Accelerated ZnMoO4 photocatalytic degradation of pirimicarb under UV light mediated by peroxymonosulfate

This paper reports the optimized synthesis of zinc molybdates by the hydrothermal method and the combination of ZnMoO₄ and peroxymonosulfate (PMS) under UV irradiation for the degradation of pirimicarb. The as‐prepared ZnMoO₄ photocatalyst was characterized using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy and UV–visible diffuse reflectance spectroscopy. The effects of operational parameters in the ZnMoO₄/PMS/UV system were evaluated and the results indicated the highest performance is achieved with pH = 9.0, 1 mM PMS and 1 g l^?1 ZnMoO₄. The degradation efficiency of pirimicarb was 98% after 3 h in the photocatalytic process. A photodegradation mechanism is proposed based on scavenger and electron spin resonance studies to decide the main active species and by using chromatography–mass spectrometry to identify the major intermediates. Pirimicarb degradation is found to be mainly driven by holes and ?O₂^? radicals, with the contribution of ?OH and SO₄^?? radicals enhancing the process in the tested catalytic system. The mechanism is proposed involving two routes, dealkylation and decarbamoylation. Lastly, the zinc molybdate photocatalyst is shown to be stable, reusable and efficient in the removal of pirimicarb from real water samples in the presence of PMS, demonstrating potential application in the treatment of contaminated and/or environmental water.     

Efficient activation of peroxymonosulfate by hollow cobalt hydroxide for degradation of ibuprofen and theoretical study

Hollow microsphere structure cobalt hydroxide (h-Co(OH)₂) was synthesized via an optimized solvothermal-hydrothermal process and applied to activate peroxymonosulfate (PMS) for degradation of a typical pharmaceutically active compound, ibuprofen (IBP). The material characterizations confirmed the presence of the microscale hollow spheres with thin nanosheets shell in h-Co(OH)₂, and the crystalline phase was assigned to α-Co(OH)₂. h-Co(OH)₂ could efficiently activate PMS for radicals production, and 98.6% of IBP was degraded at 10 min. The activation of PMS by h-Co(OH)₂ was a pH-independent process, and pH 7 was the optimum condition for the activation-degradation system. Scavenger quenching test indicated that the sulfate radical (SO₄^{? ?}) was the primary reactive oxygen species for IBP degradation, which contributed to 75.7%. Fukui index (f ^?) based on density functional theory (DFT) calculation predicted the active sites of IBP molecule for SO₄^{? ?} attack, and then IBP degradation pathway was proposed by means of intermediates identification and theoretical calculation. The developed hollow Co(OH)₂ used to efficiently activate PMS is promising and innovative alternative for organic contaminants removal from water and wastewater.     

NiCo2O4/BiOCl/Bi24O31Br10 ternary Z-scheme heterojunction enhance peroxymonosulfate activation under visible light: Catalyst synthesis and reaction mechanism

The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position, promoting the synergistic coupling of photocatalysis and peroxymonosulfate (PMS) activation. In order to fully utilize the luminous energy and realize the efficient activation of PMS, this work achieved successful construction of NiCo₂O₄/BiOCl/Bi₂₄O₃₁Br₁₀ ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo₂O₄ with NiCl₂ and CoCl₂ as the precursors. The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs, so that the oxidation and reduction processes separately occurred in different regions. Compared with the reported catalysts, the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride (TCH) in the visible light/PMS system, with a degradation efficiency of 85.30% in 2 min, and possessed good stability. Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system. The experimental and characterization results confirmed that both non-radicals (¹O₂) and radicals (SO₅^?? and SO₄^??) were involved in the reaction process and the SO₅^?? generated by the oxidation of PMS played a crucial role in the TCH degradation. The possible reaction mechanism was finally proposed. This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.     

The capacity and mechanisms of various oxidants on regulating the redox function of ZVI

It is well known that zero-valent iron(ZVI) could catalyze the oxidation of various oxidants to realize the rapid oxidation removal of pollutants. However, in this study, we found that the addition of different oxidants could regulate the redox function of ZVI system. In three different co-treatment systems, the effects of different oxidizers(peroxymonosulfate(PMS), persulfate(PDS), hydrogen peroxide(H_2O_2))dosages on the ratios of oxidative degradation rate and reductive degradation rate of p-nitrophenol(PNP)were studied. The effect of the H~+ released from oxidizers and the generated reactive oxygen species(ROS) in ZVI/PMS, ZVI/PDS, ZVI/H_2O_2 systems were detailed discussed. Especially, the contribution of generated ROS for reductive degradation of PNP was quantified in the ZVI/H_2O_2 system. Based on the results of TOC removal, UV–vis absorption spectra, and intermediates concentration curves, it was found that the degradation of PNP changed from reduction to oxidation with the increase of oxidant proportion.When the molar ratio of ZVI to oxidizer equal to 100, PNP was mainly degraded by reduction accompanied by slight oxidation. Combined with the results of SEM-EDS and XPS, it was confirmed that the enhanced degradation of PNP under the addition of oxidant was mainly related to the generated ROS,the additional H~+, and the corrosion products of ZVI.     

Degradation of carbon tetrachloride using ultrasound‐assisted nanoscaled zero‐valent iron particles@sulfur/nitrogen dual‐doped reduced graphene oxide composite: Kinetics,activation energy,effects of reaction conditions and degradation mechanism

We report a study of the synthesis of nanoscale zero‐valent iron particles stabilized by sulfur/nitrogen dual‐doped reduced graphene oxide (i.e. nZVI@SN‐rGO) and their applications as major reactants for the dechlorination of carbon tetrachloride (CT) by combining sonolysis with consideration of several operation parameters such as pH, temperature, catalyst dosage, as well as in the presence of common inorganic anions. The experimental results showed that the modified technology could remain effective for up to 180 min of reaction time under optimal conditions. Especially, there was no significant reduction in the removal efficiency toward CT even after five cycles, which was indicative of good stability. A study of the effects of common inorganic anions revealed that the presence of Clˉ and HCO₃ˉ exhibited different positive effects in the following order: Clˉ > HCO₃ˉ; NO₃ˉ and SO₄²ˉ showed inhibition effects on CT removal. The structure and properties of nZVI@SN‐rGO were characterized using X‐ray diffraction, scanning electron microscopy, surface area analysis, Raman spectroscopy and X‐ray photoelectron spectroscopy. Additionally, the corresponding activation energy was approximately 31.04 kJ mol^?1, suggesting that the surface chemical reaction rather than diffusion was the rate‐limiting step in the CT decomposition process. More importantly, the possible reaction mechanism and dechlorination pathway of CT using the ultrasound‐assisted nZVI@SN‐rGO system were also investigated.     

Highly efficient degradation of emerging contaminants by magnetic CuO@FexOy derived from natural mackinawite（FeS） in the presence of peroxymonosulfate

In this study,natural mackinawite （Fe S）,a chalcophilic mineral,was utilized to prepare iron/copper bimetallic oxides （Cu O@Fe_xO_y） by displacement plating and calcination process.Various characterization methods prove that Cu⁰is successfully coated on the surface of Fe S,which were further oxidized to Cu O,Fe₃O₄and/or Fe₂O₃during calcination process,respectively.Cu O@Fe_xO_yperformed highly efficient...     

Polyacrylonitrile/Aminated Polymeric Nanosphere Nanofibers as Efficient Adsorbents for Cr(VI) Removal

In this work, polyacrylonitrile/aminated polymeric nanosphere (PAN/APN) nanofibers were prepared by electrospinning of monodispersed aminated polymeric nanospheres (APNs) for removal of Cr(VI) from aqueous solution. Characterization results showed that obtained PAN/APNs possessed nitrogen functionalization. Furthermore, the adsorption application results indicated that PAN/APN nanofibers exhibited a high adsorption capacity of 556 mg/g at 298 K for Cr(VI) removal. The kinetic data showed that the adsorption process fits the pseudo-second order. A thermodynamic study revealed that the adsorption of Cr(VI) was spontaneous and endothermic. The coexisting ions Na⁺, Ca²⁺, K⁺, Cl⁻, NO₃⁻ and PO₄³⁻ had little influence on Cr(VI) adsorption, while SO₄²⁻ in solution dramatically decreased the removal performance. In the investigation of the removal mechanism, relative results indicated that the adsorption behavior possibly involved electrostatic adsorption, redox reaction and chelation. PAN/APN nanofibers can detoxify Cr(VI) to Cr(III) and subsequently chelate Cr(III) on its surface. The unique structure and nitrogen functionalization of PAN/APN nanofibers make them novel and prospective candidates in heavy metal removal.     

Removal of Carbamazepine in Aqueous Solution by CoS2/Fe2+/PMS Process

Carbamazepine (CBZ), as a typical pharmaceutical and personal care product (PPCP), cannot be efficiently removed by the conventional drinking water and wastewater treatment process. In this work, the CoS₂/Fe²⁺/PMS process was applied for efficient elimination of CBZ. The CBZ removal efficiency of CoS₂/Fe²⁺/PMS was 2.5 times and 23 times higher than that of CoS₂/PMS and Fe²⁺/PMS, respectively. The intensity of DMPO-HO• and DMPO-SO4•− followed the order of Fe²⁺/PMS < CoS₂/PMS < CoS₂/Fe²⁺/PMS, also suggesting the CoS₂/Fe²⁺/PMS process has the highest oxidation activity. The effects of reaction conditions (e.g., CoS₂ dosage, Fe²⁺ concentration, PMS concentration, initial CBZ concentration, pH, temperature) and water quality parameters (e.g., SO42−, NO3−, H2PO4−, Cl−, NH4+, humic acid) on the degradation of CBZ were also studied. Response surface methodology analysis was carried out to obtain the best conditions for the removal of CBZ, which are: Fe²⁺ = 70 µmol/L, PMS = 240 µmol/L, CoS₂ = 0.59 g/L. The sustainability test demonstrated that the repeated use of CoS₂ for 8 successive cycles resulted in little function decrease (<10%). These findings suggest that CoS₂/Fe²⁺/PMS may be a promising method for advanced treatment of tailwater from sewage treatment plant.     

Photogenic MnO2/Ag metal nanocomposites and their dye adsorbing activities

• Manganese dioxide/silver (MnO₂/Ag) nanoparticles were fabricated by using KMnO₄-NaBH₄ redox reaction at room temperature. The optical and structural properties of MnO₂/Ag were determined using UV–visible and Fourier transform infrared spectroscopies. The morphology was established with scanning and transmission electron microcopies, and X-ray diffraction. MnO₂/Ag showed excellent adsorbing activity to the removal of Congo red. The various kinetic models were used to determine the rate of dye removal. Congo red adsorption onto MnO₂Ag proceeds through the pseudo-second-order kinetic model. Langmuir adsorption capacity (Q⁰_max = 97.1 mg/g), and sorption intensity (n = 1.6) were estimated with Langmuir and Freundlich adsorption isotherm models for 250 mg/L Congo red. Elovich model suggest the adsorption of Congo red with the MnO₂Ag proceeds through the film diffusion. The positive values of enthalpy changes (ΔH⁰), entropy changes (ΔS⁰), and negative Gibbs free energy changes (ΔG⁰) showed that the Congo red adsorption process was endothermic, spontaneous, and chemisorption process followed with physical mechanism. The results showed that the removal efficiency decreases from 98% to 89% after the six consecutive experiments.

     

Bromate formation during oxidation of bromide-containing water by the CuO catalyzed peroxymonosulfate process

Bromate formation has been found in the SO₄^??-based oxidation processes, but previous studies primarily focused on the bromate formation in the homogeneous SO₄^??-based oxidation processes. The kinetics and mechanisms of bromate formation are poorly understood in the heterogeneous SO₄^??-based oxidation processes, although which have been widely studied in the eliminations of micropollutants. In this work, we found that the presence of CuO, a common heterogeneous catalyst of peroxymonosulfate (PMS), appreciably enhanced the bromate formation from the oxidation of bromide by PMS. The conversion ratio of bromide to bromate achieved over 85% within 10 min in this process. CuO was demonstrated to play a multiple role in the bromate formation: (1) catalyzed PMS to generate SO₄^??, which then oxidizes bromide to bromate; (2) catalyzed the formed free bromine to disproportionate to bromate; (3) catalyzed the formed free bromine to decomposed back into bromide. In the CuO-PMS-Br system, bromate formation increases with increasing CuO dosages, initial CuO and bromide concentrations, but decreases with increasing bicarbonate concentrations. The presence of NOM (natural organic matter) resulted in a lower formed bromate accompanied with organic bromine formation. Notably, CuO catalyzes PMS to transform more than 70% of initial bromide to bromate even after recycled used for six times. The formation of bromate in the PMS catalysis by CuO system was also confirmed in real water.     

New hydroxylated metabolites of 4-monochlorobiphenyl in whole poplar plants

Background

The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring. Quinoline ring has therapeutic and biological activities whereas, the indole ring occurs in Jasmine flowers and Orange blossoms. As a ligand, the isatin moiety is potentially ambidentate and can coordinate the metal ions either through its lactam or lactim forms. In a previous study, the ligational behavior of a phenolic quinolyl hydrazone towards copper(II)- ions has been studied. As continuation of our interest, the present study is planned to check the ligational behavior of an isatinic quinolyl hydrazone.

Results

New homo- and heteroleptic copper(II)- complexes were obtained from the reaction of an isatinic quinolyl hydrazone (HL) with several copper(II)- salts viz. Clˉ, Brˉ, NO₃ˉ, ClO₄ ^-, SO₄ ^2- and AcO^-. The obtained complexes have O_h, T_d and D_4h- symmetry and fulfill the strong coordinating ability of Clˉ, Brˉ, NO₃ˉ and SO₄ ^2- anions. Depending on the type of the anion, the ligand coordinates the copper(II)- ions either through its lactam (NO₃ˉ and ClO₄ ^-) or lactim (the others) forms.

Conclusion

The effect of anion for the same metal ion is obvious from either the geometry of the isolated complexes (O_h, T_d and D_4h) or the various modes of bonding. Also, the obtained complexes fulfill the strong coordinating ability of Clˉ, Brˉ, NO₃ˉ and SO₄ ^2- anions in consistency with the donor ability of the anions. In case of copper(II)- acetate, a unique homoleptic complex (5) was obtained in which the AcO^- anion acts as a base enough to quantitatively deprotonate the hydrazone. The isatinic hydrazone uses its lactim form in most complexes.     

Removal of sulfate from wastewater via synthetic Mg–Al layered double hydroxide: An adsorption,kinetics, and thermodynamic study

Sulfate-contaminated water is a major environmental problem that alters the taste of water, disturbs the digestive systems of animals and humans, and erodes both soil and metals. In this study, the layered double hydroxide LDH 4Mg2Al·NO₃ and LDH 8Mg2Al·NO₃ were prepared using a co-precipitation technique, and applied in the adsorption of SO₄^2- from an aqueous solution. The reaction is well described by the Langmuir adsorption model. LDH 4Mg2Al·NO₃ and LDH 8Mg2Al·NO₃ afforded maximum SO₄^2- adsorption values of 135.14 and 92.59 ​mg/g, respectively. The reaction is best explained by a pseudo-second-order mechanism, which suggests that chemisorption is the rate-determining step. The activation energies of LDH 4Mg2Al·NO₃ and LDH 8Mg2Al·NO₃ indicate that the adsorption of SO₄^2- on synthetic LDHs predominantly follows an anion-exchange mechanism, wherein SO₄^2- ions in the aqueous medium replaces intercalated NO₃^- ions in the synthetic LDHs. The thermodynamic parameters (ΔH̊, ΔS̊, and ΔG̊) were also calculated. The reaction was endothermic, and the synthetic LDHs afforded feasible and spontaneous adsorption of SO₄^2-.     

Layer‐by‐layer deposition of nitrilotris(methylene)triphosphonic acid and Zr(IV): an XPS,ToF‐SIMS,ellipsometry, and AFM study

Layer‐by‐layer assemblies consisting of alternating layers of nitrilotris(methylene)triphosphonic acid (NTMP), a polyfunctional corrosion inhibitor, and zirconium(IV) were prepared on alumina. In particular, a nine‐layer (NTMP/Zr(IV))₄NTMP stack could be constructed at room temperature, which showed a steady increase in film thickness throughout its growth by spectroscopic ellipsometry up to a final thickness of 1.79 ± 0.04 nm. At higher temperature (70 °C), even a two‐layer NTMP/Zr(IV) assembly could not be prepared because of etching of the alumina substrate by the heated Zr(IV) solution. XPS characterization of the layer‐by‐layer assembly showed a saw tooth pattern in the nitrogen, phosphorus, and zirconium signals, where the modest increases and decreases in these signals corresponded to the expected deposition and perhaps removal of NTMP and Zr(IV). Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) confirmed the attachment of the NTMP molecule to the surface through PO^?, PO₂^?, PO₃^?, and CN^? signals. Increasing attenuation of the Al signal from the substrate after deposition of each layer was observed by both XPS and ToF‐SIMS. Essentially complete etching of the alumina by the heated Zr(IV) solution was confirmed by spectroscopic ellipsometry, XPS, and ToF‐SIMS. Atomic force microscopy revealed that all the films were smooth with R_q roughness values less than 0.5 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

β‐Cyclodextrin‐catalyzed decomposition of Caro's acid

The kinetics and mechanism of decomposition of peroxomonosulphate (PMS) in aqueous sodium hydroxide medium in the presence β‐cyclodextrin has been investigated. The rate of decomposition of PMS is considerably enhanced by the added β‐cyclodextrin. The reaction follows first order kinetics with respect to [PMS]. The experimental results suggest the formation of β‐cyclodextrin peroxy anion by the interaction between SO₅^2?, and β‐cyclodextrin anion (BCDO^?). β‐Cyclodextrin peroxy anion subsequently reacts with PMS to give O₂, SO₄^2? and β‐cyclodextrin anion. The rate constant for the β‐cyclodextrin‐catalyzed decomposition of SO₅^2? (BCD + SO₅^2?) is of the same order of magnitude as that of the reaction HSO₅^2? + SO₅^2? products. © 2002 Wiley Periodic mals, Inc. Int J Chem Kinet 34: 508–513, 2002     

Use of Pd-catalyzed Suzuki-Miyaura coupling reaction in the rapid synthesis of 5-aryl-6-(phosphonomethoxy)uracils and evaluation of their inhibitory effect towards human thymidine phosphorylase

A number of new 5-aryl substituted pyrimidine acyclic nucleoside phosphonates were synthesized and tested for their ability to inhibit human TP. Their rapid synthesis using Pd-catalyzed Suzuki-Miyaura coupling reactions of various arylboronic acids with 5-bromo-4-(phosphonomethoxy)-2,6-dibutoxypyrimidine was successfully applied. For a series of 5-aryl-6-phosphonomethoxyuracils, an increased inhibitory effect was determined. This effect is supported by the results found for 4-fluorophenyl (K_i^dThd=4.89±0.62) and 3-nitrophenyl (K_i^dThd=3.98±0.46) substituents.     

Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity

Singlet oxygen (¹O₂) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single-site type catalysts, the control and regulation of ¹O₂ generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well-defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)-based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway with 100 % ¹O₂, whereas biphenyl-based COFs (BPD-COFs) with almost identical structures activate PMS to produce radicals (⋅OH and SO₄^.−). The BPY-COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD-COFs counterpart, surpassing most reported PMS-based AOPs systems. Mechanism analysis indicated that highly electronegative pyridine-N atoms on BPY-COFs provide extra sites to adsorb the terminal H atoms of PMS, resulting in simultaneous adsorption of O and H atoms of PMS on one pyridine ring, which facilitates the cleavage of its S−O bond to generate ¹O₂.     

Ag-single atoms modified S1.66-N1.91/TiO2-x for photocatalytic activation of peroxymonosulfate for bisphenol A degradation

In this study,Ag_0.23/(S_1.66-N_1.91/TiO_2-x) single-atom photocatalyst was synthesized by in-situ photoreducing of silver on S,N-TiO_2-x nanocomposite and used to degrade bisphenol A（BPA） through heterogeneous activation of potassium peroxymonosulfate（PMS） under visible-light illumination.The structure,physicochemical property,morphology,and electronic property were evalutated by X-ray diffraction（XRD）,Raman spectrum,X-ray photoelectron spectra（...     

Novel reusable sulfate-type zirconium alginate ion-exchanger for fluoride removal

It is still a challenge to eliminate efficiently fluoride ion from groundwater, especially to design and synthesis an adsorbent possessing high adsorption capacity, recyclability and wide pH application conditions. Herein we present millimeter-sized sulfate-type zirconium alginate hydrogel beads with 3D network structure (AHB@Zr-SO₄²⁻) that exhibited a maximum adsorption capacity of 101.3 mg/g with wide pH applicability (pH 3−9). This material have ~2.5 times higher adsorption capacity than that of pure zirconium alginate hydrogel beads (AHB@Zr) and it was ascribed to ion exchange between SO₄²⁻ and F⁻ on the surface of AHB@Zr-SO₄²⁻, which was verified via ion chromatography measurement coupled with X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectrometer (FTIR Spectrometer) analysis. Density functional theory (DFT) calculations indicated that the ion exchange process between SO₄²⁻ and F⁻ in AHB@Zr-SO₄²⁻ was energetically favorable than OH⁻ and F⁻ in AHB@Zr. In addition, 310 bed volumes (BV) of effluent was realized via column adsorption of groundwater containing fluoride on AHB@Zr-SO₄²⁻ and indicated that it is a promising candidate for mitigating the problem of fluoride-containing groundwater.     

Enhanced degradation of organic contaminants by Fe(III)/peroxymonosulfate process with l-cysteine

The difficulty in Fe(III)/Fe(II) conversion in the Fe(III)/peroxymonosulfate (PMS) process limits its efficiency and application. Herein, l-cysteine (Cys), a green natural organic ligand with reducing capability, was innovatively introduced into Fe(III)/PMS to construct an excellent Cys/Fe(III)/PMS process. The Cys/Fe(III)/PMS process, at room temperature, can degrade a variety of organic contaminants, including dyes, phenolic compounds, and pharmaceuticals. In subsequent experiments with acid orange 7 (AO7), the AO7 degradation efficiency followed pseudo-first-order kinetic which exhibited an initial “fast stage” and a second “slow stage”. The rate constant values ranged depending on the initial Cys, Fe(III), PMS, and AO7 concentrations, reaction temperature, and pH values. In addition, the presence of Cl^?, NO₃^?, and SO₄^2? had negligible impact while HCO₃^? and humic acid inhibited the degradation of AO7. Furthermore, radical scavenger experiments and methyl phenyl sulfoxide (PMSO) transformation assay indicated that sulfate radical, hydroxyl radical, and ferryl ion (Fe(IV)) were the dominant reactive species involved in the Cys/Fe(III)/PMS process. Finally, based on the results of gas chromatography-mass spectrometry, several AO7 degradation pathways, including N=N cleavage, hydroxylation, and ring opening were proposed. This study provided a new insight to improve the efficiency of Fe(III)/PMS process by accelerating Fe(III)/Fe(II) cycle with Cys.     

Constructing heterojunction interface of Co3O4/TiO2 for efficiently accelerating acetaminophen degradation via photocatalytic activation of sulfite

Achieving efficient degradation of organic pollutants via activation of sulfite is meaningful but challenging. Herein, we have constructed a heterogeneous catalyst system involving Co₃O₄ and TiO₂ nanoparticles to form the p-n heterojunction (Co₃O₄/TiO₂) to degrade acetaminophen (ACE) through photocatalytic activation of sulfite. Specifically, X-ray photoelectron spectroscopy analysis and theoretical calculations provide compelling evidence of electron transfer from Co₃O₄ to TiO₂ at the heterointerface. The interfacial electron redistribution of Co₃O₄/TiO₂ tunes the adsorption energy of HSO₃^?/SO₃^2? in sulfite activation process for enhanced the catalytic activity. Owing to its unique heterointerface, the degradation efficiency of ACE reached 96.78% within 10 min. The predominant active radicals were identified as ^?OH, h⁺, and SO_x^?? through radical quenching experiments and electron spin resonance capture. Besides, the possible degradation pathway was deduced by monitoring the generated intermediate products. Thereafter, the enhanced roles of well-engineered compositing interface in photocatalytic activation of sulfite for complete degradation of ACE were unveiled that it can improve light absorption ability, facilitate the generation of active species, and optimize reactive pathways. Considering that sulfite is a waste from flue gas desulfurization process, the photocatalytic activation of sulfite system will open up new avenues of beneficial use of air pollutants for the removal of pharmaceutical wastewater.