CHINESE JOURNAL OF CHEMICAL PHYSICS
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2021
·Vol. 34
·期 4
·406-412
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IF 1.114
Wang Chen,Xiong Ming-chen,Zhao Xuan,Liu Kun-hui
The pharmaceutically active compound atenolol, a kind of β -blockers, may result in adverse effects both for human health and ecosystems if it is excreted to the surface water resources. To effectively remove atenolol in the environment, both direct and indirect photodegradation, driven by sunlight play an important role. Among indirect photodegradation, singlet oxygen ( 1 O 2 ), as a pivotal reactive species, is likely to determine the fates of atenolol. Nevertheless, the kinetic information on the reaction of atenolol with singlet oxygen has not been well investigated and the reaction rate constant is still ambiguous. Herein, the reaction rate constant of atenolol with singlet oxygen is investigated directly through observing the decay of the 1 O 2 phosphorescence at 1270 nm. It is determined that the reaction rate constant between atenolol and 1 O 2 is 7.0×10 5 (mol/L) −1 · s −1 in D 2 O, 8.0×10 6 (mol/L) −1 · s −1 in acetonitrile, and 8.4×10 5 (mol/L) −1 · s −1 in EtOH, respectively. Furthermore, the solvent effects on the title reaction were also investigated. It is revealed that the solvents with strong polarity and weak hydrogen donating ability are suitable to achieve high rate constant values. These kinetics information on the reaction of atenolol with singlet oxygen may provide fundamental knowledge to the indirect photodegradation of β -blockers.
研究领域:
环境科学
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药理学
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化学动力学
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高影响因子
Environmental Science-Nano
·
2024
·Vol. 11
·期 5
·2275-2288
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IF 5.8
Yadan Song,Yalong Liu,Yangju Li,Haipeng Hu,Kexin Huang,Zhe Zhang,Zhongxian Li,Wanning Cao,Kai Jiang,Dapeng Wu
The poor anti-interference ability of radical-dominated processes continues to be a hindrance to the effectiveness of purification and the practical use of peroxymonosulfate-based advanced oxidation processes (PMS-AOPs). Herein, iron, nitrogen, and sulfur co-doped porous carbon sheets (Fe–SNC) were successfully synthesized via a one-step pyrolysis process by adopting Mohr's salt and ZIF-8 sheets as precursors to efficiently activate PMS. Quenching experiments and electron paramagnetic resonance (EPR) characterization indicated that singlet oxygen (1O2) played the most important role in phenol degradation. Based on the variation in the material structure and density functional theory (DFT) calculations, the study revealed the specific mechanism of sulfur embedded in rich Fe3C, Fe4N, and Fe–Nx catalytic sites as an activator of PMS in the degradation of the pollutant of interest. In addition, S-doping sites were shown to shorten the distance between PMS and the catalyst due to electron polarization of the catalyst surface, which facilitated PMS adsorption. According to ultra-high-resolution electrospray time-of-flight mass spectrometry and the predictions of ECOSAR software, the aquatic ecological environment would not be harmed by degradation intermediates. As a consequence, this heterogeneous system possesses admirable anti-interference in pollutant elimination. These conclusions provide instructions for the creation of S-doped porous carbon sheets for effective water treatment.
研究领域:
环境科学
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材料科学
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ACS Catalysis
·
2022
·
IF 13.7
Bo Sheng,Chaoyuan Deng,Yangfan Li,Shijie Xie,Zhaohui Wang,Hua Sheng,Jincai Zhao
In Fenton or Fenton-like reactions, ·OH obtained by the reductive activation of H2O2 is regarded as the major reactive oxygen species (ROS); however, the generation of other ROS like O2·– and 1O2 cannot be negligible. Since the degradation capability of a certain ROS would be varied to distinctive pollutants, the regulation of ROS production from H2O2 activation should be applicable for a more targeted pollutant degradation. Herein, a series of carbon nitride (C3N4)-supported Fe catalysts with the state of Fe ranging among single-atom, oxide-cluster, and nanoparticle catalysts were fabricated and their activities in photo-Fenton reactions were evaluated. It was uncovered that the single-atom catalyst favored the generation of O2·– and 1O2 via the oxidative activation of H2O2 and the selectivity of 1O2 toward ·OH dynamically increased with the proceeding of H2O2 activation, while the catalysts with an abundance of oxide clusters exhibited a significantly higher conversion of H2O2 to ·OH. In situ FT-IR studies demonstrated that during the H2O2 activation, the single-atom catalyst underwent a more significant surface hydroxylation than the oxide-cluster catalyst. Such a result was further consolidated by the theoretical calculation that the adsorption energy of surface hydroxyl was remarkably higher on the single-atom catalyst. Thereafter, distinctive from the easy desorption of hydroxyl during the reduction of H2O2 to ·OH in oxide-cluster catalysts, the in situ surface hydroxylation on the single-atom catalyst alters the adsorption mode of H2O2 to a H-bonded structure, which steers the selectivity of ROS generation to a more favored oxidative transformation of H2O2 to O2·–/1O2. This work uncovers the decisive role of surface hydroxyl in regulating ROS generation in a heterogeneous Fenton reaction.
研究领域:
环境科学
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催化化学
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高影响因子
APPLIED SURFACE SCIENCE
·
2026
·
IF 6.9
Lang Li,Nan Chen,Ning An,Hantian Mou,Chuanping Feng,Jianhua Wu,Lina Zhao,Junjie Li,Zejun Zhang,Donglin Wang,Yong Mao
Tetracycline (TC), a pervasive antibiotic contaminant in aquatic systems, presents critical ecological and human health threats. This study pioneers a sustainable remediation strategy by fabricating a metal-free biochar catalyst (PAC) from waste apple tree branches for persulfate (PDS) activation toward TC degradation. Among PACs pyrolyzed at 500–700°C, PAC-700 demonstrated exceptional catalytic activity, attributable to its maximized defect density and enriched surface carbonyl groups. Strong linear correlations between the rate constant (log( k )) and both I D / I G ratio ( R 2 = 0.823) and C O content ( R 2 = 0.998) suggest their potential influence on PDS activation. Mechanistic investigations elucidated a dual radical/non-radical pathway: radical species (SO 4 − , OH, and O 2 − ) and non-radical processes ( 1 O 2 , electron transfer), with 1 O 2 playing the dominant role to TC degradation. Crucially, C O groups were identified as pivotal active sites for 1 O 2 generation ( R 2 = 0.866 between C O and 1 O 2 contribution). Electrochemical analyses demonstrated that PAC materials prepared at higher pyrolysis temperatures exhibit enhanced electron transfer behavior, while LC-MS and Fukui index calculations mapped degradation pathways and reactive sites. Post-treatment toxicity assays validated significant ecological risk mitigation. This work advances green antibiotic remediation by synergizing biomass valorization with non-radical catalysis.
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Journal of Environmental Chemical Engineering
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2026
·
IF 7.2
Cong Yuan,Xiaoxiao Zhu,Xuyang Xu,Fengyun Ding,Lei Zhou,Jean-Marc Chovelon,Wanglai Cen,Chengcheng Tian
Single-atom catalysts (SACs), known for their maximized atom utilization and unique electronic structures, were widely utilized in Fenton-like reactions for organic contaminant removal. Due to prolonged use or complex reaction environments, the active sites were prone to oxidation, agglomeration, or carrier degradation, leading to deactivation. Herein, a single-site Fe catalyst anchored on N-doped carbon nanotubes (Fe SA -N-CNT) was successfully synthesized by a dual anchoring strategy of EDTA and melamine. Fe SA -N-CNT catalyst exhibited an outstanding performance in peroxymonosulfate (PMS) activation, achieving more than 90% removal of sulfasalazine (SSZ) within 10 min. Combined experimental results and density functional theory (DFT) calculations revealed that the Fe-pyridine N 4 coordination sites and the adjacent carbon atoms (sub-C) served as dual active sites, facilitating a singlet oxygen ( 1 O 2 )-dominated oxidation of SSZ. Fe-N 4 sites could promote the formation of SO 5 •− , which subsequently generated 1 O 2 , while the sub-C sites contributed to the generation of superoxide anion radical (O 2 •− ), a precursor of 1 O 2 . The present study provided a novel strategy for synthesizing highly active SACs and deeper insights into the mechanisms of reactive oxygen species (ROS) generation within SACs/PMS systems for effective organic pollutant decontamination.
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APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Xin Jiang,Xiangting Yang,Huiqin Fei,Linfeng Zhang,Huadong Wu,Yoann de Rancourt de Mimérand,Xiaoyun Jin,Jia Guo
Cold plasma discharge, surface synthesis and 3D printing were used to fabricate supported photocatalysts. • Three different approaches were employed to immobilize QDs on a fractal polymer substrate. • One of the fabrication routes allowed obtaining a 1 O 2 -generating catalyst. • This hybrid catalyst was more efficient for the purification of water than the free QDs and easy to reuse. Owing to their quantum confinement, quantum dots (QDs) can efficiently generate singlet oxygen, a highly reactive oxygen species (ROS). Although promising for photocatalytic water remediation, their practical application remains limited. Their nanoscale dimensions render them more challenging to deploy than bulk heterogeneous photocatalysts; specifically, their separation and recycling are complex, and catalyst leaching poses a significant issue. In this study, we evaluated several chemical immobilization methods initiated by cold plasma discharge (CPD) to fabricate supported QD-based catalysts for the photodegradation of organic pollutants. Using CdS QDs as a model system, we probed their capacity to generate singlet oxygen. The resin substrates were fabricated by LCD 3D printing and microtextured with fractal architectures. Among the different immobilization strategies, the most successful employed a secondary nanostructured ZnO support to enforce a monolayer dispersion of the QDs. Subsequent in situ encapsulation by a metal–organic framework (MOF) further improved the photostability of the catalyst. This study provides valuable insights and new directions for the facile surface immobilization of functional QDs within controlled architectures for the efficient remediation of organic-contaminated water. Download: Download high-res image (89KB) Download: Download full-size image
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
·
IF 19.7
Jing Zhang,Yixuan Gao,Hongna Li,Sihui Zhan
B–N doping disrupts π-conjugation and localizes electrons in biochar. • B–N sites and carbon vacancies promote axial electron transfer and PMS adsorption. • BN-Cv-Biochar enables highly selective 1 O 2 generation and rapid SMX degradation. • BN-Cv-Biochar/PMS system markedly reduces the phytotoxicity of treated water. Selective activation of peroxymonosulfate (PMS) to produce singlet oxygen ( 1 O 2 ) is desirable for efficient water purification. Graphitized biochar is a promising catalyst, but its extended π-conjugated structure favors in-plane charge delocalization and hinders axial electron transfer, leading to low 1 O 2 selectivity. Herein, we fabricated a boron-nitrogen (B–N) conjugated doped carbon-vacancy biochar (BN-Cv-Biochar) to modulate the local π-electronic system. B–N doping breaks the extended π-conjugation, creating polarized active sites and localized electrons that strengthen axial electron transfer and selective PMS adsorption. The degradation rate constant of sulfamethoxazole (SMX) of BN-Cv-Biochar is 1.68 and 4.45 times higher than that of pristine (Biochar) and nitrogen-doped carbon-vacancy biochar (N-Cv-Biochar), respectively. Experimental and theoretical results reveal that B–N sites coupled with carbon vacancies optimize the electronic environment, reduce the energy barrier for 1 O 2 generation, and preferentially promote 1 O 2 -dominated PMS activation. Product analysis clarifies the SMX degradation pathway, and toxicity assays using radish seedlings confirm the reduced toxicity of treated water. This work provides a novel strategy to tune the π-conjugated structure of biochar for high-performance carbon catalysts in advanced oxidation processes. Download: Download high-res image (201KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Hongjing Liu,Shan Ren,Xiaodi Li,Qingqing Zhou,Yao Yang,Peng Chen,Shouning Chai,Chi He,Bofeng Bai,Fan Dong
The environmental benefits of photocatalytic oxidation of nitrogen oxides (NO x ) critically depend on the selective conversion of NO to nitrate (NO 3 − ) rather than to toxic by-products like nitrogen dioxide (NO 2 ). However, conventional photocatalysts suffer from low carrier separation efficiency and insufficient generation of reactive oxygen species (ROS), resulting in low selectivity of NO 3 − and high levels of toxic by-products. To address this issue, this study incorporates sulfur into thin-layer Bi 2 MoO 6 to induce charge rearrangement, precisely regulate electron transfer pathways, and promote the generation of targeted ROS. Experimental results showed that the S-doping Bi 2 MoO 6 catalyst exhibited exceptional photocatalytic performance, achieving 71.2 % NO removal efficiency, 93.1 % NO 3 − selectivity, a low NO₂ by-product concentration (43.2 ppb), and good cycle stability. Combining electron spin resonance (ESR) and ROS quenching experiments, the S-doping mediated electron transfer mechanism and ROS dominated by 1 O 2 were revealed, and the synergistic effect between surface electron enrichment and O 2 activation was elucidated. Theoretical calculation indicated that S 2− could act as electron capture centers to promote directional transfer of electrons by the strengthen Bi S covalent interaction, achieving high chemical adsorption activation of O 2 to trigger 1 O 2 generation. This research provides a novel strategy for steering ROS generation through directed electron transfer engineering, advancing the development of efficient and eco-friendly photocatalysts for air pollution remediation.
研究领域:
环境科学
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材料科学
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催化
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物理化学
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纳米技术
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MICROCHIMICA ACTA
·
2020
·Vol. 187
·期 8
·1-9
·
IF 6.232
Tang Gangxu,Liu Wei,Chen Zhaoxia,Huang Po-Jung Jimmy,Qin Xiaojiao,Xu Shuxia
An ultrasensitive 1 O 2 -based electrochemical aptasensor by on-line assembly of photosensitizers using graphene oxide (GO) as a cartridge is reported. In the presence of target protein lysozyme, the interaction of lysozyme with aptamer led to the dissociation of dsDNA and release of the aptamer-lysozyme complex to solution, with DNA-c retaining on the electrode; then, the photosensitizer phloxine B (PB) was assembled on the electrode since GO can simultaneously adsorb DNA-c and PB molecules. Upon irradiation by a green LED, 1 O 2 was generated by photocatalysis of PB molecules and then cleaved the DNA-c, leading to remarkably decreased impedance signals that linearly respond with the logarithm of lysozyme concentration. Benefitting from the efficient photosensitization ability of PB and the high PB-loading capacity of GO, the developed sensor allowed determination of 0.001 to 100 nM lysozyme with a limit of detection of about 0.14 pM. The relative standard deviation (RSD) for five independent electrodes with 1 nM lysozyme was 3.1%, indicating satisfactory reproducibility. The sensor also showed excellent selectivity toward lysozyme in the presence of interfering substances and was applied to the determination of lysozyme in urine samples with recoveries ranging from 91 to 101%. The on-line assembly of photosensitizer technique opens a new way for amplified electrosensing of biomolecules.
An on-line assembly of photosensitizers and DNA on electrode was developed using graphene oxide a cartridge and the photocatalytic electrosensor can be used for label-free detection of lysozyme as low as 1 pM.
研究领域:
分析化学
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生物传感器
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电化学
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纳米技术
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生物医学工程
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PubMed
高影响因子
LANGMUIR
·
2023
·
IF 3.9
Zhao Yang,Jianlong Wang
The synthesis of efficient and stable catalysts for photocatalytic reactions is still a challenge. In this study, a new photocatalyst composed of two-dimensional titanium carbide (Ti3C2Tx) and CdS quantum dots (QDs) was fabricated, in which CdS QDs were intimately anchored on the Ti3C2Tx sheet surface. Due to the specific interface characteristics of CdS QDs/Ti3C2Tx, Ti3C2Tx can considerably facilitate the generation of photogenerated charge carriers, their separation, and their transfer from CdS. As expected, the obtained CdS QDs/Ti3C2Tx exhibit outstanding photocatalytic performance for carbamazepine (CBZ) degradation. Moreover, the quenching experiments demonstrated that superoxide radicals (•O2–), H2O2, 1O2, and •OH are the reactive species involved in CBZ degradation, while •O2– made a major contribution. In addition, the sunlight-driven CdS QDs/Ti3C2Tx photocatalytic system is widely suitable for the elimination of different emerging pollutants in various water matrices, suggesting its potential practical environmental applications.
研究领域:
环境科学
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材料科学
·
化学
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PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Mei Yang,Ning Feng,Lukuan Yang,Jinsuo Ma,Wenxin Ji,Yonggang Sun,Yuanyuan Li,Yulong Ma
Synthesis of a B-doped FeMn dual-atom catalyst (DAC), NH 2 –Fe 1 B 2 N 2 –Mn 1 B 1 N 2 . • Regulation of the electronic asymmetry of NH 2 –Fe 1 B 2 N 2 –Mn 1 B 1 N 2 via first-coordination-shell B doping. • B doping induces pronounced local electronic asymmetry and causes d-band shifts. • Improved understanding of the microscopic mechanism of peroxymonosulfate activation over DACs. • Introduction of a general strategy for engineering asymmetric electronic structures in dual-atom catalysts. • Bridging a critical gap between catalyst design and nonradical advanced oxidation processes. Dual-atom catalysts (DACs) are promising for advanced oxidation processes because they inherit the advantages of single-atom catalysts. However, the intrinsic symmetry of their electronic structures limits peroxymonosulfate (PMS) activation and selective nonradical-pathway generation, constraining their practical application. Heteroatom doping in the first coordination shell effectively breaks the electronic symmetry of DACs; however, the mechanism governing selective singlet oxygen ( 1 O 2 ) generation remains unclear. Herein, a B-doped FeMn DAC is synthesized via pyrolysis using boric acid and ZIF-8 as the B and N sources, respectively, to enhance PMS activation and selective 1 O 2 generation. Characterization results and density functional theory calculations reveal that B doping regulates the formation of an axial NH 2 –Fe 1 B 2 N 2 –Mn 1 B 1 N 2 asymmetric electronic structure. In the NH 2 –Fe 1 B 2 N 2 –Mn 1 B 1 N 2 /PMS system, PMS highly selectively adsorbs on the catalyst and coordinates with Mn in a bidentate configuration and Fe serves as an electron-density-regulation center. Through long-range electronic coupling, the active-site electronic structure is optimized. The asymmetric electronic structure considerably enhances antibiotic degradation efficiency in water (97.8%) and increases the reaction rate ( k = 0.12 min −1 ). Overall, this study precisely regulates the electronic asymmetry of NH 2 –Fe 1 B 2 N 2 –Mn 1 B 1 N 2 through first-coordination-shell B doping, elucidates the synergistic mechanism of dual atoms in targeted 1 O 2 generation, and provides a new perspective for designing asymmetric electronic-structure catalysts for advanced oxidation applications. Download: Download high-res image (112KB) Download: Download full-size image
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Journal of Water Process Engineering
·
2026
·
IF 6.6
Chunke Zhao,Yueying Gao,Jiaye Duan,Shiting Li,Bo Zhang,Ke Ma,Longtao Dang,Gen Wang
Polymeric removal of various FPs with concurrent defluorination is achieved in a CuO/PMS system. • FPs are efficiently converted into solid PPO-like polymers with minimal PMS consumption. • 1 O 2 and O 2 •− synergistically drive the polymerization and defluorination of FPs. • Continuous-flow operation over 120 h sustains ∼95% 4-FP removal, confirming practical applicability. Fluorophenols (FPs) are persistent organic pollutants of high concern owing to the extreme stability of their C F bonds. Here we report an oxidative polymerization strategy that enables simultaneous pollutant removal and defluorination by transforming FPs into solid polymers. In a CuO-activated peroxymonosulfate (PMS) system, a superoxide radical (O 2 •− ) and singlet oxygen ( 1 O 2 ) co-mediated oxidation process was established. The system achieved near-complete removal of a series of FPs with different fluorine substitution patterns (2-FP, 4-FP, 2,4-DFP, and 2,3,5,6-TeFP) using minimal oxidant consumption. Polymerization efficiencies ranged from ∼26% to ∼72%, accompanied by significant defluorination (up to ∼74%). Mechanistic studies reveal that FPs are converted into solid poly(phenylene oxide)-like polymers via a nucleophilic aromatic substitution route. Beyond batch performance, the system demonstrated excellent practical viability, with ∼95% removal of 4-FP sustained in a continuous-flow reactor and defluorination remaining as high as ∼47% after prolonged operation. The process also maintained high efficiency under hypersaline and complex water matrices. This integrated defluorination-polymerization approach offers a cost-effective, environmentally benign and operationally stable solution for treating FPs-contaminated wastewaters, shifting the paradigm from conventional mineralization toward sustainable resource recovery. Download: Download high-res image (163KB) Download: Download full-size image
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