Electron Spin Resonance Detection Research Articles

Covalent triazine frameworks as particle electrode for three-dimensional photoelectrocatalytic degradation of oxytetracycline: Synergy effects, pathway, and mechanism.

Photoelectrocatalysis has been widely employed for degrading antibiotics due to its high efficiency. However, the application is significantly impeded by the rapid recombination of photogenerated charge carriers and the limited surface areas of photoelectrodes. In the study, high crystallinity covalent triazine frameworks were fabricated at low temperature of 150°C and firstly used as particle photoelectrode in the three-dimensional photoelectrochemical reactor to degrade oxytetracycline (OTC). SEM, TEM, XRD, XPS, and FT-IR confirmed the successful synthesis of high crystallinity covalent triazine frameworks. Compared to CTF-120 (71.2%) and CTF-180 (46.9%), CTF-150 exhibited excellent OTC removal. Electrochemical impedance, UV-vis absorption spectra, and Mott-Schottky tests showed that CTF-150 demonstrated more wide light absorption range of 501nm and narrow bandgap of 2.52eV, and smaller Rct value under illumination, in comparing to CTF-120 and CTF-180. When the initial concentration of OTC was 50mgL-1, the 86.2% of OTC removal and 62.7% of mineralization were obtained under light irradiation (λ>420nm), current of 10mA, pH of 6.4, electrolyte of 0.1M Na2SO4. The synergy effect between photocatalytic and electrocatalytic processes of CTF-150 not only enhanced by 38.5% current efficiency but also reduced energy consumption to 1.90 kWh m-3. CTF-150 had a wide range of acid-base application and displayed resistance on coexisting ions. Electron spin resonance detection, quenching experiments, and probe experiments illustrated that h+, •O2-, 1O2, and •OH contributed to the degradation of OTC and the generation pathways of •O2-, 1O2, and •OH were verified. Moreover, •O2-, 1O2, and h+ were the main reactive species responsible for OTC removal, while 1O2 was for OTC mineralization. Based on high-performance liquid chromatography-tandem mass spectrometry detection, OTC with benzene ring was decomposed to opening ring products. The acute toxicity, developmental toxicity, bioaccumulation factor and mutagenicity of OTC and its intermediates using T.E.S.T. showed the toxicity of 82.35% degradation products decreased.

Detection of electron paramagnetic resonance of two electron spins using a single NV center in diamond

An interacting spin system is an excellent testbed for fundamental quantum physics and applications in quantum sensing and quantum simulation. For these investigations, detailed information on the interactions, e.g., the number of spins and their interaction strengths, is often required. In this study, we present the identification and characterization of a single nitrogen vacancy (NV) center coupled to two electron spins. In the experiment, we first identify a well-isolated single NV center and characterize its spin decoherence time. Then, we perform NV-detected electron paramagnetic resonance (EPR) spectroscopy to detect surrounding electron spins. From the analysis of the NV-EPR signal, we precisely determine the number of detected spins and their interaction strengths. Moreover, the spectral analysis indicates that the candidates of the detected spins are diamond surface spins. This study demonstrates a promising approach for the identification and characterization of an interacting spin system for realizing entangled sensing using electron spin as quantum reporters.

Study on photocatalytic degradation and antibacterial properties of conjugated microporous polymers/TiO2 composite membranes

Conjugated microporous polymers (CMPs) are widely used in the field of photocatalysis due to their unique conjugated structures and various synthesis methods. Herein, we report the design and synthesis of conjugated microporous polymers hollow spheres (CMPs-HS) superhydrophilic modified by acetylcysteine (CMPs-HS-S) and compounded with the inorganic semiconductor material titanium dioxide (CMPs-HS-S/TiO2) for efficient photocatalytic degradation. To facilitate recycling, the composite membrane material was prepared by combining the materials mentioned above with PVDF membrane. The composite membrane materials had good hydrophilic and photocatalytic properties. Under visible light, the degradation rate of tetracycline (TC) (10 mg/L 180 min) reached 90 %, and the bactericidal rates for Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were 89 % and 99.99 %, respectively. The efficient photocatalytic performance of the composite membranes could be attributed to the hollow sphere structure of CMPs and the role of TiO2 as a photogenic electron transfer platform. Additionally, the hydrophilicity of the membrane also helped to accelerate the occurrence of photocatalytic reactions. After electron paramagnetic resonance (EPR) detection, h+, 1O2 and O2− were proved to be important reactive substances, which played a major role in degradation. These studies reflect the versatility of CMPs-based photocatalysts and provide a new idea for the future development of CMPs-based photocatalysts.

Detection of electron spin resonance of a single nitrogen-vacancy center in diamond using the excited-state lifetime

Detection of electron spin resonance of a single nitrogen-vacancy center in diamond using the excited-state lifetime

Near-infrared light enhanced oxygen vacancies on metal organic frameworks through photothermal effect for peroxydisulfate activation to remove organic pollutants

Peroxydisulfate (PDS)-based advanced oxidation processes (AOPs) are a promising strategy for addressing the challenges of contamination in aqueous environment. Taking advantage of solar energy based photocatalysis showed great potential on PDS activation for pollution control. However, the limited usage of near-infrared (NIR) region by photocatalysts restricted the realization of using full sunlight energy. Herein, zeolitic imidazolate frameworks derived materials (ZNC) with oxygen vacancies (VO) are designed and obtained, which can efficiently activate PDS under NIR light due to the photothermal effect, exhibiting superior carbamazepine (CBZ) degradation performance (84 % of CBZ within 60 min). Further quenching tests and electron paramagnetic resonance detection demonstrate that the photothermal effect can enhance the concentration of oxygen vacancies on the surface and facilitate charge separation of ZNC, which effectively activate PDS to generate O2−, 1O2, and h+, thus significantly enhancing the photocatalytic degradation of CBZ. Additionally, combining the results of intermediates analysis and DFT calculation, a systematic CBZ degradation pathway by two tracks is proposed. Moreover, the overall potential risks of CBZ are expected to be weakened in the ZNC/PDS/NIR process through photothermal catalytic degradation. Thus, a new strategy is provided for optimizing the use of solar energy to boost PDS activation for water purification.

Pseudospin Quantum Hall Ferromagnetism Probed by Electron Spin Resonance.

We study the effect of the pseudospin ferromagnetism with the aid of an electrically detected electron spin resonance in a wide AlAs quantum well containing a high quality two-dimensional electron system. Here, pseudospin emerges as a two-component degree of freedom, that labels degenerate energy minima in momentum space populated by electrons. The built-in mechanical strain in the sample studied imposes a finite "Zeeman" splitting between the pseudospin "up" and "down" states. Because of the anisotropy of the electron spin splitting we were able to independently measure the electron spin resonances originating from the two in-plane valleys. By analyzing the relative resonance amplitudes, we were able to investigate the ferromagnetic phase transitions taking place at integer filling factors of the quantum Hall effect when the magnetic field is tilted. The pseudospin nature of these transitions is demonstrated.

Core-shell model of the clusters of CPEB4 isoforms preceding liquid-liquid phase separation

Protein solutions can undergo liquid-liquid phase separation (LLPS), where a dispersed phase with a low protein concentration coexists with coacervates with a high protein concentration. We focus on the low complexity N-terminal domain of cytoplasmic polyadenylation element binding-4 protein, CPEB4NTD, and its isoform depleted of the Exon4, CPEB4Δ4NTD. They both exhibit LLPS, but in contrast to most systems undergoing LLPS, the single-phase regime preceding LLPS consists mainly of soluble protein clusters. We combine experimental and theoretical approaches to resolve the internal structure of the clusters and the basis for their formation. Dynamic light scattering and atomic force microscopy show that both isoforms exhibit clusters with diameters ranging from 35 to 80 nm. Electron paramagnetic resonance spectroscopy of spin-labeled CPEB4NTD and CPEB4Δ4NTD revealed that these proteins have two distinct dynamical properties in both the clusters and coacervates. Based on the experimental results, we propose a core-shell structure for the clusters, which is supported by the agreement of the dynamic light scattering data on cluster size distribution with a statistical model developed to describe the structure of clusters. This model treats clusters as swollen micelles (microemulsions) where the core and the shell regions comprise different protein conformations, in agreement with the electron paramagnetic resonance detection of two protein populations. The effects of ionic strength and the addition of 1,6-hexanediol were used to probe the interactions responsible for cluster formation. While both CPEB4NTD and CPEB4Δ4NTD showed phase separation with increasing temperature and formed clusters, differences were found in the properties of the clusters and the coacervates. The data also suggested that the coacervates may consist of aggregates of clusters.

Enhanced Degradation of Micropollutants in a Peracetic Acid/Mn(II) System with EDDS: An Investigation of the Role of Mn Species.

Extensive research has been conducted on the utilization of a metal-based catalyst to activate peracetic acid (PAA) for the degradation of micropollutants (MPs) in water. Mn(II) is a commonly employed catalyst for homogeneous advanced oxidation processes (AOPs), but its catalytic performance with PAA is poor. This study showed that the environmentally friendly chelator ethylenediamine-N,N'-disuccinic acid (EDDS) could greatly facilitate the activation of Mn(II) in PAA for complete atrazine (ATZ) degradation. In this process, the EDDS enhanced the catalytic activity of manganese (Mn) and prevented disproportionation of transient Mn species, thus facilitating the decay of PAA and mineralization of ATZ. By employing electron spin resonance detection, quenching and probe tests, and 18O isotope-tracing experiments, the significance of high-valent Mn-oxo species (Mn(V)) in the Mn(II)-EDDS/PAA system was revealed. In particular, the involvement of the Mn(III) species was essential for the formation of Mn(V). Mn(III) species, along with singlet oxygen (1O2) and acetyl(per)oxyl radicals (CH3C(O)O•/CH3C(O)OO•), also contributed partially to ATZ degradation. Mass spectrometry and density functional theory methods were used to study the transformation pathway and mechanism of ATZ. The toxicity assessment of the oxidative products indicated that the toxicity of ATZ decreased after the degradation reaction. Moreover, the system exhibited excellent interference resistance toward various anions and humid acid (HA), and it could selectively degrade multiple MPs.

Enhanced degradation of emerging contaminants by Far-UVC photolysis of peracetic acid: Synergistic effect and mechanisms

Krypton chloride (KrCl*) excimer lamps (222 nm) are used as a promising irradiation source to drive ultraviolet-based advanced oxidation processes (UV-AOPs) in water treatment. In this study, the UV222/peracetic acid (PAA) process is implemented as a novel UV-AOPs for the degradation of emerging contaminants (ECs) in water. The results demonstrate that UV222/PAA process exhibits excellent degradation performance for carbamazepine (CBZ), with a removal rate of 90.8 % within 45 min. Notably, the degradation of CBZ in the UV222/PAA process (90.8 %) was significantly higher than that in the UV254/PAA process (15.1 %) at the same UV dose. The UV222/PAA process exhibits superior electrical energy per order (EE/O) performance while reducing resource consumption associated with the high-energy UV254/PAA process. Quenching experiments and electron paramagnetic resonance (EPR) detection confirm that HO• play a dominant role in the reaction. The contributions of direct photolysis, HO•, and other active species (RO• and 1O2) are estimated to be 5 %, 88 %, and 7 %, respectively. In addition, the effects of Cl−, HCO3−, and humic acid (HA) on the degradation of CBZ are evaluated. The presence of relatively low concentrations of Cl−, HCO3−, and HA can inhibit CBZ degradation. The UV222/PAA oxidation process could also effectively degrade several other ECs (i.e., iohexol, sulfamethoxazole, acetochlor, ibuprofen), indicating the potential application of this process in pollutant removal. These findings will propel the development of the UV222/PAA process and provide valuable insights for its application in water treatment.

Enhanced photocatalytic degradation of oxytetracycline by Z-scheme heterostructure ZIF-8/Bi4O5Br2

Semiconductor photocatalysis technology has a wide range of application in the treatment of environmental pollution. In this study, the Z-scheme heterojunction photocatalyst ZIF-8/Bi4O5Br2 was synthesized by hydrothermal method. The morphology, structure, mechanism and photocatalytic performance of the materials were studied. Under simulated sunlight illumination for 60 minutes, the degradation efficiency of oxytetracycline (15 mg·L−1) reached 94.2 %. In light of density functional theory calculation and liquid chromatography-mass spectrometry, the attack sites and degradation pathways of OTC were determined. The consequence of free radical capture test and electron paramagnetic resonance detection showed that ·O2-, ·OH and h+ were the primary active substances. Based on the analysis above, the charge transfer principle of Z-scheme heterojunction was further elucidation. It inhibited the recombination of photo carriers and improved the photocatalytic performance. This work provides a hopeful measure for photocatalytic degradation of OTC by Z-scheme heterojunction composite.

Underestimated role of hydroxyl radicals for bromate formation in persulfate-based advanced oxidation processes

In persulfate-based advanced oxidation processes (PS-AOPs), sulfate radicals (SO4•-) have been recognized to play more important roles in inducing bromate (BrO3−) formation rather than hydroxyl radicals (HO•) because of the stronger oxidation capacity of the former. However, this study reported an opposite result that HO• indeed dominated the formation of bromate instead of SO4•-. Quenching experiments were coupled with electron paramagnetic resonance (EPR) detection and chemical probe identification to elucidate the contributions of each radical species. The comparison of different thermal activated persulfates (PDS and PMS) demonstrated that the significant higher bromate formation in HEAT/PMS ([BrO3−]/[Br−]0 = 0.8), as compared to HEAT/PDS ([BrO3−]/[Br−]0 = 0.2), was attributable to the higher concentration of HO• radicals in HEAT/PMS. Similarly, the bromate formation in UV/PDS ([BrO3−]/[Br−]0 = 1.0), with a high concentration of HO•, further underscored the dominant role of HO•. As a result, we quantified that HO• and SO4•- radicals accounted 66.7% and 33.3% for bromate formation. This controversial result can be reconciled by considering the critical intermediate, hypobromic acid/hypobromate (HOBr/BrO−), involved in the transformation of Br− to BrO3−. HO• radicals have the chemical preference to induce the formation of HOBr/BrO− intermediates (contributing ∼ 60%) relative to SO4•- radicals (contributing ∼ 40%). This study highlighted the dominant role of HO• in the formation of bromate rather than SO4•- in PS-AOPs and potentially offered novel insights for reducing disinfection byproduct formation by controlling the radical species in AOPs.

Coupling harmful algae derived nitrogen and sulfur co-doped carbon nanosheets with CeO2 to enhance the photocatalytic degradation of isothiazolinone biocide

Removing the algae from water bodies is an effective treatment toward the worldwide frequently occurred harmful algae blooms (HAB), but processing the salvaged algae waste without secondary pollution places another burden on the economy and environment. Herein, a green hydrothermal process without any chemical addition was developed to resource the HAB algae (Microcystis sp.) into autogenous nitrogen and sulfur co-doped carbon nanosheet materials C–CNS and W–CNS, whose alga precursors were collected from pure culture and a wild bloom pond, respectively. After coupling with CeO2, the obtained optimal C–CNS/CeO2 and W–CNS/CeO2 composites photocatalytically degraded 95.4% and 88.2% of the marine pollutant 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) in 90 min, significantly higher than that of pure CeO2 (63.15%). DCOIT degradation on CNS/CeO2 was further conducted under different conditions, including pH value, coexisting cations and anions, and artificial seawater. Although different influences were observed, the removal efficiencies were all above 76%. Along with the ascertained good stability and reusability in five consecutive runs, the great potential of CNS/CeO2 for practical application was validated. UV–vis DRS showed the increased light absorption of CNS/CeO2 in comparison to pure CeO2. PL spectra and photoelectrochemical measurements suggested the lowered charge transfer resistance and thereby inhibited charge recombination of CNS/CeO2. Meanwhile, trapping experiments and electron paramagnetic resonance (EPR) detection verified the primary roles of hydroxyl radical (OH) and superoxide radical (O2−) in DCOIT degradation, as well as their notably augmented generation by CNS. Consequently, a mechanism of CNS enhanced photocatalytic degradation of DCOIT was proposed. The intermediates involved in the reaction were identified by LC-QTOF-MS, giving rise to a deduced degradation pathway for DCOIT. This study offers a new approach for resourceful utilization of the notorious HAB algae waste. Besides that, photocatalytic degradation has been explored as an effective measure to remove DCOIT from the ocean.

Degradation of Carbamazepine in Water by UV-activated Sulfite Process

In this study, the degradation efficiency and mechanism of carbamazepine (CBZ), a typical emerging contaminant in water, in the UV/sulfite process were investigated. The effects of different concentrations of dissolved oxygen [ρ(DO)] on the degradation of CBZ by UV-activated sulfite were investigated. Additionally, under a simulated natural water environment-controlled initial ρ(DO) of (8.0 ±0.2) mg·L-1, the effects of different process parameters (sulfite dosages and reaction pH) and water environmental factors (the presence of HCO3-, Cl-, and humic acids) on the degradation of CBZ were comprehensively analyzed. The results showed that the UV/sulfite process efficiently degraded CBZ with a degradation rate of 85.3% during the 30 min reaction time and followed the pseudo-first order kinetic model with the constant of 0.055 7 min-1. Using the electron spin resonance detection, reactive species quenching tests, and the competition kinetics, the sulfate radicals (SO4-·) and hydroxyl radicals (·OH) in the UV/sulfite process were determined to be the main reactive species and were responsible for the degradation of CBZ with contribution rates of 43.9% and 56.1%, respectively. In addition, the degradation efficiency of CBZ decreased with the increasing concentration of HCO3-, and the presence of Cl- had little effect on the degradation of CBZ, whereas the presence of humic acids significantly inhibited the degradation of CBZ. Moreover, the accumulation of sulfate during the reaction was significantly lower than the limit of the Standard for Drinking Water (GB5749-2022). Additionally, the sulfite consumption rate constant was 0.004 4 min-1, which was significantly lower than the degradation rate constant of CBZ, indicating that sulfite could be activated efficiently by UV light to degrade CBZ in water.

129Xe Dynamic Nuclear Polarization Demystified: The Influence of the Glassing Matrix on the Radical Properties.

129Xe dissolution dynamic nuclear polarization (DNP) is a controversial topic. The gold standard technique for hyperpolarized xenon magnetic resonance imaging (MRI) is spin exchange optical pumping, which received FDA approval in 2022. Nevertheless, the versatility of DNP for enhancing the signal of any NMR active nucleus might provide new perspectives for hyperpolarized 129Xe NMR/MRI. Initial publications about 129Xe DNP underlined the increased complexity in the sample preparation and lower polarization levels when compared to more conventional 13C-labeled molecules, at same experimental conditions, despite very close gyromagnetic ratios. Herein, we introduce, using a Custom Fluid Path system, a user-friendly and very robust sample preparation method. Moreover, investigating the radical properties at real DNP conditions by means of LOngitudinal Detected Electron Spin Resonance, we discovered a dramatic shortening of the electron spin longitudinal relaxation time (T1e) of nitroxyl radicals in xenon DNP samples' matrices, with respect to more commonly used water:glycerol ones. Mitigating those challenges through microwave frequency modulation, we achieved over 20% 129Xe polarization without employing any deuterated solvent.

A Low-Cost, Tabletop LOD-EPR System for Nondestructive Quantification of Iron Oxide Nanoparticles in Tissues.

Iron oxide nanoparticles (IONPs) have wide utility in applications from drug delivery to the rewarming of cryopreserved tissues. Due to the complex behavior of IONPs (e.g., uneven particle distribution and aggregation), further developments and clinical translation can be accelerated by having access to a noninvasive method for tissue IONP quantification. Currently, there is no low-cost method to nondestructively track IONPs in tissues across a wide range of concentrations. This work describes the performance of a low-cost, tabletop, longitudinally detected electron paramagnetic resonance (LOD-EPR) system to address this issue in the field of cryopreservation, which utilizes IONPs for rewarming of rat kidneys. A low-cost LOD-EPR system is realized via simultaneous transmit and receive using MHz continuous-wave transverse excitation with kHz modulation, which is longitudinally detected at the modulation frequency to provide both geometric and frequency isolation. The accuracy of LOD-EPR for IONP quantification is compared with NMR relaxometry. Solution measurements show excellent linearity (R2 > 0.99) versus Fe concentration for both measurements on EMG308 (a commercial nanoparticle), silica-coated EMG308, and PEG-coated EMG308 in water. The LOD-EPR signal intensity and NMR longitudinal relaxation rate constant (R1) of water are affected by particle coating, solution viscosity, and particle aggregation. R1 remains linear but with a reduced slope when in cryoprotective agent (CPA) solution, whereas the LOD-EPR signal is relatively insensitive to this. R1 does not correlate well with Fe concentration in rat kidney sections (R2 = 0.3487), while LOD-EPR does (R2 = 0.8276), with a linear regression closely matching that observed in solution and CPA.

A dual-mode sensing platform for electron spin resonance and UV-vis detection of alkaline phosphatase based on Cu-based metal-organic frameworks.

Alkaline phosphatase (ALP) is an indispensable hydrolase in living organisms and the abnormality of ALP activity is correlated with a variety of diseases. Exploring ALP activity is important for clinical diagnosis and biomedical research to understand its physiological function. In this study, a dual-mode biosensing platform was constructed based on Cu-based metal-organic frameworks (Cu-MOFs) for electron spin resonance (ESR) and ultraviolet-visible (UV-vis) sensing of ALP. Cu-MOFs, as peroxidase mimics, catalyzed the decomposition of hydrogen peroxide (H2O2) and the generation of reactive oxygen species (ROS) which could oxidize ABTS into ABTS˙+ with good ESR and UV-vis signals. Pyrophosphate ions (PPi) with high affinity to Cu2+ in Cu-MOFs could suppress the peroxidase-like activity of Cu-MOFs, and ALP could hydrolyze PPi, resulting in the recovery of Cu-MOF catalytic activity. Thus, a quantitative dual-mode method for detection of ALP activity was established with good linearity in the range of 0-42 U L-1 and limits of detection as low as 0.386 and 0.523 U L-1 respectively for ESR and UV-vis detection. Benefiting from its high sensitivity and excellent selectivity, this method was applied for ALP detection in human serum and satisfactory recoveries were achieved. The off-on dual-mode sensing platform is more reliable than the single-mode sensor and shows merits like simple operation and cost-friendliness, making it have great potential in the diagnosis of ALP-related diseases.

Progress and limitations in reactive oxygen species quantitation.

Reactive oxygen species (ROS) are a set of oxygen- and nitrogen-containing radicals. They are produced from a wide range of sources. In biological contexts, cellular stress leads to an overproduction of ROS, which can lead to genetic damage and disease development. In industry, ROS are often productively used for water purification or for analyzing the possible toxicity of an industrial process. Because of their ubiquity, detection of ROS has been an analytical goal across a range of fields. To understand complicated systems and origins of ROS production, it is necessary to move from qualitative detection to quantitation. Analytical techniques that combine quantitation, high spatial and temporal resolution, and good specificity represent detection methods that can fill critical gaps in ROS research. Herein, we discuss the continued progress and limitations of fluorescence, electrochemical, and electron paramagnetic resonance detection of ROS over the last ten years, giving suggestions for the future of the field.

Mechanism exploration in tetracycline degradation by Ni-Fe layered double hydroxide-biochar/peroxymonosulfate system: Nonradical-dominated oxidation process

Metal-based materials are widely regarded as promising catalysts for activating peroxymonosulfate (PMS) to remove refractory organic contaminants with high efficiency. In our study, Ni-Fe layered double hydroxide (LDH)-biochar (BC) composite-induced PMS-based advanced oxidation process (AOP) was utilized to elucidate the degradation of tetracycline hydrochloride (TCH). In Ni-Fe LDH-BC/PMS system, more than 99% TCH (45 μM) could be removed effectively at low doses of oxidant (PMS, 0.10 mM) and catalyst (Ni-Fe LDH-BC, 0.10 g/L) addition within 80 min. Besides, the Ni-Fe LDH-BC/PMS system showed high resistance to some inorganic anions, and the Ni-Fe LDH-BC composite possessed excellent reusability in the degradation of TCH (>99% in four cyclic experiments). The reaction mechanisms were investigated via electron paramagnetic resonance detection, chemical quenching tests, probe experiments, and electrochemical measurements. These results indicated that the electron-shuttle mechanism played the dominant role in the removal of TCH. It is worth noting that determination of PMS concentration can reflect the reliability of quenching experiments. In the Ni-Fe LDH-BC composite, BC could not only improve the dispersion of Ni-Fe LDH, but also increase the conductivity of Ni-Fe LDH. Overall, a successful modification strategy was proposed in our study to improve the catalytic property of Ni-Fe LDH, and reaction mechanisms of TCH degradation were discussed deeply and comprehensively.

Study on the dominant mechanism of direct hole oxidation for the photodegradation of tetracycline.

Antibiotic contamination has a significant negative impact on China, one of the largest producers and consumers of antibiotics worldwide. In this study, a three-dimensional flower-like structure of CoFe-LDHs was used to efficiently degrade tetracycline (TC) in a system triggered by peroxymonosulfate (PMS) and exposed to visible light. After exploring the effects of different metal ratios, catalyst dosage, initial TC concentrations, and pH, the optimal reaction conditions were determined. In comparison to pure CoFe-LDHs, the TC elimination rate was dramatically increased by the addition of the PMS. The strong environmental resistance, excellent stability and reusability, and universal flexibility were shown. The quenching experiments and electron spin resonance detection showed that the creation of reactive oxygen species was facilitated by the synergistic transmission of electrons between the active bimetallic components. Further, photogenerated holes was the dominant oxidizing species, which contributed more to the degradation of TC. The potential degradation pathways and intermediate toxicity of TC were suggested. This work offers a new method dominated by photogenerated holes for efficiently removing TC effluent.

Fe-N coordination moieties regulate the defect formation in carbon nanomaterial for efficient peroxydisulfate activation: Significant role of surface complex

An iron (Fe)-modified carbon dots (CDs) doped ZIF-8 zeolite imidazole metal-organic frame pyrolyzed composite (5Fe@NC) was prepared and then evaluated as a peroxydisulfate (PDS) activator for the oxidative removal of organic pollutants. The 5Fe@NC/PDS system not only has a good recovery performance, wide pH adaptability, and low activation energy, but also is resistant to environmental interference. The quenching experiments, electron paramagnetic resonance (EPR) detection, and electrochemical analysis all revealed that unlike the widely reported singlet oxygen (1O2) dominated nonradical mechanism, an electron transfer process (ETP) involving a surface bound PDS complex played the main role in pollutants’ degradation by 5Fe@NC/PDS system. The FeNx, defect, graphitic N and hydroxyl group (-OH) acting as active sites, prompted the 5Fe@NC-PDS complex to capture electrons (e−) from acetaminophen (ACT). This study provides a new approach for xFe@NCs rational design, and deepen the understanding of FeNx activation mechanism of PDS in carbon nanomaterials.