Pd-Fe/C催化氯酚还原脱氯-氧化联合降解

以Pd和Fe为活性金属组分通过沉积沉淀法制备了负载型Pd-Fe/C双金属催化剂,针对氯酚类污染物进行催化还原脱氯和催化氧化的连续降解处理.通过ICP-MS、XRD和TEM对催化剂进行表征,证实0.5%Pd-0.5%Fe/C催化剂中活性金属组分Pd和Fe在载体表面分散性最好,催化剂比表面积达到718.8 m~2·g~(-1).在温和条件下,以水作为反应介质,研究了负载型Pd-Fe/C催化剂对4-氯苯酚(4-CP)和2,4-二氯苯酚(2,4-DCP)的连续降解过程和反应条件,以及催化剂的重复使用情况.考察了Pd和Fe的负载量及p H值对催化剂活性的影响,得到了最佳反应条件,以0.5%Pd-0.5%Fe/C为催化剂,20 min内完成4-CP和2,4-DCP的催化还原脱氯,产物都为苯酚;之后加酸调节pH=5,并加入H2O2继续进行催化氧化,苯酚被彻底降解为H_2O和CO_2,而且转化率在60 min内可以达到97.5%以上,从而实现4-CP和2,4-DCP的彻底降解.     

UV/Fe3+/H2O2体系降解活性艳橙X-GN废水的研究

采用UV/Fe3 /H2O2体系光解活性艳橙X-GN模拟废水,考察了X-GN,Fe3 和H2O2的初始浓度、初始pH值及温度对光解的影响,探讨了X-GN的降解途径和机理.结果表明,在8W低压汞灯(λ＝254nm)照射下,UV/Fe3 /H2O2能够有效地降解X-GN,在pH=3.0,T=50 ℃,时间为120 min,Fe3 和H2O2的初始浓度分别为2.5×10-5 mol·l-1和1.5×10-4 mol·l-1时,对含200 mg·l-1 X-GN模拟废水的色度去除率和矿化率分别达到100%和90.15%.用IC和GC/MS对X-GN降解的中间产物和最终产物进行分析,推导出UV/Fe3 /H2O2体系中X-GN降解的途径和机理.     

改性碳纳米管负载Pd基催化剂对二氯乙酸的催化加氢脱氯

以壳聚糖(chitosan,CS)为单体,采用表面沉积交联法对多壁碳纳米管(CNT)改性得到壳聚糖修饰的碳纳米管(CS-CNT).分别以CS-CNT和CNT为载体,用硼氢化钠还原法制备Pd/CNT和Pd/CS-CNT负载型催化剂.采用元素分析仪、电感耦合等离子体发射光谱仪(ICP)、透射电镜(TEM)、比表面积与孔径分布测定仪(BET)、X射线光电子能谱(XPS)等对材料进行表征,并对二氯乙酸的液相催化加氢脱氯反应进行了研究.结果表明,与Pd/CNT相比,Pd/CS-CNT对二氯乙酸有更高的催化活性.此外,该催化加氢脱氯反应受溶液pH及催化剂表面Pd颗粒的影响.二氯乙酸的催化加氢脱氯反应符合Langmuir-Hinshelwood模型,表明该反应过程由二氯乙酸在催化剂表面的吸附所控制.     

Fe（0）/H_2O_2协同降解亚甲基蓝的研究

进行了Fe（0）和H2O2协同催化降解亚甲基蓝的研究,分析了Fe（0）投加量、H2O2投加量、溶液初始pH值和染料初始质量浓度等因素的影响。研究表明：Fe（0）和H2O2协同可有效催化降解亚甲基蓝;在pH为4.5,Fe（0）用量为2.0 g.L-1,H2O2用量为3.0 mmol.L-1时对10 mg.L-1亚甲基蓝的去除率在60 min内达到90%以上。MB的降解去除率随着Fe（0）投加量与H2O2用量的增加而增加,但随着其初始质量浓度的增大而降低。研究结果还表明,Fe（0）和H2O2可在接近中性条件下有效协同催化降解亚甲基蓝。UV-Vis光谱在反应过程的变化说明亚甲基蓝降解生成了一些小分子物质。     

光助Fe/BiOCl活化过硫酸盐降解橙黄Ⅱ

为研究Fe/BiOCl在光照下活化过硫酸盐(PS)产生硫酸根自由基(·SO_4~-)降解偶氮染料橙黄Ⅱ的催化效果,采用一步水热合成法制备铁掺杂BiOCl纳米催化剂,并用X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线光电子能谱(XPS)对其形貌与组成成分进行表征.结果显示,铁元素成功掺杂进入BiOCl的结构中,呈现出纳米盘状形貌结构.在光照辐射下,考察Fe/BiOCl活化PS降解橙黄Ⅱ过程中初始pH、底物浓度、Fe/BiOCl催化剂投加量和PS投加量等影响因素对橙黄Ⅱ降解处理效果的影响.结果显示,橙黄Ⅱ降解效率随着pH值的降低而升高,Fe/BiOCl和PS投加量的增加对橙黄Ⅱ的去除率出现先增加后降低的趋势.Fe/BiOCl催化剂投加量为0.5 g·L~(-1),PS的投加量为1 mmol·L~(-1)的条件下时,溶液pH值为3.0,反应60 min后,橙黄Ⅱ降解的效果最佳,其降解速率符合拟一级反应动力学.通过对催化剂Fe/BiOCl稳定性研究,经5次连续循环使用后,脱色率仍然可以保持在79.6%,说明该催化剂具有良好的循环使用性能.通过投加叔丁醇(TBA),甲醇(MeOH),草酸铵(AO),对苯醌(BQ)等自由基猝灭剂,证明光助Fe/BiOCl/PS体系中具有光生空穴,硫酸根自由基,羟基自由基和超氧自由基,其中超氧自由基和光生空穴在反应体系中起重要作用.反应过程中橙黄Ⅱ的降解产物运用GC/MS进行检测,推导得出橙黄Ⅱ的降解路径.     

镍/铁和铜/铁双金属降解四氯乙烯的研究

选用镍 /铁和铜 /铁双金属对四氯乙烯 (PCE)进行脱氯试验 .结果表明 ,双金属系统对四氯乙烯有明显的脱氯作用 ,且脱氯反应符合准一级反应动力学方程 ,双金属在降解PCE的过程中 ,无三氯乙烯 (TCE)、二氯乙烯 (DCE)和氯乙烯 (VC)等中间产物形成 ,与零价铁系统相比 ,双金属系统对PCE的降解速率有明显提高 ,尤其是Ni/Fe双金属 ,反应速率常数kSA从 0 1 2 89ml·m- 2 ·h- 1 提高到 0 3697ml·m- 2 ·h- 1 ,Cu/Fe双金属的反应速率常数kSA为 0 2 2 79ml·m- 2 ·h- 1 .无论是哪种反应介质 ,在制备过程中干燥与否对脱氯速率都有很大的影响     

Al2O3负载Pd催化剂对溴氯代乙酸的催化加氢脱卤研究

分别以氧化铝、氧化硅和多壁碳纳米管为载体,采用沉淀-沉积法制备负载型Pd催化剂.采用透射电镜(TEM)、X射线衍射(XRD)、电感耦合等离子体发射光谱(ICP-AES)、X射线光电子能谱(XPS)等手段对材料进行表征,并对溴氯代乙酸(BCAA)的液相催化加氢脱卤反应进行了研究.结果表明,由于Pd/Al_2O_3催化剂具有较高的等电点,因此相对于Pd/CNT、Pd/SiO_2在BCAA的加氢脱卤反应中具有更高的活性.以Pd/Al_2O_3为目标催化剂,对BCAA的加氢脱卤展开研究,发现催化活性随Pd的负载量的增加而提高.当反应物的初始浓度为0. 1 mmol·L~(-1),pH值为5.6,Pd(1.39)/Al_2O_3用量为25 mg·L~(-1)时,BCAA在20 min时可以实现完全脱溴并在反应2 h后脱氯达60.5%.另外,pH的升高不利于脱卤反应的进行.当反应物的浓度从0. 05 mmol·L~(-1)提高到0.4 mmol·L~(-1)时,反应初活性从1.55 mmol·L~(-1) min~(-1) gCat~(-1)提高到8.37 mmol·L~(-1) min~(-1) gCat~(-1).进一步通过拟合Langumir-Hinshelwood模型,相关系数达到0.97,说明BCAA的加氢脱卤是吸附控制机制.催化过程中溴氯代乙酸的脱溴和脱氯具有协同作用,反应最终生成乙酸.     

纳米Co/Fe脱氯3,3＇,4,4＇-四氯联苯（BZ#77）

用气-质联用仪（GC-MS）监测厌氧条件下溶液中3,3’,4,4’-四氯联苯（BZ#77）被纳米级零价铁、Ni/Fe和Co/Fe双金属脱氯的情况,并尝试了用纳米级Co/Fe脱氯污染沙土中的四氯联苯,GC-MS结果表明：在3,3’,4,4’-四氯联苯浓度为10mg·l-1的乙醇/水体系中,纳米级Fe,Ni/Fe,Co/Fe的脱氯率分别为23.4%,68.6%和74.2%,其中,Co/Fe效果最好.溶液初始pH值为酸性时,纳米Co/Fe完全脱氯溶液中的3,3’,4,4’-四氯联苯可在几小时内实现,而溶液的离子强度对脱氯反应影响不大.对于模拟污染沙土含量为100mg·kg^-1的3,3’,4,4’-四氯联苯,10d后约11%的四氯联苯被纳米Co/Fe脱氯,添加乙醇可使脱氯率增加到25%,但不能完全脱氯.同位素实验证明,纳米Co/Fe脱氯3,3’,4,4’-四氯联苯是逐步进行的,氢取代苯环上的氯,氢原子源自反应介质中的水,最终脱氯产物为联苯.     

树脂D001负载纳米Pd/Fe双金属脱溴2,2＇,4,4＇-四溴联苯醚（BDE-47）的研究

采用大孔树脂D001交换吸附Pd2＋、Fe2＋并在厌氧条件下以硼氢化钠溶液还原吸附的钯铁离子制备成负载纳米Pd/Fe双金属树脂。利用该树脂对2,2＇,4,4＇-四溴联苯醚（BDE-47）进行脱溴反应,探讨了该法的可行性和特性。结果表明：当大孔树脂D001、氯化钯、硫酸亚铁用量分别为0.75 g、2μg和0.2 g时所制备的双金属树脂脱溴水-乙醇溶液中的BDE-47效果最佳,反应遵循准一级动力学,速率常数k约为0.161 d-1,半减期为1.21 d。负载Pd/Fe的D001连续3次脱溴反应都有较好的效果,水-乙醇溶液中超过90%以上的BDE-47在反应6 d后被降解。负载Pd/Fe双金属的树脂可以重复活化再生,但再生2次后其脱溴效率变差,反应6 d只有47.3%的BDE-47被降解。用气相色谱-质谱联用仪和离子色谱仪跟踪Pd/Fe双金属树脂脱溴BDE-47反应,可知产物包括溴离子、三溴联苯醚、二溴联苯醚、一溴联苯醚和联苯醚。     

纳米级Fe0与普通Fe0还原降解偶氮染料的比较

采用Fe0 对偶氮染料进行催化还原处理是染料废水脱色的一种重要方法 .经过Fe0 降解 ,偶氮染料的N =N双键断裂 ,还原生成芳香胺 ,增加了废水的可生化性 ,有利于后续处理 .因此 ,提高Fe0的催化还原效率是进一步研究的方向 .1 996年 ,Johnson等人在研究了一系列氯代脂肪烃的Fe0 脱     

制备条件对Fe/AC脱硫活性的影响

考察了Fe/AC脱硫剂的煅烧温度和载铁量对脱硫活性的影响，并对脱硫剂进行了X－射线衍射（XRD）和EXAFS表征，结果表明：经250℃煅烧的Fe/AC脱硫剂具有最高的脱硫活性，200℃煅烧，前驱体未完全分解，高于250℃煅烧，会使活性组分聚集，二者均导致脱硫活性降低。Fe/AC脱硫剂适宜的载铁量为3．5－14％，大于14％担载量使脱硫剂微孔堵塞严重，致使其脱硫活性下降。     

The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Application of Fe0/C/Clay ceramics for decoloration of synthetic Acid Red 73 and Reactive Blue 4 wastewater by micro-electrolysis

Dyes are common pollutants in textile wastewaters, and the treatment of the wastewater has now attracted much attention due to its wide application and low biodegradability. In this study, Fe⁰/C/Clay ceramics, a kind of novel micro-electrolysis filler, were sintered and employed in a dynamic micro-electrolysis reactor for synthetic Acid Red 73 (AR73) and Reactive Blue 4 (RB4) wastewater treatment. The effects of influent pH, hydraulic retention time (HRT), and aeration on the decoloration efficiencies of AR73 and RB4 were studied. The optimum conditions for wastewater treatment were: AR73, influent pH of 4, HRT of 2 h and aeration; RB4, influent pH of 5, HRT of 6 h and aeration. Under the optimum conditions, decoloration efficiency of AR73 and RB4 wastewater was 96% and 83%, respectively. Results of UV-vis spectrum scanning demonstrated that the chromophores were broken. Continuous running tests showed that improvement of micro-electrolysis system with Fe⁰/C/Clay ceramics for AR73 and RB4 synthetic wastewater treatment could avoid failure of micro-electrolysis reactor, which indicated great potential for the practical application of the ceramics in the field of actual industrial wastewater treatment.     

Promotional effect of ion-exchanged K on the low-temperature hydrothermal stability of Cu/SAPO-34 and its synergic application with Fe/Beta catalysts

• K⁺ hinder the structural degradation of Cu/SAPO-34 under humid condition<100°C. • K⁺ on Cu/SAPO-34 brings lower acidity and inferior SCR activity at high temperature. • Fe/Beta was used to compensate the low activity of Cu/SAPO-34 at high temperature. • The hybrid catalysts with KCu/SAPO-34 and Fe/Beta show a great potential for using. K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging. The changes in structure and copper-species contents of these catalysts upon hydrothermal aging were probed in order to investigate their effects on selective catalytic reduction (SCR) activity. For the fresh Cu/SAPO-34 catalysts, K ions had little influence on the chabazite framework but effected their acidities by exchanging with acid sites. After hydrothermal aging, the structural integrity and amount of active sites decreased on pure Cu/SAPO-34. While the K-loaded catalysts showed improved chabazite structure, acidity, and active site conservation with increasing K loading. However, although the 0.7 wt% K catalyst maintained the same crystallinity, active site abundance, and low-temperature SCR activity as the fresh catalyst upon aging, an apparent decrease in SCR activity at high temperature was observed because of the inevitable decrease in the number of Brönsted acid sites. To compensate for the activity disadvantage of K-loaded Cu/SAPO-34 at high temperature, Fe/Beta catalysts were co-employed with K-loaded Cu/SAPO-34, and a wide active temperature window of SCR activity was obtained. Thus, our study reveals that a combined system comprising Fe/Beta and K-loaded Cu/SAPO-34 catalysts shows promise for the elimination of NO_x in real-world applications.     

零价铁/炭去除水中的As(Ⅴ)

将零价铁(ZVI)分别与活性炭,石墨,碳纤维和碳纳米管按照质量比10:1组成电偶腐蚀体系用于水中As(Ⅴ)去除,结果显示零价铁/活性炭组合的去除效果略高于其它组合.XRD测试表明,组合体系中零价铁腐蚀的主要反应产物为纤铁矿,磁铁矿/磁赤铁矿.对零价铁阳极/活性炭阴极不同质量比例的研究表明,1:1时效果最佳.随着电解质浓度升高,As(Ⅴ)去除效率增大,在0.03 mol·1-1 NaCl电解质条件下,初始As(Ⅴ)为5 mg·1-1时,零价铁/活性炭组合与As(Ⅴ)反应2.5 h后,As(Ⅴ)的去除率达到100%.SO2-4,NO-3,CO2-3,SiO4-4,PO3-4等共存阴离子,以及腐殖酸对零价铁/活性炭组合去除As(Ⅴ)影响的研究结果表明,CO2-3,PO3-4和腐殖酸对As(Ⅴ)的去除效率影响不大,SiO4-4具有一定的抑制作用,相反,SO2-4和NO-3表现为明显的促进作用.     

铁炭微电解法降解1-丁基-3-甲基咪唑六氟磷酸盐

使用铁炭微电解法降解1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6),并探讨了铁炭微电解法降解[BMIM]PF6的影响因素、工艺条件及其反应动力学.结果表明,影响铁炭微电解降解[BMIM]PF6的因素按从大到小的顺序为:炭铁比、pH、反应时间;铁炭微电解降解[BMIM]PF6的最佳工艺条件是:铁粉用量3g.l-1、水样pH2.5、炭铁比2、反应时间为60—90min;在此条件下,[BMIM]PF6的去除效率可以达到90%以上且该降解反应为三级反应.     

Separation/degradation behavior and mechanism for cationic/anionic dyes by Ag-functionalized Fe3O4-PDA core-shell adsorbents

● PDA-Fe₃O₄-Ag was made by hydrothermal and oxidation self-polymerization method. ● PDA-Fe₃O₄-Ag had great magnetic separation performance. ● PDA-Fe₃O₄-Ag had good adsorption and degradation performance for ionic dyes. ● PDA-Fe₃O₄-Ag showed NR and MO degradation potential of 91.2% and 87.5%, respectively. High-performance adsorbents have been well-studied for the removal of organic dye pollutants to promote environment remediation. In this study, an Ag nanoparticle-functionalized Fe₃O₄-PDA nanocomposite adsorbent (PDA-Fe₃O₄-Ag) was synthesized, and the adsorption/separation performance of commonly used cationic and anionic organic dyes by the PDA-Fe₃O₄-Ag adsorbent were assessed. Overall, PDA-Fe₃O₄-Ag exhibited a significantly higher adsorption capacity for cationic dyes compared to anionic dyes, the highest of which was more than 110.0 mg/g (methylene blue (MB)), which was much higher than not only the adsorption capacities of the anionic dyes in this study but also other dye adsorption capacities reported in the literature. The dye adsorption kinetics data fitted well to both the pseudo second-order kinetics model and the Langmuir isotherm model, suggesting a monolayer-chemisorption-dominated adsorption mode. Thermodynamics analysis indicated that the adsorption process was both endothermic and spontaneous. Furthermore, the PDA-Fe₃O₄-Ag adsorbent achieved high photodegradation removal rates of the dyes, especially neutral red (NR) and methyl orange (MO), which were 91.2% and 87.5%, respectively. With the addition of PDA-Fe₃O₄-Ag, the degradation rate constants of NR and MO increased from 0.08 × 10⁻² and 0 min⁻¹ to 2.11 × 10⁻² and 1.73 × 10⁻² min⁻¹, respectively. The high adsorption and photocatalytic degradation performance of the PDA-Fe₃O₄-Ag adsorbent make it an excellent candidate for removing cationic and anionic dyes from the industrial effluents.     

Fe3O4@SA/Ce微球的表征及对染料的吸附特性

以天然高分子化合物海藻酸钠(sodium alginate,SA)为骨架,结合磁性Fe₃O₄和稀土铈离子Ce(Ⅲ)通过溶液反应制备出一种新型的磁性海藻酸铈复合微球(Fe₃O₄@SA;Ce).采用X射线衍射(XRD)、孔结构比表面积分析(BET)、扫描电子显微镜(SEM)、红外光谱(FT-IR)及振动样品强磁计(VSM)对Fe₃O₄@SA;Ce的结构进行了表征,并以直接桃红12B(direct red 12B,DR 12B)和直接橙S(direct orange S,DO S)两种染料为吸附对象,探讨了Fe₃O₄@SA;Ce的吸附剂性能、吸附动力学和热力学.结果表明,Fe₃O₄@SA;Ce对室温下自然pH染料溶液中DR 12B和DO S均表现出良好的吸附效果,吸附量分别可达464 mg·g^-1和730 mg·g^-1.在不同温度下(298、313、328 K),Fe₃O₄@SA;Ce对DR 12B和DO S的吸附过程均可用拟二级吸附动力学方程准确描述.通过等温吸附研究,发现Fe₃O₄@SA;Ce对两种染料的等温吸附较好地符合Freundlich模型.各种表征结果表明,SA与Ce(Ⅲ)和Fe₃O₄交联反应后生成的Fe₃O₄@SA;Ce凝胶球表面有大量深浅不一的褶皱沟纹,形貌发生了显著变化.作为一种绿色环保、制备方法简单、可高效吸附的磁性高分子复合吸附剂,Fe₃O₄@SA;Ce对高浓度染料具有很好的吸附效果,期望能够在染料废水处理中得到广泛应用.