C-N共掺杂固废衍生沸石的制备及其活化过一硫酸盐降解水中四环素的研究

碳基催化剂因其具有优异的催化活性、可控的表面活性特性和无二次污染的优点，在活化过硫酸盐去除水中有机污染物方面极具潜力. 然而，碳基材料存在制备成本高、重复使用催化活性大幅度降低等问题，限制了其实际应用. 以固废酒糟、粉煤灰为原料利用水热法制备新型掺碳沸石，通过进一步原位负载N得到具有高稳定性的C-N共掺杂沸石催化剂，并用于活化过一硫酸盐(PMS)降解四环素(TC). 结果表明:①制备的C-N共掺杂沸石催化剂具有一定吸附TC的效果及优异的活化PMS的性能，在一定范围内，TC的去除率随沸石、PMS投加量的增加而提高. ②对于初始浓度为10 mg/L的TC，沸石投加量为0.4 g/L、PMS投加量为3.25 mmol/L时，30 min对TC的去除率可达89.07%. ③该反应体系有较强的pH适应性，在pH为2~10范围内，体系对四环素的去除率保持在82.61%以上. ④无机阴离子Cl?对该体系降解TC有显著的促进作用，在Cl?浓度为0.2 mol/L时，20 min对TC的去除率可达100.00%. ⑤自由基淬灭试验表明，该降解反应中的非自由基(1O₂)发挥了主要作用. ⑥紫外可见吸收光谱分析的结果表明，反应过程中TC的苯环结构被破坏. ⑦催化剂重复利用3次后对TC的去除率仍达76.01%，高于含碳沸石对TC的去除率. 研究显示，C-N共掺杂沸石催化剂+PMS体系对TC具有较强的去除能力、适用范围广、重复利用率高. 

Fabrication of C-N Co-Doped Solid Waste-Based Zeolite for Treatment of Tetracycline in Water by Activation of Peroxymonosulfate

Carbon-based materials are highly promising catalysts in activating persulfate for the removal of organic pollutants, owing to their excellent catalytic activity, high specific surface area, controllable surface activity without producing secondary pollution. However, the disadvantages of carbon-based catalysts, such as relatively high preparation cost, low degree of regeneration, limit their practical application. This paper presents the fabrication of a novel carbon-doped zeolite via hydrothermal method using solid waste distillers' grain and fly ash as raw materials, nitrogen was further introduced in-situ to obtain C-N co-doped zeolite with high stability. The produced C-N zeolite was used as a catalyst to activate peroxymonosulfate (PMS) for tetracycline (TC) degradation. The results show that: (1) The prepared C-N co-doped zeolite catalyst exhibits excellent PMS activation performance. Within a certain range, the removal rate of TC increases with the increase of the dosage of zeolite and PMS. (2) For the initial concentration of TC 10 mg/L, when the dosage of zeolite and PMS are 0.4 and 3.25 mmol/L, respectively, the removal rate of TC can reach 89.07% in 30 min. (3) The reaction system has strong pH adaptability, and the removal rate of tetracycline remains above 82.61% in the pH range of 2-10. (4) Cl? can significantly promote the degradation of TC. When Cl? concentration is 0.2 mol/L, the removal rate of TC can reach 100.00% in 20 min. (5) Free radical quenching test shows that non-free radical (1O₂) plays a major role in the degradation reaction. (6) The UV-vis spectral analysis shows that the benzene ring structure of TC is eliminated in the reaction process. (7) After reusing the catalyst for 3 times, the removal rate of TC remains at 76.01%, which is higher than that of carbon containing zeolite. The results revealed that the C-N co-doped zeolite coupling PMS system can effectively remove TC in a broad application range with high reusability.