Lasers Research Articles

Axially coordinated dual-atomic-site catalysts for nearly 100% peroxymonosulfate conversion to 1O2 in membrane filtration

Reactive membrane filtration, integrating membrane technology with catalytic processes, offers a promising avenue for efficiently generating and utilizing active species in environmental remediation. Herein, a dual-atom Co-Mn site achieved through axial coordination on N-doped graphene catalyst (sp-CoMn@NG) has been developed and applied in membrane filtration for the targeted removal of specific pollutants. Experimental investigations, alongside density functional theory (DFT) calculations, have substantiated that axial coordination can effectively reduce the adsorption energy and activation barrier of PMS, thereby facilitating nearly 100% conversion of PMS to 1O2 and enhancing catalytic performance. Mechanistic studies further elucidate the 1O2 production mechanism through a superoxide-mediated chain reaction at the axially coordinated Co-Mn center, as well as the inactivation mechanism of catalytic membranes via the addition reaction of 1O2 and phenolic-hydroxyl compounds. This research underscores the intelligent prefabrication of axial coordination in dual-atomic-site catalysts, offering an efficient approach for scalable 1O2 production in reactive membrane filtration.

Deeply revealing the mechanism of the synergistic effect of Cu and P on alleviating CaO poisoning performance of V-W-Ti catalysts in cement kilns

CaO was the inevitable cause of V2O5-WO3-TiO2 catalyst (VWTi) poisoning in cement kilns. The significant reduction in NO conversion was due to the combination of CaO and active species of the vanadium-based catalyst. In this work, the VWTi catalysts were modified with different contents of Cu and P to improve resistance to CaO, thereby extending the service life of catalysts in cement kilns. By doping Cu and P, the Ca-VWCu3P5Ti had better catalytic activity, reduced the poisoning effect of CaO to V5+, thus protecting the redox properties and increasing the surface acidic sites of the catalyst. Meanwhile, the in-situ DRIFTs results showed that the poisoning effect of CaO was weaker on the Ca-VWCu3P5Ti than that of the Ca-VWTi. In addition, the NH3 and NO species could be effectively adsorbed and activated on the surface of the Ca-VWCu3P5Ti by E-R mechanism. In this way, the harm of CaO to the vanadium-based catalysts was effectively reduced. This work provided a promising strategy to design vanadium-based catalysts with superior resistance to CaO in NH3-SCR reaction.

Development of a novel polydopamine-imprinted MOFs targeted for removal of refractory organic pollutants: Synergistic mechanisms of adsorption and degradation

In this study, a novel dopamine-imprinted MOFs (metal organic frameworks) was developed for the first time to achieve targeted degradation of refractory organic pollutants (ROPs) in advanced oxidation process. The targeted adsorption and degradation capacity of sulfamethoxazole (SMX) by molecularly imprinted catalyst (Fe-MOFs@MIP) was 3.17 times and 5.47 times that of Fe-MOFs, respectively. The results showed that the polydopamine (PDA) imprinted layer not only enhanced the targeted adsorption of SMX, but also improved the activity of the catalyst by promoting electron transfer. The physicochemical properties of Fe-MOFs@MIP were investigated. In situ Fourier transform infrared spectroscopy and molecular dynamics theory were used to investigate targeted adsorption mechanism. The active species were identified by quenching experiments and electron paramagnetic resonance (EPR). The reaction sites of SMX were predicted using density functional theory (DFT) and the possible degradation pathways of SMX were proposed. Finally, the targeted degradation mechanism of Fe-MOFs@MIP was elucidated. This study has a guiding significance for the deep removal of refractory organic pollutants in wastewater.

Sulfur-doped manganese-cobalt hydroxide with promoted surface reconstruction for glycerol electrooxidation assisted hydrogen production

Glycerol electrooxidation reaction (GOR), as an attractive alternative to oxygen evolution reaction, not only produces value-added formic acid but also facilitates H2 production. However, its practical application suffers from the lack of efficient electrocatalysts with high activity at low potentials. Herein, sulfur doped manganese-cobalt hydroxide nanosheets on nickel foam (Mn-Co-S/NF) has been demonstrated as a promising electrocatalytic electrode for GOR, showing high current density at low potentials and high Faradaic efficiency for formate production. The combination of ex situ characterization, operando Raman analysis, and in situ electrochemical impedance spectroscopy measurement unveils that S doping leads to the formation of hierarchically porous structure with abundant oxygen vacancies during the reaction, enabling the surface reconstruction to proceed in an easier manner and to a higher degree. As a result, the reconstructed Mn-Co-S/NF possesses highly enhanced charge/mass transfer capability and enriched high valence Co active species. Impressively, in a practical flow electrolyzer, an industrial-level current density of 900 mA cm−2 can be achieved at a cell voltage of 2.0 V. It also exhibits H2 yield rate of 3.5 mmol cm−2 h−1 at 200 mA cm−2, realizing up to 30.2% energy saving efficiency compared to water electrolysis.

Hemp-ball-like structured Fe3O4-hollow carbon sphere nanozymes functionalized carbon fiber cathode for efficient flow-through electro-Fenton

Electro-Fenton (EF) technology has been recognized as a highly promising electrochemical advanced oxidation process. Promoting effective contact between active species and contaminant is crucial in electrocatalysis. Herein, we had innovatively designed a unique nanozymes in the form of hemp-ball-like structures, consist of the uniform growth of Fe3O4 nanoparticles on nitrogen-doped nano hollow carbon spheres (NHCS). This catalyst was employed in a flow-through EF system with carbon felt (CF) filters serving as the work electrode. The active sites were fully exposed through the ultradispersed Fe3O4 nanoparticles, and the NHCS facilitated efficient cycling of Fe3+/Fe2+. The results showed that the generation capacity of hydroxyl radicals (·OH) was enhanced, and the oxidation flux reached 370.080 mg h−1m−2 with low energy consumption. The superiority of the hollow carrier was proved by the degradation results and COMSOL calculation for various carbon carriers. Moreover, the active catalyst exhibited adaptability in complex water matrices. This study offers a new perspective to synergize nanomaterials, EF reactions and flow-type systems.

Feasibility of Using Green Laser for Underwater Infrastructure Monitoring: Case Studies in South Florida

Scour around bridges present a severe threat to the stability of railroad and highway bridges. Scour needs to be monitored to prevent the bridges from becoming damaged. This research studies the feasibility of using green laser for monitoring the scour around candidate railroad and highway bridges. The laboratory experiments that provided the basis for using green laser for underwater mapping are also discussed. The results of the laboratory and field experiments demonstrate the feasibility of using green laser for underwater infrastructure monitoring with limitations on the turbidity of water that affects the penetrability of the laser. This method can be used for scour monitoring around offshore structures in shallow water as well as corrosion monitoring of bridges.

Ga doped TiO2 with enhanced photocatalytic degradation performance benefited from rich oxygen vacancies

Titanium dioxide (TiO2) is widely regarded as one of the most promising semiconductors among the various photocatalytic materials. In this demonstration, Ga-doped TiO2 with rich oxygen vacancies (OVs) was synthesized by a sol–gel method. Systematic characterization provides soild attest for the successful doping of Ga and the enhancement level of OVs. The large specific surface area provides richer surface-active sites for Ga/OVs-TiO2 samples through BET test. The photoelectric performance test shows that Ga doping and the existence of rich OVs can effectively improve the photogenerated carriers separation and migration efficiency of TiO2. The degradation results for rhodamine B (RhB) and tetracycline hydrochloride (TC) attest that the photocatalytic efficiency of Ga-doped TiO2 is better than that of the reference TiO2. The capture experiment further exhibits that hydroxyl radical and superoxide radical are the main active species in photocatalytic degradation. The synergistic effect of Ga doping and OVs significantly improves the separation and migration of photogenerated carriers, therefore boosting the photocatalytic performance. This work provides a reliable guide for utilization of Ga and a solid strategy of element doping to improve the photocatalytic performance of TiO2.

Photocatalytic activation of peroxydisulfate by UV-LED through rGO/g-C3N4/SiO2 nanocomposite for ciprofloxacin removal: Mineralization, toxicity, degradation pathways, and application for real matrix

If trace amounts of antibiotics remain in the environment, they can lead to microbial pathogens becoming resistant to antibiotics and putting ecosystem health at risk. For instance, ciprofloxacin (CIP) can be found in surface and ground waters, suggesting that conventional water treatment technologies are ineffective at removing it. Now, a rGO/g-C3N4/SiO2 nanocomposite was synthesized in this study to activate peroxydisulfate (PDS) under UVA-LED irradiation. UVA-LED/rGO-g–C3N4–SiO2/PDS system performance was evaluated using Ciprofloxacin as an antibiotic. Particularly, rGO/g-C3N4/SiO2 showed superior catalytic activity for PDS activation to remove CIP. Operational variables, reactive species determination, and mechanisms were investigated. 0.85 mM PDS and 0.3 g/L rGO/g-C3N4/SiO2 eliminated 99.63% of CIP in 35 min and mineralized 59.78% in 100 min at pH = 6.18. By scavenging free radicals, bicarbonate ions inhibit CIP degradation. According to the trapping experiments, superoxide (O2•−) was the main active species rather than sulfate (SO4•−) and hydroxyl radicals (•OH). RGO/g-C3N4/SiO2 showed an excellent recyclable capability of up to six cycles. The UVA-LED/rGO-g–C3N4–SiO2/PDS system was also tested under real conditions. The system efficiency was reasonable. By calculating the synergistic factor (SF), this work highlights the benefit of combining composite, UVA-LED, and PDS. UVA-LED/rGO-g–C3N4–SiO2/PDS had also been predicted to be an eco-friendly process based on the results of the ECOSAR program. Consequently, this study provides a novel and durable nanocomposite with supreme thermal stability that effectively mitigates environmental contamination by eliminating antibiotics from wastewater.

Facile synthesis of Ni-doped ZnS nanostructures and their photocatalytic activity to RhB

In this paper, pure ZnS and Ni-doped ZnS nanostructures (Ni–ZnS) were prepared by facile template-free hydrothermal method. The as-prepared Ni–ZnS was characterized by XRD, SEM, EDS, XPS, and UV–Vis DRS. The effects of different Ni doping amounts and hydrothermal reaction temperatures were investigated. The photocatalytic ability was evaluated for the degradation of Rhodamine B (RhB) under visible light irradiation. The results indicated that the doping of Ni effectively enhanced the photocatalytic activity of pure ZnS. Ni–ZnS exhibited significantly enhanced photocatalytic properties, the reaction rate constant (0.01154 min−1) is higher than that of pure ZnS (0.00218 min−1). Carrier separation efficiency and charge transport efficiency were investigated by transient photocurrent response (TPS) and electrochemical impedance spectroscopy (EIS). Scavenger test was used to determine the role of active species, combining the analysis results of UV–Vis DRS, TPS, and EIS, accordingly the photocatalytic mechanism of Ni–ZnS was proposed.

Peroxymonosulfate activation by superparamagnetic mixed-valent Cu/N-(L-cysteine)-O-(carboxymethyl)chitosan/cobalt ferrate-rice hull hybrid nanocomposite for efficient degradation of naproxen: Synergetic adsorption-catalysis, kinetics, pathway, and relevant mechanism

Naproxen (NPX) as an emerging anthropogenic contaminant was detected in many water sources, which can pose a serious threat to the environment and human health. Peroxymonosulfate (PMS) decomposed by Cu(I) has been considered an effective activation method to produce reactive species. However, this decontamination process is restricted by the slow transformation of Cu(II)/Cu(I) by PMS. Herein, new N-(L-cysteine/triazine)-O-(carboxymethyl)-chitosan/cobalt ferrate-rice hull hybrid biocomposite was constructed to anchor the mixed-valent Cu(I)-Cu (II) (CuI, II-CCCF) for removing pharmaceutical pollutants (i.e., naproxen, ciprofloxacin, tetracycline, levofloxacin, and paracetamol). The structural, morphological, and catalytic properties of the CuI,II-CCCF have been fully identified by a series of physicochemical characterizations. Results demonstrated that the multifunctional, hydrophilic character, and negative ζ-potential of the activator, accelerating the redox cycle of Cu(II)/Cu(I) with hydroxyl amine (HA). The negligible metal leaching, well-balanced thermodynamic-kinetic properties, and efficient adsorption-catalysis synergy are the main reasons for the significantly enhanced catalytic performance of CuI,II-CCCF in the removal of NPX (98.6 % at 7.0 min). The main active species in the catalytic degradation of NPX were identified (●OH > SO4●− > 1O2 > > O2●−) and consequently suggested a degradation path. It can be noted that these types of carbohydrate-based nanocomposite offer numerous advantages, encompassing simple preparation, excellent decontamination capabilities, and long-term stability.

Revealing the Enhanced Visible-light-driven Photocatalytic Activity of In2S3/CeO2 Heterojunction: Bandgap Structure Analysis and Active Radicals Determination

Background: The widespread presence of persistent organic pollutants, such as dyes in effluent from printing and textile industries, poses a significant threat to aquatic life and human health. Photocatalytic degradation is widely recognized as a promising technology to address this pollution crisis. The efficiency of photocatalysis is intricately tied to both the active radicals and the band structure of the catalyst. These factors play a crucial role in governing the photodegradation of dye molecules. Methods: In2S3/CeO2 heterojunctions were synthesized using an in-situ precipitation method and subsequently analyzed through SEM, XRD, and XPS techniques. Notably, the bandgap structure of the heterojunctions was examined through UV-Vis DRS. The photocatalytic performance of the synthesized samples was assessed by studying the degradation of methyl orange. To further validate the photocatalytic process, EPR spectroscopy was employed to confirm the presence of radicals generated within the heterojunction. Results: The heterojunction displayed a characteristic type-II structure, enhancing light absorption and facilitating the separation of photoinduced carriers. Among the In2S3/CeO2 composites, the one with a 15 wt% CeO2 content exhibited the highest photocatalytic activity, achieving an 88% degradation of methyl orange after 90 min of exposure to visible light irradiation. Additionally, •O2 − is identified as the primary active species responsible for degradation. Conclusion: UV-Vis DRS illustrated the improved transfer and separation of photogenerated electrons attributed to the optimized band structure of the heterojunction. EPR spectroscopy yielded valuable information on active radicals, thereby proposing the photocatalytic degradation mechanism.

Coupled capture and photocatalysis of g-C3N4 based magnetic composites: Mechanism and disinfection activity against Staphylococcus aureus

The disinfection ability of g-C3N4 by photocatalysis is restricted, owing to its small surface area and rapid combination of holes (h+) and electrons (e−). Moreover, recycling of g-C3N4-based photocatalysts from aqueous solution is difficult, which increases the cost of application. In the present study, g-C3N4 was combined with magnetic biochar (MBC) by high temperature calcination to fabricate g-C3N4/MBC composites. The as-prepared g-C3N4/MBC composites acquired larger specific surface area, narrow bandgap, and broad-range of visible absorption capability. The g-C3N4/MBC composites showed good killing efficiency towards Staphylococcus aureus (S. aureus) under visible light irradiation. Efficient photocatalysis was achieved by the effective separation of e−/h+ within the g-C3N4/MBC composites. Moreover, the capture effect of MBC for S. aureus reduced the distance and increased the contact area between the g-C3N4/MBC composite and S. aureus. The g-C3N4/MBC-10 % showed notable stability and reusability over a broad pH range of 4–8 and in presence of different inorganic ions (Cl− and SO42−) and humic acid. After 5 cycles, the g-C3N4/MBC-10 % could still eliminate about 95 % of S. aureus cells. The g-C3N4/MBC-10 % was also highly effective in reducing the bacterial population in water samples taken from a nearby lake, thus showing considerable promise for use in water sterilization. In addition, g-C3N4/MBC composites were highly effective in eliminating the biofilm and inhibiting the growth of the new biofilm of S. aureus. The main active species in photocatalytic disinfection were determined, to be •OH, h+, and •O2−. This study would help to understand the capture and photocatalysis of g-C3N4 based composites for environmental applications.

Microbiome dynamics and environment driving factors throughout pit fermentation of Jiang-flavor Baijiu: A multi-omics study

Pit fermentation process has a significant impact on Baijiu production. However, the dynamics patterns and environmental driving mechanisms in Jiang-flavor Baijiu pit fermentation remain unclear. Here, we present a multi-omics study on 180 Jiang-flavor Baijiu fermentation samples across the pit fermentation process. We revealed and validated the dynamics and metabolic functions of the core species employing both culture-independent (i.e., metagenomics and metatranscriptomics) and culture-dependent tools. Our findings delineate the fermentation into three distinct stages, each characterized by a unique microbial community, functional profile, and accumulation of flavor compounds. In stage I, Bacillus subtilis, Pichia kudriavzevii, and Saccharomyces cerevisiae were the most abundant species, while Acetilactobacillus jinshanensis, S. cerevisiae, P. kudriavzevii, Schizosaccharomyces pombe, and Zygosaccharomyces bailii had the highest transcriptional activity. In stage II, A. jinshanensis emerged as the most abundant and metabolically active species in stage II, reaching a proportion of 45.69% ± 20.21%, and maintained a leading role in stage III with a proportion of 65.75% ± 6.56%, a period marked by minimal microbial diversity and significant accumulation of key flavor substances, notably esters and acids. In addition, A. jinshanensis was isolated and its core acid-producing microbial status confirmed based on culture-dependent tools. Structural equation modeling indicated that A. jinshanensis plays crucial roles in the heterogeneous succession of alcohol-producing microorganisms, with spatial differences in acidity being a key factor. This work not only provides a robust analytical framework for understanding the Baijiu fermentation microbiome but also lays the groundwork for technological innovation in the fermentation industry.

Time-resolved characteristics of a nanosecond pulsed multi-hollow needle plate packed bed dielectric barrier discharge

In this paper, self-designed multi-hollow needle electrodes are used as a high-voltage electrode in a packed bed dielectric barrier discharge reactor to facilitate fast gas flow through the active discharge area and achieve large-volume stable discharge. The dynamic characteristics of the plasma, the generated active species, and the energy transfer mechanisms in both positive discharge (PD) and negative discharge (ND) are investigated by using fast-exposure intensified charge coupled device (ICCD) images and time-resolved optical emission spectra. The experimental results show that the discharge intensity, number of discharge channels, and discharge volume are obviously enhanced when the multi-needle electrode is replaced by a multi-hollow needle electrode. During a single voltage pulse period, PD mainly develops in a streamer mode, which results in a stronger discharge current, luminous intensity, and E/N compared with the diffuse mode observed in ND. In PD, as the gap between dielectric beads changes from 0 to 250 μm, the discharge between the dielectric bead gap changes from a partial discharge to a standing filamentary micro-discharge, which allows the plasma to leave the local area and is conducive to the propagation of surface streamers. In ND, the discharge only appears as a diffusion-like mode between the gap of dielectric beads, regardless of whether there is a discharge gap. Moreover, the generation of excited states and is mainly observed in PD, which is attributed to the higher E/N in PD than that in ND. However, the generation of the radical in ND is higher than in PD. It is not directly dominated by E/N, but mainly by the resonant energy transfer process between metastable and . Furthermore, both PD and ND demonstrate obvious energy relaxation processes of electron-to-vibration and vibration-to-vibration, and no vibration-to-rotation energy relaxation process is observed.

Boosted peroxymonosulfate activation by bimetallic organometallic frameworks via by-produced and dominated H2O2 generation

Verifying the role of H2O2 is a critical challenge for deepening the understanding of the mechanism of peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs). In this research, Co, Fe bimetallic organometallic frameworks (ZIF-L@Fe28) were prepared, and their ultrahigh activities via H2O2 generation at Fe and Co sites were experimentally and theoretically verified. The important contribution of H2O2 to 1O2 production was identified through the quantifications of the mutual transformation of active species. Co sites were identified as the most active positions for PMS activation because of they strongly triggered 1O2, SO4·−, ⋅O2−, ·OH, and H2O2. However, the self-quenching of active species suppressed the efficiency and selectivity of 1O2 generation at Co sites. In contrast to Co sites, Fe sites had selective preference for H2O2 generation, and the transformation of H2O2 to 1O2 further enhanced the performance of ZIF-L@Fe28. The supplementary discussion from the perspective of H2O2 will enable the further application of the PMS activation mechanism.

Kirkendall effect induced the formation of hollow Co2P in Co-N-C for ORR, OER, HER and flexible Zn–Air battery

Enhancing the exposure of active sites and optimizing the electronic structure of the catalysts are indispensable for efficient catalyst design, yet remains challenging in the renewable energy field. Herein, a sequential pyrolyzing and phosphating approach for a well-designed GO/CoTPP gel precursor has been explored to prepare a Co-based carbon catalyst containing single-atom Co-Nx and hollow Co2P active species (Co2P/Co-N-C) for multifunctional electrocatalytic reactions. Kirkendall effect occurring during the template-free one-pot phosphating approach induced the formation of the hollow Co2P structure in the catalyst, simultaneously optimizing the electron structure and allowing the active sites to be exposed to a greater extent. DFT calculations demonstrated that the Co2P and Co-Nx structures enable Co2P/Co-N-C to have a suitable d-band center depending on the electron transfer from Co2P to Co-Nx, which enhances the adsorption of O* and the dissociation of OH* in oxygen electrode reactions, thereby facilitates catalytic reactions. As a result, the Co2P/Co-N-C exhibits excellent trifunctional activity with a half-wave potential of 0.89 V in alkaline for oxygen reduction reaction (ORR), overpotentials of 330 mV for oxygen evolution reaction (OER) and 190 mV for hydrogen evolution reaction (HER), respectively, which are among the best results reported to date for Co-containing carbon-based catalysts. Furthermore, the flexible Zinc-air battery with Co2P/Co-N-C electrodes also demonstrates a high open circuit voltage of 1.35 V, which is applied to build the self-powered device for water splitting continuously. Our work provides a facile strategy to prepare high-performance trifunctional catalysts by morphology/structure control of metal-based NPs on carbon-based materials.

Multimodal Insights of Regeneration Dynamics of Spent Bimetallic Catalysts by Full Field Hyperspectral Quick‐EXAFS Imaging and Environmental Transmission Electron Microscopy

Multimodal measurements involving time‐resolved Ni and Cu K edges Quick‐EXAFS, time‐resolved hyperspectral Full Field quick‐EXAFS imaging with micrometer spatial resolution and aberration‐corrected Environmental Scanning Transmission Electron Microscopy have been performed over a NiCu catalyst used for the ethanol steam reforming reaction to establish structure‐activity relationships after regeneration. Activated catalysts are composed of 5‐10 nm monometallic nickel nanoparticles and 20 nm or larger bimetallic randomly alloyed NiCu nanoparticles. After 3h time on reactive stream, the monitoring of the regeneration of the coked deactivated catalyst at 500°C by Full Field hyperspectral XAS imaging evidences that the oxidative propagation front affects faster metallic Ni species than metallic Cu ones. This is ascribed to the presence of both NPs populations and to a restructuration of the alloyed bimetallic particles from a homogeneous solid solution towards a Ni‐rich shell upon oxygen adsorption. Furthermore, ESTEM characterization of the deactivated catalyst when passing from H2 to O2 atmosphere at 500°C for burning coke deposits evidences the fragmentation of the Ni and NiCu‐NPs driven by the Kirkendall effect in the encapsulated coked catalyst. The resulting increase of specific surface of active species is assumed to be responsible for the activity boost observed after regeneration.

Selective oxidation behavior based on iron-doped MOF derived carbon-based catalysts: Active site regulation and degradation mechanism analysis

Selective removal of target organic pollutants in complex water quality of municipal sewage is extremely important for the deep treatment of water quality. Here, energetic MOF and Fe-MOF are doped in electrostatic spinning process to adjust the structure and composition of the catalysts, active oxygen species (ROSs), realizing the selective removal of organic pollutants. Non-azo and azo pollutants are selected as target pollutants. Catalysts PCFe-8 with Fe nanoclusters, EPCFe-8 with Fe-Nx, and EPC-8 without Fe doping are used to activate peroxymonosulfate (PMS) for degrading pollutants. The results show that the PCFe-8/PMS system can produce the most SO4− and exhibit superior removal of azo pollutants, whereas the degradation behavior of non-azo pollutants is more inclined to occur in the EPCFe-8/PMS system and the EPC-8/PMS system. This work provides a reference for elucidating the relationship between catalyst structure and components, types of ROSs, and selective degradation of pollutants.

Synergetic Manipulation Mechanism of Single-Atom M-N4 and M-OH (M = Mn, Fe, Co, Ni) Sites for Ozone Activation: Theoretical Prediction and Experimental Verification.

Carbon-based single-atom catalysts (SACs) have been gradually introduced in heterogeneous catalytic ozonation (HCO), but the interface mechanism of O3 activation on the catalyst surface is still ambiguous, especially the effect of a surface hydroxyl group (M-OH) at metal sites. Herein, we combined theoretical calculations with experimental verifications to comprehensively investigate the O3 activation mechanisms on a series of conventional SAC structures with N-doped nanocarbon substrates (MN4-NCs, where M = Mn, Fe, Co, Ni). The synergetic manipulation effect of the metal atom and M-OH on O3 activation pathways was paid particular attention. O3 tends to directly interact with the metal atom on MnN4-NC, FeN4-NC, and NiN4-NC catalysts, among which MnN4-NC has the best catalytic activity for its relatively lower activation energy barrier of O3 (0.62 eV) and more active surface-adsorbed oxygen species (Oads). On the CoN4-NC catalyst, direct interaction of O3 with the metal site is energetically infeasible, but O3 can be activated to generate Oads or HO2 species from direct or indirect participation of M-OH sites. The experimental results showed that 90.7 and 82.3% of total organic carbon (TOC) was removed within 40 min during catalytic ozonation of p-hydroxybenzoic acid with MnN4-NC and CoN4-NC catalysts, respectively. Phosphate quenching, catalyst characterization, and EPR measurement further supported the theoretical prediction. This contribution provides fundamental insights into the O3 activation mechanism on SACs, and the methods and ideals could be helpful for future studies of environmental catalysis.

A Mechanistic Investigation of the N-Hydroxyphthalimide Catalyzed Benzylic Oxidation Mediated by Sodium Chlorite.

A detailed investigation into the mechanistic course of N-hydroxyphthalimide catalyzed oxidation of benzylic centers using sodium chlorite as the stoichiometric oxidant is reported. Through a combination of experimental, spectroscopic, and computational techniques, the transformation is interrogated, providing improved reaction conditions and an enhanced understanding of the mechanism. Performing the transformation in the presence of acetic acid or a pH 4.5 buffer leads to extended reaction times but improves the catalyst lifetime, leading to the complete consumption of the starting material. Chlorine dioxide is identified as the active oxidant that is able to oxidize the N-hydroxyphthalimide anion to the phthalimide-N-oxyl radical, the proposed catalytically active species, which is able to abstract a hydrogen atom from the substrate. A second molecule of chlorine dioxide reacts with the resultant radical and, after loss of hypochlorous acid, leads to the observed product. Through a broad variety of techniques including UV/vis, EPR and Raman spectroscopy, isotopic labeling, and the use of radical traps, evidence for the mechanism is presented that is supported through electronic structural calculations.