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基于胺基悬挂金属有机框架和二醛的具有增强染料亲和力的无铬皮革加工。

Chrome-free leather processing based on amine pendant metal-organic frameworks and dialdehyde with enhanced dye affinity.

作者信息

Ramesh Renganath Rao, Chandrasekar Inbasekar, Rathinam Aravindhan, Jonnalagadda Raghava Rao

机构信息

Leather Process Technology Department, CSIR - Central Leather Research Institute (CLRI), Chennai, Tamil Nadu, India, 600020.

Department of Leather Technology (Housed at CSIR-Central Leather Research Institute), Alagappa College of Technology, Anna University, Chennai, Tamil Nadu, India, 600025.

出版信息

Environ Sci Pollut Res Int. 2024 Dec;31(58):66477-66496. doi: 10.1007/s11356-024-35501-1. Epub 2024 Dec 5.

DOI:10.1007/s11356-024-35501-1
PMID:39636540
Abstract

To overcome the stringent regulations in the usage of chromium salts and dye-rich effluent let out by the tanning industry, a sustainable way of leather processing has been demonstrated utilizing amine pendant metal-organic frameworks (MOF) UiO-66-NH along with glyoxal. It was found that an offer of 8% (w/w) MOF along with 6% (w/w) glyoxal increased the shrinkage temperature of the leathers to 89 ± 2 °C with exhaustion of MOF up to 84.3 ± 1.5%. The presence of cationic amine sites in the MOF aided in the fixation of anionic post-tanning agents and improved the adsorption of dyes from 74.3 ± 2.5% in the case of conventional leather to 91.8 ± 1.7% for experimental leather. In comparison to chrome-tanned leather, the experimental leathers were rated the highest in terms of dye fastness concerning rubbing action and against perspiration, showcasing the washable properties and better affinity and irreversible binding of dyes to the leather matrix. Mechanism studies through XPS spectroscopy revealed the interaction between the acidic amino acids of collagen and free zirconium metal sites and the imine linkage between amine pendants of MOF and basic amino acids of collagen protein. Further, the BOD/COD ratio of 0.36 confirmed the better treatability of the wastewater emanating from the proposed process making it a sustainable tanning system. Thus, the combination of amine pendant MOFs with dialdehyde can be a promising strategy for the development of robust chrome-free leathers with excellent functional properties.

摘要

为了克服铬盐使用方面的严格规定以及制革行业排放的富含染料的废水问题,人们展示了一种利用胺基悬挂金属有机框架(MOF)UiO - 66 - NH以及乙二醛进行皮革加工的可持续方法。研究发现,添加8%(w/w)的MOF和6%(w/w)的乙二醛可使皮革的收缩温度提高到89 ± 2°C,MOF的吸收率高达84.3 ± 1.5%。MOF中阳离子胺位点的存在有助于固定阴离子复鞣剂,并将染料的吸附率从传统皮革的74.3 ± 2.5%提高到实验皮革的91.8 ± 1.7%。与铬鞣革相比,实验皮革在摩擦和耐汗液方面的色牢度评级最高,展现出可洗涤性能以及染料与皮革基质更好的亲和力和不可逆结合。通过XPS光谱进行的机理研究揭示了胶原蛋白的酸性氨基酸与游离锆金属位点之间的相互作用,以及MOF的胺基侧链与胶原蛋白碱性氨基酸之间的亚胺键合。此外,0.36的BOD/COD比值证实了所提出工艺产生的废水具有更好的可处理性,使其成为一种可持续的鞣制系统。因此,胺基悬挂MOF与二醛的组合可能是开发具有优异功能特性的坚固无铬皮革的一种有前景的策略。

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