Phenolic Products Research Articles

Novel halogen-free deep eutectic solvents for efficient extraction of phenolic compounds from real coal tar

The separation of phenolic compounds from coal tar is conducive to the manufacture of high value-added phenolic products and the further processing of oil. Herein, three novel halogen-free choline dihydrogen citrate (CDC)-alcohols deep eutectic solvents (DESs) were prepared to extract phenolic compounds from real coal tar. The effects of the critical parameters including components and constituent mole ratio of DESs, mass ratio of DESs to coal tar, temperature, and time on extraction efficiency were systematically investigated. It was demonstrated that the extraction efficiency decreased with the extension of alkyl chain of alcohols. Hence, CDC-ethylene glycol (EG) was selected as the appropriate extractant, and the extraction efficiency reached 89.3% under the optimal conditions. Fourier transform infrared spectra revealed that the hydrogen bond interaction between CDC and EG was the main reason for their formation of DES. Phenolic compounds also had hydrogen bond interactions with DES, which was the main driving force for the separation of phenolic compounds from coal tar by DES. Differential scanning calorimeter results displayed that the CDC-EG had no definite melting point, and its glass transition temperature was significantly lower than the melting point of individual components. The CDC was recovered by using ethyl acetate as the back extraction agent. Moreover, to avoid back extraction operation, phenolic resin gel was prepared by one-pot method, which was expected to be suitable candidate as the precursor for functional carbon materials.

Experimental and Kinetic Study on the Gas-Phase Pyrolysis of Syringol

Syringyl (3,5-dimethoxy-4-hydroxyphenyl) units are abundant in hardwood lignin, which explains the large amount of syringol present in bio-oils derived from these feeds. To improve understanding of the decomposition chemistry of these syringyl units, the gas-phase pyrolysis kinetics of syringol have been studied experimentally and theoretically under typical fast pyrolysis conditions. The experiments were performed at 673–923 K in a micropyrolyzer unit hyphenated with a gas chromatography (GC) × gas chromatography-flame ionization detection/time-of-flight mass spectrometry and a customized gas chromatograph, which allows to detect and quantify products with boiling points up to 823 K next to permanent gases and water. New obtained experimental data show that 2,3-dihydroxybenzaldehyde is the most important phenolic product, and a large amount of pyrolytic water was formed. The proposed decomposition pathways of syringol to these two products show two new features: (1) 2,3-dihydroxybenzaldehyde is formed from a unimolecular decomposition of syringol without any stable intermediates and (2) both pathways leading to 2,3-dihydroxybenzaldehyde and water involve one more H-atom migration step to form the more stable radicals. Potential energy surface calculations at the CBS-QB3 level of theory indicate that the new features are kinetically favorable. Furthermore, a detailed kinetic model for syringol pyrolysis including 361 reactions and 93 species was constructed. Thermodynamic data for important species and kinetics for crucial reactions were determined with ab initio calculations at the CBS-QB3 level of theory. The model predicts well the conversion of syringol and the formation of major products. A rate of production analysis shows that the new proposed pathway is the major decomposition pathway of syringol. These findings shed new light on the pyrolysis and oxidation chemistry of syringyl species.

Mild modification of lignin pyrolysis vapors by metal oxide catalysts: A comparative study with molecular sieve catalysts

ABSTRACT Compared with strongly acidic molecular sieve catalysts, metal oxide catalysts are less prone to deactivation by coking due to their mild acid-base properties. Several metal oxides (Al2O3, MgO, CaO, CuO, Fe2O3, NiO, ZnO, ZrO2, TiO2 and CeO2) were selected for mild catalytic pyrolysis of lignin and compared with molecular sieve catalysts (MCM-41, HZSM-5, ZSM-5). Among the metal oxide catalysts studied, CuO, Fe2O3 and TiO2 inhibited the formation of acids/alcohols (1–2%) and promoted the production of hydrocarbons (15.31%, 20.17% and 28.83%, respectively). Especially when TiO2 catalyst was added, the proportion of hydrocarbons reached the highest (28.83%), but it inhibited the production of phenols (3.3%). The presence of CuO promoted the production of phenols (9.70%), showing a good deoxidation performance. Compared with the oxide catalysts, the addition of molecular sieve catalysts only resulted in 2 ~ 3% phenols. Compared with strongly acidic molecular sieve catalysts, metal oxide catalysts showed certain catalytic activity in deoxidation and cracking, and showed some advantages in the formation of phenols.

Optimizing elicitation strategy of salicylic acid for flavonoid and phenolic production of fed-batch cultured Oplopanax elatus adventitious roots.

Oplopanax elatus is a valuable medicinal plant, but its plant resource is lacking. Adventitious root (AR) culture of O. elatus is an effective way for the production of plant materials. Salicylic acid (SA) exerts enhancement effect on metabolite synthesis in some plant cell/organ culture systems. To clarify the elicitation effect of SA on fed-batch cultured O. elatus ARs, this study investigated the effects of SA concentration, and elicitation time and duration. Results showed that flavonoid and phenolic contents, and antioxidant enzyme activity obviously increased when the fed-batch cultured ARs were treated with 100μM SA for 4 days starting on day 35. Under this elicitation condition, total flavonoid and phenolic contents reached 387 rutin mg/g DW and 128 gallic acid mg/g DW, respectively, which were significantly (p<0.05) higher than those in the SA-untreated control. In addition, DPPH scavenging and ABTS+ scavenging rates, and Fe2+ chelating rate also greatly increased after SA treatment, and their EC50 values were 0.0117, 0.61, and 3.34mg/L, respectively, indicating the high antioxidant activity. The findings of the present study revealed that SA could be used as an elicitor to improve the flavonoid and phenolic production in fed-batch O. elatus AR culture.

A 3D porous Fe-MoS2/CMF catalyst for high-efficient catalytic reforming of lignin vapor by microwave irradiation

Improving the yield of target monophenols plays an important role in increasing the economic competitiveness of lignin valorization. In this study, a 3D porous Fe-MoS2/CMF catalyst with nanoflower microstructure was successfully fabricated by a simple one-step hydrothermal method. The catalytic depolymerization of the lignin β-O-4 model showed that Fe-doping increased the efficiency of the catalytic conversion reaction and promoted the cleavage of the β-O-4 ether bond, in agreement with theoretical calculations. Reforming of lignin depolymerization vapor revealed that the Fe-MoS2/CMF catalysts significantly improved the selectivity of phenol (30.01 wt%) and styrene (16.34 wt%) with the decrease of oligomers. Moreover, finite element simulation showed that the Fe-MoS2/CMF catalysts can also enhancing the local thermal effect by creating hot spots on the surface, thereby facilitate the lignin vapor reforming. Consequently, this work provides a promising method for the efficient production of phenol and styrene from lignin using bimetallic nanoarray microwave responsive catalyst.

A Distinct Mode of Strain-Driven Cyclic Allene Reactivity: Group Migration to the Central Allene Carbon Atom.

Strained cyclic allenes are reactive species that can be trapped in a variety of complementary fashions that capitalize on their inherent high potential energy. 1,2,4-Cyclohexatrienes represent a subclass of allenes that, notably, can be conveniently generated by a net [4 + 2] cycloaddition within a 1,3-enyne bearing a tethered alkyne via a tetradehydro-Diels-Alder reaction. A limitation to the use of this type of thermally generated cyclic allene as a construct for the introduction of molecular complexity is their propensity to isomerize to benzenoids via a simple net 1,5-hydrogen atom migration. We have discovered that when the enyne component of the substrate is modified as an enol silyl ether (or an enol ester), migration of the silyl (or acyl) group can become the predominant event. Specifically, an appropriately electrophilic group can migrate from the O atom to the central allene carbon adjacent to the 1-siloxy(acyloxy) substituent. This process leads to highly substituted phenolic products (e.g., o-silyl phenols) following tautomerization of the intermediate cyclohexa-2,4-dienone. Experimental studies show that this novel mode of reactivity is general; DFT studies reveal the unimolecular nature of the group migration.

Non-Noble Metal Aromatic Oxidation Catalysis: From Metalloenzymes to Synthetic Complexes

The development of selective aromatic oxidation catalysts based on non-noble metals has emerged over the last decades, mainly due to the importance of phenol products as intermediates for the generation of pharmaceuticals or functional polymers. In nature, metalloenzymes can perform a wide variety of oxidative processes using molecular oxygen, including arene oxidations. However, the implementation of such enzymes in the chemical industry remains challenging. In this context, chemists have tried to mimic nature and design synthetic non-noble metal catalysts inspired by these enzymes. This review aims at providing a general overview of aromatic oxidation reactions catalyzed by metalloenzymes as well as synthetic first-row transition-metal complexes as homogeneous catalysts. The enzymes and complexes discussed in this review have been classified based on the transition-metal ion present in their active site, i.e., iron, copper, nickel, and manganese. The main points of discussion focus on enzyme structure and function, catalyst design, mechanisms of operation in terms of oxidant activation and substrate oxidation, and substrate scope.

Comparative effects of mesopores and framework defects on the deactivation of HZSM-5 catalyst during alkylphenol dealkylation

The dealkylation of alkylphenols over HZSM-5 is regarded as a promising way for the production of phenol from both fossilized and raw lignocellulose-derived oils. However, the pure microporous HZSM-5 deactivates fast due to coking. Although the introduction of mesopores into microporous HZSM-5 can enhance the catalyst stability, the relationship between the catalytic performance and changed properties caused by alkaline treatment remains ambiguous. In this study, the coke analysis reveals that the mesopore introduction primarily promotes the formation of external coke by providing additional diffusion paths for coke precursors. However, the phenolates bound to the Lewis acid sites generated on external surface facilitates the deposition of external coke, the total coke amount is thus not significantly impacted. Furthermore, the reduction of internal silanols (Si-related framework defects) and Lewis acid sites (Al-related framework defects) by ammonium hexafluorosilicate treatment declines the total amount of coke and alleviates catalyst deactivation.

NaOH solution-assisted pyrolysis of waste polycarbonate for co-production of phenolic compounds and supercapacitor material

A green way for the sustainable utilization of waste polycarbonate (PC) was developed, i.e., NaOH solution-assisted pyrolysis to co-produce phenolic compounds and supercapacitor material. A lab-scale setup was employed for the pyrolysis of PC to explore the regulation effects of NaOH concentration and pyrolytic temperature on the production of phenol and 4-isopropenylphenol (IPP). The yields of phenol and IPP were up to 35.3 wt% and 29.9 wt% at 600 °C and NaOH concentration of 0.5 mol/L, which were much higher than those from pure PC pyrolysis (7.2 wt% and 3.6 wt%). Furthermore, the pyrolytic solid residue was directly subjected to the high-temperature activation to prepare activated carbon, which could be used as a supercapacitor material with an outstanding specific gravimetric capacitance of 182.1 F/g at 1 A/g.

Total Phenolic, Flavonoids Contents, and Antioxidant Activities in The Stems and Rhizomes of Java Cardamom as Affected by Shading and N Fertilizer Dosages

Java cardamom is an herbal medicinal plant known as the "queen of spices." This research aims to determine the influence of shading and nitrogen fertilizer dose on the total phenolics, flavonoids, and antioxidant activity of Java cardamom stems and rhizomes. The study employed a split-plot design with two factors: the level of shading (0, 25, 50, and 75%) as the main plot and the dosage of nitrogen (N) fertilizer (0, 0.9, and 1.36 g polybag-1) as the subplots. Twelve months after planting, the rhizome and stem dried powder were extracted using the sonication-maceration technique with ethanol as the solvent. The 75% shading affected the more outstanding production of total phenolics (1.65 ± 0.59 mg GAE g-1 DW), DPPH antioxidant (4.95 ± 0.50 µmol TEAC g-1 DW), and FRAP antioxidant (8.94 ± 2.56 µmol TEAC g-1 DW) activities of the rhizomes cultivated with 0 g/polybag N in comparison to the stems of the plants. Contrary to phenolics and antioxidant activities, total flavonoids cultivated at 0% shading with 1.36 g polybag-1 N of the stems increased concentration than the rhizomes. The results indicated that the 75% shading affected the Java cardamom rhizome's phenolic content and antioxidant activities.

Pomoea batatas(L.) Lam. (Convolvulaceae) as a source of polyphenols with antitumor activity and prospects for in vitro production using chemical elicitors -A Review

Ipomoea batatas has an enormous projection as functional food and it is an excellent source of anticancerous or chemopreventive substances. Plant tissue culture offers the possibility of inducing secondary metabolites production under controlled conditions and their projection for industrial purposes. To establish the state of knowledge regarding advances in polyphenols chemical elicitation from I. batatas and the possibility of producing potential anticancerous compounds in vitro culture systems, a bibliometric review and an analysis of information available until 2020 were made. Results showed that research field on which review was carried out is current and has a growing trend; however, sweet potato cell suspensions evaluation is scarce. Elicitation using compounds with hormonal effects represents a good alternative to increase phenolic acids production in this species. Advances in phenols elicitation from sweet potato cell suspensions will require search superior genotypes, and associating this knowledge with in vivo and in silico studies.

Catalytic transalkylation of alkylphenol to phenol in supercritical benzene fluid over MFI type zeolite in a fixed-bed reactor: Diffusion and reaction limitations

The transalkylation reaction kinetics of 4-propylphenol (ppp) and supercritical benzene (11.0 MPa) over H-MFI-type zeolites, using different particle size and Si/Al ratios, in the temperature range of 623 K – 673 K, was studied in a fixed bed reactor.A 1st order parallel reaction kinetic model was evaluated for transalkylation of ppp and benzene, and ppp isomerization. High conversion of ppp and phenol production with low coke formation was obtained with nanometer-sized particles, transalkylation reaction proceeded under reaction control conditions.Thiele modulus was calculated to evaluate internal diffusion limitations, clearly observed when increasing the particle size (activation energies over micrometer- and nanometer- sized particles, 60.0 and 120 kJ mol−1, respectively). Nonetheless, decreasing the particle size (2.00 × 103 to 100 nm) successfully reduced the internal diffusion limitations and increased the selectivity of the reaction.The study showed that increasing Al sites in the framework not only increases the specific constant rate of the reaction, but also its selectivity, with a low impact on the effectiveness of the reaction according to the Thiele Modulus equation and the particle size obtained.

Catalytic pyrolysis of pine sawdust over activated carbon-supported Fe for phenol-rich bio-oil

In this study, catalytic pyrolysis was used to decompose pine sawdust into platform chemicals. A strategy to produce valuable alkylphenol compounds through catalytic pyrolysis was proposed by introducing surface active groups (metal iron species and oxygen-containing groups) to strengthen biochar-based catalyst. The results showed that the multiple active sites jointly promoted the further reaction of the pyrolytic intermediates absorbed on the Fe-activated carbon catalyst during the catalytic pyrolysis, and the furans and ketones, etc., were all converted into phenolic compounds under the action of fresh Fe-activated carbon catalyst (AC-Fe-1). After the fifth recycling of the catalyst (AC-Fe-5), the catalytic performance of deactivated catalyst could be well recovered by the simple regeneration treatment, showing a good selectivity for phenol production (AC-Fe-CO2, 87 %). Compared with non-catalytic pyrolysis, the relative content of phenolic substances generated by Fe-activated carbon in the catalytic pyrolysis increased from 15.42 % to more than 90 %, mainly methyl phenolics such as phenol, 2-methylphenol and 3-methylphenol. By contrast, the deactivation of Fe-activated carbon catalyst was not significant and the selectivity to phenol increased to 73.62 %─80.01 %, while the original activated carbon (without adding iron species) was seriously deactivated and the selectivity to phenol decreased by 38.26 %.

Efficient Lignin Depolymerization Process for Phenolic Products with Lignin-Based Catalysts and Mixed Solvents

Due to their diverse functional groups and structural composition, carbon-based catalysts exhibit superior performance in various catalytic reaction systems, such as hydrogenolysis, hydrogenation, and oxidation. Herein, we propose an effective strategy of lignin liquid-phase depolymerization by applying the designed lignin-based carbon catalysts to produce aromatic chemicals. A series of Ni–Mo bimetallic carbon-based catalysts were synthesized to explore the effect of different preparation methods on the catalytic activity. The results demonstrate that the embedded Ni–Mo/C-WMO catalyst with multi-active sites of Ni, MoO3, and Mo2C results in a prominent catalytic effect on lignin depolymerization. The Ni–Mo/C-WMO catalyst can achieve a lignin conversion of 87.62% with a 42.25% monophenol yield in the methanol and water system. With the synergistic contribution of multiple active sites of the catalyst and the mixed-solvent system (water, methanol, and 1, 4-dioxane), a remarkably high yield of 62.95% of mono-phenolic compound was achieved at 260 °C and 3 MPa N2 with a reaction time of 4 h. The selectivity of 2-methoxy-4-methylphenol and 2-methoxy-4-ethylphenol in liquid products was 40.85 and 36.42%, respectively. Vanillin, a typical product from lignin depolymerization reported in the literature, was further degraded to monophenol in this system. The outcomes also confirmed that the in situ hydrogen production system of methanol and water coupled with 1,4-dioxane facilitated the lignin depolymerization significantly.

Exogenous melatonin induces phenolic compounds production in Linum album cells by altering nitric oxide and salicylic acid

Melatonin is a pleiotropic molecule that can influence various aspects of plant performance. Recent studies have exhibited that it mediates plant defensive responses, probably through managing redox homeostasis. We tried to track the regulatory effects of melatonin on the antioxidant machinery of Linum album cell culture. To this, different concentrations of melatonin were applied, and the oxidative status of cells was investigated by measuring the levels of oxidative molecules and antioxidant agents. The results showed that H2O2 content did not change at the low melatonin levels, while it increased at the high concentrations. It can be correlated with the low melatonin dosages capacity to remove excessive amounts of H2O2, while the high melatonin dosages exhibit toxicity effects. In contrast, the NO enhancement occurred at 50 μM melatonin, proposing its role in triggering melatonin-induced defensive responses. The MDA results stated that NO led to oxidative stress in melatonin-treated cells at 50 μM melatonin. Antioxidant enzyme POD was activated by melatonin treatment, while SOD enzyme behaved reversely which can explain the changes in the H2O2 level. In addition, the analysis of the phenolics profile showed that the contents of phenolic acids, flavonoids, and lignans enhanced following an increase in PAL enzyme activity. The increased level of phenolic hormone SA can indicate that melatonin affects the defensive responses in L. album cells through a SA-dependent pathway. In general, it seems that melatonin, by modulating NO and SA levels, can induce the activity of antioxidant enzymes and the production of phenolics, especially lignans, in L. album cells.

Phenolic Compound Production Increased In Vitro Regenerated Cichorium intybus L.

Chicory (Cichorium intybus L.) is a low-height perennial or biennial herb from the family of Asteraceae. Investigation of different in vitro regeneration strategies of Cichorium intybus and increasing the number of secondary metabolites in vitro regenerated plant samples were the aims of the research. Callus and plant regenerations were achieved in basal plant growth media supplemented with plant growth regulators (PGRs). Whole plant regeneration was carried out by direct organogenesis from leaf explant in Murashige and Skoog (MS) and B5 media supplemented with naphthalene acetic (NAA) acid and indole-3-butyric acid (IBA). The highest callus quantity was produced in MS medium supplemented with indole-3-acetic acid (IAA) and benzyl amino purine (BAP). The combination and concentrations of PGRs used in MS and B5 media not only provided root and shoot formation with callus, but also caused a change in the amounts of phenolic components. In addition, some PGRs used caused an increase in the number of phenolic compounds in callus and shoots developed from the leaf explant. When plants that grow in vitro and in vivo are compared with each other, it has been determined that plants grown in vivo contain higher amounts of some phenolic compounds. In vivo and in vitro samples were extracted in ethanol/water (80:20 v/v). The analysis of phenolic compounds (caftaric, chicoric, and chlorogenic acids and esculin) were performed in high-performance liquid chromatography (HPLC) and inulin was in UV spectrophotometry. The caftaric and chlorogenic acids and inulin concentrations were higher in vivo samples than that in vitro. Contrarily, esculin, and chicoric acid concentrations were higher in the in vitro regenerated samples. The higher concentration of valuable compounds in the in vitro regenerated samples, especially in callus tissue, gives hope for large-scale production of secondary metabolites under laboratory conditions.

Improved Light Hydrocarbon, Furans, and BTEX Production from the Catalytic Assisted Pyrolysis of Agave salmiana Bagasse over Silica Mesoporous Catalysts

The pyrolysis of the biomass Agave salmiana bagasse (10 K/min, ambient to 700 °C) was investigated in the absence and presence of Aerosil and MCM-41 catalysts. MCM-41 was synthetized using a typical hydrothermal method and characterized with XRD, SAXS, SEM, TEM, and nitrogen physisorption to confirm the presence of unidimensional 3.4 nm diameter pores. Pyrolysis products were monitored online with mass spectrometry (MS), analyzing the production of 29 different compounds, clustered in several groups, namely, olefins (ethene, 2-butene, 1,3-butadiene), oxygenated compounds (methanol, 2-methylbutanol, acetic acid), furan derivatives (furan, furfural, 2-methylfurane), and aromatic compounds (BTEX). Complete decomposition of the cellulose and hemicellulose content of the biomass was observed at temperatures below 400 °C. Lignin decomposition was completed by 550 °C. Catalyst-assisted pyrolysis showed reduced acetic acid and methanol formation with Aerosil and MCM-41. The use of Aerosil does not affect the overall production of olefins, yet increases benzene yield, while reducing the production of phenol, furan, and furan derivatives. With MCM-41, there is increased production of olefins, furan, furan derivatives, cyclohexanone and BTEX, yet phenol production is decreased. At temperatures below 400 °C, the product formation pattern is comparable to non-catalytic pyrolysis.

Essential oils prolonged the cut carnation longevity by limiting the xylem blockage and enhancing the physiological and biochemical levels.

Postharvest characteristics, such as vase life and antimicrobial preservation of commercial cut flowers are some of the major determinants of their market value worldwide. Extending vase life while restricting microbial proliferation in cut flowers is an important challenge faced by floricultural researchers. This study evaluates the preservative efficiency of different essential oils used as additive solutions in prolonging the longevity of carnation cv. Madam Collette cut flowers and restricting microbial growth in them. Cut carnations were treated with four essential oils: geranium, thyme, marjoram, and anise at concentrations of 0, 25, 50, and 75 mg/L. While treatment with all the essential oils prolonged the longevity of the cut flowers, thyme and marjoram oils were most effective at concentrations of 50 mg/L each. The vase life of thyme-treated and marjoram-treated carnations almost doubled to 18.5 days and 18.25 days, respectively, as compared to untreated flowers. Treatment with essential oils also led to an increase in water uptake by the cut flowers enhancing their relative water content (RWC). It also restricted the sharp decline of chlorophyll and total carbohydrates content of the flowers during their vase life period. Morphological features of the stem bases of treated and untreated carnations were analyzed using scanning electron microscopy (SEM). The stem ends of geranium and anise-treated carnations showed less bacterial growth than untreated flowers and no apparent xylem blockage was observed even after nine days of treatment. Furthermore, the presence of essential oils also reduced lipid peroxidation and free radical generation as observed by malondialdehyde (MDA) and H2O2 quantification, respectively. It also led to increased production of total phenols leading to enhanced membrane stability. The use of thyme and marjoram essential oils as antimicrobial preservatives and green antioxidants appears to have promising applications in both the industrial and scientific sectors.

Isolation of Bioactive Metabolites from Soil Derived Fungus-Aspergillus fumigatus

Fungi produce numerous secondary metabolites with intriguing biological properties for the health, industrial, and agricultural sectors. Herein, we report the high-yield isolation of phenolic natural products, N-formyl-4-hydroxyphenyl-acetamide 1 (~117 mg/L) and atraric acid 2 (~18 mg/L), from the ethyl acetate extract of the soil-derived fungus, Aspergillus fumigatus. The structures of compounds 1 and 2 were elucidated through the detailed spectroscopic analysis of NMR and LCMS data. These compounds were assayed for their antimicrobial activities. It was observed that compounds 1 and 2 exhibited strong inhibition against a series of fungal strains but only weak antibacterial properties against multi-drug-resistant strains. More significantly, this is the first known instance of the isolation of atraric acid 2 from a non-lichen fungal strain. We suggest the optimization of this fungal strain may exhibit elevated production of compounds 1 and 2, potentially rendering it a valuable source for the industrial-scale production of these natural antimicrobial compounds. Further investigation is necessary to establish the veracity of this hypothesis.

Kinetic and thermodynamic analysis of biomass catalytic pyrolysis with nascent biochar in a two-stage reactor

The interaction between nascent biochar and volatiles is critical and complex during the biomass thermochemical conversion processes. Despite various experiments showing a link between pyrolysis products and biochar catalysts, it is difficult to interpret the detailed mechanistic for the interplay between kinetic and thermal effects. To improve the understanding of the effect of nascent biochar catalyst on the pyrolysis of biomass, both kinetic and thermodynamic analysis was carried out in this work. Several catalytic processes were designed to analyze the catalytic reactivity combined with the online characterization of TG-MS and TG-FTIR. The catalytic pyrolysis kinetics analysis revealed that the particle size exhibited limited influence on the pyrolysis activation energy and product evolution. However, the nascent biochar could effectively decrease the pyrolytic activated energy of corn cob and facilitate the decomposition of lignin. Furthermore, the biochar promoted the conversion from CO2 to CO and the production of H2. In addition, the nascent biochar effectively improved the purity of the pyrolysis product and reduced the selectivity of acid, alcohol and ester. In-situ and ex-situ catalysis achieved high selectivity of phenolic products, whose selectivity reached 46.71% and 55.96%, respectively. Hybrid feeding catalysis attained significant productions of ethers, achieving the selectivity of 48.88%.