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羧酸阳离子交换剂基质中氧化铜向金属铜的转化:新型复合材料的合成与热重研究

Transformation of CuO into Metallic Copper within Matrix of Carboxylic Cation Exchangers: Synthesis and Thermogravimetric Studies of Novel Composite Materials.

作者信息

Kociołek-Balawejder Elżbieta, Winiarska Katarzyna, Winiarski Juliusz, Mucha Igor

机构信息

Department of Industrial Chemistry, Wroclaw University of Economics and Business, Komandorska 118/120, 53-345 Wrocław, Poland.

Department of Inorganic Chemistry, Wroclaw University of Economics and Business, Komandorska 118/120, 53-345 Wrocław, Poland.

出版信息

Materials (Basel). 2024 Aug 6;17(16):3893. doi: 10.3390/ma17163893.

Abstract

In order to systematize and expand knowledge about copper-containing composite materials as hybrid ion exchangers, in this study, fine metallic copper particles were dispersed within the matrix of a carboxyl cation exchanger (CCE) with a macroporous and gel-type structure thanks to the reduction of CuO particles precipitated within the matrix earlier. It was possible to introduce as much as 22.0 wt% Cu into a gel-type polymeric carrier (G/H#Cu) when an ascorbic acid solution was used to act as a reducer of CuO and a reagent transforming the functional groups from Na into the H form. The extremely high shrinkage of the porous skeleton containing -COOH groups (in a wet and also dry state) and its limited affinity for water protected the copper from oxidation without the use of special conditions. When macroporous CCE was used as a host material, the composite material (M/H#Cu) contained 18.5 wt% Cu, and copper particles were identified inside the resin beads, but not on their surface where Cu ions appeared during drying. Thermal analysis in an air atmosphere and under N showed that dispersing metallic copper within the resin matrix accelerated its decomposition in both media, whereby M/H#Cu decomposed faster than G/H#Cu. It was found that G/H#Cu contained 6.0% bounded water, less than M/H#Cu (7.5%), and that the solid residue after combustion of G/H#Cu and M/H#Cu was CuO (26.28% and 22.80%), while after pyrolysis the solid residue (39.35% and 26.23%) was a mixture of carbon (50%) and metallic copper (50%). The presented composite materials thanks to the antimicrobial, catalytic, reducing, deoxygenating and hydrophobic properties of metallic copper can be used for point-of-use and column water/wastewater treatment systems.

摘要

为了系统整理和拓展关于含铜复合材料作为混合离子交换剂的知识,在本研究中,由于先前沉淀在基质内的CuO颗粒的还原,细小的金属铜颗粒分散在具有大孔和凝胶型结构的羧基阳离子交换剂(CCE)基质中。当使用抗坏血酸溶液作为CuO的还原剂以及将官能团从Na型转化为H型的试剂时,能够向凝胶型聚合物载体(G/H#Cu)中引入多达22.0 wt%的Cu。含有 -COOH基团的多孔骨架在湿态和干态下都具有极高的收缩率,并且其对水的亲和力有限,从而在不使用特殊条件的情况下保护铜不被氧化。当使用大孔CCE作为主体材料时,复合材料(M/H#Cu)含有18.5 wt%的Cu,并且在树脂珠粒内部而非干燥过程中出现Cu离子的表面发现了铜颗粒。在空气气氛和N气氛下的热分析表明,将金属铜分散在树脂基质中会加速其在两种介质中的分解,其中M/H#Cu比G/H#Cu分解得更快。研究发现,G/H#Cu含有6.0%的结合水,少于M/H#Cu(7.5%),并且G/H#Cu和M/H#Cu燃烧后的固体残留物是CuO(26.28%和22.80%),而热解后的固体残留物(39.35%和26.23%)是碳(50%)和金属铜(50%)的混合物。由于金属铜具有抗菌、催化、还原、脱氧和疏水特性,所呈现的复合材料可用于现场和柱式水/废水处理系统。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4f8a/11355710/d719f8c3bcdd/materials-17-03893-sch001.jpg

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