CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Min Wang,Runren Jiang,Guanghua Lu,Tianjian Dang,Yufang Chen,Jianchao Liu,Jun Hou
The development of efficient and sustainable environmentally functional material is a crucial approach to global water pollution control. Single-atom catalysts (SACs) Fenton technology, as a promising means of water treatment, still suffers from problems such as the single active site and secondary pollution caused by metal ion leaching. In this study, trace Co single atoms (SAs) are chelated by tannic acid to reduce metal ion leaching and anchored to g-C 3 N 4 containing nitrogen vacancy (V N ). DFT calculation results reveal that the d-band structure of Co SAs is regulated by orbital hybridization with the electronic states of coordinating atoms in V N -CoN 3 O 1 , which further improves the intrinsic activity of Co SAs in asymmetric coordination. In addition, V N acts as the charge transfer bridge of the V N -CoN 3 O 1 /PMS/BPS system, transferring the electrons captured from BPS to the adjacent asymmetric Co SAs, further enhancing the activation ability of the Co SAs sites. Benefiting from the tuning between the dual active sites, V N -CoN 3 O 1 with asymmetric coordination and nitrogen vacancies in the PMS system exhibits a high degradation rate (99%) and high mineralization (75.1%) for bisphenol S (BPS) in 30 min. After multi-factor experiments and five consecutive cycles, the system maintained high efficiency in degrading electron-rich BPS. In addition, BPS as the electron provider transporting to V N -CoN 3 O 1 and was effectively degraded by a non-radical dominated 1 O 2 conversion pathway of (PMS → PMS* → OH* + SO 4 * → O* + H* → OO* → 1 O 2 ) with OO* as the rate-determining step. This study highlights the feasibility of dual-active site structural engineering-nitrogen vacancy and asymmetric coordination tuning for single-atom Fenton chemistry and inspires rational SACs design in water purification.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 20
·7064
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IF 4.927
Jia Liu,Chao Ding,Sicheng Gong,Kun Fu,Huiping Deng,Jun Shi
The nonradical process in the peroxydisulfate (PDS) oxidation system is a promising method for antibiotic removal in water. In this study, CuO@CNT was successfully synthesized by a facile approach to catalyze PDS. The removal efficiency of the antibiotic sulfamethoxazole (SMX) was 90.6% in 50 min, and the stoichiometric efficiency (ΔSMX/ΔPDS) was 0.402. The very different degradation efficiency of common organic contaminants revealed the selective oxidation of the surveyed system. The process of1O2oxidation and the electron-transfer regime was exhibited by chemical quenching tests, electron paramagnetic resonance (EPR) determination, a UV–vis spectrophotometer, X-ray photoelectron spectroscopy (XPS) detection, and cyclic voltammetry (CV) measurements. Sustainable catalysis was promoted by the circulation between the surface electron-rich centers of Cu(II) and Cu(III). Dissolved oxygen (DO) and a metastable Cu(III) intermediate contributed to the generation of1O2. Still, a portion of SMX was removed by the mildly activated PDS. Moreover, the influence factors (pH, dosage, water matrix) were examined, and suppressions were acceptable by common anions and real water. Distinguished from the radical process, unique intermediate products were ascertained via the theoretical calculation and liquid chromatography–mass spectrometry (LC-MS) detection. Furthermore, CuO@CNT showed a satisfactory activation ability in the cycling experiments. Overall, this study developed CNT to be a supporter of CuO, unveiled the mechanism of catalysis, and evaluated the application potential of the nonradical process.Keywords:peroxydisulfate;nonradical process;singlet oxygen;trivalent copper;electron transfer
研究领域:
环境科学
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化学
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DOI
PubMed
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 35
·e202402568
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IF 1.9
Rui Zhu,Xinglong Li
Graphical A photocatalytic selective oxidation strategy for preparing DFF from HMF is developed, using Ag/Ag 3 PO 4 as the photocatalyst and O 2 as the oxidizing agent. In contrast to previous photocatalytic oxidation strategies for HMF transformation, this catalytic system could efficiently generate 1 O 2 without other ROS under visible light irradiation. DFF would be obtained with 88 % selectivity with the optimal reaction conditions. The synthesis of 2,5-diformylfuran (DFF) through photocatalytic oxidation of 5-hydroxymethylfurfural (HMF) is an attractive approach. In this manuscript, a photocatalytic selective oxidation strategy for HMF was developed, using Ag/Ag 3 PO 4 as the photocatalyst and O 2 as the oxidizing agent. The prepared catalyst was characterized systematically by SEM, XRD, XPS, UV-Vis, PL spectra, and so on. In contrast to previous photocatalytic oxidation strategies for HMF conversion, this catalytic system could efficiently generate 1 O 2 without other reactive oxygen species (ROS) under visible light irradiation. DFF would be obtained with about 90 % selectivity. Moreover, the exclusive formation of 1 O 2 was linked to the more positive conduction band potential (+0.90 eV) of Ag/Ag 3 PO 4 , confirmed by an array of characterization techniques. Additionally, the stability of the catalyst was assessed through cyclic testing and analyses including XRD, and XPS. Nonetheless, this catalytic system could potentially serve as a robust platform for various selective oxidation reactions in the future, due to its exclusive presence of 1 O 2 without the involvement of other ROS.
研究领域:
化学
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环境科学
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材料科学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2021
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IF 7.312
Huan Xia,Hailan Qin,Yushan Zhang,Hang Yin,Qiang Li,Fei Pan,Dongsheng Xia,Dongya Li,Haiming Xu
Enhance the concentration of singlet oxygen ( 1 O 2 ) to ameliorate the photocatalytic performance is a promising strategy. Therefore, Z-scheme Mo 2 S 3 /BiOCl heterostructure with rational oxygen vacancies (OVs) was successfully synthesized by in-situ template method to tackle these issues. Characterization results reveal that the OVs were efficiently passivated by forming Mo–O bond at the interface of Mo 2 S 3 and BiOCl. Moreover, the photocatalytic mechanism research reflects that the interfacial electric field not only enhance the spatial separation and migration efficiency of the photo-induced carriers but also benefit producing abundant 1 O 2 , and thus TC-HCl was purified 90.8% in 90 min. Meanwhile, the contribution of the reactive oxygen species to the photocatalytic activity and the formation path of 1 O 2 were comprehensively studied for the first time. This work provides a new avenue to study the formation path of 1 O 2 and offer a polishing strategy to mend the photocatalytic activity by modulate the concentration of 1 O 2 .
研究领域:
材料科学
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环境科学
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光催化技术
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DOI
高影响因子
NANO
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2024
·
IF 1
Sai Wang,En-Ni Wu,Liang Meng,Zhen-Jun Wang,Tuan-Tuan Wang
To improve the activation efficiency of PMS to efficiently degrade antibiotic sulfadiazine (SD), herein, a Co@MoS 2 catalyst was prepared by a one-step hydrothermal process. The unique petal-like structure of MoS 2 enables the transition metal Co to achieve high dispersion and avoid agglomeration. Mo(IV) and unsaturated S accelerate the electron transfer between Co 2 + and Co 3 + to improve the cycling efficiency and thus realize the efficient activation of PMS. The results of active substance quenching experiment and ESR analysis show that the main active substance for the efficient degradation of SD by Co@MoS 2 is the non-radical 1 O 2 , while the other three radicals ⋅ O − 2 , ⋅OH and SO • − 4 contribute significantly to the efficient degradation of SD. And after 5 cycles, the degradation could still be as high as 90%. The strong consolidation of Co on the petal-shaped sheet of MoS 2 ensures the stability of Co@MoS 2 catalyst.
研究领域:
环境科学
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催化
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纳米技术
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化学工程
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DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Yuzheng Wu,Jinyi Tan,Zifan Li,Luwen Liang,Bing Chen,Xinwen Ou,Shan Yao,Guiquan Che,Youqun Wang,Bin Han
Singlet oxygen ( 1 O 2 ) is one of the most important pivotal reactive oxygen species (ROSs) in environmental remediation; however, the selective formation of 1 O 2 in Fenton-like reactions is severely hindered by the disordered redox reactions of oxidants. Here, by microenvironment engineering of the anthraquinone site in covalent organic frameworks (COFs), we present a facile approach for the directed oxidation of peroxymonosulfate (PMS) to produce 1 O 2 efficiently and selectively. Under visible light irradiation, anthraquinone-based COFs with β -ketoenamine units (DQTp COFs) deliver efficient 1 O 2 generation with near 100 % selectivity, outperforming most reported systems, while its counterpart with imine linkage (DQTb COFs) produces mixed ROSs with much lower efficiency. Hence, the DQTp COFs/PMS photocatalytic system can selectively degrade various emerging pollutants with boosted performance. A DQTp COFs-based membrane reactor (20 × 30 × 2 cm) exerts long-lasting pollutants degradation under natural sunlight, demonstrating great application potential. Experiments and theoretical results reveal that β -ketoenamine units facilitate the separation of charge pairs, facilitate the hole aggregation, and PMS adsorption simultaneously on the adjacent anthraquinone sites. Therefore, the adsorbed PMS is oxidized to SO 5 •− intermediates, which can then dimerize to produce 1 O 2 . This work provides atomic-level insights for precisely controlling the formation of ROSs in Fenton-like reactions by site engineering of COFs.
研究领域:
环境化学
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材料科学
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光催化
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高级氧化技术
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纳米材料
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DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·Vol. 13
·期 6
·120354
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IF 7.2
Dan Dang,Xinyi Jiang,Juncheng Zhang,Yichao Wu,Baoxin Zha,Yingying Zhao
The valorization of crude glycerol, a major byproduct of biodiesel production, into high-value chemicals is critical for sustainable biorefineries. Herein, we report a novel alkali-free and homogeneous photocatalytic strategy for selectively converting glycerol to glycolic acid (GLYA) and formic acid (FA) using H 2 O 2 as a radical initiator under 365 nm UV irradiation. By optimizing volume fraction of H 2 O 2 (3.18％), light intensity (10 W), and temperature (35 °C), 99.3 % glycerol conversion with 23.47 % GLYA yield and 22.66 % FA yield was achieved within 2 h at ambient pressure. Crucially, scavenging experiments, post-illumination reactivity studies and the electron paramagnetic resonance (EPR) spectra revealed a synergistic •OH /•O 2 ⁻/ 1 O 2 radical cycle triggered by H 2 O 2 photolysis: (1) •OH initiates glycerol oxidation to glyceraldehyde; (2) •O 2 ⁻ (generated from O 2 reduction or H 2 O 2 decomposition) produces 1 O 2, which drives selective C-C cleavage to GLYA; (3) •OH/•O 2 ⁻/ 1 O 2 cycle enables mutual regeneration of active species, sustaining oxidation even after light cessation. This autocatalytic cycle eliminates the need for strong bases or noble metals, offering a green, energy-efficient route for glycerol upcycling.
研究领域:
催化化学
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绿色化学
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可再生能源
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环境科学
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化学工程
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DOI
高影响因子
ENVIRONMENTAL RESEARCH
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2025
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IF 7.7
Zhiying Lv,Feng Liu,Hong You,Haoran Leng,Weirun Li,Zhipeng Li,Jing Zhu,Guoyu Zhang
The massive use of antibiotics had induced gene mutations in microbial communities within waste sludge. It was necessary for environment treatment to co-disposal of sludge and antibiotic-containing residues. In this paper, ultrasonic (US) coupling of iron carbon (Fe-C) activated persulfate (PDS) demonstrated exceptional efficacy for sludge conditioning with the dehydration efficiency (88 %), the bound water content reduction (28 %) and the sludge reduction efficiency (25 %). The contents of characteristic organic matter were effectively degraded, such as humic acid (C1), tryptophan-protein-like (C2) and fulvic acid-like (C3) in sewage sludge. The free radical capture and EPR were utilized to determine reactive oxygen species (ROS) in the US/Fe-C/PDS system, where concentration of singlet oxygen ( 1 O 2 ) was as high as 1.2 × 10 −10 mol/L to enhance the non-radical attack pathways. In addition, the degradation efficiency of model antibiotic - ciprofloxacin (CIP) was as high as 71 % in the sludge conditioning process. The CIP degradation pathways were speculated to attacked mainly by free radical (4C- quinolones) and 1 O 2 (11N- piperazine ring and 8C- quinolones) to degrade small molecules. TEST analytical results confirmed that 1 O 2 -mediated degradation of CIP significantly reduced both ecotoxicological effects and mutagenic potential, as validated through comprehensive toxicity evaluation assays.
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PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2018
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IF 11.698
Shuai Zhao,Zan Dai,Wenjin Guo,Fengxi Chen,Yunling Liu,Rong Chen
Selective oxidation of glycerol to produce aimed high-value added products is of great importance in chemical industry. Photocatalytic oxidation provides a promising and green strategy for selective glycerol oxidation. In this work, we develop a Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure via a facile solvothermal method for the selective oxidation glycerol to 1, 3-dihydroxyacetone (DHA) in water under visible light irradiation. The excellent performance in activity and selectivity of Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure for DHA production is attributed to a dual-pathway photocatalytic reaction process. The mass production 1 O 2 ascribed to the reduced energy gap (ΔE ST ), the enhanced spin-orbit coupling (SOC) and the presence of oxygen vacancy is beneficial for the selective oxidation of glycerol to DHA. Simultaneously, the metallic bismuth in the heterostructure promotes the separation of photogenerated holes with efficient redox potential and facilitates the binding bismuth with ortho-hydroxyl in glycerol, thus enhancing the yield and selectivity of DHA production. This work provides a novel strategy and thorough understanding of the development of highly efficient bismuth-based photocatalyst for selective oxidation in organic reactions.
研究领域:
化学工程
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材料科学
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催化反应
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2026
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IF 9.1
Huirong Zhang,Xueer Luo,Yang Bai,Bin Li,Hao Fu,Kunlin Wu,Bo Wang,Yun Zhang
The non-selective decomposition of hydrogen peroxide into hydroxyl radicals often plagues heterogeneous oxidation, critically limiting its chemoselectivity for applications like oxidative desulfurization (ODS). Here, we demonstrate a strategy to program the H 2 O 2 activation pathway by designing a ZrO 2 @W 2 C-WO x heterostructure. Interfacial electron transfer from ZrO 2 to W 2 C establishes a built-in electric field, inducing an amorphous, mixed-valent WO x shell. This unique electronic interface enables synergistic dual-site activation of H 2 O 2 at adjacent Zr and WO x motifs, promoting a surface peroxo-intermediate pathway that selectively yields singlet oxygen ( 1 O 2 ). The catalyst exhibits a high turnover frequency (TOF) of 470 h −1 for ODS under mild conditions. Crucially, it demonstrates exceptional chemoselectivity, with reactive oxygen species (ROS) partitioning dominated by 1 O 2 ( 1 O 2 ≫ •O 2 − > •OH). This selectivity ensures robust performance across high sulfur loadings (500–2000 ppm S) and in the presence of fuel-relevant interferents. The catalyst's proven stability and low leaching highlight its industrial potential. By engineering an interfacial charge-transfer heterojunction with a built-in electric field coupled with a redox-active WO x shell, this work provides a blueprint for steering ROS generation toward non-radical pathways for precise, selective oxidation.
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高影响因子
Surfaces and Interfaces
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2026
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IF 6
Xiaoyan Li,Hongbin Zhang
CaO/MgO-Mn 3 O 4 catalysts were prepared for the activation of PMS to degrade TC. • Revealing the non-radical degradation pathway dominated by 1 O 2 . • The system demonstrated excellent anti-interference ability and stability. • The surface -OH played a bridging role in the generation of ROSs. • Predicted the biological toxicity of the TC intermediate. In advanced oxidation processes, free radical-mediated mechanisms have garnered considerable research interest for the remediation of emerging contaminants (ECs). However, compared with non-radical pathways, free radical pathways were prone to side reactions and exhibited poorer environmental adaptability. In this study, alkaline earth metal-doped Ca/Mg-Mn 3 O 4 catalysts with different doping ratios were synthesized to activate peroxymonosulfate (PMS) for the degradation of tetracycline (TC). The optimized catalyst, Ca-Mn 3 O 4 - 10%, achieved 86% TC removal within 90 min, with an apparent rate constant of 0.0218 min −1 , which is 3.04 times higher than that of the pristine Mn 3 O 4 /PMS system. Free radical quenching experiments demonstrated that the degradation of TC was predominantly attributed to a non-radical pathway dominated by singlet oxygen. After five consecutive cycles, the Ca-Mn 3 O 4 - 10% catalyst still maintained a degradation efficiency over 82%, showing excellent catalytic stability. Furthermore, the catalyst exhibited strong resistance to common anions, organic substances, changes in solution pH, and various water matrices. Based on the identification of intermediate products, three degradation pathways were proposed. Toxicity assessment using a predictive model indicated that the biological toxicity of most degradation products was significantly reduced. This study offers new insights and theoretical support into the degradation of wastewater containing ECs via a non-radical mechanism. Download: Download high-res image (273KB) Download: Download full-size image
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DOI
高影响因子
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
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2025
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IF 7.8
Fali Hou,Wei Li,Kaiying Yang,Daoli Yang,Wenjie Zhu,Yongming Luo,Xiaoya Gao
Developing highly anti-interference and nonmetallic peroxymonosulfate (PMS) based advanced oxidation systems is of great importance to remove the persistent contaminants. Herein, the modified biochar (MBC) by Na 2 CO 3 was successfully prepared via ball milling and pyrolysis treatments. Characterization results showed that the MBC had better-developed porosity, richer C=O content, higher defective degree, and lower charge-transfer resistance than the original biochar. The performance of CBZ removal by the MBC was systematically investigated in terms of biochar dosage, PMS concentration, pH, and water matrixes. 0.1 g/L MBC could firstly adsorb 44% of CBZ (2.5 mg/L) within 20 min and then completely remove CBZ within 40 min in the presence 2.0 mM of PMS. A nonradical process of CBZ degradation dominated by 1 O 2 and electron transfer was identified via quenching experiments, electron paramagnetic resonance spectra, and electrochemical characterizations. Consequently, the MBC/PMS system could realize a high CBZ degradation in a wide pH range (3.0−11.0), exhibit strong water matrixes tolerance, and display excellent performance in the real environmental water systems. Furthermore, the removal rate of CBZ could still reach 90% after five reuses. Overall, this study developed an efficient metal-free biochar catalyst that demonstrates exceptional adaptability, stability, and reusability for removing emerging contaminants in environmental remediation applications.
研究领域:
环境科学
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催化化学
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DOI
高影响因子
危险品化学品经营许可证（带存储）