Halide Anions Research Articles

Rational Atom Substitution to Obtain Efficient, Lead-Free Photocatalytic Perovskites Assisted by Machine Learning and DFT Calculations.

Inorganic lead-free halide perovskites, devoid of toxic or rare elements, have garnered considerable attention as photocatalysts for pollution control, CO2 reduction and hydrogen production. In the extensive perovskite design space, factors like substitution or doping level profoundly impact their performance. To address this complexity, a synergistic combination of machine learning models and theoretical calculations were used to efficiently screen substitution elements that enhanced the photoactivity of substituted Cs2 AgBiBr6 perovskites. Machine learning models determined the importance of d10 orbitals, highlighting how substituent electron configuration affects electronic structure of Cs2 AgBiBr6 . Conspicuously, d10 -configured Zn2+ boosted the photoactivity of Cs2 AgBiBr6 . Experimental verification validated these model results, revealing a 13-fold increase in photocatalytic toluene conversion compared to the unsubstituted counterpart. This enhancement resulted from the small charge carrier effective mass, as well as the creation of shallow trap states, shifting the conduction band minimum, introducing electron-deficient Br, and altering the distance between the B-site cations d band centre and the halide anions p band centre, a parameter tuneable through d10 configuration substituents. This study exemplifies the application of computational modelling in photocatalyst design and elucidating structure-property relationships. It underscores the potential of synergistic integration of calculations, modelling, and experimental analysis across various applications.

Crystal structures of the isotypic complexes bis-(morpholine)-gold(I) chloride and bis-(morpholine)-gold(I) bromide.

The compounds bis-(morpholine-κN)gold(I) chloride, [Au(C4H9NO)2]Cl, 1, and bis-(morpholine-κN)gold(I) bromide, [Au(C4H9NO)2]Br, 2, crystallize isotypically in space group C2/c with Z = 4. The gold atoms, which are axially positioned at the morpholine rings, lie on inversion centres (so that the N-Au-N coordination is exactly linear) and the halide anions on twofold axes. The residues are connected by a classical hydrogen bond N-H⋯halide and by a short gold⋯halide contact to form a layer structure parallel to the bc plane. The morpholine oxygen atom is not involved in classical hydrogen bonding.

Surface defect passivation by copper incorporation for efficient perovskite solar cells

Defects play an important character in the degradation processes of hybrid halide perovskite, hindering their application for solar cells. Ion transport is facilitated by the ubiquitous organic cation and halide anion vacancy defects, which lead to perovskite disintegration at grain boundaries. In this article, a thorough investigation of the vacancy defect and defect density on perovskite is conducted by using VASP and SCAPS-1D. From SCAPS-1D, the PCE of the device increases from 17.82 % to 23.04 % when the defect state density drops from 10+15 to 10+14 cm-3. Therefore, reducing the defect density is very important to improve the performance of perovskite solar cells. Effective perovskite solar cells based on CH3NH3PbI3 incorporated copper ions passivation defects were carried out. Compare to pristine hybrid perovskite, Cu2+-doped hybrid perovskite have remarkably lower trap-state densities, greater film quality, and higher crystallinity. Especially, the maximum power conversion efficiency of up to 20.1 % was achieved with 0.5 % copper ion doping. After 500 h of not being enclosed in dry air, the devices still has 87 % of its original power conversion efficiency. Therefore, this work suggests that careful control the formation of Cu2+ in perovskite films is very important for diverse optoelectronic applications in the future.

Hydrogen-Bonding Assembly Meets Anion Coordination Chemistry: Framework Shaping and Polarity Tuning for Xenon/Krypton Separation.

Hybrid hydrogen-bonded (H-bonded) frameworks built from charged components or metallotectons offer diverse guest-framework interactions for target-specific separations. We present here a study to systematically explore the coordination chemistry of monovalent halide anions, i.e., F- , Cl- , Br- , and I- , with the aim to develop hybrid H-bond synthons that enable the controllable construction of microporous H-bonded frameworks exhibiting fine-tunable surface polarity within the adaptive cavities for realistic xenon/krypton (Xe/Kr) separation. The spherical halide anions, especially Cl- , Br- , and I- , are found to readily participate in the charge-assisted H-bonding assembly with well-defined coordination behaviors, resulting in robust frameworks bearing open halide anions within the distinctive 1D pore channels. The activated frameworks show preferential binding towards Xe (IAST Xe/Kr selectivity ca. 10.5) because of the enhanced polarizability and the pore confinement effect. Specifically, dynamic column Xe/Kr separation with a record-high separation factor (SF=7.0) among H-bonded frameworks was achieved, facilitating an efficient Xe/Kr separation in dilute, CO2 -containing gas streams exactly mimicking the off-gas of spent nuclear fuel (SNF) reprocessing.

Hydrogen‐Bonding Assembly Meets Anion Coordination Chemistry: Framework Shaping and Polarity Tuning for Xenon/Krypton Separation

AbstractHybrid hydrogen‐bonded (H‐bonded) frameworks built from charged components or metallotectons offer diverse guest‐framework interactions for target‐specific separations. We present here a study to systematically explore the coordination chemistry of monovalent halide anions, i.e., F−, Cl−, Br−, and I−, with the aim to develop hybrid H‐bond synthons that enable the controllable construction of microporous H‐bonded frameworks exhibiting fine‐tunable surface polarity within the adaptive cavities for realistic xenon/krypton (Xe/Kr) separation. The spherical halide anions, especially Cl−, Br−, and I−, are found to readily participate in the charge‐assisted H‐bonding assembly with well‐defined coordination behaviors, resulting in robust frameworks bearing open halide anions within the distinctive 1D pore channels. The activated frameworks show preferential binding towards Xe (IAST Xe/Kr selectivity ca. 10.5) because of the enhanced polarizability and the pore confinement effect. Specifically, dynamic column Xe/Kr separation with a record‐high separation factor (SF=7.0) among H‐bonded frameworks was achieved, facilitating an efficient Xe/Kr separation in dilute, CO2‐containing gas streams exactly mimicking the off‐gas of spent nuclear fuel (SNF) reprocessing.

Parametric Evaluation of the Energy of Tetrel Bonds in Complexes of Tetrahedral Molecules with Ammonia and Halide Anions

Parametric Evaluation of the Energy of Tetrel Bonds in Complexes of Tetrahedral Molecules with Ammonia and Halide Anions

Binding Study of Antibacterial Drug Ciprofloxacin with Imidazolium-Based Ionic Liquids Having Different Halide Anions: A Spectroscopic and Density Functional Theory Analysis.

Herein, we have shown the interaction of an antibiotic drug ciprofloxacin (CIP) with three surface-active ionic liquids (ILs), having the same cation and different anions, namely, 1-decyl-3-methylimidazoliumtetrafluoroborate [C10mim][BF4], 1-decyl-3-methylimidazolium bromide [C10mim][Br], and 1-decyl-3-methylimidazolium chloride [C10mim][Cl]. This study has been performed by exploiting various spectroscopic techniques such as steady-state fluorescence, time-resolved fluorescence, and UV-visible spectroscopy. The fluorescence emission study of CIP with ILs was performed at various concentrations of all the three ILs. The emission spectra of CIP decreased in the presence of ILs, suggesting complex formation between CIP-IL. The effect of different concentrations of ILs on the emission spectra of CIP was exploited in terms of quenching and binding parameters. Further, fluorescence emission study was validated by the time-resolved fluorescence technique by measuring the average lifetime (τavg) of CIP in the presence of all the three ILs. The τavg value of the drug changed with the addition of ILs, which suggests complex formation between the drug and ILs. This complex formation was also confirmed by UV-visible spectroscopy results of CIP with all the three ILs. Further, for evaluating the thermodynamic parameters of the CIP-IL interactions, isothermal titration calorimetry (ITC) was performed. The ITC experiment yielded the thermodynamic parameters, ΔH (change in the enthalpy of association), ΔG (Gibbs free energy change), ΔS (entropy change), and binding constant (Ka). The binding parameters driven by ITC revealed that CIP-IL interactions are spontaneous in nature and enthalpy-driven, involving hydrophobic forces. Further, the classical density functional theory (DFT) calculations were performed, which provided deep insight for CIP-IL complex formation.

Dicationic ionic liquids (DILs) as rapid esterification catalyst of butyric fatty acid

In the presented work, a series of asymmetric dicationic ionic liquids (ADILs) with different alkyl chain length spacer between the two cation nuclei (imidazolium and pyridinium) with chlorine halide anion was designed, synthesized with excellent yield (89, 90 and 88%) and well characterized via different tools of analysis (FT-IR and 1H-NMR spectroscopy and thermal gravimetric analysis; TGA). The synthesized ADILs were examined for potential esterification as recyclable catalysts including the activity of catalytic performance, the reaction conditions justifying. The noted resulted data indicated that the butyric acid was converted perfectly into ester in presence of ADILs with short time of reaction. By completing our studies through the effect of chemical structures, concentrations, time and temperatures, we found that the synthesized Py-6-Imi exhibit the best catalytic performance with 96% as conversion value after 20 min at the ambient temperature (25 °C). The synthesized ADILs also recovered and reused for minimum three rounds without any significant reduction in the catalytic performance. Totally, the usage of ADILs in the esterification process offers lots of benefits such as perfect yield, quick time and environmentally friendly characteristics which make them the optimum sustainable compounds to be achieved in variety of industrial applications.

CsPbBr3 Perovskite Nanocrystals for Photocatalytic [3+2] Cycloaddition.

Visible-light-induced halide-exchange between halide perovskite and organohalide solvents has been studied in which photoinduced electron transfer from CsPbBr3 nanocrystals (NCs) to dihalomethane solvent molecules produces halide anions via reductive dissociation, followed by a spontaneous anion-exchange. Photogenerated holes in this process are less focused. Here, for CsPbBr3 in dibromomethane (DBM), we discover that Br radical (Br⋅) is a key intermediate resulting from the hole oxidation. We successfully trapped Br⋅ with reported methods and found that Br⋅ is continuously generated in DBM under visible light irradiation, hence imperative for catalytic reaction design. Continuous Br⋅ formation within this halide-exchange process is active for photocatalytic [3+2] cycloaddition for vinylcyclopentane synthesis, a privileged scaffold in medicinal chemistry, with good yield and rationalized diastereoselectivity. The NC photocatalyst is highly recyclable due to Br-based self-healing, leading to a particularly economic and neat heterogeneous reaction where the solvent DBM also acts as a co-catalyst in perovskite photocatalysis. Halide perovskites, notable for efficient solar energy conversion, are demonstrated as exceptional photocatalysts for Br radical-mediated [3+2] cycloaddition. We envisage such perovskite-induced Br radical strategy may serve as a powerful chemical tool for developing valuable halogen radical-involved reactions.

Exploiting the Catenane Mechanical Bond Effect for Selective Halide Anion Transmembrane Transport.

The first examples of [2]catenanes capable of selective anion transport across a lipid bilayer are reported. The neutral halogen bonding (XB) [2]catenanes were prepared via a chloride template-directed strategy in an unprecedented demonstration of using XB⋅⋅⋅anion interactions to direct catenane assembly from all-neutral components. Anion binding experiments in aqueous-organic solvent media revealed strong halide over oxoanion selectivity, and a marked enhancement in the chloride and bromide affinities of the catenanes relative to their constituent macrocycles. The catenanes additionally displayed an anti-Hofmeister binding preference for bromide over the larger iodide anion, illustrating the efficacy of employing sigma-hole interactions in conjunction with the mechanical bond effect to tune receptor selectivity. Transmembrane anion transport studies conducted in POPC LUVs revealed that the catenanes were more effective anion transporters than the constituent macrocycles, with high chloride over hydroxide selectivity, which is critical to potential therapeutic applications of anionophores. Remarkably these outperform existing acyclic halogen bonding anionophores with regards to this selectivity. Record chloride over nitrate anion transport selectivity was also observed. This represents a rare example of the direct translation of intrinsic anion binding affinities to anion transport behaviour, and demonstrates the key role of the catenane mechanical bond effect for enhanced anion transport selectivity.

Exploiting the Catenane Mechanical Bond Effect for Selective Halide Anion Transmembrane Transport

AbstractThe first examples of [2]catenanes capable of selective anion transport across a lipid bilayer are reported. The neutral halogen bonding (XB) [2]catenanes were prepared via a chloride template‐directed strategy in an unprecedented demonstration of using XB⋅⋅⋅anion interactions to direct catenane assembly from all‐neutral components. Anion binding experiments in aqueous‐organic solvent media revealed strong halide over oxoanion selectivity, and a marked enhancement in the chloride and bromide affinities of the catenanes relative to their constituent macrocycles. The catenanes additionally displayed an anti‐Hofmeister binding preference for bromide over the larger iodide anion, illustrating the efficacy of employing sigma‐hole interactions in conjunction with the mechanical bond effect to tune receptor selectivity. Transmembrane anion transport studies conducted in POPC LUVs revealed that the catenanes were more effective anion transporters than the constituent macrocycles, with high chloride over hydroxide selectivity, which is critical to potential therapeutic applications of anionophores. Remarkably these outperform existing acyclic halogen bonding anionophores with regards to this selectivity. Record chloride over nitrate anion transport selectivity was also observed. This represents a rare example of the direct translation of intrinsic anion binding affinities to anion transport behaviour, and demonstrates the key role of the catenane mechanical bond effect for enhanced anion transport selectivity.

Effects of alkyl chain length and halide anion on hydrogen bonding, electrochemical transport properties and double layer capacitance in eutectic solvents

Eutectic solvents (ESs) have been widely studied due to their tunable solvation and physical properties. The properties of eutectic solvents that are formed from mixtures of hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs) are governed by a complex hydrogen (H) bonded network among their constituents. However, an understanding of the key factors effecting the H-bonding structure and dynamics, and the resulting physical and electrochemical properties at interfaces is still in its infancy. In this study, the influence of the cation’s alkyl chain length and the anion chemical identity on the characteristics of the H-bonding network in eutectic solvents were examined. In particular, ESs formed from mixtures of tetraalkylammonium salts as HBAs and ethylene glycol as the HBD were studied. Complementary spectroscopic studies revealed the changes in the solvation environment as a function of the ammonium chain length (C1, C2, C3, and C4) and the anion type (Cl−, Br−, I−). With an increase in the alkyl chain length or a decrease in the electronegativity of halide anions (X−), it was found that the O–H bond length shortens and the H···X− bond elongates in the H-bond (O–H···X−) structure, thus resulting in an increase of the solvated ion size and a decrease in the bulk ionic conductivity. Further, double layer capacitance measurements showed that increased capacitance was correlated with shorter H-bonds in anion solvates.

Ein bidentates Antimon‐Pniktogenbrücken‐Wirtsystem

AbstractEin zweizähniges Pniktogenbrücken‐Wirtsystem auf der Basis von 1,8‐Diethinylanthracen wurde mittels einer selektiven Zinn‐Antimon‐Austauschreaktion hergestellt und auf seine Fähigkeit untersucht, als Lewis‐saure Wirtskomponente für die Komplexierung von Lewis‐basischen oder anionischen Gästen zu fungieren. In dieser Arbeit wurde mit der C≡C−Sb(C2F5)2‐Gruppe eine neuartige Akzeptorfunktion etabliert, mit der das Potenzial von Antimon(III)‐Funktionen als Vertreter der kaum erforschten Pniktogenbrücken‐Donatoren untersucht werden kann. Die Akzeptorfähigkeit dieses teilfluorierten Wirtsystems wurde gegenüber Halogenidanionen (Cl−, Br−, I−), Dimethylchalkogeniden Me2Y (Y = O, S, Se, Te) und Stickstoffheterozyklen (Pyridin, Pyrimidin) untersucht. Einblicke in das Adduktbildungsverhalten sowie die Bindungssituation solcher E⋅⋅⋅Sb−CF‐Einheiten wurden in Lösung mittels NMR‐Spektroskopie, im festen Zustand durch Röntgenbeugung, durch Elementaranalysen sowie durch rechnerische Methoden (DFT, QTAIM, IQA) gewonnen.

A Bidentate Antimony Pnictogen Bonding Host System.

A bidentate pnictogen bonding host-system based on 1,8-diethynylanthracene was synthesized by a selective tin-antimony exchange reaction and investigated regarding its ability to act as a Lewis acidic host component for the complexation of Lewis basic or anionic guests. In this work, the novel C≡C-Sb(C2 F5 )2 unit was established to study the potential of antimony(III) sites as representatives for the scarcely explored pnictogen bonding donors. The capability of this partly fluorinated host system was investigated towards halide anions (Cl- , Br- , I- ), dimethyl chalcogenides Me2 Y (Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine). Insights into the adduct formation behavior as well as the bonding situation of such E⋅⋅⋅Sb-CF moieties were obtained in solution by means of NMR spectroscopy, in the solid state by X-ray diffraction, by elemental analyses, and by computational methods (DFT, QTAIM, IQA), respectively.

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid‐Based Copolyesters

AbstractTo synthesize high molecular weight poly(phenolic ester) via a living ring‐opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back‐biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra‐n‐butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid‐based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn=361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl‐quaternaryammonium cation work synergistically, where the alkyl‐quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non‐classical hydrogen bonding. Moreover, these salicylic acid‐based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid-Based Copolyesters.

To synthesize high molecular weight poly(phenolic ester) via a living ring-opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back-biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra-n-butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid-based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn =361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl-quaternaryammonium cation work synergistically, where the alkyl-quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non-classical hydrogen bonding. Moreover, these salicylic acid-based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.

Enhanced peroxymonosulfate activation via heteroatomic doping defects of pyridinic and pyrrolic N in 2D N‑doped carbon nanosheets for BPA degradation

Understanding the role of intrinsic defects and nonmetallic heteroatom doping defects in activating peroxymonosulfate (PMS) and subsequently degrading endocrine-disrupting compounds is crucial for designing more efficient carbon catalysts. Therefore, we synthesized N-rich carbon nanosheets (NCs) through pyrolysis of a glutamic acid and melamine mixture and utilized them to activate PMS for bisphenol A (BPA) degradation. Different weight ratios of the above mixtures were allowed for manipulating NCs' defect level and N configuration. The reaction rate constant (k) was significantly positively correlated with the pyridinic and pyrrolic N content, and negatively and weakly positively correlated with graphite N and intrinsic defects, respectively. These findings suggest pyridinic and pyrrolic N, rather than graphitic N and intrinsic defects, enhance PMS activation to generate reactive oxygen species (specifically O•–2 and 1O2) and oxidize BPA. The NC-activated PMS system with the highest N content (17.9 atom%) demonstrated a remarkably high k (0.127 min−1) using minimal concentrations of PMS (0.4 mM) and NC (0.15 g/L), highlighting the system's efficiency. Excess halide anions led to significantly increased k with only a limited formation of trichloromethane (disinfection byproducts) in presence of 100 mM Cl−. This study offers novel perspectives on identifying catalytic sites within N-doped carbonaceous materials.

Microwave-Assisted Synthesis, Characterization, Crystal Structures and Antibacterial Activities of Zinc Complexes Derived from 5–Bromo-2-((cyclohexylimino)methyl)phenol

A dinuclear zinc complex [Zn2L2] (1), and four mononuclear zinc complexes [ZnBr2(LH)2] (2), [ZnCl2(LH)2] (3), [Zn(LH)2(NCS)2] (4) and [ZnI(CH3OH)L] (5), have been prepared from the Schiff base 5-bromo-2-((cyclohexylimino) methyl)phenol (HL) by microwave irradiation method. All the zinc complexes were characterized by CHN elemental analyses, infrared and electronic spectra. Structures of the complexes were further studied by single crystal X-ray determination, which reveals that all the zinc atoms in the complexes are in tetrahedral geometry. The halide and pseudohalide anions are preferred co-ligands in the preparation of such complexes with binary ligands. The biological activity of the complexes on the bacterial strains Bacillus subtilis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli was evaluated. The complexes bearing halide and pseudohalide ligands show effective activities on the bacteria strains.

Molecular engineering of inorganic halide perovskites and HTMs for photovoltaic applications

AbstractA comprehensive study was performed for the design of ABX3 perovskites, (A = Li, K, Na, B = Ge, Sn, Pb, X = F, Cl, Br, I) and organic hole transfer materials, HTMs (Fu‐2a, Fu‐2b, Fu‐2c, and Dm‐Q) for efficient perovskite solar cells (PSCs) through quantum chemistry calculations. Photovoltaic characteristics of the investigated perovskites are strongly affected by the halide anions. The results reveal that reducing the exciton binding energy of perovskites enhances the rate of the formation/dissociation of holes and electrons so F‐based perovskites are superior from this viewpoint. Additionally, the electron and hole injection processes are more favorable in the case of the F‐based perovskites in comparison with other studied perovskites. Moreover, spectroscopic properties of the perovskites demonstrate that KSnCl3, NaSnCl3, and F‐based perovskites exhibit a greater ability of the light‐harvesting and incident photon to current conversion efficiency. Ultimately, based on diverse analyses, F‐based perovskites, KSnCl3 and NaSnCl3 are the preferred candidates to be applied in the PSCs due to an excellent incident photon to current conversion efficiency, light‐harvesting efficiency, short circuit current, and solar cell final efficiency.

Synergistic activation of peroxymonosulfate by intrinsic defect and graphitic N of N, P co-doped carbon microspheres for BPA degradation

Doping nonmetallic heteroatoms into carbonaceous materials is a proven strategy for enhancing peroxymonosulfate (PMS) activation in the degradation of endocrine-disrupting compounds (EDCs). Understanding the role of heteroatom doping defects and intrinsic defects (topological, vacancies, or edge defects) on PMS activation is crucial for designing more efficient carbon catalysts. Herein, we synthesized nitrogen (N) and phosphorus (P) co-doped carbon microspheres (NPCs) through the pyrolysis of aminophosphonic acid resin (D418) precursors and utilized them to activate PMS for bisphenol A (BPA) degradation. The pyrolysis temperature was found to regulate the type and degree of defects, as well as the configuration of N and P. NPC-1000 (pyrolysis temperature at 1000 °C) exhibited the highest reaction rate constant (k) (1.20 × 10−1 min−1) with the lowest N and P doping defects and the highest intrinsic defect intensity resulting from the removal of N and P during pyrolysis. Density functional theory (DFT) calculations and correlation analysis between defect sites and k suggest that the adsorption of PMS was facilitated by graphitic N-coordinated C and intrinsic defect sites rather than P doping defect sites, resulting in the degradation of BPA through electron transfer and radical mechanisms, specifically superoxide radicals (O•–2). Excess halide anions led a significant increase of k with only a limited formation of trichloromethane (TCM) (disinfection byproducts) in presence of 100 mM Cl−. This research offers fundamental insights into constructing intrinsic defects through regulating heteroatom configuration, intending to enhance the catalytic activity of metal-free materials.