基于SEM-EDS及GC-MS技术研究有机氯分子结构对零价铜脱氯机制的影响

零价铜作为一种廉价金属很少应用于促进氯代有机物脱氯研究,其原因是零价铜的催化还原脱氯活性差,且反应机制复杂。本文采用机械球磨技术制备了Cu-Fe和Cu-Ni合金,研究零价铜在不同微观环境下对对氯苯酚(4-CP)的脱氯行为,旨在考察有机氯分子结构对零价铜脱氯机制的影响。应用扫描电镜-能谱(SEM-EDS)及色相色谱-质谱(GC-MS)分析发现,铜原子的微环境及有机氯分子结构均影响铜的脱氯机制。在Cu-Fe体系中,Cu遵循经典的催化加氢脱氯机制,4-CP的降解产物为苯酚;Cu-Ni体系的还原作用来源于零价铜,其中的镍金属并未起到催化加氢作用,Cu-Ni合金及单独零价铜对4-CP的降解产物是环己酮。零价铜对4-CP的降解率可达70%以上,而Cu-Fe体系的降解率仅为34%,两者对芳香族氯代物的降解效率差距显著。零价铜能够降解化学稳定性高的4-CP和苯酚,但不能降解化学稳定性相对较差的脂肪族氯代有机物(如一氯乙酸和二氯乙酸),因此认为零价铜脱氯机制并非传统的催化加氢机制,而是遵循直接电子传递还原机制,且有机氯分子的苯环结构是零价铜直接电子传递还原的诱因。

Effect of Molecular Structure in Chlorinated Organic Compounds on Zero-valent Copper Degradation Mechanism Based on SEM-EDS and GC-MS Techniques

Zero-valent copper, even cheap, is rarely used in hydrodechlorination (such as chlorinated aromatic hydrocarbons), because Cu has poor catalytical dechlorination activity and complex reaction mechanisms. In this study, Cu-Fe and Cu-Ni alloys were prepared by mechanical ball-milling, and the effect of micro-environment for the chlorophenol (4-CP) dechlorination behavior of Cu was studied in order to investigate the effect of organic chlorine molecular structure on Cu dechlorination. Two reaction mechanisms were examined for low-cost copper during dechlorination. SEM-EDS and GC-MS analyses show that the structure of organic chlorine and Cu metal environment could directly affect the mechanism. In the Cu-Fe system, Cu follows the classic catalytic hydrodechlorination mechanism and the degradation product 4-CP is phenol. But in the Cu-Ni system, nickel metal does not play a catalytic hydrogenation of action, the degraded product for 4-CP by Cu-Ni alloy is cyclohexanone. Copper acts as hydrogen-metal and shows a strong reducing activity by direct electron transfer. 4-CP degradation for Zero-valent copper was up to 70%, while only 34% for Cu-Fe system. These differences concluded that the aromatic ring was a direct electron transfer for Cu. Zero-valent copper can degrade 4-CP and phenol with high chemical stability, but cannot degrade aliphatic chlorinated organics (e.g., monochloroacetic acid and dichloroacetic acid) with relatively poor chemical stability. In conclusion, dechlorination mechanism for zero-valent copper is not traditional catalytic hydrodechlorination, but the direct electron transfer reduction mechanism which is affected by target molecule structure.