CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Qiunan Sun,Xuejiang Wang,Yiyang Liu,Yanan Zhang,Siqing Xia,Jianfu Zhao
In this study, floating carbon nitride incorporating copper ferrite catalyst (CNCFEp) was synthesized by a simple coprecipitation-calcination method. The prepared catalyst was applied to the catalytic activation of peroxymonosulfate (PMS) for the degradation of antibiotics under visible light irradiation (Vis/CNCFEp/PMS system). In the presence of CNCFEp (2.0 g/L) and PMS (0.1 g/L), 97.6 % of sulfamethazine (SMT, 10 mg/L) was degraded in 30 min under neutral conditions, whereas negligible influence was observed accompanied by water matrixes. The floating composite catalyst showed excellent stability after 5 times recycling experiments. Singlet oxygen ( 1 O 2 ) and high-valent oxo-metal species were unveiled to be the major reactive oxygen species (ROS), rather than conventional hydroxyl radicals or sulfate radicals. These nonradical species were produced by direct oxidation or the transformation of superoxide ions and metastable metal composite at neutral pH. SMT was broken down by four degradation pathways in this system and a remarkable reduction in toxicity has been demonstrated by the quantitative structure–activity relationship (QSAR) prediction. Likewise, the nonradical species were capable of inactivating the bacteria ( E. coli) . This work was the first study dedicated to the mechanism of PMS activation by CNCFEp and provides a novel catalytic system for removal of organic contaminants and bacteria in environmental waters.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Sciences
·
2022
·
IF 6.796
Wenjin Chen,Jin Huang,Yaqian Shen,Ke Zhu,Lele Lei,Hongmei He,Yushi Ai
Fe-N co-doped coral-like hollow carbon shell (Fe-N-CS) was synthesized via a simply impregnation-pyrolysis method. The Fe-N-CS showed an excellent ability for activating peroxymonosulfate (PMS), which could degrade about 93.74% tetracycline (20 mg/L) in 12 min. The Fe-N-CS/PMS system exhibited a good anti-interference capacity of various pH, inorganic anions, HA and different water qualities. More importantly, the Fe nanoparticles were anchored uniformly in the carbon layer, effectively limiting the metal leaching. The quenching tests and electron spin resonance (ESR) manifested that non-radical singlet oxygen ( 1 O 2 ) was the main reactive oxygen species (ROS) for TC degradation. The mechanism study showed that Fe nanoparticles, defect and graphite N played a key role in activating PMS to produce ROS. Moreover, three probable degradation pathways were proposed by using LC-MS measurements. Generally, this work had a new insight for the synthesis of heterogeneous Fe-N-C catalysts in the advanced oxidation process based on PMS.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Yujiao Wang,Li Wang,Yuqing Cao,Fang Ma
The construction of oxygen vacancies (Vo) is a promising strategy for designing an efficient catalyst toward peroxydisulfate (PDS) activation. However, the unstable interface electron transfer and deactivation of Vo have been the bottleneck, and Vo-mediated PDS activation mechanisms remain vaguely interpreted. Herein, we innovatively synthesized a low-cost and durable Fe-Cu bimetallic mineral-based magnetic biochar with abundant Vo (Fe-CuFe 2 O 4 @BC). Fe-CuFe 2 O 4 @BC exhibited 6.64, 22.91, and 79.22-fold PDS activation rates for sulfamethazine (SMT) degradation (100%) and mineralization (91.58%) compared with [email protected] , [email protected] , and pristine BC, respectively. The outstanding performance of the Fe-CuFe 2 O 4 @BC/PDS system was ascribed to the Vo-induced sustainable electron transfer and singlet oxygen ( 1 O 2 ) generation, determined by chemical probes and kinetics study. pH-dependence adsorption of SMT dominated by the strengthened H-bonding and π–π EDA interaction was the key rate-limited step to PDS activation. Based on the surface investigation, electronic measurement, and Density functional theory (DFT) calculations, we proposed new insights into the electron-rich Vo and electron-deficient Cu co-induced PDS activation mechanism. Different from conventional perspectives, Vo preferentially activated PDS to generate 1 O 2 , subsequently delocalizing and accumulating residual electrons from the Cu site. Simultaneously, metastable copper intermediates activated PDS through thermodynamically feasible reactions, promoting nano-confinement Vo-triggered 1 O 2 pathway. This study provides a new perspective for synthesizing Vo-rich catalysts and essentially deepens insights into nonradical mechanisms of refractory organics.
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2021
·
IF 9.028
Jingyi Lin,Qin Dai,He Zhao,Hongbin Cao,Tianyu Wang,Guangwei Wang,Chuncheng Chen
Photoinduced interfacial release of volatile organic compounds (VOCs) from surfactants receives emerging concerns. Here, we investigate the photoreaction of 1-nonanol (NOL) as a model surfactant at the air–water interface, especially for the important role of 1O2 in the formation of VOCs. The production of VOCs is real-time quantitated. The results indicate that the oxygen content apparently affects the total yields of VOCs during the photoreaction of interfacial NOL. The photoactivity of NOL is about 8 times higher under air than that under nitrogen, which is mainly attributed to the generation of 1O2. Additionally, the production of VOCs increased by about 4 times with the existence of the air–water interface. Quenching experiments of 1O2 also illustrate the contribution of 1O2 to VOC formation, which could reach more than 95% during photoirradiation of NOL. Furthermore, density functional theory calculations show that 1O2 generated via energy transfer of photosensitizers can abstract two hydrogen atoms from a fatty alcohol molecule. The energy barrier of this reaction is 72.3 kJ/mol, and its reaction rate coefficient is about 2.742 s–1 M–1. 1O2 significantly promotes photoinduced oxidation of fatty alcohols and VOC formation through hydrogen abstraction, which provides a new insight into the interfacial photoreaction.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SCIENCE OF THE TOTAL ENVIRONMENT
·
2019
·
IF 5.589
Zhiping Chen,Sijing Bi,Guangyi Zhao,Yuancai Chen,Yongyou Hu
Spinel is a kind of desirable catalyst to activate peroxymonosulfate (PMS) for chemical oxidation of organic contaminants in wastewater treatment. However, apart from classic sulfate radical based AOPs (SR-AOPs), the generation and oxidative pathways of singlet oxygen ( 1 O 2 ) by Co/Mn spinels have been little explored in PMS catalysis. In this study, spinel-type oxide Co 2 Mn 1 O 4 was successfully synthesized, and used as highly effective catalyst in PMS activation for heterogeneous degradation of TCS (up to 96.4% within 30 min) at initial pH of 6.8, which was also slightly impacted by coexisting ions. Based on radical scavengers and electron paramagnetic resonance (EPR) experiments, sulfate radicals and singlet oxygen ( 1 O 2 ) were unveiled to be the dominant reactive oxygen species (ROS) in Co 2 Mn 1 O 4 /PMS system. Co 2 Mn 1 O 4 catalyst exhibited reversible redox properties based on the results of cyclic voltammetry (CV). More importantly, the generation of 1 O 2 might not only promote the TCS removal rate directly, but also facilitate the metal redox cycle in spinel structure in Co 2 Mn 1 O 4 /PMS system. Finally, degradation pathways of TCS in Co 2 Mn 1 O 4 /PMS system were proposed, which involved the breakage of ether bond and cycloaddition reaction.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Zhenyu Yan,Xiuyun Zhao,Chenkai Zhong,Wenyu Gao,Yujie Feng,Jia Liu
FeNx sites show significant superiority in the degradation of antibiotic contaminants, but there are difficulties in successfully constructing highly dispersed FeNx sites. In this work, Fe-N/C catalysts doped with hierarchical ordered pores structure and FeNx active sites were prepared by metal node exchange strategy. Among them, Fe-N/C-2 had more excite species for peroxymonosulfate (PMS) owing to the synergy between Fe and N coordination, which achieved 89.36 % tetracycline (TC) removal rate within 20 min, and its reaction kinetic ( k = 0.245 min −1 ) is 7.66 times more than original PMS system. Moreover, the material exhibited excellent activation performance in a variety of complex water environments, such as the coexistence of multiple anions, strong acids and alkalis (pH = 2.90 ∼ 10.73), and natural organic matter interference. Chemical bond detection confirmed the successful formation of FeNx sites, free radical trapping experiments showed that FeNx was the main catalytic site, and 1 O 2 was the main active component. Furthermore, the reaction principle of the FeNx site catalyzing the production of 1 O 2 from PMS was revealed in detail through mechanism exploration. Next, the probable pathways of TC decomposition were elaborated in terms of the intermediates identified by Liquid Chromatograph Mass Spectrometer (LC-MS). This study emphasized the significant potential of synthesizing Fe-N/C catalysts with activated FeNx sites, elucidated mechanism of FeNx in PMS activation, and confirmed its feasibility in TC degradation.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Cong Yuan,Xiaoxiao Zhu,Jiaqi Pan,Minghao Xu,Yongjun Jiang,Sheng Dai,Yikai Huang,Leixi Lu,Lei Zhou,Chengcheng Tian
The understanding of how single atoms anchoring on oxides contribute to high-activity catalysis in the sulfate radical-advanced oxidation process (SR-AOP) remains obscure. Here we presented a new strategy for regulating singlet oxygen ( 1 O 2 ) generation in peroxymonosulfate-based advanced oxidation processes (PMS-AOPs) by engineering the Co-O-X active sites on oxide supports in this study. The Co single atoms supported on mesoporous oxides (Co SA -XO 2 ) were first successfully developed using a modified sol–gel solvent vaporization self-assembly method. We found that Co SA -XO 2 catalysts served as efficient PMS activators for pollutant decomposition over a wide pH range. Notably, Co SA -TiO 2 exhibited exceptional performance, achieving nearly 100% removal of sulfasalazine (SSZ) within 10 min. Furthermore, evidenced by experimental results and density functional theory (DFT) calculations, 1 O 2 was confirmed to be predominately active oxidizing species by the unique Co-O-X bonds for activating PMS in Co SA -XO 2 /PMS system, resulting in an excellent pollution degradation. This study provides valuable insights into the construction of highly loaded single-atom catalysts using oxide substrates in the PMS-AOP system, along with the mechanism of regulating reactive oxygen species (ROS) formation through interfacial bonding between active metal and support.
✓ 已验证
产品关联
DOI
高影响因子
LANGMUIR
·
2025
·
IF 3.9
Hua Zhong,Qin Qin,Zhuozhuo Wang,Hua Zhang,Yanling Qiu,Daqiang Yin,Xiaochang Liu,Zhiliang Zhu
Water pollution caused by emerging contaminants poses significant environmental and health risks, while the management of invasive algal biomass remains an underutilized resource. This study presents a novel Fe/Mn-modified in situ N-doped Enteromorpha prolifera-derived biochar catalyst (Fe/Mn/EP), addressing the dual challenges of efficient peroxymonosulfate (PMS) activation and utilization of invasive algal biomass. Through a straightforward one-step pyrolysis approach, the obtained catalyst integrated nitrogen functionalities and bimetallic active sites, enabling it to achieve an outstanding catalytic performance. It completely degraded carbamazepine (CBZ) in water samples within 30 min. The degradation process relied on the synergy between radical and nonradical pathways, primarily dominated by singlet oxygen (1O2) and superoxide radicals (·O2–). Specifically, in situ nitrogen doping, particularly involving pyrrole and graphite nitrogen, enhanced PMS activation by regulating the electronic properties and increasing the density of active sites. The degradation of CBZ significantly reduces the toxicity of the system by analysis prediction based on quantitative structure–activity relationship. The Fe/Mn/EP catalyst demonstrated broad adaptability across various emerging pollutants and real water matrices. This work highlights a sustainable strategy to transform problematic algae into high-performance biochar-based catalysts, offering a scalable solution for water pollution remediation.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Shaobo Cao,Lei Wu,Jun Li,Yang Li,Kang Da,Wenting Chen,Ruiting Xue,Jian Yang,Ximei Fan
Photocatalytic degradation volatile organic compounds (VOCs) represent an appealing strategy since the inexhaustible solar energy and facile reaction condition. In this work, a flower-like microsphere Bi 2 W x Mo 1-x O 6 solid solution photocatalysts with abundant oxygen vacancies (OVs) were prepared via HTAB-assisted hydrothermal method. The mole ratio of W and Mo atoms were regulated by adjusting the stoichiometric ratio of their precursor. The optimized Bi 2 W 0.25 Mo 0.75 O 6 presented outstanding photocatalytic performance with 96.8% of toluene degradation rate after 180 min of irradiation under visible light (>420 nm), which was 13.76 times higher than that of pure Bi 2 MoO 6 and 10.32 times higher than that of pure Bi 2 WO 6 , respectively. The enhanced photocatalytic activity of Bi 2 W 0.25 Mo 0.75 O 6 was attributed to the optimized band structure and efficient separation efficiency of carriers as well as the participation of singlet oxygen ( 1 O 2 ) radicals. Free radical trap experiments and electron spin resonance investigations revealed that 1 O 2 , hydroxyl radical, and holes were the predominated reactive oxygen species (ROSs) in toluene degradation. Meanwhile, the generation of 1 O 2 was related to abundant OVs of Bi 2 W 0.25 Mo 0.75 O 6 solid solution. This work suggested that solid solution with abundant OVs was an effective photocatalyst to improve the VOCs degradation activity under visible-light irradiation.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Junren Zhu,Juanjuan Zou,Ting Peng,Xinyi Li,Chaohan Jiang,Shiyang Bai,Wei Ding,Zhenzhen Jiang
HCO 3 − coordination-enabled high-valent cobalt-oxo pathway absent without HCO 3 − • Quantitative Co(IV) contribution elevation from 2.5% to 28% with bicarbonate • Oxidation pathway switch from radical to non-radical regime by bicarbonate • CoCO 3 SO 3 2− complex identified as kinetically competent intermediate • Efficient performance across real waters with Co dosage below discharge limit Bicarbonate, a ubiquitous constituent of natural waters, is typically regarded as a radical scavenger in sulfate-radical-based advanced oxidation processes (SR-AOPs); however, its coordinative interaction with the catalytic metal center and the consequent modulation of oxidative pathways remain poorly understood. In this work, the role of HCO 3 − in the Co(II)-catalyzed activation of calcium sulfite (CaSO 3 ) was systematically investigated. HCO 3 − species is identified to coordinate with Co(II) to assemble a ternary Co(II) − HCO 3 − −S(IV) complex that facilitates the rate-limiting Co(II)-to-Co(III) oxidation, while the subsequent Co(III) − HCO 3 − complexation prevents Co(III) precipitation and sustains the catalytic cycle. Critically, this coordination is a prerequisite for Co(IV) generation: by depressing the Co(IV)/Co(II) redox potential, it unlocks the otherwise forbidden oxygen-atom transfer pathway, yielding a non-radical oxidant entirely absent without HCO 3 − . Together with 1 O 2 , this HCO 3 − -exclusive Co(IV) pathway operates in parallel with the SO 4 •− radical pathway, redirecting the dominant oxidation mechanism from a radical-driven regime toward a non-radical-driven regime, accompanied by a pronounced reduction in apparent activation energy (37.46 kJ mol −1 ). This system functions effectively across a wide pH, exhibits high tolerance to common anionic interferents, and achieves efficient performance across multiple authentic water matrices. In short, this work establishes HCO 3 − as a coordination-directed switch that sustains the catalytic cycle while uniquely gating access to the Co(IV) oxidation pathway, offering a ligand-engineering strategy for tuning reactive species speciation in S(IV)-based AOPs. The HCO 3 − enhanced- and altered- CaSO3 activation by Co(II). Download: Download high-res image (301KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL RESEARCH
·
2025
·
IF 7.7
Lingzhi He,Guangjian Liao,Zihan Xie,Yanru Liu,Yadong Yang
Herein, Fe-N co-doped highly graphitized biochar catalyst, which exhibits high catalytic activity toward peroxymonosulfate, was successfully synthesized via a simple one-pot pyrolysis method and applied for the efficient degradation of persistent organic pollutants. The co-doping of iron and nitrogen markedly increased the graphitization degree of the material, thereby enhancing peroxymonosulfate activation and achieving complete degradation of bisphenol A at an initial concentration of 20 mg/L within 40 minutes, which significantly outperformed other non-doped catalysts. Mechanism studies revealed that bisphenol A degradation via non-radical pathways (singlet oxygen and electron transfer) as the dominant mechanism. The proposed catalyst exhibited significantly enhanced stability, with performance comparable to or exceeding that of commercial catalysts. It was also successfully applied for the degradation of other persistent organic pollutants in real environmental water samples. Due to its robustness under broad working conditions, this catalyst holds significant potential for green environmental remediation.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yunhe Li,Ming Yi,Jiangwei Shang,Yilong Hou,Shengwen Zhou,Xiuwen Cheng
Singlet oxygen ( 1 O 2 ) is an excellent reactive species with solid resistance to refractory pollutants, and it is critical to enhancing the generation of 1 O 2 in the persulfate system. In this work, we developed a vacancy-containing copper oxide supported Co single atom catalyst (Co SACs /CuO(O v )) containing abundant cobalt active sites for the activation of PMS to achieve efficient 1 O 2 selective generation, thereby exhibiting ultra-high ciprofloxacin removal efficiency. Density functional theory calculations revealed that Co SACs /CuO(O v ) adsorbed the single O atom from the SO 4 side chain of PMS, facilitating its oxidation into *OH and subsequent efficient production of 1 O 2 . The Co SACs /CuO(O v )/PMS system exhibited strong resistance to variations in pH and coexisting substances in water, and the toxicity of CIP was significantly reduced after treatment. Furthermore, when the Co SACs /CuO(O v ) catalyst was immobilized on the PTFE filter membrane, it maintained the CIP removal efficiency above 75 % for 20 h under low temperatures (0℃) and in various complex aqueous environments. This work provides new insights into the design of catalysts featuring single-atom active sites and high-efficiency 1 O 2 generation, which is essential for potential applications in water purification.
研究领域:
环境科学
·
催化化学
·
水处理技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）