文献速递|内蒙古农业大学王喜明/姚利宏/张晓涛ASS:超多孔碳负载Fe3Co合金活化PMS降解BPA

第一作者：宋雅茹 硕士

通信作者：王喜明 教授/姚利宏 教授/张晓涛 教授 

通信单位：内蒙古农业大学

DOI:10.1016/j.apsusc.2025.164321

过渡金属催化剂如铁(Fe)、钴(Co)和镍(Ni)已经用于双金属催化剂如Bi₂Fe₄O₉、CoFe₂O₄和MnFe₂O₄，已被证实作为PMS活化剂的巨大潜力。在过渡金属复合催化剂中，Fe-Co基催化剂，如Fe/Co-MOF和Fe/Co-CN最常用于PMS活化，Fe-Co合金是PMS驱动的AOP催化剂中有前途的材料。合金化过程引入了特定的第二金属，与稀释主要金属成分的不寻常的双金属催化剂相比，赋予了更高的催化活性和稳定性。合金化也使活性位点均匀化，并调节电子性质，从而抑制降低单金属催化剂性能的聚集效应。碳基材料因其优异的稳定性和高导电性而闻名，提供了一个防止金属浸出的保护层，并通过介导电子转移促进了污染物降解。因此，碳材料可有效地负载，以提高催化剂的活化效率。生物质碳前景尤为诱人，因为其比表面积更大、孔隙率更高，这有利于其对过硫酸盐（PMS）和其他污染物的吸附去除。此外，金属能够均匀负载于生物炭（BC）上，从而使活性物质广泛分散。最后，生物质废弃物是一种环保且易于获取的资源。在本研究中，利用农业废弃物松针构建了一种碳层结构。该结构中的众多孔隙提高了Fe₃Co合金的负载能力，并促进了过硫酸盐的催化活性。这种负载有Fe₃Co合金催化剂的松针衍生生物炭（Fe₃Co@BC）具有高效催化性能，此前在公开的科学文献中尚未有相关描述。Fe₃Co@BC 催化剂能在超短反应时间内活化过硫酸盐并降解双酚A。

Fig. 1. (a, b) SEM image, (c) TEM image, (d) HRTEM image, (e) SAED pattern, and (f) EDS images of 0.5Fe₃Co@BC. Panel (d) confirms the presence of C, O, Fe, and Co in the sample.

Fig. 2. (a) XRD patterns and (b) Raman images of the different samples; N₂adsorption–desorption curves and pore size distributions (insets) of (c) HB, (d) C800, and (e) 0.5Fe₃Co@BC.

Fig. 3. (a) BPA removal efficiencies of the prepared catalysts; effects of (b) initial BPA concentration (c) PMS dosage, (d) catalyst dosage (e) pH, and (f) temperature on the removal efficiencies of the catalyst.

Fig. 4. (a) Effects of different inorganic ions and HA on BPA degradation. All anions (NaCl, NaH₂PO₄, NaNO₃, Na₂SO₄, and Na₂CO₃) are added at 5 mM and the HA dosage is 20 mg. (b) Reusability, (c) BPA degradation efficiency in different environments, and (d) removal efficiencies of antibiotics and dyes by 0.5Fe₃Co@BC. Basic Blue 1 (pH = 7.12), malachite green (pH = 6.83), tetracycline hydrochloride (pH = 7.01), and oxytetracycline hydrochloride (pH = 6.97) were each dosed at 20 mg/L in a volume of 100 mL.

Fig. 5. (a) Effects of different scavengers on BPA removal via PMS activation by 0.5Fe₃Co@BC. Initial BPA concentration = 20 mg/L, volume = 100 mL, catalyst dosage = 20 mg, PMS dosage = 20 mg, pH = 7.1, KI = L-His = p-BQ dosage = 2 mM, TBA = MeOH = DMSO dosage = 50 mM, temperature = 25 ℃. EPR spectra of the 0.5Fe₃Co@BC + PMS system: (b) DMPO for trapping OH• and SO₄•⁻, (c) DMPO for trapping O₂•⁻, and (d) TEMP for trapping ¹O₂.

Fig. 6. CV plots and (b) electrochemical impedance spectroscopy results of the 0.5Fe₃Co@BC and C800 composites; XPS survey spectra of the fresh and used 0.5Fe₃Co@BC catalysts; high-resolution XPS spectra of the fresh and used 0.5Fe₃Co@BC composite: (d) Co 2p and (e) Fe 2p.

Fig. 7. Possible pathways and intermediates of BPA degradation.

Fig. 8. Hazard analysis of the intermediates: (a) 48-h LC₅₀ in large water flea (Daphnia magna) (b) 48-h IGC₅₀ in Tetrahymena pyriformis; (c) 96-h LC₅₀ in fathead minnow (Pimephales promelas); (d) bioconcentration factors, (e) developmental toxicities, and (f) mutagenicities of the individual intermediates.