One-Step Carbonization Synthesis of Magnetic Biochar with 3D Network Structure and Its Application in Organic Pollutant Control

In this study, a magnetic biochar with a unique 3D network structure was synthesized by using a simple and controllable method. In brief, the microbial filamentous fungus Trichoderma reesei was used as a template, and Fe³⁺ was added to the culture process, which resulted in uniform recombination through the bio-assembly property of fungal hyphae. Finally, magnetic biochar (BMFH/Fe₃O₄) was synthesized by controlling different heating conditions in a high temperature process. The adsorption and Fenton-like catalytic performance of BMFH/Fe₃O₄ were investigated by using the synthetic dye malachite green (MG) and the antibiotic tetracycline hydrochloride (TH) as organic pollutant models. The results showed that the adsorption capacity of BMFH/Fe₃O₄ for MG and TH was 158.2 and 171.26 mg/g, respectively, which was higher than that of most biochar adsorbents, and the Fenton-like catalytic degradation effect of organic pollutants was also better than that of most catalysts. This study provides a magnetic biochar with excellent performance, but more importantly, the method used can be effective in further improving the performance of biochar for better control of organic pollutants.     

铁掺杂类石墨相氮化碳类芬顿/光催化氧化作用机制

采用热聚合法制备并优化了不同铁掺杂比的铁掺杂类石墨相氮化碳(Fe-g-C₃N₄)类芬顿光催化剂,铁元素可完全掺杂进入类石墨相氮化碳(g-C₃N₄)结构中并组成Fe—N配位键,最佳的Fe掺杂比为10%(质量分数)。Fe-g-C₃N₄类芬顿/光催化氧化对罗丹明B的降解速率和降解率均远高于g-C₃N₄的,反应10 min时降解率已达到87. 9%,反应过程中起主要作用的活性基团为羟基自由基,超氧自由基和空穴电子也有一定作用。在pH值为3～9范围内,Fe-g-C₃N₄类芬顿/光催化氧化对罗丹明B的降解率均高于90%,大幅度拓宽了适用范围; H₂O₂的投加量会显著影响Fe-g-C₃N₄类芬顿/光催化氧化的降解效能,H₂O₂最佳投量范围为1. 0～1....     

配体-金属电子转移强化类芬顿技术的破络特性与机制

为有效分解近中性废水中典型难降解强络合物Ni-EDTA,构建配体-金属电子转移强化类芬顿技术（LFGR）,基于Ni(Ⅱ)去除效能等系统分析其在近中性条件下对Ni-EDTA的破络特性,重点探究Fe(Ⅲ)与H₂O₂投加量、pH值、浊度、常见有机酸与常规无机盐对LFGR破络特性的影响。结合H₂O₂消耗观测、自由基淬灭实验、自由基信号检测与降解产物分析等科学识别LFGR体系中主要活性氧物种,并进一步剖析Ni-EDTA的破络过程与主导机制。定量比较分析LFGR与其他UV活化氧化技术去除多种重金属EDTA络合物（M-EDTA）的特性,并进一步阐明LFGR的运行成本优势。对于络合物浓度为1.0 mmol/L的近中性模拟废水,LFGR的优化反应条件为：Fe(Ⅲ)投加量为0.1 mmol/L,H₂O₂投加量为50 mmol/L,UV光照时间为20 min。该条件下,EDTA可完全转化,且经碱沉淀后Ni(Ⅱ)去除率可高达99.40%;LFGR对水中常见有机酸与常规无机盐呈现出良好的抗干扰性;H₂O₂主要通过与配体-金属电子转移产生的Fe(Ⅱ)发生类芬顿反应消耗;LFGR的主要作用过程是Fe(Ⅲ)置换Ni(Ⅱ)并激发配体-金属电子转移反应从而促进EDTA光解,UV进一步驱动Fe(Ⅲ)还原并加快Fe物种循环,进而强化类芬顿技术活性氧自由基（主要为·OH和·O₂^-）的催化作用。LFGR可在近中性条件下实现多种M-EDTA的良好破络效果,水处理费用合计为4.21元/t,具有良好技术经济性。     

Azo-dye Orange II degradation by heterogeneous Fenton-like reaction using carbon-Fe catalysts

In this work, the degradation and mineralization of the non-biodegradable azo dye Orange II (OII) was studied, making use of a heterogeneous Fenton-like oxidation process. For that, hydrogen peroxide activation was achieved by means of two different carbon-based catalysts, which have been impregnated with 7 wt% of iron. The carbon supports employed are quite different, one of them being an activated carbon prepared from agricultural by-products (olive stone), while the other one is a carbon aerogel, prepared by carbonization of an organic resorcinol–formaldehyde polymer. The solids have been characterized using several techniques, namely N₂ and CO₂ adsorption at −196 and 0 °C, respectively, mercury porosimetry, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). Then, the catalyst's performance in the Fenton-like oxidation of OII was compared, and the effects of the most relevant operating conditions (pH, catalyst concentration, H₂O₂ concentration and temperature) analyzed for the most promising one (the carbon aerogel based catalyst). In this catalyst, characterization data point for a very good iron dispersion on the carbon surface. This sample showed very good catalytic performances, with mineralization degrees as high as 90%. However, iron leaching from the support is also considerable leading to a progressive deactivation in consecutive reaction cycles.     

Fe3+、Co2+、Ni2+、Cu2+参与UV/类Fenton反应动力学研究

以活性艳红X-3B为研究对象,用4种3d轨道过渡金属离子协同UV作催化剂,以H2O2为氧化剂,探讨不同pH值、不同催化剂和氧化剂投入量对色度、COD去除效果的影响;通过改变温度研究4种过渡金属离子进行催化反应的活化能。结果表明,4种过渡金属离子都能发生类Fenton反应,且对活性艳红X-3B的降解速率模型符合二级反应速率模型,通过对反应速率、体系活化能和指前因子的量化研究,得知催化能力的大小顺序为Fe^3＋〉Cu^2＋〉Ni^2＋〉Co^2＋;受温度影响的大小程度排序为：Ni^2＋〉Co^2＋〉Cu^2＋〉Fe^3＋。     

非均相微波协同类Fenton催化降解废水中的苯酚

通过等体积浸渍法制备了CuO/γ-Al_2O_3催化剂,并对非均相微波协同类Fenton催化降解苯酚溶液进行了实验研究。实验结果表明,在溶液初始pH为6,H_2O_2投加量为4 m L/L,催化剂投加量为4 g/L,微波功率为500 W,反应时间为13 min的条件下,苯酚降解率可达98%,TOC去除率为62%。催化剂重复使用9次后,苯酚降解率为90.88%。通过比较不同氧化体系处理效果及添加·OH捕获剂证实,微波-催化剂-H_2O_2产生了明显的协同作用。     

Molecular Engineering toward Pyrrolic N-Rich M-N4 (M = Cr,Mn, Fe,Co, Cu) Single-Atom Sites for Enhanced Heterogeneous Fenton-Like Reaction

Heterogeneous Fenton-like reactions (HFLR) are promising alternative strategies to address the inherent limitations of the classic Fenton systems. Herein, a facile and scale-up approach for the synthesis of transition metal single-atom sites (SA-TM, TM = Cr, Mn, Fe, Co, Cu) coordinated onto pyrrolic N-rich g-C₃N₄ (PN-g-C₃N₄) scaffold is developed. The regulated pyrrolic N-rich SA-TM catalytic sites exhibit excellent performances for HFLR. As a model of SA-TM/PN-g-C₃N₄, SA-Cr/PN-g-C₃N₄ is efficient for the catalytic oxidation of bisphenol A via HFLR under visible light with outstanding cyclic stability and wide effective pH range (3.0–11.0). The synergy of photocatalysis and single-atom catalysis leads to accelerated production and separation of charge carriers as well as the cycling of Cr³⁺/Cr²⁺ couple, consequently boosting the performance in HFLR. Theoretical calculations indicate that the Cr(II)-N₄ sites with the metalloporphyrin-like structure are more reactive than the doped Cr(II) sites in the g-C₃N₄ matrix, which act as the peroxidase-mimicking nanozyme for efficient and homolytic cleavage of peroxide O O in H₂O₂. This study expands the family of the iron-free Fenton-like systems and provides new strategies to the rational design and precise regulation of on-demand multifunctional single-atom catalysts for advanced water remediation.     

Reactive species in resin supported heterogeneous Fenton-like oxidation of Malachite green solution

During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra was found to be different between the top layer and the bottom layer in this column. Based on the data from XPS spectra and DMPO-OH·signal by EPR spectra,it is shown that the formation of ferryl (IV) is the key step for the oxidation of MG. The ferryl (IV) species can oxidize MG,and its redox potential is about 0. 739 - 0. 803 V measured by cyclic voltammograms (CV) . The catalytic capability of ferryl (IV) species was also evaluated,and it is found that it can promote the decomposition of H2O2 more efficiently than ferric iron. The removal rate of MG mainly depends on the adsorption of catalyst. Both ferryl (IV) and HO·radicals are the reactive species in the system. The oxidation of HO·is only a small part of the overall removal rate. Based on the obtained results,a possible mechanism for a resin-supported Fenton-like oxidation reaction is proposed.     

Magnetic CuFe2O4 Prepared by Polymeric Precursor Method as a Reusable Heterogeneous Fenton-like Catalyst for the Efficient Removal of Methylene Blue

The heterogeneous Fenton-like catalysts based on CuFe₂O₄ were prepared by polymeric precursor method at several annealing temperatures. The obtained catalysts were respectively characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, point of zero charge measurement, and vibrating sample magnetometer. The Fenton-like catalytic activity was evaluated via the oxidation of methylene blue with H₂O₂. The results show that the CuFe₂O₄ phase content and the particle size increase with the annealing temperatures whereas the surface OH groups and the surface acidity decrease. The prepared powders possess typical ferromagnetic properties which allow them to be easily recovered and reused. These catalysts also present highly catalytic activities for the oxidation of methylene blue, which is principally attributed to the catalysis of the CuFe₂O₄ phase. When the annealing temperature increased, the catalytic performance was reduced, corresponding to the increase of particle size and the decrease of surface OH groups.     

磁性树脂催化H_2O_2降解盐酸黄连素制药废水的研究

通过化学合成法制备出磁性大孔树脂类Fenton催化剂,研究其催化降解盐酸黄连素制药废水的效能,同时考察了pH值、H_2O_2投加量、催化剂投加量及废水初始浓度对其降解效能和反应速率的影响。结果表明:在盐酸黄连素的初始质量浓度为800 mg/L、催化剂投加量为15 g/L、H_2O_2投加量为297 mmol/L、pH值为4、室温(25.0±0.5)℃的条件下,盐酸黄连素的降解率为84.4%,达到最高。研究表明,该非均相类Fenton反应体系对pH值的使用范围广,且催化剂易于分离,反应数次后依然具有较高的催化活性,重复利用率高。