SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Shuhong Liu,Zhongping Yao,Yanjing Liu,Jiankang Wang,Xiao Zhang,Ying Song,Wanqian Guo,Xiaohong Wu
Singlet oxygen ( 1 O 2 ) offers unique advantages for contaminant degradation owing to its high oxidative selectivity, long half-life, and pH-independent reactivity. However, the spin-forbidden transition between molecular oxygen (triplet state, 3 O 2 ) and 1 O 2 severely limits their interconversion under energy-free conditions. Herein, we innovatively prepared a nitrogen-doped carbon-coated copper-cobalt alloy catalyst (CuCo@NC) that hierarchically activated molecular oxygen into 1 O 2 . The optimized CuCo@NC600 demonstrated exceptional performance: achieving 96.79 %-98.91 % Norfloxacin (NOR) removal and ∼70 % mineralization within 40 min across a broad pH range of 3–11 under conditions of 1.0 g/L catalyst and 20 mg/L NOR. The catalyst exhibited remarkable versatility, degrading diverse organic pollutants (rhodamine B, tetracycline hydrochloride, etc.) with > 90 % efficiency and strong anti-interference capability against common ions and organic matter. No significant performance degradation was observed in both real wastewater and surface water systems. Radical quenching experiments confirmed 1 O 2 as the dominant reactive species generated through hierarchically activating O 2 by Cu-Co collaboration: molecular oxygen is initially activated at Cu sites, generating •O 2 – and •OH, which are then captured and converted to 1 O 2 at Co sites. The preserved catalytic stability (>70 % efficiency after 3 cycles) originated from the protective carbon matrix and self-compensating Cu + /Cu 2+ –Co 2+ /Co 3+ valence transitions. LC-MS-identified intermediates revealed three detoxification pathways. This work provided an energy-efficient and environmentally friendly strategy for 1 O 2 -dominated advanced oxidation processes, demonstrating significant potential for antibiotic-polluted water remediation.
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JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Chenghui Luo,Shengkun Zhang,Yue Chen,Lixiao Wang,Lihua Cheng,Jianna Jia,Xinhua Xu
Single-atom catalysts hold great promise for peroxymonosulfate (PMS)-activated non-radical pathways, yet achieving high singlet oxygen ( 1 O 2 ) selectivity remains a significant challenge. In this work, we developed a six-coordinated Fe-N 6 single-atom catalyst via a cascading anchoring strategy, enabling efficient PMS activation. Remarkably, this catalyst achieves 99.18 % 1 O 2 generation selectivity and demonstrates outstanding degradation performance for levofloxacin (LEV) with a reaction rate constant of 1.475 min −1 . Experimental and theoretical analyses reveal that the isolated Fe sites enhance the adsorption selectivity of terminal oxygen atoms of PMS, creating an optimal platform for generating metastable Fe intermediates. The highly oxidized metal centers of Fe act as electron acceptors to receive electrons from adsorbed PMS, thereby producing highly reactive 1 O 2 for rapid LEV oxidation. This work elucidates the crucial role of Fe-N 6 coordination in dictating PMS activation pathways, offering mechanistic insights for designing catalysts with high selective 1 O 2 generation.
研究领域:
环境催化
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环境化学
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材料化学
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分子催化
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水处理技术
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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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JOURNAL OF HAZARDOUS MATERIALS
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2025
·
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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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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ENVIRONMENTAL RESEARCH
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2020
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IF 5.715
Li Liu,Yunong Li,Wei Li,Ruixue Zhong,Yeqing Lan,Jing Guo
Co 3 O 4 –SnO 2 /rice straw biochar (RSBC) was prepared for the first time via calcining oxalate precipitation precursor dispersed on the surface of RSBC and used as a catalyst for activating PMS to degrade sulfisoxazole (SIZ). The results demonstrated that Co 3 O 4 –SnO 2 /RSBC possessed much better catalytic performance than Co 3 O 4 , Co 3 O 4 –SnO 2 , Co 3 O 4 /RSBC, and SnO 2 /RSBC, which is ascribed to the synergy of Co 3 O 4 , SnO 2 and RSBC. Approximately 98% of SIZ (50 mg/L) was decomposed by PMS (1 mmol/L) activated with Co 3 O 4 –SnO 2 /RSBC (0.1 g/L) within 5 min. The optimal degradation efficiency of SIZ was realized at the initial pH 9. Co 3 O 4 –SnO 2 /RSBC also displayed remarkable stability and reusability, and the degradation rate of SIZ maintained over 90% even after the fifth recycle run. The electron paramagnetic resonance (EPR) technique and quenching experiments proved singlet oxygen ( 1 O 2 ) to be the main reactive oxygen species (ROS) responsible for the SIZ decomposition in the Co 3 O 4 –SnO 2 /RSBC/PMS system. On the basis of the characterization analysis, the identification of the ROS and the SIZ degradation products , the possible mechanism and pathways of the SIZ degradation by a combination of PMS and Co 3 O 4 –SnO 2 /RSBC were further proposed. This study provides not only a new insight into non-radical mechanism for the heterogeneous activating PMS over Co 3 O 4 –SnO 2 /RSBC to degrade organic pollutants but also an eco-friendly synthetic route for exploring novel and efficient catalysts.
研究领域:
环境科学
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催化化学
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Science China-Materials
·
2022
·Vol. 65
·期 11
·3053-3061
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IF 8.64
Ma Yiyuan,An Yurong,Xu Zhuo,Cheng Laifei,Yuan Wenyu
The poor oxygen evolution reaction (OER) activity of two-dimensional (2D) transition metal carbides (MXenes) is a major obstacle to their application in highperformance water splitting and fuel cells due to the high energy barriers for the absorption of intermediates. Here, we demonstrate that the lattice oxygen of M n X n −1 O 2 MXenes can be activated by 0D graphene quantum dots (GQDs), thereby activating the OER via the lattice-oxygen oxidation mechanism (LOM) instead of the conventional adsorbate evolving mechanism. The pH-dependent OER activity of M n X n −1 O 2 @GQDs and 18 O isotope-labelling experiments with time-of-flight secondary-ion mass spectrometry (TOF-SIMS) provide the direct evidence of LOM. Interestingly, the activated lattice oxygen amount can be controlled by the GQDs. The as-prepared 0D/2D Ti 3 C 2 O 2 @GQDs heterostructure delivers a highly reduced overpotential of 390 mV (bare Ti 3 C 2 O 2 : 530 mV) at a benchmark current density of 10 mA cm −2 . Through optimizing the thickness and the additional conductive substrate, the overpotential at 10 mA cm −2 decreases to 250 mV, while the Tafel slope is reduced to 39 mV dec −1 ; these values indicate the as-prepared heterostructure is superior to the state-of-the-art MXene-based OER catalysts. This work provides a new strategy to enhance the OER activity of M n X n −1 O 2 and extends the application of LOM from perovskite to MXenes.
研究领域:
材料科学
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能源化学
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SCIENCE OF THE TOTAL ENVIRONMENT
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2022
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IF 10.753
Lijun Guo,Liming Zhao,Yuling Tang,Jianfei Zhou,Bi Shi
Efficient degradation of organic contaminants by oxidative radicals remains a challenge due to invalid consumption of radicals and easy generation of secondary halogenated pollutants. In this work, an efficient and recyclable bimetallic biochar (Cr-Ti/BC) was developed through peroxydisulfate (PDS) activation via nonradical pathway for sulfamethoxazole (SMX) degradation. The Cr-Ti/BC exhibited excellent catalytic activity for 99.9 % of SMX removal with a high k obs of 0.13 min −1 , and negligible inhibitory effects were observed under various pH condition. The activation mechanisms were (i) metastable reactive intermediates (Cr-Ti/BC-PDS) formation via an interaction between Cr-Ti/BC and PDS on the active defective sites (e.g., OH/C O C, COOH, C O, nitric oxides, graphitic N, and pyridinic N), and (ii) 1 O 2 generation through electron transfer between Cr-Ti/BC-PDS intermediates and dissolved oxygen. The high reusability and strong stability of Cr-Ti/BC also verified the outstanding advantage of the Cr-Ti/BC during practical application. This study not only is the first study the catalytic performance of Cr and Ti co-doped biochar for PDS activation, but also successfully provides a promising strategy to induce a nonradical pathway for PDS activation, which is of great significance for the subsequent method design, and thus paving the path for exploiting advanced oxidation systems in practical application for organic contaminant removal toward polluted site remediation.
研究领域:
环境科学
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污染修复
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
·
IF 21.1
Qian-Qian Tang,Bang-Xiang Wu,Xiao-Wen Huang,Yi Hu,Dongmei Hou,Wei Ren,Ling-Ling Liu,Ying Chen,Lei Tian,Long-Shuai Zhang,Qing Sun,Jian-Ping Zou
Highly selective generation of singlet oxygen ( 1 O 2 ) in the electro-Fenton system remains challenging due to susceptibility of the O-O bond to break in O 2 reduction reaction and activation process of H 2 O 2 . Herein, the nitrogen-coordinated Fe single-atom catalyst with a high coordination number (FeN 6 /CN) was synthesized, allowing the Fe sites to remain trivalent while presenting a high spin state. The quenching experiments and EPR tests proved that the electro-Fenton system of FeN 6 /CN achieved high selectivity generation of 1 O 2 , showing excellent degradation performance of different organic pollutants. Combined with theoretical calculations, the FeN 6 sites displayed a lower energy barrier for the transfer from *H 2 O 2 to 1 O 2 . In the FeN 6 /CN’s electro-Fenton system, the high spin state of FeN 6 site ensured generation of H 2 O 2 via 2e - reduction. Simultaneously, the high oxidation state of FeN 6 site further achieved a highly selective generation of 1 O 2 by in situ activation of H 2 O 2 in the electro-Fenton system. Particularly, the FeN 6 /CN’s electro-Fenton system showed a high energy-efficient for pollutant removal (23.79 kWh·kg toc −1 ) compared to other electro-Fenton systems (50–300 kWh·kg toc −1 ). The electronic structure regulation of single atom sites provides a new avenue for highly selective generation of 1 O 2 in the electro-Fenton system.
研究领域:
环境科学
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材料科学
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化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Ming Ma,Yuxin Lu,Sheng Wang,Shangkun Pei,Chong-Chen Wang,Xiang Li,Bo Wang
Slfamethoxazole (SMX) has been considered as one kind of important micropollutants in water which need to be removed effectively. Developing one kind of material for effectively removing SMX in water is crucial in treatment process. In this study, core–shell structured metal–organic frameworks (MOFs) with increasing shell thickness (5, 10, and 20-ZIF-8@ZIF--67 s) were selected as an ideal platform to develop water-stable hierarchical porous carbons (HPCs) using one-step calcination, showing the dual functionals of both adsorption and catalysis by producing large amount of acitve species ( 1 O 2 ). These novel HPCs systematically optimized at increasing temperatures and ratios of two metals. The 10-Co-NHPC-900 at optimal conditions shows highest adsorption capacities and initial adsorption rates, which are 4.56 and 10.35 times higher than those of calcinated ZIF-67 s. The decomposition mechanisms based on PMS were systematically studied by analyzing oxidant consumption, reactive oxygen species and by-products of SMX. In addition, Co ions leached amount of 10-Co-NHPC-900 was 63.6 times lower than that of MOF precursor, indicating that the cobalt-based porous carbon have higher water stabilities. This study offers an efficient approach for reducing micropollutants risk using water-stable hierarchical porous carbons.
研究领域:
环境科学
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材料科学
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Kaige Li,Jianhua Qu,Zhengni Pan,Yuxin Hou,Wenzhen Li,Mingyao Ma,Jingyi Wang,Juncheng Wang,Chengjun Ge,Jiwei Luo,Ying Zhang
Near-100% selective 1 O 2 generation via Fe-pyridinic N 4 sites. • Metal-atom utilization enhanced by 10 2 -10 4 -fold in FeSA-N-C-2S. • Fe-pyridinic N 4 shifts d -band center, lowering 1 O 2 energy barrier and tuning pathway. • 1 O 2 steady-state concentration positively correlates with Fe-pyridinic N 4 proportion. • A universal strategy creates various metal-based SACs with > 90% 1 O 2 selectivity. The type and quantity of nitrogen ligands in the first-shell coordination structure (FSCS) of single-atom catalysts (SACs) govern catalytic performance. However, current research largely focuses on nitrogen atom count, overlooking its chemical structure. Herein, by reconfiguring the FSCS from Fe-pyrrolic N 4 to Fe-pyridinic N 4 (FeSA-N-C-2S), we achieve selectivity approaching 100% for singlet oxygen ( 1 O 2 ) generation. Mechanistically, Fe-pyridinic N 4 shifts the d -band center toward the Fermi level via axial d_z² orbital hybridization, reducing Fe d -orbital occupancy, which enhances electron transfer through the conjugated π-system of pyridinic N, lowering the activation barrier for 1 O 2 generation and optimizing the reaction pathway. This facilitates complete degradation of electron-rich pollutants like 2,4,6-trichlorophenol, with a 4.3-fold increase in rate constant and a 21.5-fold higher metal-atom utilization efficiency compared to the FeSA-N-C-1S. Moreover, 1 O 2 steady-state concentration exhibits a significant linear positive correlation with Fe-pyridinic N 4 proportion, which can be precisely modulated by adjusting the pyrolysis temperature and metal-to-precursor ratio. This insight extends to other transition metals (Co, Cu, Mn), affording > 90% 1 O 2 selectivity. Long-term continuous-flow experiments and life-cycle assessments highlight the potential for scalable water treatment. Our work deciphers how coordination structure governs reactive oxygen species, providing a universal design paradigm for metal-pyridinic N 4 catalysts. Download: Download high-res image (210KB) Download: Download full-size image
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JOURNAL OF ENVIRONMENTAL MANAGEMENT
·
2026
·
IF 9.2
Guangya Zhou,Dong Zhang,Zhengzheng Lou,Miaomiao Zhao,Dihua Wu,Suling Zhang,Ying Pan,Ting Lü,Hongting Zhao,Jun Lin,Li Lu,Ming Zhang
Porous biochar has emerged as a promising heterogeneous catalyst for the activation of persulfate (specifically peroxymonosulfate, PMS) to degrade organic contaminants, owing to its highly-developed pore structure and abundant surface functionalities. However, its catalytic efficiency is critically influenced by intrinsic structural defects and surface chemistry, yet the underlying structure–activity relationships remain elusive. Notably, the specific mechanisms governing electron transfer within non-radical pathways during PMS activation require further clarification. In this study, a series of porous biochars were synthesized from waste Myriophyllum aquaticum via KOH activation followed by pyrolysis at varying temperatures. The results demonstrate that the synergistic effect of high-temperature pyrolysis and alkali activation significantly augments structural defects and the density of oxygen-containing functional groups, thereby accelerating electron transfer and PMS activation. Among these catalysts, the PMaB-800-1/PMS system achieved complete removal of 2,4,6-trichlorophenol (2,4,6-TCP) within 15 min, exhibiting a high apparent rate constant ( k obs ) of 0.35 min −1 and an ultra-high PMS utilization efficiency of 0.53. Radical quenching experiments, electron paramagnetic resonance (EPR), and electrochemical analyses confirmed that 2,4,6-TCP degradation was predominantly driven by a non-radical oxidation pathway involving 1 O 2 , O 2 •- , and direct electron transfer. Insights from XPS, Raman spectroscopy, and density functional theory (DFT) calculations further revealed that C=O/O–C=O groups and pyridinic N served as the primary active sites for PMS activation and the selective generation of reactive oxygen species. This study not only provides a sustainable route for the upcycling of spent aquatic plants, but also offers a robust strategy for constructing efficient remediation systems for organic pollutants.
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