonite clay as a heterogeneous base catalyst for use in Knoevenagel condensation as an alternative to hazardous base catalysts like pyridine, piperidine, etc., we purify the naturally occurring bentonite clay and Ru3+ cation incorporated into its interlayers of bentonite clay to improve its porosity and to increase the surface area of bentonite clay. Purified bentonite and Ru-bentonite were characterized by FTIR, PXRD, HRTEM, SEM & EDS, BET surface area analysis, and TGA. Base activation was done to these clays and a comparative study of these clays as recyclable heterogeneous catalysts for Knoevenagel Condensation was undertaken in water as a solvent for the chemical transformation of 2,4-dichlorobenzaldehyde and 4-hydroxybenzaldehyde with ethyl cyanoacetate into their corresponding α,β-unsaturated acids. The products were characterized by FTIR, 1H NMR, and 13C NMR analyses. The essential key points of this reaction are mild reaction conditions, absence of hazardous chemicals as used in classical Knoevenagel condensation, reusability of the catalyst, and high yield percentage of the products.

Amine-rich Nickel(II)-Xerogel as a Highly Active Bifunctional Metallo-organo Catalyst for Aqueous Knoevenagel Condensation and Solvent-free CO2 Cycloaddition.

Metallogels formed from supramolecular interactions of low-molecular-weight gelators (LMWGs) combine the qualities of heterogeneous catalysts and offer the advantages of multifunctionality owing to the facile installation of desired task-specific moieties on the surface and along the channels of the gels. We discuss the applications of a triazole-based Ni(II) gel-derived xerogel (NiXero) having a high density of Ni(II)-nodes and appended primary amines as a recyclable heterogeneous catalyst for Knoevenagel condensation of aldehyde and malononitrile in water and the solvent-free cycloaddition of CO2 to form a series of cyclic carbonates with near-quantitative conversion of the respective epoxides, with low catalyst loading (0.59 mol %), high catalyst stability, and recyclability. The structural advantages of NiXero, due to the concurrent presence of bifunctional Lewis acid-base sites on the channels, open Ni(II) nodes, Ntriazole, pendant -NH2 and its chemical stability, are conducive to the cooperative heterogeneous catalytic activity under mild conditions. This work emphasizes the effective amalgamation of metals with purpose-built ligand systems for the construction of metallogels and their utility as heterogeneous catalysts for desired organic transformations.

Development of new 2-(Benzothiazol-2-ylimino)-2,3-dihydro-1H-imidazol-4-ol complexes as a robust catalysts for synthesis of thiazole 6-carbonitrile derivatives supported by DFT studies

Here, using Pd2+, Fe3+, and Ni2+ ions, we established new imidazole complexes. These complexes were described in the initial section to provide their chemical formulas. With the exception of the Pd (II) chelate (BIL-Pd), which has a square-planer configuration, the octahedral geometry was recommended for the other examined complexes. The condensation reaction of three components of aromatic aldehyde, 2,4 thiazolidinedione, and malononitrile results in the straightforward and highly efficient one-pot synthesis of 5-amino-2-oxo-3,7-dihydro-2H-pyrano[2,3-d]thiazole-6-carbonitrile derivatives under controlled and environmentally friendly reaction conditions. (BIL-Pd) provides an effective, recyclable and promising heterogeneous solid catalyst. Utilizing a green solvent (EtOH/H2O), a shorter reaction time, and excellent efficiency (98%) were the main benefits of the recommended catalyst. In addition, the environmentally friendly features of this synthetic procedure were further investigated by looking at BIL-capacity Pd's to be recycled for six consecutive cycles without significantly losing catalytic activity. In addition, the BILPd complex outperformed alternative Lewis acids, basic catalysts, and ionic liquids in the production of 5-amino-2-oxo-3,7-dihydro-2H-pyrano[2,3-d]thiazole-6-carbonitrile derivatives.It is desired due to its mild conversion and compatibility with a variety of functional groups. Additionally, computational issues were usually taken into account in conjunction with how they influenced identifying or announcing functionally relevant variable qualities. In order to elucidate the reasons for the superiority of the BILPd complex, DFT analysis was also used. To support the proposed methodology, the optimization procedure for intermediates was also put into practice. Using a combination of H2O and C2H5OH as an environmentally friendly solvent and green catalytic technique the catalyst exhibits high selectivity and reactivity under mild reaction conditions, making it a promising candidate for a wide range of applications in green chemistry. This strategy's simplicity, safety, commercially accessible catalyst, stability, fast reaction time, and outstanding yields may be used in the industry in the future.

Smart and recyclable Fe3O4@APTES-β-CD nanoparticles with supramolecular host-guest synergistic enhancement effect for 2-chloro-4-nitrophenol removal

A facile and efficient strategy was introduced to prepare p-tolylsulfonyl-β-cyclodextrin (TsO-β-CD). Subsequently, the smart and recyclable Fe3O4@APTES-β-CD nanoparticles were prepared via between Fe3O4@APTES and TsO-β-CD. And then, the structures of TsO-β-CD and Fe3O4@APTES-β-CD were characterized and analyzed. Finally, the Fe3O4@APTES-β-CD nanoparticles was utilized as a heterogeneous Fenton-like catalyst. The catalytic performance of Fe3O4@APTES-β-CD for 2-chloro-4-nitrophenol (4-C-2-NP) were assessed and studied. Accordingly, the degradation process of 4-C-2-NP fitted the pseudo-first-order kinetics model. In the meantime, the catalytic activity of Fe3O4@APTES-β-CD was higher than that of Fe3O4@APTES-α-CD or Fe3O4@APTES-γ-CD. More importantly, the Fe3O4@APTES-β-CD possessed good regeneration and reuse ability. In addition, the possible reaction route and degradation mechanism were proposed with synergistic effects. Consequently, the Fe3O4@APTES-β-CD can potentially serve as a smart and recyclable heterogeneous Fenton-like catalyst.

Nylon fabric supported poly (styrene sulfonic acid) brush catalyst: A superior heterogeneous Brønsted acid catalyst with stable performance and facile recyclability

The development of highly efficient and easily recyclable heterogeneous catalysts is of great significance for green synthesis. By adopting a facile photoinduced grafting strategy, we have successfully developed fabric nylon-supported poly (styrene sulfonic acid) brush catalyst which can serve as efficient and recyclable Brønsted acid catalyst. The fabric-supported catalyst was prepared from commercially available nylon nonwoven fabric, and characterized by XPS, FTIR, EA, SEM and Hammett acidity. Results obtained indicate that the fabric catalyst possesses high catalytic activity for the condensation of anthranilamide with aldehydes or ketones in ethanol (15 examples yields 90–97%), as well as the advantage to be easily recycled and reused, with superior stability and catalytic activity even after 15 runs. What's more, application of the fabric catalyst for scale-up synthesis of pharmaceutical molecule NSC-145669 further demonstrated its promising potential in industrial production. Attractively, this method could be easily extended to various olefin-containing monomers and thus provided a general strategy for designing textile catalysts.

Titania Nanoparticle Catalysed N‐Alkylation of Amines by Hydrogen Auto‐Transfer Mechanisms

AbstractUnlike well‐defined homogenous metal complex catalysts, no distinct heterogeneous catalysts are available for hydrogen auto‐transfer or borrowing hydrogen methodologies. Alternatively, a variety of noble metals, base metals, and bimetallic systems supported on various metal oxides are scrutinized for this purpose, mainly by modulating the ability of metals and supports in a multistep reaction. Herein, we demonstrate that pristine defect‐induced titania nanoparticle catalyst is an efficient and recyclable heterogeneous catalyst for the preparation of N‐alkylated products (>90 %) in the absence of expensive hydrogen source, costly ligands, additives, or costly metals under greener conditions. Furthermore, the nano‐sized titania catalyst tolerates functional groups with high yields. In addition, the ‐alkylation of aniline affords the corresponding alkylated products in d yields with long aliphatic alcohols. Finally, the results of the control tests show that a process of Hydrogen Auto transfer is responsible for carrying out the reaction.

Ce-Zr UiO-66 MOF as recyclable heterogeneous catalyst for selective N-methylation

Metal-organic frameworks (MOFs) are proven heterogeneous recoverable catalysts in a number of organic transformations. However, their role in the reaction of amines with dialkyl carbonates has only been partially investigated. In this paper, the catalytic potential of Ce-Zr UiO-66 MOF towards the N-alkylation of secondary amines with dimethyl carbonate has been investigated. The desired MOF catalyst was prepared by the solvothermal method and its morphology, texture, porosity, functionality, and crystallinity were examined before its catalytic investigation. The MOF consisted of sphere-like particles with a surface area of 272 m2/g and an average pore size of 3.4 nm. Under the optimized conditions, the aromatic and heterocyclic amines yielded the N-methylated derivatives as the sole or the major product in the presence of Ce-Zr UiO-66 MOF. The maximum methylation percentage achieved was 100%. The reaction followed the pseudo-first-order rate kinetics and the heterogeneous bimetallic Ce-Zr UiO-66 MOF was reused four times without any significant activity loss. Thus, the Ce-Zr UiO-66 MOF serves as an efficient, selective, and reusable heterogeneous catalyst in N-methylation reactions.

Construction of silsesquioxane and phosphinum‐based ionic porous hypercrosslinked polymers for efficient heterogeneous catalytic CO2 cycloaddition

AbstractIn this work, we reported a facile one‐pot route to construct polyhedral oligomeric silsesquioxane (POSS) and phosphonium‐based ionic porous hypercrosslinked polymers (denoted as P‐iPHCPs) with multiple catalytic active sites, which could be regarded as efficient heterogeneous catalysts for the conversion of carbon dioxide (CO2) to highly value‐added cyclic carbonates. The targeted polymers P‐iPHCPs were prepared from a rigid building block octavinylsilsesquioxane (VPOSS) and a low‐cost commercially available organic ionic salt methyltriphenylphosphonium bromide ([Ph3PMe]Br) by the AlCl3‐catalyzed Friedel‐Crafts reaction. The series of polymers P‐iPHCPs that synthesized by different molar ratios of VPOSS to [Ph3PMe]Br possess hierarchical micro/mesoporous structures with high surface areas ranging from 376 to 429 m2 g−1 and behave the flower‐like nano‐morphology. Especially, the desired multiple active sites involved the mixed anions including free Cl−, Br− anions and the in‐situ formed metal‐halogen complex anion [AlCl3Br]− within phosphonium segments, and the enriched POSS‐derived SiOH hydrogen bond donor (HBD) groups that derived from the breakage of POSS cages during the synthetic process. The typical polymer P‐iPHCP‐14 has the aforementioned nucleophilic‐electrophilic multiple catalytic active sites, which was regarded as an efficient recyclable heterogeneous catalyst for synergistic catalytic conversion of CO2 with various epoxides into cyclic carbonates under mild conditions.

Novel Spinel Nanomaterials for Photocatalytic Hydrogen Evolution Reactions: An Overview

The energy demand generated by fossil fuels is increasing day by day, and it has drastically increased after the COVID-19 pandemic as industries and household utilities rejuvenate. Renewable sources are thus becoming more essential as easily available, alternative methods of low-cost energy generation. Among these renewables, solar energy, i.e., solar power, is a promising energy source and can be used for solar-based H2 evolution because H2 technology is a leading source of eco-friendly electricity generation, and most of the worldwide efforts to develop this method involve heterogeneous catalysis for H2 evolution via water splitting and its storage, i.e., using a fuel cell. In the current scenario, there is a need to develop a stable, recyclable, and reusable heterogeneous catalyst system, which is a great challenge. In the current study, we have focused on novel ferrite magnetic nanomaterials for recyclable and reusable robust photocatalysis. Moreover, discussions of the factors contributing to the photocatalytic hydrogen evolution, low-cost synthesis techniques, and prospects for making them ideal photocatalysts are uncommon in the literature. The study will impart possible approaches for the design and development of novel ferrite nanomaterials and their nanocomposites for H2 generation in the forthcoming years.

Ion-imprinted magnetic adsorbents for the selective capture of Cu(II) and their cascade application as heterogeneous recyclable catalysts for Ullmann and Glaser coupling reactions

The selective capture and efficient reuse of Cu(II) from contaminated seawater requires a multifunctional adsorbent with a high Cu(II) selectivity and magnetic properties to facilitate recycling. Moreover, the cascade application of the recycled adsorbent is important but has not been extensively investigated. Accordingly, in this study, ion-imprinted magnetic adsorbents, particularly, copper ion-imprinted polymers (Fe3O4@mSiO2@CIIP) were prepared using magnetic mesoporous silica microspheres (Fe3O4@mSiO2) as carriers, with organosilicon containing hydroxyl and Schiff bases as the polymer backbone to selectively collect Cu(II) from aqueous media. The adsorption isotherms, kinetics, selectivity, and mechanisms were examined under various adsorption conditions. Fe3O4@mSiO2@CIIP-2 shows high selectivity and fast adsorption kinetics, and the equilibrium adsorption amount of Cu(II) is 263.2 mg/g within 30 min. The pseudo-second-order model and the Langmuir model are supported by the adsorption kinetics and isotherms, respectively. Particularly, the adsorption amount of Fe3O4@mSiO2@CIIP-2 could be reused eight times without substantial loss. Additionally, specific functional monomers bound to Fe3O4@mSiO2@CIIP-2 could both selectively adsorb Cu and serve as functional ligands for catalysts that can heterogeneously catalyze the Ullmann and Glaser coupling reactions after adsorbing Cu(II).

Hexaazatrinaphthalene-Based Covalent Triazine Framework-Supported Rhodium(III) Complex: A Recyclable Heterogeneous Catalyst for the Reductive Amination of Ketones to Primary Amines.

The development of efficient and recyclable heterogeneous catalysts is an important topic. Herein, a rhodium(III) complex Cp*Rh@HATN-CTF was synthesized by the coordinative immobilization of [Cp*RhCl2]2 on a hexaazatrinaphthalene-based covalent triazine framework. In the presence of Cp*Rh@HATN-CTF (1 mo l% Rh), a series of primary amines could be obtained via the reductive amination of ketones in high yields. Moreover, catalytic activity of Cp*Rh@HATN-CTF is well maintained during six runs. The present catalytic system was also applied for the large scale preparation of a biologically active compound. It would facilitate the development of CTF-supported transition metal catalysts for sustainable chemistry.

Green is the New Black: Emerging Environmentally Friendly Prospects in the Synthesis of Quinoxaline Derivatives

Abstract: Functionalized polysubstituted quinoxalines have been widely reported to possess appealing biological activities of great pharmaceutical importance which drew researchers into exploring promising synthetical protocols. On top of that, prospects on green chemistry are driving research paradigms into more cost-effective, facile, environmental-friendly, sustainable, and scalable approaches. This paper reviews the green synthesis methods of quinoxaline derivatives using recyclable heterogeneous catalysts, green solvents and energy-mediated methods that have been extensively studied and published since 2010 to offer an insight into the ongoing greener trend in the scientific field.

A Novel Powerful γ-Fe2O3 @ CPTMS - Diethylene Triamine (DETA) @SO3H as a Heterogeneous Nanocatalyst, Recyclable and Efficient via Microwave-assisted for the Synthesis of Benzoxazinone- 4(3H)-one Derivatives in Green Media

Background: In order to synthesize benzoxazin-4 (3H) -one derivatives, a new inorganic- organic super-magnetic nano-hybrid (γ‐Fe2O3@ CPTMS-DETA @SO3H) nanocatalyst of the modified sulfuric acid represents a green and efficient catalyst to perform a three-component condensation reaction between various acyl chlorides, anthranilic acid and acetic anhydride (as cyclization agent), in one-pot and solvent-free conditions under microwave irradiation (4a-q). Introduction: In recent years, one of the most important subjects in synthetic organic chemistry has been green synthesis, which has applied environmentally friendly and efficient methods to synthesize biological derivatives. The use of catalysts has significant advantages, including simple separation and preparation, chemical and thermal stability, and eco-friendly nature and their features such as reusability, low cost, high efficiency and easy operation. Therefore, the mechanism is performed by a non-toxic organic catalyst that uses the chemical reactants and the least energy in accordance based on the least waste and green chemistry. Methods: Sequential addition and one-pot methods were applied to produce benzoxazinone derivatives. In the sequential addition approach, the reaction was begun by adding anthranilic acid and acetic anhydride to the reaction vessel under microwave irradiation and continued by adding γ‐ Fe2O3@ CPTMS-DETA @SO3H as super-magnetic nano-hybrid recyclable green catalysts and the desired acyl chlorides. Results: The main objective of this project was to synthesize benzoxazin-4 (3H) -one derivatives in the presence of super-paramagnetic organic-inorganic nanohybrid particles based on improved sulfonic acid (γ- Fe2O3 @ SiO2 - DETA @ SO3H) as an efficient recyclable heterogeneous catalyst. Conclusion: This paramagnetic nano-organocatalyst was characterized by EDX, VSM, TGA, FESEM, FT-IR, and XRD. Advantages of this catalyst include easy preparation, clear and easy operation, short reaction time (15–30 min), as well as without the use of toxic catalysts. In addition, the catalyst can be separated from the reaction solution using an external magnet by magnetic decantation; it can be recycled up to six times without reducing its activity.

Cooperative Catalysis by Boronic Acid-Amine Bifunctionalized Polyacrylonitrile Fibers in Henry Reaction

The acid–base pairing and fabrication method was herein employed to construct acid–base bifunctional heterogeneous catalysts. The boronic acid group was introduced into primary amine-functionalized polyacrylonitrile fiber (PANEAF) via amide bond formation to fabricate boronic acid-amine bifunctional PANFs as recyclable heterogeneous catalysts by using the amino N atoms of PANEAF as anchoring points. The so-obtained fiber catalysts PANEA–BA1F and PANEA–BA2F containing boronic acid groups attached on benzene and pyridine rings, respectively, were employed in the Henry reactions of aryl aldehydes with nitromethane. Catalytic investigations showed that their performance had great correlation with the change of boronic acid. PANEA–BA2F exhibited a higher substrate selectivity than PANEA–BA1F, and only the benzaldehydes with hydroxy, dimethylamino, and amide groups were reactive, which showed preliminary substrate specificity like enzyme catalysis. The in situ investigation with cyclododecane as solvent by Raman and Fourier transform infrared spectroscopy (FT-IR) analysis was conducted to clarify the catalytic difference. Moreover, the uncommon reverse reactivity order of benzaldehydes in PANEA–BA1F-catalyzed condensation was explained.