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Synthesis of Fibrous Metal Adsorbent with a Piperazinyl-Dithiocarbamate Group by Radiation-Induced Grafting and Its Performance.
ACS Omega ( IF 3.7 ) Pub Date : 2020-02-07 , DOI: 10.1021/acsomega.9b03799
Yuji Ueki 1 , Noriaki Seko 1
Affiliation  

A fibrous grafted metal adsorbent with a piperazinyl-dithiocarbamate (PZ-DTC) group was synthesized by radiation-induced emulsion grafting of glycidyl methacrylate onto a polyethylene-coated polypropylene nonwoven fabric (PE/PP-NF) and subsequent three-step chemical modifications consisting of amination with N-(tert-butoxycarbonyl)piperazine (N-Boc-piperazine, NBPZ), deprotection of the Boc group with HCl, and dithiocarbamation with carbon disulfide (CS2). By using the NBPZ reagent in the amination step, the self-cross-linking of piperazine (PZ) could be completely suppressed, unlike using the PZ reagent. Consequently, the PZ-DTC group density of the fibrous grafted metal adsorbent synthesized through NBPZ attained 2.122 mmol-PZ-DTC/g-adsorbent, which was approximately 6 times higher than that of the metal adsorbent synthesized through PZ. The fibrous grafted metal adsorbent with the PZ-DTC group selectively adsorbed heavy metal ions over light metal ions. Furthermore, it exhibited high adsorption capacity, particularly for Cu2+. The Cu2+ adsorption capacity was determined to be 1.903 mmol-Cu2+/g-adsorbent by a batchwise adsorption test using a single-metal-ion aqueous solution at pH 6. The order of metal ion selectivity of the fibrous grafted metal adsorbent with the PZ-DTC group was Na+ < Mg2+, Ca2+, Co2+, Cd2+ < Pb2+ ≪ Cu2+, and Co2+ ≈ Ni2+ < Zn2+ ≪ Cu2+. In addition, the fibrous grafted metal adsorbent with the PZ-DTC group did not lose its metal adsorption function even under highly alkaline conditions (pH 15). It could recover Cu2+ efficiently and selectively from a high-concentration Na+ aqueous solution at this pH. The Cu2+ adsorption capacity of the fibrous grafted metal adsorbent with the PZ-DTC group was 0.754 mmol-Cu2+/g-adsorbent under a highly alkaline condition, a 10 M NaOH aqueous solution at pH 15. This value was approximately 2.4 times higher than that of the other grafted adsorbent with an amine-type functional group.

中文翻译:


辐射接枝法合成具有哌嗪基二硫代氨基甲酸酯基团的纤维状金属吸附剂及其性能。



通过将甲基丙烯酸缩水甘油酯辐射诱导乳液接枝到聚乙烯涂覆的聚丙烯非织造布(PE/PP-NF)上并随后进行三步化学改性,合成了具有哌嗪基二硫代氨基甲酸酯(PZ-DTC)基团的纤维接枝金属吸附剂用N-(叔丁氧基羰基)哌嗪(N-Boc-哌嗪,NBPZ)进行胺化,用HCl对Boc基团进行脱保护,以及用二硫化碳(CS2)进行二硫代氨基甲化。通过在胺化步骤中使用NBPZ试剂,与使用PZ试剂不同,可以完全抑制哌嗪(PZ)的自交联。因此,通过NBPZ合成的纤维接枝金属吸附剂的PZ-DTC基团密度达到2.122mmol-PZ-DTC/g-adsorbent,比通过PZ合成的金属吸附剂高约6倍。具有PZ-DTC基团的纤维接枝金属吸附剂选择性地吸附重金属离子而不是轻金属离子。此外,它还表现出高吸附能力,特别是对 Cu2+ 的吸附能力。通过使用pH 6的单金属离子水溶液进行间歇吸附试验,确定Cu2+吸附容量为1.903 mmol-Cu2+/g-吸附剂。具有PZ-的纤维接枝金属吸附剂对金属离子选择性的顺序DTC组为Na+<Mg2+、Ca2+、Co2+、Cd2+<Pb2+≪Cu2+、Co2+≈Ni2+<Zn2+≪Cu2+。此外,具有PZ-DTC基团的纤维接枝金属吸附剂即使在高碱性条件(pH 15)下也不会丧失其金属吸附功能。在此pH值下,它可以从高浓度Na+水溶液中高效、选择性地回收Cu2+。 PZ-DTC基团的纤维接枝金属吸附剂对Cu2+的吸附容量为0。在高碱性条件下,10 M NaOH 水溶液,pH 15 下,754 mmol-Cu2+/g-吸附剂。该值比其他带有胺型官能团的接枝吸附剂高约 2.4 倍。
更新日期:2020-02-18
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