Degradation of phenol by metal-free electro-fenton using a carbonyl-modified activated carbon cathode: Promoting simultaneous H2O2 generation and activation.

The low yield of hydrogen peroxide, narrow pH application range, and secondary pollution due to iron sludge precipitation are the major drawbacks of the electro-Fenton (EF) process. Metal-free electro-Fenton technology based on carbonaceous materials is a promising green pollutant degradation technology. Activated carbon cathodes enriched with carbonyl functional groups were prepared using a two-step annealing method for the degradation of phenol pollutants. The •OH in the activation process of H2O2 were identified using the EPR test technique. The action mechanism of carbonyl groups on H2O2 activation was investigated in conjunction with density functional theory (DFT) calculations. The EPR tests demonstrated that the modified activated carbon could promote the in-situ activation of H2O2 to •OH. And the results of material analysis and DFT showed that C=O could facilitate the activation of hydrogen peroxide through the electron transfer mechanism as an electron-donating group. Electrochemical tests showed that both the oxygen reduction activity and 2e-ORR selectivity of the modified activated carbons were significantly improved. Compared with the original activated carbon cathode and EF, the degradation efficiency of phenol in the ACNH-1000/GF cathode was increased by 58.10% and 45.61%, respectively. Compared with EF, ACNH-1000/GF metal-free electro-Fenton effectively expands the pH application range, and is proven to be less affected by solution initial pH, while avoiding secondary pollution. The metal-free electro-Fenton system can save more than a quarter of the cost of EF system. This study has a deep understanding of the reaction mechanism of the carbonyl modified activated carbon, and provides valuable insights for the design of metal-free catalysts, so as to promote its application in the degradation of organic pollutants.

Catalytic Edges in One-Dimensional Covalent Organic Frameworks for the Oxygen Reduction Reaction.

Metal-free covalent organic frameworks (COFs) are employed in oxygen reduction reactions (ORR) because of their diverse structural units and controllable catalytic sites, and the edge sites have high catalytic activity than the basal sites. However, it is still challenge to modulate the edge sites in COFs, because the extended frameworks in two- or three-dimensional topologies resulted in limited edge parts. In this study, we have demonstrated the edge site modulation engineering based on one dimensional (1D) COFs to catalyze the ORR, which featured distinct edge groups-carbonyl, diaminopyrazine, phenylimidazole, and benzaldehyde imidazole units. The synthesized COFs had same ordered frameworks, similar pore structure, but had different electronic states of the carbons along the edge sites, which results in tailored catalytic properties. Notably, the COF functionalized with a phenylimidazole edge group exhibited superior catalytic performance compared to the other synthesized COFs. And the theoretical calculation further revealed the different edge sites have tunable binding ability of the intermediates OOH*, which contributed modulated activity. Our findings introduce a novel way for designing COFs optimized for ORR applications through molecular level control of edge sites.

The Development of Metal-Free Porous Organic Polymers for Sustainable Carbon Dioxide Photoreduction.

A viable tactic to effectively address the climate crisis is the production of renewable fuels via photocatalytic reactions using solar energy and available resources like carbon dioxide (CO2) and water. Organic polymer material-based photocatalytic materials are thought to be one way to convert solar energy into valuable chemicals and other solar fuels. The use of porous organic polymers (POPs) for CO2 fixation and capture and sequestration to produce beneficial compounds to reduce global warming is still receiving a lot of interest. Visible light-responsive organic photopolymers that are functionally designed and include a large number of heteroatoms and an extended π-conjugation allow for the generation of photogenerated charge carriers, improved absorption of visible light, increased charge separation, and decreased charge recombination during photocatalysis. Due to their rigid structure, high surface area, flexible pore size, permanent porosity, and adaptability of the backbone for the intended purpose, POPs have drawn more and more attention. These qualities have been shown to be highly advantageous for numerous sustainable applications. POPs may be broadly categorized as crystalline or amorphous according to how much long-range order they possess. In terms of performance, conducting POPs outperform inorganic semiconductors and typical organic dyes. They are light-harvesting materials with remarkable optical characteristics, photostability, cheap cost, and low cytotoxicity. Through cocatalyst loading and morphological tweaking, this review presents optimization options for POPs preparation techniques. We provide an analysis of the ways in which the preparative techniques will affect the materials' physicochemical characteristics and, consequently, their catalytic activity. An inventory of experimental methods is provided for characterizing POPs' optical, morphological, electrochemical, and catalytic characteristics. The focus of this review is to thoroughly investigate the photochemistry of these polymeric organic photocatalysts with an emphasis on understanding the processes of internal charge generation and transport within POPs. The review covers several types of amorphous POP materials, including those based on conjugated microporous polymers (CMPs), inherent microporosity polymers, hyper-crosslinked polymers, and porous aromatic frameworks. Additionally, common synthetic approaches for these materials are briefly discussed.

The Facile Production of p-Chloroaniline Facilitated by an Efficient and Chemoselective Metal-Free N/S Co-Doped Carbon Catalyst.

The catalytic hydrogenation of the toxic and harmful p-chloronitrobenzene to produce the value-added p-chloroaniline is an essential reaction for the sustainable chemical industry. Nevertheless, ensuring satisfactory control of its chemoselectivity is a great challenge. In this work, a N/S co-doped metal-free carbon catalyst has been fabricated by using cysteine as a source of C, N, and S. The presence of calcium citrate (porogen agent) in the mixture subjected to pyrolysis provided the carbon with porosity, which permitted us to overcome the issues associated with the loss of heteroatoms during an otherwise necessary activation thermal treatment. Full characterization was carried out and the catalytic performance of the metal-free carbon material was tested in the hydrogenation reaction of p-chloronitrobenzene to selectively produce p-chloroaniline. Full selectivity was obtained but conversion was highly dependent on the introduction of S due to the synergetic effect of S and N heteroatoms. The N/S co-doped carbon (CYSCIT) exhibits a mesoporous architecture which favors mass transfer and a higher doping level, with more exposed N and S doping atoms which act as catalytic sites for the hydrogenation of p-chloronitrobenzene, resulting in enhanced catalytic performance when compared to the N-doped carbon obtained from melamine and calcium citrate (MELCIT) used as a reference.

In Vivo Optogenetics Based on Heavy Metal-Free Photon Upconversion Nanoparticles.

Photon upconversion (UC) from red or near-infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal-free TTA-UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA-UC efficiency. The TTA-UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light-responding photoactivatable Cre-recombinase (PA-Cre), TTA-UC nanoparticles promote Cre-reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep-tissue control of neural activities based on heavy metal-free fully organic UC systems.

Novel Metal-Free Nanozyme for Targeted Imaging and Inhibition of Atherosclerosis via Macrophage Autophagy Activation to Prevent Vulnerable Plaque Formation and Rupture.

Atherosclerosis is a primary cause of cardiovascular and cerebrovascular diseases, with the unpredictable rupture of vulnerable atherosclerotic plaques enriched with lipid-laden macrophages being able to lead to heart attacks and strokes. Activating macrophage autophagy presents itself as a promising strategy for preventing vulnerable plaque formation and reducing the risk of rupture. In this study, we have developed a novel metal-free nanozyme (HCN@DS) that integrates the functions of multimodal imaging-guided therapy for atherosclerosis. HCN@DS has demonstrated high macrophage-targeting abilities due to its affinity toward scavenger receptor A (SR-A), along with excellent photoacoustic and photothermal imaging capabilities for guiding the precise treatment. It combines mild photothermal effects with moderate reactive oxygen species (ROS) generation to treat atherosclerosis. This controlled approach activates autophagy in atherosclerotic macrophages, inhibiting foam cell formation by reducing the uptake of oxidized low-density lipoproteins (oxLDL) and promoting efferocytosis and cholesterol efflux in macrophages. Additionally, it prevents plaque rupture by inhibiting apoptosis and inflammation within the plaque. Therefore, this metal-free nanozyme holds great potential for reducing the risk of atherosclerosis due to its high biosafety, excellent targeting ability, dual-modality imaging capability, and appropriate modulation of autophagy.

Improvement of photocatalytic CO2 reduction with conjugated organic polymers by rational modulation of donor, acceptor and bonding method.

The use of metal-free catalysts to convert CO2 into valuable chemicals is very challenging. Here, we synthesized a conjugated organic polymer (TpTf-1) featuring 2,4,6-Triphenyl-1,3,5-Triazine as the acceptor unit, triphenylamine as the donor unit, and vinylidene bond as the linkage. The local structure of donor-acceptor (D-A) forms an intramolecular electric field that can promote the separation of photogenerated electrons and charges, meanwhile, the vinylidene bond can further change the charge distribution to promote exciton dissociation. Without the use of photosensitizers, the TpTf-1 exhibits outstanding selectivity of CO of up to 91.96%, with a production rate of 45.2 µmol·g-1·h-1 at visible light, which is 3.4-fold than TaTf-1 with the same D-A structure but linking in imine bond and is 2.8-fold than TpTf-2 linking in vinylidene bond but with a different donor unit. Moreover, TpTf-1 has a CO production rate of up to 117.3 µmol·g-1·h-1 under full wavelength light irradiation.

Entropy-Driven 60 mol% Li Electrolyte for Li Metal-Free Batteries.

Highly Li-concentrated electrolytes are acknowledged for their compatibility with Li metal negative electrodes and high voltage positive electrodes to achieve high-energy Li metal batteries, showcasing stable and facile interfaces for Li deposition/dissolution and high anodic stability. This study aims to explore a highly concentrated electrolyte by adopting entropy-driven chemistry for Li metal-free (so-called anode-free) batteries. The combination of lithium bis(fluorosulfonyl)amide (LiFSA) and lithium trifluoromethanesulfonate (LiOTf) salts in a pyrrolidinium-based ionic liquid is found to significantly modify the coordination structure, resulting in an unprecedented 60 mol% Li concentration and a low solvent-to-salt ratio of 0.67:1 in the electrolyte system. This novel 60 mol% Li electrolyte demonstrates unique coordination stricture, featuring a high ratio of monodentate-anion structures and aggregates, which facilitates an enhanced Li+ transference number and improved anodic stability. Moreover, the developed electrolyte provides a facile de-coordination process and leads to the formation of an anion-based solid electrolyte interface, which enables stable Li deposition/dissolution properties and demonstrates excellent cycling stability in the Li metal-free full cell with a Li[Ni0.8Co0.1Mn0.1]O2 (NCM811) positive electrode.

Macrocyclic porphyrin photocatalysts without metal chelation: A novel pathway for complete degradation of tough halophenols with longwave visible LED light source.

Halophenols are toxic and persistent pollutants in water environments which poses harm to various organisms. Due to their high stability and long residence time, ultraviolet radiation, heavy metals and oxidizing agents have been largely adopted on treating these compounds. However, these treatment methods could pose toxicity or hazardous risks to the marine environment and plant operators. In this study, a water-soluble porphyrin photocatalyst was synthesized and introduced for halophenol treatment using UV-free LED white light. The porphyrin catalyst is a macrocyclic ring consisting of pyrroles linked with methine bridges, the highly conjugated ring provided the superior functionality of visible light absorption. Surprisingly, over 99 % degradation of halophenols and over 90 % dehalogenation have been achieved without metal chelation, even higher than those of transition metal porphyrins with inclusion of Fe3+, Zn2+, Cu2+, Co2+, Ni2+, and Mn2+. Ring-opening reactions were confirmed with the formation of carboxylic acids; dicarboxylic acids like acrylic acid, and malonic acid; while fumaric acid was the main product. Total organic carbon results indicated no CO2 produced during the reaction. Triplet absorbance and scavenger studies also indicated that singlet oxygen and conduction band electrons are the main radical species for halophenol degradation. The 100-fold singlet emission quenching over triplet absorption quenching indicated that the excited electrons tend to be transferred via singlet state. This concept brings along new approaches detoxifying halophenol-related wastewater without UV, metals and other additives, which is more environmentally-friendly and sheds light to the conversion of toxic materials into useful chemical precursors.

Fabrication of sulfur doped exfoliated gCN photocatalyst for enhanced visible light degradation of pernicious organic pollutants and their photocatalytic antibacterial activity.

The synthesis of sulfur-doped exfoliated graphitic carbon nitride (S-gCN) photocatalyst was achieved by the implementation of a two-step calcination technique. The XRD results revealed that all the fabricated photocatalytic materials were crystalline in nature. The inclusion of 5% sulfur in gCN led to a conspicuous escalation in the surface area of photocatalyst, rising from 10.294 to 61.185 m2g⁻1. Morphological scrutiny of the samples using FE-SEM revealed that pristine gCN exhibited tightly stacked small nanosheets, whereas inclusion of sulfur and exfoliation resulted in generation of loosely distributed large nanosheet. Furthermore, the inclusion of sulfur also induced a shift in the energy band gap (Eg) from 2.81 eV to 2.63 eV, making it felicitous for investigation as proficient visible light photocatalyst. Additionally, the photoluminescence photo-induced charge carrier recombination behavior revealed a reduced peak intensity for 5% S-gCN compared to other synthesized compositions. This observation can be directly linked to the minimized electron-hole pairs recombination during photocatalysis, underscoring its superior photocatalytic performance. Our findings revealed that the 5% S-gCN photocatalyst exhibit the most promising attributes, it degraded Tetracycline drug, Chlorpyrifos pesticide and Eriochrome Black T dye under visible light irradiation almost ∼4 times more efficiently than pristine gCN. Additionally, exceptional visible light photocatalytic antibacterial efficacy was also perceived by 5% S-gCN against S. aureus bacteria. Overall, the present research sheds light on how doping and exfoliation interact to modify the structure and catalytic properties of gCN, paving the way for the development of outstanding performance, visible light-responsive efficient photocatalysts for environmental restoration.

Polymerizable Ionic Liquid-Derived N, S co-Doped sp3/sp2 Carbon as Electrocatalyst for H2O2 Generation.

The H2O2 generation via the green electrochemical process is of high interest. For the H2O2 electrochemical generation, the oxygen reduction reaction (ORR) is important. Unfortunately, the ORR is kinetically sluggish and catalysts are needed. However, noble metal ORR catalysts are pricy and scarcely applicable in applications. Therefore, non-precious metal catalysts are desired. Heteroatom-doped carbons show promise as metal-free ORR catalysts. The ORR catalytic activity will be enhanced by the carbon's sp2 and/or sp3 engineering. For N, S co-Cdoped and sp2/sp3 modulated carbon, a polymerizable ionic liquid of hydrolyzed vinyl imidazolium was studied. The carbon is studied as a metal-free catalyst for the ORR via the 2e- process. It is possible to get an onset potential of 0.88 V vs. RHE with approximately 50 % selectivity for the H2O2. The current study offers a simple technique for synthesizing heteroatom-doped sp2/sp3 designed carbon as catalysts for the electroreduction of O2 to produce H2O2, and a new way of tunning the sp3/sp2 carbon catalytic activity by modulating the ionic liquid.

Nitrogen-Rich Covalent Organic Polymer for Metal-Free Tandem Catalysis and Postmetalation-Actuated High-Performance Water Oxidation.

Development of high-performing catalytic materials for selective and mild chemical transformations through adhering to the principles of sustainability remains a central focus in modern chemistry. Herein, we report the template-free assembly of a thermochemically robust covalent organic polymer (COP: 1) from 2,2'-bipyridine-5,5'-dicarbonyl dichloride and 2,4,6-tris(4-aminophenyl)triazine as [2 + 3] structural motifs. The two-dimensional (2D) layered architecture contains carboxamide functionality, delocalized π-cloud, and free pyridyl-N site-decked pores. Such trifunctionalization benefits this polymeric network exhibiting tandem alcohol oxidation-Knoevenagel condensation. In contrast to common metal-based catalysts, 1 represents a one of a kind metal-free alcohol oxidation reaction via extended π-cloud delocalization-mediated free radical pathway, as comprehensively supported from diverse control experiments. In addition to reasonable recyclability and broad substrate scope, the mild reaction condition underscores its applicability in benign synthesis of valuable product benzylidene malononitrile. Integration of 2,2'-bipyridyl units in this 2D COP favors anchoring non-noble metal ions to devise 1-M (M: Ni2+/ Co2+) that demonstrate outstanding electrochemical oxygen evolution reaction in alkaline media with high chronoamperometric stability. Electrochemical parameters of both 1-Co and 1-Ni outperform some benchmark, commercial, as well as a majority of contemporary OER catalysts. Specifically, the overpotential and Tafel slope (280 mV, 58 mV/dec) for 1-Ni is better than 1-Co (360 mV, 78 mV/dec) because of increased charge accumulation as well as a higher number of active sites compared to the former. In addition, the turnover frequency of 1-Ni is found to be 6 times higher than that of 1-Co and ranks among top-tier water oxidation catalysts. The results provide valuable insights in the field of metal-free tandem catalysis as well as promising electrochemical water splitting at the interface of task-specific functionality fuelling in polymeric organic networks.

Green Synthesis of Diphenyl-Substituted Alcohols Via Radical Coupling of Aromatic Alcohols Under Transition-Metal-Free Conditions.

Alcohols are common alkylating agents and starting materials alternative to harmful alkyl halides. In this study, a simple, benign and efficient pathway was developed to synthesize 1,3-diphenylpropan-1-ols via the ß-alkylation of 1-phenylethanol with benzyl alcohols. Unlike conventional borrowing hydrogen processes in which alcohols were activated by transition-metal catalyzed dehydrogenation, in this work, t-BuONa was suggested to be a dual-role reagent, namely, both base and radical initiator, for the radical coupling of aromatic alcohols. The cross-coupling reaction readily proceeded under transition metal-free conditions and an inert atmosphere, affording 1,3-diphenylpropan-1-ol with an excellent yield. A good functional group tolerance in benzyl alcohols was observed, leading to the production of various phenyl-substituted propan-1-ol derivatives in moderate-to-good yields. The mechanistic studies proposed that the reaction could involve the formation of reactive radical anions by base-mediated deprotonation and single electron transfer.

GFP Chromophore Integrated Conjugated Microporous Polymers toward Bioinspired Photocatalytic CO2 Reduction to CO.

The development of highly active, durable, and low-cost metal-free catalysts for the photocatalytic CO2 reduction reaction (CO2RR) is an efficient and environmentally friendly solution to address significant problems like global warming and high energy demand. In the present study, we have demonstrated the design and synthesis of a donor-acceptor based conjugated microporous polymer (CMP), TPA-GFP, by integrating an electron donor, tris(4-ethynylphenyl)amine (TPA), with a green fluorescent protein chromophore analogue (Z)-4-(2-hydroxy-3,5-diiodobenzylidene)-1-(4-iodophenyl)-2-methyl-1H-imidazol-5(4H)-one (o-HBDI-I3) (GFP). In comparison to nondonor 1,3,5-triethynylbenzene (TEB) based TEB-GFP CMP, photocatalytic CO2 reduction using donor-acceptor based TPA-GFP CMP displays a 3-fold increment of CO production yield with a maximum CO yield of 1666 µmol g-1 at 12 h. Further, the CO selectivity increases significantly from a mere 54% in TEB-GFP to an impressive 95% in TPA-GFP. The impressive CO2 reduction efficiency and selectivity for TPA-GFP can be attributed to the efficient light-harvesting capability and facile charge separation and migration through donor-acceptor building units of the CMP. The mechanistic aspect of the photocatalytic CO2 reduction process is explored using in situ DRIFTS and DFT calculation, and a plausible photocatalytic mechanism is proposed.

Transition-Metal-Free Radical Relay Cascade Annulation of Amides: Access to Antitumor Active Benzo[b]azepine and Oxindole Derivatives.

Efficient metal-free synthesis of benzo[b]azepines and oxindoles is achieved via a radical relay cascade strategy employing halogen atom transfer (XAT) for aryl radical generation followed by intramolecular hydrogen atom transfer (HAT). Optimization yielded moderate to substantial yields under visible light irradiation. Preliminary biological assessments revealed promising anti-tumor activity for select compounds. This study underscores the potential of XAT-mediated radical relay cascades in medicinal chemistry and anticancer drug discovery.

Engineering Three-Dimensional Interconnected Pores with Plentiful Edge Sites via a Confined Space for Enhanced Oxygen Reduction.

N-Doped carbon sheets based on edge engineering provide more opportunities for improving oxygen reduction reaction (ORR) active sites. However, with regard to the correlation between porous structural configurations and performances, it remains underexplored. Herein, a silica-assisted localized etching method was employed to create two-dimensional mesoporous carbon materials with customizable pore structures, abundant edge sites, and nitrogen functionalities. The mesoporous carbon exhibited superior electrocatalytic performance for the ORR compared to that of a 20 wt % Pt/C catalyst, achieving a half-wave potential of 0.88 V versus RHE, situating them in the leading level of the reported carbon electrocatalysts. Experimental data suggest that the edge graphitic nitrogen sites played a crucial role in the ORR process. The three-dimensional interconnected pores provided a high density of active sites for the ORR and facilitated the efficient transport of electrons. These unique properties make the carbon sheets a promising candidate for highly efficient air cathodes in rechargeable Zn-air batteries.

Aromative Dephosphinidenation of a Bisphosphirane-Fused Anthracene toward E-H (E = H, Si, N and P) Bond Activation.

A bisphosphirane-fused anthracene (5) was prepared by treatment of a sterically encumbered amino phosphorus dichloride (3) with MgA•3THF (A = anthracene). X-ray diffraction analysis revealed a pentacyclic framework consisting of 5 with two phosphirane rings fused to the anthracene in a trans-fashion. Compound 5 has been shown to be an efficient phosphinidene synthon, readily liberating two transient phosphinidene units for subsequent downstream bond activation via the reductive elimination of anthracene under mild conditions. The formal oxidative addition of H2 and E-H (E = Si, N, P) bonds by the liberated phosphinidene provided diphosphine and substituted phosphines. Furthermore, phosphinidene transfer to alkenes and alkynes smoothly yielded the corresponding phosphiranes and phosphirenes. The mechanism of the H2 activation by 5 was investigated by density functional theory (DFT) calculations.

HFIP-Mediated Dual C(Ar)-Alkylation Process towards the Regioselective Synthesis of Triarylmethanes (TRAMs).

The distinct roles of different chemical species are essential for the discovery of novel chemical transformations in organic synthesis. Here, we have designed a potential strategy for the synthesis of triarylmethanes (TRAMs) using the dual C(aryl)-alkylation process. This protocol was influenced by 1,1,1,3,3,3-hexafluoro isopropanol (HFIP) as a pivotal reagent and proceeds through the selective para C-H functionalization method. The described approach has been proven to be highly efficient in terms of substrate scope with excellent functional group tolerance and gram scale synthesis of the desired product with 90% yield. The recyclability and reusability of HFIP has enhanced the feasibility of this protocol towards the sustainable synthesis of TRAMs.

Selective Hydroboration of C-C Single Bonds without Transition-metal Catalysis.

Selective hydroboration of C-C single bonds presents a fundamental challenge in the chemical industry. Previously, only catalytic systems utilizing precious metals Ir and Rh, in conjunction with N- and P- ligands, could achieve this, ensuring bond cleavage and selectivity. In sharp contrast, we discovered an unprecedented and general transition-metal-free system for the hydroboration of C-C single bonds. This methodology is transition-metal and ligand-free and surpasses the transition-metal systems regarding chemo- and regioselectivities, substrate versatility, or yields. In addition, our system tolerates various functional groups such as Ar-X (X = halides), heterocyclic rings, ketones, esters, amides, nitro, nitriles, and C=C double bonds, which are typically susceptible to hydroboration in the presence of transition metals. As a result, a diverse range of γ-boronated amines with varied structures and functions has been readily obtained. Experimental mechanistic studies, density functional theory (DFT), and intrinsic bond orbital (IBO) calculations unveiled a hydroborane-promoted C-C bond cleavage and hydride-shift reaction pathway. The carbonyl group of the amide suppresses dehydrogenation between the free N-H and hydroborane. The lone pair on the nitrogen of the amide facilitates the cleavage of C-C bonds in cyclopropanes.

Unveiling the activity origin of electrochemical oxygen evolution on heteroatom-decorated carbon matrix.

Chemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure-performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high-electronegative F and N co-doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic-N (Py-N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential-limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential-limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER.