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腐殖酸类型对铁(III)-5,10,15,20-四(对羟基苯基)卟啉引入对苯二酚衍生腐殖酸制备的杂化催化剂氧化五氯苯酚产物的影响。

Influence of humic acid type on the oxidation products of pentachlorophenol using hybrid catalysts prepared by introducing iron(III)-5,10,15,20-tetrakis(p-hydroxyphenyl) porphyrin into hydroquinone-derived humic acids.

机构信息

Division of Solid Waste, Resources and Geoenvironmental Engineering, Graduate School of Engineering, Hokkaido University, Sapporo, Japan.

出版信息

Chemosphere. 2010 Feb;78(9):1155-9. doi: 10.1016/j.chemosphere.2009.12.010. Epub 2009 Dec 29.

Abstract

An iron(III)-5,10,15,20-tetrakis(p-hydroxyphenyl) porphyrin (FeTHP) was introduced into hydroquinone-derived humic acids via formaldehyde polycondensation. The influence of humic acid (HA) type on the catalytic oxidation of pentachlorophenol (PCP) was investigated using two HAs as follows: Shinshinotsu peat (SHA) with a lower carboxylic acid content; Tohro ando soil (THA) with a higher carboxylic acid content. The levels of PCP degradation and dechlorination for the catalysts prepared using SHA (SHA-FeTHP) and THA (THA-FeTHP) were significantly higher than those for FeTHP. In terms of oxidation products, the more toxic dimer, octachlorodibenzo-p-dioxin (OCDD), was not produced in the case of the SHA-FeTHP system, while 4-7% of the PCP was converted to OCDD when the FeTHP and THA-FeTHP catalytic systems were used. These results indicate that a catalyst prepared using SHA is more active, in terms of the detoxification of PCP, than other catalysts. Comparisons of UV-Vis absorption spectra before and after the catalytic oxidation showed that the Soret band for SHA-FeTHP clearly remained after a 30-min incubation period, while the intensity of the majority of Soret bands for FeTHP and THA-FeTHP were rapidly reduced after a 5-min incubation period. These results suggest that the SHA-FeTHP is a stable catalyst, and this stability results in a more extensive oxidation of the more toxic byproducts.

摘要

一种铁(III)-5,10,15,20-四(对-羟苯基)卟啉(FeTHP)通过甲醛缩聚被引入到邻苯二酚衍生的腐殖酸中。研究了两种腐殖酸(HA)对五氯苯酚(PCP)催化氧化的影响:羧酸含量较低的新津诺苏泥炭(SHA);羧酸含量较高的户田土(THA)。使用 SHA(SHA-FeTHP)和 THA(THA-FeTHP)制备的催化剂对 PCP 的降解和脱氯水平明显高于 FeTHP。就氧化产物而言,在 SHA-FeTHP 体系中没有产生更具毒性的二聚体,八氯二苯并对二恶英(OCDD),而当使用 FeTHP 和 THA-FeTHP 催化体系时,4-7%的 PCP 转化为 OCDD。这些结果表明,与其他催化剂相比,使用 SHA 制备的催化剂在 PCP 的解毒方面更具活性。催化氧化前后的紫外-可见吸收光谱比较表明,SHA-FeTHP 的 Soret 带在 30 分钟孵育期后明显保持,而 FeTHP 和 THA-FeTHP 的大多数 Soret 带的强度在 5 分钟孵育期后迅速降低。这些结果表明,SHA-FeTHP 是一种稳定的催化剂,这种稳定性导致更广泛地氧化更具毒性的副产物。

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