Adsorption Of Glycerol Research Articles

Long-Term Selective Photoelectrochemical Glycerol Oxidation via Oxygen Vacancy Modulated Tungsten Oxide with Self-Healing.

The photoelectrochemical selective oxidation of biowaste glycerol into the high value-added material, along with hydrogen production, holds significant promise for advancing renewable and sustainable energy technologies. Here, the surface oxygen state of tungsten oxide is modified to selectively oxidize glycerol into glyceraldehyde, a high-value-added material, and the selectivity is maintained over a prolonged period using the photo-stimulated self-recovery capability. The surface-coordinated photoelectrode exhibits high charge transfer efficiency to glycerol and favorable glycerol adsorption capacity, enabling the selective conversion of glycerol. At 1.2 VRHE in a 2m glycerol electrolyte adjusted to pH 2, the tungsten oxide photoelectrode achieves a photocurrent density of 2.58mA cm-2 and a production rate of 378.8mmol m-2h-1 with selectivity of 86.1%. The high selectivity is preserved for 18 h by utilizing the self-healing capability of tungsten oxide to restore initial states modified by photoelectrochemical oxidation. This work sheds light on the design of highly efficient metal oxide photoelectrodes for selective biomass oxidation over extended periods.

Manipulating Pt-ZnO interface for fast selective oxidation of glycerol to glyceric acid in base-free medium

Fine constructing the desirable active sites of catalysts is critical for the efficient polyol oxidation. Herein, we conceptually manipulate the Pt-ZnO interfacial active site instead of traditional Pt-Pt active site to isolate oxidation reaction and carboxylic acid desorption for fast selective oxidation of glycerol to glyceric acid in base-free medium. Multiple characterizations (including in-situ spectroscopy, reaction kinetics and density functional theory calculation, etc.) revealed that the strong electronic delocalization of Pt d-partial and the synergistic effect of ZnO adsorption could collectively strengthen the adsorption of glycerol and then promote the C-H bond of RCH2O intermediate in the primary hydroxyl group oxidation, resulting in higher catalytic activity over the Pt-ZnO interface. Meanwhile, the abundant oxygen vacancy of well-dispersed nano-ZnO could preferentially adsorb the formed glyceric acid product, preventing the coverage of the efficient Pt-Pt and Pt-O-Zn active sites by carboxylic acid products. Such tailored interface strategy achieves 80.4 % glycerol conversion and 84.6 % glyceric acid selectivity in only 1 h, and the turnover frequency could also be as high as 1338.4 h−1 over the optimal Pt/ZnO-MCM-41 (200) catalyst. The methodology provided here constitutes a promising basis for highly efficient polyol oxidation catalysis under mild and green conditions.

Selective oxidation of glycerol mediated by surface plasmon of gold nanoparticles deposited on titanium dioxide nanowires

This paper describes an alternative method for the in situ synthesis of gold nanoparticles (AuNPs) with a particle size of less than 3 nm, using nanoreactors formed by reverse micelles of 1,4-bis-(2-ethylhexyl) sulfosuccinate sodium (AOT) and nanoparticle stabilization with l-cysteine, which favor the preparation of nanoparticles with size and shape control, which are homogeneously dispersed (1% by weight) on the support of titanium dioxide nanowires (TNWs). To study the activity and selectivity of the prepared catalyst (AuNPs@TNWs), an aqueous solution of 40 mM glycerol was irradiated with a green laser (λ = 530 nm, power = 100 mW) in the presence of the catalyst and O2 as an oxidant at 22 °C for 6 h, obtaining a glycerol conversion of 86% with a selectivity towards hydroxypyruvic acid (HA) of more than 90%. From the control and reactions, we concluded that the Ti–OH groups promote the glycerol adsorption on the nanowires surface and the surface plasmon of the gold nanoparticles favors the selectivity of the reaction towards the hydroxypyruvic acid.

Harnessing waste Pd-based powders contaminated with ZrO2 as efficient photoelectrocatalysts for glycerol oxidation

Pd-based electrocatalysts synthesized by mechanical alloying were contaminated with ZrO2 due to an excessive process time that wore down the ZrO2 milling media balls. Instead of disposing the materials and taking into account the synergistic properties that Pd-based materials and ZrO2 could present since ZrO2 is an active oxide with photocatalytic activity, these samples were characterized through physicochemical and electrocatalytic tests, to finally be used as non-reported Pd-ZrO2-based (photo)electrocatalysts for the glycerol oxidation reaction (GOR). XRD measurements confirmed the metals alloy formation and the presence of zirconium oxide to obtain the bimetallic composites PdCo/ZrO2, PdNi/ZrO2, and PdRu/ZrO2, as well as the trimetallic PdRuCo/ZrO2 and PdRuNi/ZrO2. Physicochemical analysis showed that PdRuNi/ZrO2 presented the smallest crystallite size (14.55 nm) and the highest surface area (8.76 m2/g). Photoluminescence measurements also show that PdRuNi/ZrO2 presented the lowest emission signal, which indicates a lower charge carrier’s recombination rate. XPS measurements demonstrate the presence of different metal oxide species in alkaline medium responsible for electrostatic interactions that improve the glycerol adsorption onto the metallic centers. Electrochemical tests showed high stability for all the composites; however, the analysis of the capacitive region allowed us to calculate the electrochemical surface area (ECSA), PdRuNi/ZrO2 gave the highest value (above 7 cm−2). Confirming the results mentioned above, PdRuNi/ZrO2 showed the highest activity to carry out the electrochemical oxidation of glycerol. Regarding photoactivity, the Pd-ZrO2-based composites presented a glycerol oxidation increase up to 17 % when they were light-irradiated through a photoelectrocatalytic arrangement. PdRuNi/ZrO2 seems to be a promising material to perform the electro- but also the photoelectro- GOR in alkaline medium.

Boric acid-modified activated carbon for glycerol removal from high-salt wastewater

Epoxy resin production wastewater contains glycerol and NaCl, which cause high energy consumption and environmental pollution during wastewater treatment. Therefore, the adsorption of glycerol on boric acid in low-temperature modified activated carbon was investigated for the first time. Under the optimum conditions of a modification temperature of 80℃, a mass ratio of boric acid to activated carbon of 1:1, and a modification time of 6 h, the modification of activated carbon was realized. It was found that the removal of glycerol by activated carbon before and after modification was found to be 0.10 % and 99.67 % (10 °C), indicating that boric acid endows activated carbon with a stronger ability to adsorb glycerol; The higher the pH of the wastewater, the higher the removal rate of glycerol, while the salt content of the wastewater has little effect. This study used batch adsorption to show that modified activated carbon could adsorb up to 1100 mg g−1 of glycerol, which was in line with the proposed pseudo-second-order kinetic model. After 8 cycles of adsorption and desorption, the modified activated carbon lost only 12.46 % of the adsorption capacity. Combined with the results, the existence of boron hydroxyl groups on activated carbon is the key to glycerol adsorption.

Combustion Behavior of Cellulose Ester Fibrous Bundles from Used Cigarette Filters: Kinetic Analysis Study.

This study is focused on the detailed examination of the combustion properties and kinetic analysis of a cellulose acetate fibrous bundle (CAFB), separated from used cigarette filters. It was shown that the faster rate of CAFB heating allows a large amount of heat to be supplied to a combustion system in the initial stages, where the increase in heating rate has a positive response to ignition behavior. The best combustion stability of CAFB is achieved at the lowest heating rate. Through the use of different kinetic methods, it was shown that combustion takes place through two series of consecutive reaction steps and one independent single-step reaction. By optimizing the kinetic parameters within the proposed reaction models, it was found that the steps related to the generation of levoglucosenone (LGO) (by catalytic dehydration of levoglucosan (LG)) and acrolein (by breakdown of glycerol during CAFB burning-which was carried out through glycerol adsorption on a TiO2 surface in a the developed dehydration mechanism) represent rate-controlling steps, which are strongly controlled by applied heating rate. Isothermal predictions have shown that CAFB manifests very good long-term stability at 60 °C (which corresponds to storage in a sea shipping container), while at 200 °C, it shows a sudden loss in thermal stability, which is related to the physical properties of the sample.

Electric Field Redistribution Triggered Surface Adsorption and Mass Transfer to Boost Electrocatalytic Glycerol Upgrading Coupled with Hydrogen Evolution

AbstractElectrocatalytic glycerol oxidation reaction (GOR) stands out as an economical and prospective technology to replace oxygen evolution reaction for co‐producing high‐valued chemicals and hydrogen (H2). Regulating the adsorption of glycerol (GLY) and hydroxyl (OH) species is of great significance for improving the GOR performance. Herein, a hierarchical p–n heterojunction by combining Co‐metal organic framework (MOF) nanosheets with CuO nanorod arrays (CuO@Co‐MOF) is developed to realize the optimization on GOR. Specifically, CuO@Co‐MOF electrode exhibits superior performance with a conversion of 98.4%, formic acid (FA) selectivity of 87.3%, and Faradaic efficiency (FE) of 98.9%. The flow‐cell system with the bifunctional CuO@Co‐MOF electrode for pairing GOR with the hydrogen evolution reaction (HER) reveals better energy conversion efficiency. Experimental results and theoretical calculations unravel the redistributed electric field by introducing Co‐containing species that contribute to the improved performance, which not only enhances the OH adsorption but also modulates the excessive GLY adsorption of CuO, thus reducing reaction energy barriers of FA desorption. Simultaneously, finite element analysis reveals that the novelty hierarchical structure can increase the concentration of OH− and facilitate the mass transfer of OH− in the solution.

High DHA selectivity and low-cost electrode for glycerol oxidation: CuO regulates MnO2 electron density to promote DHA desorption

Glycerol oxidation reaction (GOR) is an attractive alternative reaction for oxygen evolution reaction (OER) in the electrochemical water splitting and can be used to generate high-value products. However, the development of GOR electrocatalysts with high catalytic activity and low cost is challenging. In this research, a self-supported copper-manganese electrode (MnO2-CuO/CF) was developed, which attains a current density of 10.7 mA cm−2 at a low potential of 1.3 V, while yielding 1,3-dihydroxyacetone (DHA), with a selectivity of 60%. DFT calculations reveal the synergistic effect between CuO and MnO2, enhancing glycerol adsorption. Additionally, the overlap configuration of CuO and MnO2 results in a lower electron density on MnO2, preventing further oxidation and increasing DHA selectivity. By coupling GOR and water electrolysis, the dual output of high value-added organic products and high-purity hydrogen can be realized, which provides a new idea for green hydrogen production and electrochemical synthesis of high value-added chemicals.

Adsorption of Glycerol at Brønsted Sites in Mordenite: a Density Functional Theory Study

Adsorption of Glycerol at Brønsted Sites in Mordenite: a Density Functional Theory Study

Mathematical modeling by fractional calculus applied to separation processes

Process modeling is a way of representing real problems through equations and while the traditional models of mass and heat transfer processes consider the transient term as a first-order derivative, fractional order modeling is applied to verify that the order of the derivative of the transient term would not be represented by a non-integer number. In this context, the objective of this work was to apply fractional calculus to the kinetics study of adsorption and extraction processes and compare the results obtained with traditional models. The Caputo derivative was used to solve the proposed equations, and the analyzed processes were the adsorption of glycerol for biodiesel at different temperatures and the solid–liquid extraction of antioxidant compounds from corn for different proportions of solvent. For the adsorption, the fractional order model was compared with the pseudo-first, pseudo-second, and first-order models, and the fractional order model represented adsorption satisfactorily, with method efficiencies of 0.9603 and 0.9433 for the temperatures of 45 °C and 60 °C, respectively, while the performance of traditional models depends on the mechanisms that control the process. In addition, the α values obtained with the fractional order model were less than 1, indicating that glycerol adsorption does not follow an integer order derivative and implies that the adsorption exhibits a level of complexity that is not fully characterized by traditional models. The extraction of antioxidant compounds was analyzed and compared with the first-order and So and MacDonald’s models. It was verified that the derivative order values for the fractional order model were close to 1 and, therefore, the behavior is similar to the first order model and with indications that diffusion occurs as described by Fick’s law of diffusion. Thus, the results indicated that fractional order modeling can be used efficiently to describe chemical engineering processes such as adsorption and extraction.

Catalytic evaluation of Pd-promoted Ni-Co/Al2O3 catalyst for glycerol dry reforming: Assessing hydrogen-rich syngas production, kinetics and mechanisms

The Pd-promoted Ni-Co bimetallic catalysts were prepared using ultrasonic-assisted impregnation, and their performance was subsequently assessed in a fixed-bed reactor. The catalyst's performance was evaluated in glycerol dry reforming (GDR) over a range of temperatures, from 873 K to 1173 K and reactant partial pressures ranging from 10 kPa to 40 kPa. The results indicated that as the temperature was raised from 873 K to 1073 K, there was a noticeable rise in both reactant conversion and product yield. However, beyond 1173 K, catalytic performance declined due to glycerol thermal cracking and sintering of the support at high temperatures, resulting in increased carbon formation. The presence of excessive CO2 was found to suppress glycerol adsorption on the catalyst surface, causing a decline in catalytic activity with a CO2 partial pressure of more than 20 kPa, regardless of reaction temperature. Additionally, excess CO2 were found to enhance the side reaction, particularly reverse water-gas shift (RWGS) that related to produce intermediate H2O. Similarly, the glycerol partial pressure was found to impact catalytic performance, with a decrease in performance beyond 20 kPa due to competing reactants between glycerol and CO2. According to the Langmuir-Hinshelwood kinetic mechanism, a dual molecular adsorption site for glycerol and CO2 was appropriate for this GDR reaction, with an associated activation energy of 47.3 kJ mol−1. The GDR reaction was identified as a kinetically controlled process due to its high activation energy, more than 25 kJ mol−1. The plausible mechanism of GDR over Pd-Ni-Co/Al2O3 occurred through the dissociative-type of adsorption of on active metallic sites of the catalysts for both reactant (glycerol and CO2). This was further facilitated by the bifunctional mechanisms based on H2 generated from dissociative adsorption involving both catalyst's basic sites and metallic active sites. This was ascribed to the highly dispersed and strong interaction between metal-support in Pd-promoted Ni-Co bimetallic catalysts.

Ambient γ-Rays-Mediated Noble-Metal Deposition on Defect-Rich Manganese Oxide for Glycerol-Assisted H2 Evolution at Industrial-Level Current Density.

Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy-saving hydrogen production. Herein, we report an ambient and controllable γ-ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect-rich manganese oxides (M@MnO2-x , M=Ru, Pt, Pd, Ir) for glycerol-assisted H2 evolution. Benefiting from the strong penetrability of γ-rays, nanoparticles and defect supports are formed simultaneously and bridged by metal-oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru-O-Mn bonds activate the Ru and Mn sites in Ru@MnO2-x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm-2 in a continuous-flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2-x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect-rich MnO2 support promotes the dissociation of H2 O, while the defect-regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol-assisted hydrogen production.

Ambient γ‐Rays‐Mediated Noble‐Metal Deposition on Defect‐Rich Manganese Oxide for Glycerol‐Assisted H2 Evolution at Industrial‐Level Current Density

AbstractDeveloping novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy‐saving hydrogen production. Herein, we report an ambient and controllable γ‐ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect‐rich manganese oxides (M@MnO2‐x, M=Ru, Pt, Pd, Ir) for glycerol‐assisted H2 evolution. Benefiting from the strong penetrability of γ‐rays, nanoparticles and defect supports are formed simultaneously and bridged by metal‐oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru−O−Mn bonds activate the Ru and Mn sites in Ru@MnO2‐x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm−2 in a continuous‐flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2‐x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect‐rich MnO2 support promotes the dissociation of H2O, while the defect‐regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol‐assisted hydrogen production.

Achieving high selectivity in photoelectrochemical oxidation of glycerol on WO3 nanosheets coupled with TiO2 nanorods arrays

Developing highly efficient photocatalysts for the selective conversion of glycerol into valuable chemicals is of paramount importance. However, achieving the selective oxidation of glycerol to valuable C3 chemicals poses significant challenges. In this study, we employed a two-step hydrothermal method to synthesize a photoelectrochemical (PEC) photocatalyst composed of WO3 nanosheets assembled on TiO2 nanorod arrays. The synergistic interaction between WO3 and TiO2 led to outstanding performance in the selective conversion of glycerol (GLY) into glyceraldehyde (GLD) and 1,3-dihydroxyacetone (DHA). The photocatalyst achieved a selectivity of 61% for GLD and 92% for GLD + DHA, with formation rates of 319 and 160 mmol m-2h−1, respectively. Despite the excellent charge transfer properties of TiO2 nanorods, they displayed suboptimal glycerol conversion rates and tended to oxidize glycerol into lower-value products. The introduction of WO3 nanosheets in the Z-scheme heterojunction improved charge separation, enhanced glycerol adsorption and facilitated the desorption of GLD and DHA, thus improving the selectivity of GLD + DHA. This study unveils a promising approach to efficiently oxidize glycerol and demonstrates the crucial role of catalyst design in achieving selective and high-yield chemical transformations.

Single tungsten atom-modified Pt/Al2O3 to boost glycerol hydrogenolysis to 1,3-propanediol

Pt-WOx-based catalyst has been considered as a promising candidate for the conversion of glycerol to 1,3-propanediol, but the catalytic performance was quite susceptible to the structure and chemical state of WOx species. Herein, we develop a facile approach to construct the single-atom tungsten-doped Al2O3 with a low chemical state through in-situ migration of WO3 nanoparticles under the H2 atmosphere. The characterization results demonstrated that the tetrahedral W5+ could disperse and stabilize the platinum species more effectively, and exhibited stronger interaction with platinum than the octahedral W6+ species. The enhanced catalytic performance is attributed to the rich oxygen defects on in-situ generated tetrahedral WOx on the catalyst, which facilitated the construction of Pt-WOx interface and strengthened the synergetic effects between them. The analysis of structure-performance correlation revealed that the mono-dispersed tetrahedral W5+ species [(-O-)3W(=O)] played a pivotal role in tuning catalyst acidity and improving the catalytic performance, which assists the adsorption of glycerol and captures H for in-situ formation of Brønsted acid site, and ultimately affected the selectivity toward 1,3-PDO and catalytic activity.

Ethyl ester production with immobilized lipase in tin modified SBA‐15: Effect of the support characteristic and reaction conditions

AbstractThis study investigated the use of immobilized lipase in SBA‐15 and pore‐expanded SBA‐15 surface modified with tin, denoted as SnS23B (mean pore size of 21.6 nm) and SnS8B (with mean pore size of 9.6 nm), respectively, to produce ethyl esters. The effects of various reaction parameters, including biocatalyst type, oil (refined and degummed soybean oil), water addition, oil‐to‐ethanol molar ratio, immobilized lipase concentration, agitation speed, reaction temperature, and glycerol addition, were examined. The optimal conditions were found to be the use of SnS23B as the biocatalyst, degummed soybean oil as the substrate, 1% (w/w oil) water, 1:3 oil‐to‐ethanol molar ratio, 5% (w/w oil) immobilized lipase, 800 rpm agitation speed, and 25°C reaction temperature. The presence of glycerol negatively impacted the reaction. Under the optimal conditions, the mass percent of ethyl ester obtained was 98.2% ± 0.16. The immobilized lipase showed stability, as no lipase activity was detected upon removing the biocatalyst from the reaction. However, the biocatalyst lost 50% of its activity after 10 successive reactions, likely due to thermal deactivation and lipase inhibition caused be the adsorption of glycerol and other chemical species. Attenuated total reflectance analysis supported this hypothesis.

Study on the mechanism of adsorption and hydrophobic modification of glycerol monooleate/kerosene mixed collector on low-rank coal surface

A new collector (GK) consisting of GMO (glycerol monooleate)/kerosene was developed to address the problem that low-rank coal is difficult to be recovered by flotation with conventional non-polar oil collector. The flotation test proved that GK collector has excellent flotation performance for low-rank coal (combustible recovery rate close to 90 % while the ash content of clean coal is about 6 %). The contact angle, infiltration time, wetting heat and XPS analysis demonstrated that GK collector can significantly improve the hydrophobicity of low-rank coal, resulting in a great improvement of flotation efficiency. Molecular dynamics simulation shows that the hydrophilic head of GMO molecules can adsorb with low-rank coal directly through hydrogen bonding or indirectly through water bridges. The presence of GMO molecules in GK collector can increase the overall interaction strength of collector oil droplet with low-rank coal surface by more than half. A schematic diagram of collector adsorption on the surface of low-rank coal is drawn, which gives a complete overview of the stacking and hydrogen bonding connection modes at the molecular level of low-rank coal, water, GMO and kerosene adsorbed at the interface. The adsorption mechanism of this mixed collector on the surface of low-rank coal was clarified.

Selective Adsorption Behavior Modulation on Nickel Selenide by Heteroatom Implantation and Heterointerface Construction Achieves Efficient Co-production of H2 and Formate.

Glycerol-assisted hybrid water electrolysis is a potential strategy to achieve energy-efficient hydrogen production. However, the design of an efficient catalyst for the specific reaction is still a key challenge, which suffers from the barrier of regulating the adsorption characteristics of distinctive intermediates in different reactions. Herein, a novel rationale that achieves selective adsorption behavior modulation for self-supported nickel selenide electrode by heteroatom implantation and heterointerface construction through electrodeposition is developed, which can realize nichetargeting optimization on hydrogen evolution reaction (HER) and glycerol oxidation reaction (GOR), respectively. Specifically, the prepared Mo-doped Ni3 Se2 electrode exhibits superior catalytic activity for HER, while the NiSe-Ni3 Se2 electrode exhibits high Faradaic efficiency (FE) towards formate production for GOR. A two-electrode electrolyzer exhibits superb activity that only needs an ultralow cell voltage of 1.40V to achieve 40mA cm-2 with a high FE (97%) for formate production. Theoretical calculation unravels that the introduction of molybdenumcontributes to the deviation of the d-band center of Ni3 Se2 from the Fermi level, which is conducive to hydrogen desorption. Meanwhile, the construction of the heterojunction induces the distortion of the surface structure of nickel selenide, which exposes highly active nickel sites for glycerol adsorption, thus contributing to the excellent electrocatalytic performance.

Application of passion fruit seed meal in alternative biodiesel purification process: study of glycerol adsorption mechanism and incorporation into polymeric membrane

The search for renewable energy sources is a global concern that strengthens the expansion of the biodiesel industry. In view of the environmental and economic problems of the conventional purification process of this biofuel, there is a need to explore alternative methods of purification. In this way, this manuscript evaluated the use of passion fruit seed meal as an alternative for biodiesel purification. In the adsorption tests, with a concentration of the biosorbent equal to 40 g L−1, at 45 °C, for 90 min, there was a removal of 72.2% of free glycerol and reduction in the content of glycerol to values below the maximum limit imposed by the legislation. Furthermore, through the characterization of the meal and the adsorption equilibrium data, it was possible to propose the mechanism involved in the adsorption process corresponds to hydrogen interactions between the glycerol and the oxygenated groups of the biosorbent. In the membrane separation process, the free glycerol removals obtained with the meal functionalized membrane were three times higher than those with the commercial membrane. Thus, the passion fruit seed meal can be a promising alternative for biodiesel purification, bringing economic and environmental advantages due to the reduction in the generation of effluents.

Carbon-based metal-free catalysts for selective oxidation of glycerol to glycolic acid

Exploring efficient and cheap catalyst for the selective oxidation of glycerol to valuable carboxylic acids is a critical and complicated challenge. Herein, we innovatively realized the efficient oxidation of glycerol to glycolic acid over metal-free catalyst under mild conditions via carbon material defect engineering. Multiple characterizations revealed that the stepwise functionalization of active carbon caused by simple high temperature control is adopted to fine-tune the composition and electronic structure of oxygen-containing functional groups. Specifically, the abundant ester and carboxyl functional groups exhibit stronger electronegativity than the hydroxyl group, and this enhanced electronic coupling effect strengthens the adsorption of glycerol, thus improving the catalytic activity. Kinetic analysis and density functional theory calculations demonstrated that the oxygen-containing functional groups (mainly ester and carboxyl) could promote the C–H bond activation of RCH2O* intermediate and once C–C bond cleavage of glyceric acid, ensuring the high selectivity of glycolic acid (53.2% over AC-400 catalyst). We anticipate that this work could sheds some light on the application and design of more new type of carbon-based metal-free catalysts in the aqueous phase oxidation of various polyols.