Unlocking the superior flexibility and enhanced catalytic oxidation performance of CoTiO3 nanofibrous membranes through zirconium doping

Haoru Shan, Wenqiang Wang, Zhirong Wang,Junxiong Zhang, Jiayi Xia,Qixia Liu,Wei Zhang,Jianlong Ge,Qiuxia Fu

Separation and Purification Technology(2024)

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Abstract
The development of continuous CoTiO3 (CTO) fibers with prominent catalytic oxidation activity, tunable fibrous structures, and improved recyclability is appealing for application in efficient organic wastewater treatment; however, inescapable flaws remain, such as their inherent brittleness and adverse operability. Herein, a facile and effective strategy is proposed for the fabrication of flexible and mechanically robust CTO nanofibrous membranes through a combination of element doping and sol–gel-assisted electrospinning. Compared with pristine CTO fibers, the resulting zirconium-doped CoTiO3 (ZCTO) nanofibrous membranes displayed remarkably enhanced flexibility and tensile mechanics, which were attributed to their lower crystallinity, smaller grain size, and fewer fiber surface defects. The developed ZCTO fibrous membrane demonstrated exceptional resistance to bending fatigue, retaining a polymer-like bending rigidity of approximately 25 mN even after undergoing 200 reciprocating bending cycles. Furthermore, the incorporation of zirconium into CTO clearly had an advantageous effect on the formation of oxygen vacancies, thereby enhancing the surface adsorption of peroxymonosulfate (PMS), accelerating the electron transfer process, and weakening the peroxy bonds. The tetracycline degradation efficiency of the ZCTO fibers remained at 81.4 % within 10 min after 5 continuous cycles. Benefiting from their robust mechanical properties and excellent catalytic activity, the fabricated membranes demonstrated outstanding dynamic catalytic performance under gravity-driven conditions. More importantly, the reported strategy might be adopted and extended to develop a wide range of ceramic fibers with enhanced flexibility and mechanics for catalytic oxidation.
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Key words
Superior flexibility,Zr-doped CoTiO3,Nanofibrous membrane,Catalytic oxidation,Sulfate radical
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