文献速递|东北师范大学ACB:通过聚光驱动的光热耦合芬顿式过氧化单硫酸盐活化系统促进硫酸根自由基的产生

第一作者：Fang Zhang

通讯作者：李兴华 教授

通讯单位：东北师范大学紫外发光材料与技术教育部重点实验室

DOI:10.1016/j.apcatb.2024.124923

Fig. 1. Concentrated-light-driven photo-thermal coupled Fenton-like floating system. (a) Scheme for the concentrated-light-driven system for high-speed and continuous treatment of organic wastewater. (b) Materials design diagram for photo-thermal coupled Fenton-like reactions. (c) Preparation CoPc@CB/PAN nanofibers with floating (optical photographs) and photothermal conversion (infrared photographs) performance. (d), (e) TEM, STEM, and the corresponding energy dispersive X-ray (EDX) elemental mapping images of C, N, Co, and O elements of CoPc@CB/PAN nanofibers.

Fig. 2. Light-intensity dependent photo-thermal coupled Fenton-like wastewater treatment. (a) Schematic illustration of the in-situ surface/solution temperature monitoring during the degradation process. (b) In-situ catalyst surface and reaction solution temperatures during the degradation process under different light intensities for CB/PAN, CoPc@PAN, and CoPc@CB/PAN (from left to right). (c), (d) Degradation curves and the corresponding pseudo-first-order k-values for CB/PAN, CoPc@PAN, and CoPc@CB/PAN under light intensity of 1-, 5-, and 10-kW m−2 (TC = 0.02 g L−1, 100 mL, catalyst = 0.1 g L−1, PMS = 0.1 g L−1).

Fig. 3. Synergistic effect of CB and CoPc on the peroxymonosulfate activation process. (a-c) Comparison of ATR-IR spectra for PMS activation including that without catalysts, and with CB/PAN, CoPc@PAN, and CoPc@CB/PAN nanofibers, under dark and light irradiation of 1 and 10 kW m−2 after 10 min, respectively. (d), (e) ATR-IR spectra evolution at 1-min intervals over 10 min of CoPc@PAN and CoPc@CB/PAN nanofibers at light irradiation of 1 and 10 kW m−2. (f) Transient fluorescence spectra and fluorescence lifetime of CoPc@PAN and CoPc@CB/PAN nanofibers. (g) The ESR and light-ESR (LESR) spectra of CoPc@PAN and CoPc@CB/PAN nanofibers. (h) Enlarged distribution of relaxation times (DRT) spectra of CoPc@PAN and CoPc@CB/PAN measured in PMS electrolyte under dark and light conditions.

Fig. 4. Concentrated-light-driven photo-thermal coupled Fenton-like floating system. (a) Schematic illustration of the experimental setups with Fresnel lens to simulate concentrated-light. (b) Degradation curves and cycle tests of TC solution using CoPc@CB/PAN as catalyst under light intensity of 10- and 30-kW m−2 (TC = 0.1 g L−1, flow rate = 0.3 mL min−1, PMS = 0.1 g L−1, flow rate = 0.7 mL min−1, catalyst = 0.1 g L−1). (c) Comparisons of pollutant removal rate considering the doses of the catalyst, PMS, and pollutants versus PMS/pollutant concentration ratios (Relevant raw data and corresponding references are available in Table S3). (d) Total organic carbon (TOC) and Co-leaching during five cycles. (e) Comparison of TOC removal, PMS dose, and Pollutant concentration with previous reports (Relevant raw data and corresponding references are available in Table S4). (f), (g) The steady-state concentration of •OH and SO4•− and the reactive species contributions under light intensity of 1, 10, and 30 kW m−2. (h) The synergistic enhancement ratio of photogenerated electrons and photothermal effects (ISPTE), the photogenerated electrons enhancement ratio (IPEE), and the thermal enhancement ratio (ITE). (i) PMS decomposition processes during TC degradation in photo-thermal coupled Fenton-like reaction (PTCFL), Photo-Fenton-like reaction at room temperature (PFL-R), and Fenton-like reaction at room temperature (FL-R) systems. (j) The corresponding PMS utilization efficiencies in the above three catalytic systems. (k) Comparison of PMS utilization efficiencies of this work with other reported PMS activation systems (Relevant raw data and corresponding references are available in Table S7).

Fig. 5. Co-center electron density dependent PMS activation. (a) Illustration of active species generation via the bond-breaking sites of HSO5¯ (Oi–Oii and Oi–Hi). (b) Adsorption energy (|Eads|), the bond lengths of Oi–Oii and Oi–Hi bonds, and Bader charges (|Q|) for CoPc-HSO5¯ systems with different Co-center electron densities (valence states). (c) Charge density difference (CDD) for CoPc-HSO5¯ systems with an isosurface level of 0.0045 e Bohr−3 (yellow: electron depletion; cyan: electron aggregation). (d) Bond length variation between absorbed and free HSO5¯ (R: the optimized Oi−Oii and Oi−Hi bond lengths for CoPc-HSO5¯ systems, R0: the optimized Oi−Oii and Oi−Hi bond lengths of free HSO5¯). (e) Total and Co-3d DOS of pure CoPc and CoPc-HSO5¯ systems with + 2 and + 1.5 valence states of Co-centers.

Fig. 6. Concentrated-light effects on degradation pathway and pollutant removal diversity. (a) The possible degradation pathway-Ⅰ of TC in CoPc@CB/PAN-PMS system under light irradiations (concentrated light intensity: 30 kW m−2 and low light intensity: 1 kW m−2, TC = 0.02 g L−1, 40 mL, catalyst = 0.1 g L−1, PMS = 0.1 g L−1). (b) Molecular structures of different pollutants, their degradation efficiencies, and the corresponding k-values in CoPc@CB/PAN-PMS system under light irradiation (light intensity: 1 kW m−2 and 30 kW m−2, types of contaminants: Rhodamine B (Rh B), Methyl Orange (MO), Sulfamerazine (SMZ), Sulfadiazine (SDZ), Atrazine (ATZ), 4-Chlorophenol (4-CP), NB, BA, CBZ, Ofloxacin (OFX), and Norfloxacin (NOR), [Pollutant] = 0.01 g L−1 100 mL, catalyst = 0.1 g L−1, PMS = 0.1 g L−1).