近日,美国莱斯大学和中国南开大学科学家合作,首次对6种钯基和铁基催化剂清除致癌物三氯乙烯(TCE)的能力进行了对比测试,发现钯破坏TCE的能力比铁要快得多,甚至高出铁粉10亿倍。研究人员指出,对于开展大规模TCE催化治理实验来说,这一发现有助人们从成本和效率两方面综合考虑,实现成本最优化。相关论文将发表在8月出版的《应用催化B:环境》(Applied Catalysis B: Environmental )期刊上。
TCE广泛用作脱脂剂和溶剂,已经有许多地区污染了地下水。在美国环保署有毒废弃物堆场污染清除基金国家优先项目列表中,超过一半废品堆场发现含有TCE,单是清除地下水中TCE的成本估计要超过50亿美元。
TCE分子中的碳—氯键非常稳定,这在工业上很有用,但却对环境不利。“要打破碳—氯化学键非常困难,而处理TCE要求只打破某些键而不是所有碳—氯键,否则可能带来更危险的副产物如氯乙烯。这是个大难题。”论文作者之一、莱斯大学化学与生物分子工程教授迈克尔·翁说,“通行方法是不破坏这些键,而用气体或碳吸收方法物理性除去污染地下水中的TCE。这些方法容易实施却成本很高。”后来人们发现纯铁和纯钯能将TCE转变为无毒物质,以往的金属降解TCE是让其在水中发生腐蚀作用,但可能产生氯乙烯;后来人们用金属作催化剂来促进碳—氯键断裂,其本身并不与TCE反应。因为铁比钯要廉价得多,更容易操作,因此行业内已普遍用铁来除去TCE,钯只在实验室中使用。
迈克尔·翁和曾在莱斯大学做访问学者的中国南开大学李淑景(音译)等人对6种铁基和钯基催化剂进行了一系列实验,包括两种铁纳米粒子、两种钯纳米粒子,其中就有研究小组2005年开发的用于TCE治理的金—钯纳米粒子催化剂、铁粉和氧化钯铝粉末。
他们测试了6种催化剂分解掉含TCE的水溶液中90%的TCE所需时间。结果是,钯催化剂只花了不到15分钟,两种铁纳米粒子超过25小时,而铁粉则超过了10天。李淑景说:“以往我们知道钯的催化速度更快,但经过对比测试才知道能快这么多。”(生物谷Bioon.com)
doi:10.1016/j.apcatb.2012.05.025
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Environmental - Establishing the trichloroethene dechlorination rates of palladium-based catalysts and iron-based reductants
Shujing Lia, b, d, Yu-Lun Fangb, Chris D. Romanczukb, Zhaohui Jina, Tielong Lia, Michael S. Wongb,
The removal of undesired chlorinated hydrocarbon contaminants through chemical destruction using ex situ Pd-based catalytic or in situ Fe-based reductive nanomaterials offers unique advantages over current physical displacement methods for groundwater treatment. While these two types of chemical methods has been studied in-depth in recent years, their respective hydrodechlorination and dechlorination transformations have not been analyzed together before. Here, the reactivities of Pd catalysts and Fe reductants were experimentally assessed for trichloroethene (TCE) degradation using room-temperature, atmospheric-pressure, dihydrogen-headspace-filled batch reactor studies under buffered and non-buffered conditions. Pseudo-first order reaction rate constants at pH 7 spanned 9 decades: 1.2 × 104, 1.0 × 103, 4.5 × 102, 2.41 × 10?4, 4.2 × 10?4, and 7.09 × 10?6 L/gactive-metal/min for Pd-on-Au nanoparticles (Pd/Au NPs), Pd NPs, Pd-on-alumina powder, and two nano-sized forms and one micron-sized form of commercial zerovalent iron, respectively. With rates measured in the range of commonly reported values, the Fe-based materials produced ethane, ethene, and vinyl chloride; ethene hydrogenated into ethane at sufficiently long reaction times. The much more active Pd-based materials produced ethane as the primary TCE degradation reaction product. This study presents, for the first time, a quantitative comparison of TCE degradation rates determined under identical experimental conditions.