Electrodepositing Polyvinyl Ferrocene Films to Enhance Oxyanion Recovery and Electrode Longevity

IF 7.4 Q1 ENGINEERING, ENVIRONMENTAL

ACS ES&T engineering Pub Date : 2025-02-28 DOI:10.1021/acsestengg.4c0078710.1021/acsestengg.4c00787

Yurui Li, Anaira Román Santiago, Kwiyong Kim, Junhyung Park, Joseph R. Hladik, Xiao Su and Roland D. Cusick*,

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Abstract

Rhenium, a critical high-value mineral, naturally occurs as perrhenate (ReO₄^–) and is difficult to separate from competing anions. Polyvinyl ferrocene (PVF) coated electrodes have exhibited selective adsorption of transition metal oxyanions, but performance degradation with cycling is poorly understood. This study examines the impact of two PVF film fabrication strategies (electrodeposition (ED) and dip-coating (DC)) on (i) rhenium uptake capacity and selectivity, (ii) electrode regeneration and performance longevity, and (iii) lifecycle cost of Re recovery. Electrodeposited PVF films exhibited nearly twice the rhenium uptake (351 ± 82.1 mg Re/g coating) of dip-coating PVF films (158 ± 32.7 mg Re/g coating). Additionally, after 15,000 charge/discharge cycles, Re uptake remained 69.1 ± 11.3% for ED but only 28.0 ± 12.3% for DC films, indicating improved PVF attachment to carbon scaffolds. Operational conditions significantly affected rhenium release after adsorption, with regeneration of 82.6 ± 9.4% at −0.8 V vs Ag/AgCl compared to 30.78 ± 6.2% at 0 V vs Ag/AgCl, due to reduction of both Fe and Re which promoted electrode regeneration at −0.8 V vs Ag/AgCl. A preliminary technoeconomic analysis indicates the high selectivity and longevity of PVF-ED electrodes could facilitate Re recovery at ∼5% of the current market price.

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电沉积聚乙烯烃二茂铁薄膜提高氧离子回收率和电极寿命

铼是一种重要的高价值矿物，天然存在于过铼酸盐（ReO4 -）中，很难与竞争阴离子分离。聚乙烯醇二茂铁（PVF）包覆电极表现出对过渡金属氧阴离子的选择性吸附，但对循环过程中性能的退化了解甚少。本研究考察了两种PVF薄膜制造策略（电沉积（ED）和浸涂（DC））对(i)铼吸收能力和选择性，（ii）电极再生和性能寿命，以及（iii） Re回收的生命周期成本的影响。电沉积PVF膜的铼吸收率（351±82.1 mg Re/g涂层）几乎是浸涂PVF膜（158±32.7 mg Re/g涂层）的两倍。此外，在15000次充放电循环后，ED膜的Re吸收率仍为69.1±11.3%，而DC膜的Re吸收率仅为28.0±12.3%，这表明PVF与碳支架的附着有所改善。操作条件显著影响吸附后铼的释放，在−0.8 V /Ag /AgCl条件下再生率为82.6±9.4%，而在0 V /Ag /AgCl条件下再生率为30.78±6.2%，这是由于−0.8 V /Ag /AgCl条件下Fe和Re的还原促进了电极再生。一项初步的技术经济分析表明，PVF-ED电极的高选择性和寿命可以促进Re的回收，其价格为当前市场价格的5%。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS ES&T engineering ENGINEERING, ENVIRONMENTAL-

CiteScore

8.50

自引率

0.00%

发文量

期刊介绍： ACS ES&T Engineering publishes impactful research and review articles across all realms of environmental technology and engineering, employing a rigorous peer-review process. As a specialized journal, it aims to provide an international platform for research and innovation, inviting contributions on materials technologies, processes, data analytics, and engineering systems that can effectively manage, protect, and remediate air, water, and soil quality, as well as treat wastes and recover resources. The journal encourages research that supports informed decision-making within complex engineered systems and is grounded in mechanistic science and analytics, describing intricate environmental engineering systems. It considers papers presenting novel advancements, spanning from laboratory discovery to field-based application. However, case or demonstration studies lacking significant scientific advancements and technological innovations are not within its scope. Contributions containing experimental and/or theoretical methods, rooted in engineering principles and integrated with knowledge from other disciplines, are welcomed.