Surface Active Centers Research Articles

Impact of Zn addition on structural, morphological, and magnetic properties of thermally annealed Li–Zn nanoferrite

The effect of Zn addition on cationic distribution, structural and magnetic properties of nanocrystalline Li-Zn ferrites are reported. X-ray diffraction confirms the formation of spinel nanoferrites with an average grain diameter of 34 − 82 nm. The addition of Zn results in a linear increase of lattice parameter and X-ray density. Magnetism in the studied samples is governed by the Yafet-Kittel three-sub-lattice model, shown by a non-zero canting angle. The variation in magnetic properties is correlated with the calculated cationic distribution. A new antistructural modeling explains the changes in the concentration of donor and acceptor surface active centers.

Phosphorus-modulated surface active center reconstruction in cerium oxide for polyols conversion into carbonates

Ionic liquids (ILs) can effectively regulate the surface morphology and acid-base sites of metal oxides, which is of great significance in the preparation of metal oxide nanomaterials. Here, cerium oxide (CeO2) was prepared in phosphonium-based ILs and P-doped CeO2 materials were obtained by doping phosphorous (P) on the surface of CeO2. Moreover, the yield and selectivity for ethylene carbonate (EC) synthesis catalyzed by CeO2 catalyst prepared were 77.26 % and 95.99 % respectively. The results indicated that an appropriate content of P could generate both Lewis acidic and basic sites related to P on the catalyst surface, and P-mediated frustrated Lewis acid-base pairs (FLPs) composed of P-OH as the basic center and Ce3+ as the acidic center was constructed. This work provides a new strategy for preparing novel CeO2 catalysts and regulating acid-base sites on the surface of that.

Pt-N catalytic centres concisely enhance interfacial charge transfer in amines functionalized Pt@MOFs for selective conversion of CO2 to CH4

Improving ligand-to-active metal charge transfer (LAMCT) by finely tuning the organic ligand is a decisive strategy to enhance charge transfer in metal organic frameworks (MOFs)-based catalysts. However, in most MOFs loaded with active metal catalysts, electron transmission encounters massive obstacle at the interface between the two constituents owing to poor LAMCT. Herein, amines (–NH2) functionalized MOFs (NH2-MIL-101(Cr)) encapsulated active metal Pt nanoclusters (NCs) catalysts are synthesized by the polyol reduction method and utilized for the photoreduction of CO2. Surprisingly, the introduction of –NH2 (electron donating) groups within the matrix of MIL-101(Cr) improved the electron migration through the LAMCT process, fostering a synergistic interaction with Pt. The combined experimental analysis exposed the high number of metallic Pt (Pt0) in Pt@NH2-MIL-101(Cr) catalyst through seamless electron shuttling from N of –NH2 group to excited Pt generating versatile hybrid Pt-N catalytic centres. Consequently, these versatile hybrid catalytic centres act as electro-nucleophilic centres, which enable the efficient and selective conversion of CO bond in CO2 to harvest CH4 (131.0 µmol.g−1) and maintain excellent stability and selectivity for consecutive five rounds, superior to Pt@MIL-101(Cr) and most reported catalysts. Our study verified that the precise tuning of organic ligands in MOFs immensely improves the surface-active centres, electron migration, and catalytic selectivity of the excited Pt NCs catalysts encaged inside MOFs through an improved LAMCT pathway.

Low-temperature microwave-assisted synthesis of Bi2WO6/Bi2S3 heterojunction for photocatalytic reduction of Cr(VI) in industrial wastewater

Cr(VI) pollution has become a worldwide environmental issue due to its toxicity and non-biodegradability in wastewater. Herein, a Bi2S3/Bi2WO6 (BWS) Z-scheme heterojunction was successfully fabricated via a low-temperature in situ sulfurization process assisted by microwave irradiation and applied to the photocatalytic reduction of Cr(VI) in industrial electroplating wastewater. The effects of Bi2S3 loading, catalyst dosage, light source, and synthesis method on the catalytic performance of the heterojunctions were investigated. Remarkably, the optimized BWS-6 heterojunction achieved 100% Cr(VI) removal within 50 min under LED light irradiation and 30 min under sunlight irradiation, which greatly exceeded the pure Bi2S3 and Bi2WO6. In addition, BWS-6 exhibited high photostability, and it still sustained preferable photocatalytic Cr(VI) reduction activity under sunlight irradiation when the experiment was scaled up 20 times. The high photocatalytic activity of BWS photocatalysts can be ascribed to enlarged surface area, active centers, and intimate interfacial contact of Z-scheme heterojunction, which greatly improve visible-light harvesting, surface adsorption, and the transport efficiency of interfacial charge. Experimental and theoretical calculation results further evidenced a built-in electric field forming at the interface of the Z-scheme heterojunction and unveiled a possible photocatalytic reduction pathway. This work provides valuable information for large-scale applications in the removal of Cr(VI) from industrial wastewater by Z-scheme heterojunctions.

Pharmaceutical Nanoparticles Formation and Their Physico-Chemical and Biomedical Properties.

The use of medicinal substances in nanosized forms (nanoforms, nanoparticles) allows the therapeutic effectiveness of pharmaceutical preparations to be increased due to several factors: (1) the high specific surface area of nanomaterials, and (2) the high concentration of surface-active centers interacting with biological objects. In the case of drug nanoforms, even low concentrations of a bioactive substance can have a significant therapeutic effect on living organisms. These effects allow pharmacists to use lower doses of active components, consequently lowering the toxic side effects of pharmaceutical nanoform preparations. It is known that many drug substances that are currently in development are poorly soluble in water, so they have insufficient bioavailability. Converting them into nanoforms will increase their rate of dissolution, and the increased saturation solubility of drug nanocrystals also makes a significant contribution to their high therapeutic efficiency. Some physical and chemical methods can contribute to the formation of both pure drug nanoparticles and their ligand or of polymer-covered nanoforms, which are characterized by higher stability. This review describes the most commonly used methods for the preparation of nanoforms (nanoparticles) of different medicinal substances, paying close attention to modern supercritical and cryogenic technologies and the advantages and disadvantages of the described methods and techniques; moreover, the improvements in the physico-chemical and biomedical properties of the obtained medicinal nanoforms are also discussed.

Regulating Ru−O Bonding Interactions by Ir Doping Boosts the Acid Oxygen Evolution Performance

AbstractHighly active and stable oxygen evolution reaction (OER) catalysts are crucial for the large‐scale application of proton exchange membrane water electrolyzers. However, the dynamic reconfiguration of the catalyst surface structure and active centers is still undefined, which greatly hinders the development and application of efficient OER catalysts. Herein, we report an Ir0.3Ru0.7Ox/C catalyst with a facile low‐temperature synthesis route, which can reach 10 mA cm−2 at an overpotential of 217 mV with a Tafel slope as low as 39.4 mV dec−1, and yields a mass activity 61 times that of commercial IrO2/C at an overpotential of 300 mV. The lattice oxygen structure of RuOx is stabilized by the introduction of Ir species, thus greatly promoting the OER activity and durability. Further in situ Raman reveals that RuOx emerges as the active species at high potentials, and Ru−O bonding interactions are enhanced with Ir regulation, stabilizing the solvation of Ru at high potentials and accelerating the nucleophilic attack of water molecules, leading to the improved OER performance. This work deepens the fundamental understanding of OER and offers an effective way to advance the utilization of Ru‐based OER catalysts.

Electrokinetic-mechanism of water and furfural oxidation on pulsed laser-interlaced Cu2O and CoO on nickel foam

The electrocatalytic oxidation of biomass-derived furfural (FF) feedstocks into 2-furoic acid (FA) holds immense industrial potential in optics, cosmetics, polymers, and food. Herein, we fabricated CoO/NiO/nickel foam (NF) and Cu2O/NiO/NF electrodes via in situ pulsed laser irradiation in liquids (PLIL) for the bifunctional electrocatalysis of oxygen evolution reaction (OER) and furfural oxidation reaction (FOR), respectively. Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu2O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR. CoO/NiO/NF electrocatalyst provides a consistently low overpotential of ∼359 mV (OER) at 10 mA/cm2, achieving the maximum FA yield (∼16.37 mM) with 61.5% selectivity, 79.5% carbon balance, and a remarkable Faradaic efficiency of ∼90.1% during 2 h of FOR at 1.43 V (vs. reversible hydrogen electrode). Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates (NiOOH and CoOOH) as surface-active centers during electrochemical oxidation. The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products. This method holds promise for large-scale applications, enabling simultaneous production of renewable building materials and fuel.

In Ukrainian

The aim of the work is the synthesis of nanodispersed phosphors based on lanthanum fluoride and phosphate, activated by terbium (LaF3:Tb3+ and LaРО4:Tb3+, respectively), promising for use in photodynamic therapy and optopharmacology, the study of their structural properties and luminescence spectra when excited by ultraviolet and X-ray radiation, as well as the possibility of their use in the composition of nanocomposites with magnetically sensitive nanosized Fe3O4 carriers and bioactive glass 60S. Nanocrystalline lanthanum fluoride and phosphate of hexagonal syngonium were synthesized, activated with terbium. The structural properties, chemical activity and biocompatibility of the surface, UV and X-ray luminescence spectra of the synthesized crystals were studied. The possibility of their use in the composition of nanocomposites with magnetically sensitive nanosized drug carriers and bioactive sol-gel glass is shown. The acid-base nature of the surface active centers of LaF3 and LaF3:Tb3+ NPs has been revealed. The proportions of negatively a––, positively a+ charged and neutral a0 active centers were calculated in the range of pH 2.4 – 12.7. The identified active surface centers can be represented by acidic (La3+) and basic (F-) Lewis centers, as well as basic Brønsted centers (OH- groups). The obtained data can be useful in optimizing the conditions of adsorption immobilization from a physiological solution of molecules of photosensitive substances (sensitizers) on the surface of phosphors based on lanthanum fluoride. Ensembles of particles of magnetically sensitive Fe3O4/LaF3:Tb3+ NCs of core-shell type were synthesized. The conditions of synthesis of NCs did not significantly change the magnetic properties of their cores – the initial single-domain Fe3O4 NPs. Composites of bioglass 60S with nanodispersed crystalline LaF3:Tb3+ and LaPO4:Tb3+ in the dry state and in distilled water medium demonstrated the presence of luminescence when excited by UV and X-ray radiation. The given data indicate the prospects of research of nanodispersed phosphors based on lanthanum fluoride and phosphate, their composites with magnetically sensitive nanosized carriers and bioactive glass, for use in optopharmacology and photodynamic therapy of tumor diseases, in particular, localized in organs of skull and bone tissues. In addition, research results can be useful for technical applications, in particular, in the creation of fluorescent detectors of high-energy electromagnetic radiation, development of photo- and optoelectronic devices, etc.

(Invited) Enhancement of Activity of Low-Pt-Content-Catalysts Toward Oxygen Reduction through Admixing with Metal Oxide Cocatalysts

The proton-exchange membrane fuel cell (PEMFC) technology is one of the most promising approaches for energy conversion in automotive applications. Despite the use of expensive noble metal electrocatalysts, the sluggish kinetics of the oxygen reduction reaction (ORR) in acid media, and formation of the undesirable hydrogen peroxide intermediate are still the main drawbacks, on top of the stability problems, when it comes to the widespread commercialization of PEMFC devices. The progress in this subject is greatly hindered by the high cost and scarcity of the state-of-the-art platinum-based materials which are regarded as the most effective cathode catalysts. Therefore, most of the current research studies have been devoted to the optimization of active centers and maximization of their utilization, which should allow the lowering of the cathode Pt loadings without loss of performance and durability. Unfortunately, the problem of electrochemical stability and the danger of generation of higher quantities of the undesirable hydrogen peroxide intermediate may become even more serious in the case of systems utilizing lower amounts of the Pt catalystAmong important strategies is hybridization, activation, and stabilization of carbon-supported Pt catalysts by functionalization through admixing with certain nanostructured and typically substoichiometric metal oxides. Special attention is paid to application of the bi- or multi-metallic Pt-based alloys in their various forms and structures. Additionally, doping of carbon carriers with heteroatoms would produce surface functional groups and active centers capable of not only improving the catalysts’ performance, but also affecting their stability. Among other important issues are such features as porosity, hydrophilicity, and degree of graphitization of carbon components, in addition to the existence of metal–support interactions, high electrochemical active surface area, electronic structure of interfacial Pt, and the feasibility of adsorptive or activating interactions with oxygen molecules.Platinum is a main catalyst for the electroreduction of oxygen, the reaction of primary importance to the technology of low-temperature fuel cells. Because of high cost of platinum. there is a need to significantly lower its loadings at interfaces. But then O2-reduction proceeds often at less positive potentials and produces higher amounts of undesirable H2O2-intermediate. Hybrid supports, which utilize metal oxides (e.g., CeO2, WO3, Ta2O5, Nb2O5, ZrO2), stabilize Pt and carbon nanostructures, diminish their corrosion while exhibiting high activity toward the four-electron (most efficient) reduction of oxygen. Porosity of carbon supports facilitates dispersion and stability of Pt nanoparticles. The catalytic efficiency depends on geometric (decrease of Pt–Pt bond distances) and electronic (increase of d-electron vacancy in Pt) factors, in addition to possible metal-support interactions and interfacial structural changes affecting adsorption and activation of O2-molecule.

The Role of Surface Complexes in Ketene Formation from Fatty Acids via Pyrolysis over Silica: from Platform Molecules to Waste Biomass.

Fatty acids (FA) are the main constituents of lipids and oil crop waste, considered to be a promising 2G biomass that can be converted into ketenes via catalytic pyrolysis. Ketenes are appraised as promising synthons for the pharmaceutical, polymer, and chemical industries. Progress in the thermal conversion of short- and long-chain fatty acids into ketenes requires a deep understanding of their interaction mechanisms with the nanoscale oxide catalysts. In this work, the interactions of fatty acids with silica are investigated using a wide range of experimental and computational techniques (TPD MS, DFT, FTIR, in situ IR, equilibrium adsorption, and thermogravimetry). The adsorption isotherms of linear and branched fatty acids C1-C6 on the silica surface from aqueous solution have been obtained. The relative quantities of different types of surface complexes, as well as kinetic parameters of their decomposition, were calculated. The formation of surface complexes with a coordination bond between the carbonyl oxygens and silicon atoms in the surface-active center, which becomes pentacoordinate, was confirmed by DFT calculations, in good agreement with the IR feature at ∼1680 cm 1. Interestingly, ketenes release relate to these complexes' decomposition as confirmed by the thermal evolution of the absorption band (1680 cm-1) synchronously with the TPD peak of the ketene molecular ion. The established regularities of the ketenezation are also observed for the silica-induced pyrolysis of glyceryl trimyristate and real waste, rapeseed meals.

Reinforced photogenerated electrons transfer on a novel graphdiyne(CnH2n-2) based heterojunction for enhanced photocatalytic hydrogen production

The development of non-noble metal catalysts with adjustable electronic structures is one of the strategies for the sustainable development of photocatalytic technology. Herein, graphdiyne (GDY) was prepared by mechanical ball milling and coupled with semi-metallic CoS2 to form a typical S-scheme heterojunction photocatalyst. The introduction of curly thin layer GDY avoids the agglomeration of CoS2 particles and provides a substrate for the dispersion of CoS2 nanoparticles, forming a tighter contact interface and shorter carrier migration distance. Based on the electronic structure advantages of GDY, that is, bond-order average effect and dispersed electron delocalization structure, a large-scale electron transfer space is formed, which makes it a charge acceptor with rich surface active centers. The formation of heterojunction between CoS2 and GDY can effectively improve the light energy efficiency and accelerate the carrier transfer, thus showing good hydrogen evolution activity and stability. In addition, the S-scheme carrier transfer mechanism, that is, the spatial separation of photogenerated carriers with strong redox ability, is demonstrated by in-situ irradiation X-ray photoelectron spectroscopy and density functional theory (DFT) calculation. This work expands the application of GDY prepared by mechanical ball milling in heterojunction photocatalysts.

Dispersible Supertetrahedral Chalcogenide T3 Clusters: Photocatalytic Activity and Photogenerated Carrier Dynamics

Herein, we synthesized two isostructural supertetrahedral T3 cluster-based chalcogenide compounds by an ionic liquid-assisted precursor technique, namely [Bmmim]6In10Q16Cl4∙(MIm)4 (Q = S (In-S), Q = Se (In-Se), Bmmim = 1-butyl-2,3-dimethylimidazolium, MIm = 1- methylimidazole). The two compounds consist of a pure inorganic discrete supertetrahedral [In10Q16Cl4]6- T3 cluster and six charge-balancing [Bmmim]+ anions. The T3 clusters could be highly dispersed in dimethyl sulfoxide (DMSO), exposing more photocatalytic active sites, which makes the highly-dispersed In-Se cluster exhibit ~5 times higher photocatalytic H2 evolution activity than that of the solid-state under visible light irradiation. Comparatively, the photocatalytic performance of the highly-dispersed In-S cluster is only slightly higher than that of the solid state, as its inferior visible-light absorption capability limits the effective utilization of photons. More importantly, through tracking the photogenerated carriers dynamics of highly-dispersed T3 clusters by ultrafast transient absorption (TA) spectroscopy, we found that the photogenerated electrons in the In-S cluster would suffer a rapid internal deactivation process under illumination, whereas the photoexcited electrons in the In-Se cluster can be captured by its surface active centers that would effectively reduce its photogenerated carrier recombination, contributing to the significantly enhanced photocatalytic activity. This work enriches the species of highly-dispersed metal-chalcogenide nanoclusters and firstly investigates the relationship between the structures and photocatalytic performances of nanoclusters by ultrafast excited-state dynamics, which is expected to promote the development of atomically precise nano-chemistry.

Effect of 16O6+ ion-irradiation on structural, magnetic properties and antistructural modeling of Zn-nanoferrites

XRD analysis and magnetic measurements were used to study the effect of 80 MeV 16O6+ ion-irradiation on structural, magnetic properties, and anti-structural modeling of as-burnt ZnFe2O4 synthesized by sol-gel auto-combustion technique. XRD confirms the formation of single-phase spinel nanoferrite. Irradiation leads to modification of (i) lattice-parameter; strain; oxygen parameter, Fe3+, Zn2+ions on A, B site; inversion degree; A-O-B, A-O-A, B–O–B super-exchange-interaction; (ii) saturation magnetization; anisotropy; squareness-ratio; surface dead-layer-thickness. Antistructural modeling describes the surface-active centers for pristine and irradiated samples. Studies reveal strong connection between structural and magnetic properties, useful for ion-irradiation-induced tuning properties of ZnFe2O4.

Activation of peroxymonosulfate by Co2P via interfacial radical pathway for the degradation and mineralization of carbamazepine

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) have raised wide attention due to the efficient degradation of pollutants. However, the low efficiency in PMS activation is still a challenge for practical application. Herein, an economic Co2P catalyst with surface-active center was constructed for PMS activation to induce fast degradation of carbamazepine (CBZ). Particularly, the removal ratio of CBZ in the Co2P/PMS system could achieve at 98% in 10 min, accompanied with the removal ratio of total organic carbon (TOC) reached 60% in 60 min. Characterizations indicated that interfacial transformation of Coδ+ to Co2+ promoted electron-rich Co center formation, which supplied electrons for PMS to produce SO4•–and •OH that were responsible for the efficient degradation of CBZ. Furthermore, potential interferences from the real water matrix, dosage of the catalyst and PMS, and variation of initial pH were carefully studied for practical applications. Besides, three possible degradation pathways of CBZ were proposed and the toxicity of the products was predicted. However, the generation of more toxic intermediates was found in the system for the radical (SO4•–and •OH) oxidation is a non-selective oxidation process. Particularly, we expect that this work can provide new insights into the regulation of reaction mechanisms, degradation routes and safe transformation in PMS-AOPs for wastewater treatment.

Construction of surface active centers on the mesoporous Co/CeO2-δ catalysts for CO2 hydrogenation

The surface active centers, which include metal Co, surface oxygen vacancies, and Co0–CeO2-δ interface structures, can be constructed on the mesoporous Co/CeO2-δ catalysts by wet impregnation method. And the surface active centers can be regulated by the Co species dosage. The interaction between the metal Co and CeO2-δ can promote surface oxygen vacancies and Co0–CeO2-δ interface structures to be formed and be conducive to inhibit the aggregation and sintering of Co species in high temperature environment. The prepared Co/CeO2-δ catalysts have better catalytic performances for CO2 hydrogenation than the single component Co and CeO2-δ catalysts, which can be attributed to the synergistic effect between Co0 active centers, surface oxygen vacancies, and Co0–CeO2-δ interface structures. Therefore, the Co/CeO2-δ catalysts have strong adsorption and activation ability for reactant CO2 and H2 molecules to improve the CO2 hydrogenation activity. At atmospheric pressure and 400 °C, the CO2 conversion and CH4 selectivity on the Co/CeO2-δ catalyst with Co loading of 12% could reach 59.7% and 95.7%, respectively, and maintained good stability in 9 cycles for CO2 hydrogenation reaction.

Positive Valent Metal Sites in Electrochemical CO2 Reduction Reaction.

The discovery of high-performance catalysts for the electrochemical CO2 reduction reaction (CO2 RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO2 RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO2 ) activation and conversation but are always unstable under reduction potentials. Many advanced technologies in theory and experiment have been utilized to understand and develop excellent catalysts with PVMS for CO2 RR. Here, we present an introduction of some typical catalysts with PVMS in CO2 RR and give some understanding of the activity and stability for these related catalysts.

Atomically Dispersed Co-Anchored N Rich Graphitic Carbon Network: A Highly Efficient Oxygen Reduction Electro Catalyst

Rational design of non-precious and highly efficient electrocatalyst for oxygen reduction reaction (ORR) is of great importance for sustainable energy exploitation to solve the energy crisis and environmental jeopardy. In this regard herein, we report work function tailored zeolite derived hierarchically porous and active site enrich electrocatalyst for ORR in acidic and alkaline medium. The electrochemical analysis proposes that the optimized electrocatalyst for surface area, porosity and active center density facilitate the electronic transfer from atomic Co to Nitrogen doped carbon framework and, further to antibonding oxygen state. The optimized catalyst shows the high ORR activity, remarkable onset potential (E onset acid- 0.89 V, E onset alkaline – 0.951 V) and large number of active site density (ASD acid -7.84×1023 /g, ASD acid - 1.51×1024 /g) with excellent stability and durability. It is proposed that the high performance of the catalyst is attributed to the reduction in work function (ф ZIF 67- 5.2 to ф optimized- 4.6) as an effect of temperature followed by post ‘acid leaching’ (AL) treatment to alter the surface area of the catalyst. Here, we represent a favorable strategy for highly efficient and durable ORR catalyst. This hybrid structure provides a new perspective to catalyst architectures.

Modeling of Hydrocarbons and Hydrogen Oxidation in the Presence of Surface-Active Centers Water-Negative Halogen Ion in Terms of the Formation of Weak Shock Waves

Modeling of Hydrocarbons and Hydrogen Oxidation in the Presence of Surface-Active Centers Water-Negative Halogen Ion in Terms of the Formation of Weak Shock Waves

Intense microwave heating at strongly polarized solid acid/water interface for energy-efficient platform chemical production

A strongly polarized solid/liquid interface is constructed to create a “micro-hydrothermal” environment under microwave and promote reaction energy efficiency. Specifically, TiO2 with open crystal structure was synthesized to maximize the density of surface-active centers and the degrees of interfacial polarization. Acidic groups were grafted on the catalyst surface, which served as catalytically active sites as well as heat-generation spots under microwave irradiation. Benefited by enhanced interfacial polarization, 10 times higher energy efficiency (6.8 mmol (kJ L)−1) than commercial TiO2 can be achieved in fructose dehydration reaction. MD simulation revealed that sulfonic group polarized surface water molecules and acted as “hot-spots” to accelerate fructose dehydration to HMF. Such alignment of site-specific heating and reaction by material design has great potential to shift the energy efficiency for a wide range of chemical reactions.

Insight into the roles of microenvironment and active site on the mechanism regulation in metal-free persulfate activation process coupling with an electric field

The regulation of the persulfate activation mechanism is highly desirable and meaningful for the treatment of different wastewaters. The role of active sites for mechanism regulation in carbon-driven persulfate activation is still ambiguous due to the complex and easily neglected microenvironment (concentration distributions of organics and oxidants) nearby carbon catalyst. This work aims to reveal the critical roles of active site and microenvironment on the activation mechanism through N-doped modification and application of an electric field (AC/PS/EC). Several N-doped activated carbon catalysts were prepared by activating for different times to adjust the surface active center and adsorption selectivity under an electric field. The contribution ratio of radical pathway and non-radical pathway for organic elimination significantly varied with the concentration distribution of organics and oxidants nearby the microelectrodes. The increased electro-adsorption of persulfate anion was found to be the primary promoting factor for the radical pathway for organic oxidation, resulting in a synergistic increase in degradation rate in the AC/PS/EC system. The quantitative structure-activity relationships analysis also revealed that the electro-adsorption selectivity was dominated by the surface graphitic N and pore structure of catalyst. This study sheds new light on the oxidative pathway regulation to deal with complex wastewater in a flexible and efficient manner.