金属六氰基铁氧体中氰基的 C/N 顶端定向配位以高效回收钯:增强吸附亲和力和选择性。

IF 7.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES
Meng Liu , Xiaoping Li , Sijian Liu , Xiaobao Chen , Yu Liu , Lanxuan Wen , Zonghan Huang , Shengjiong Yang , Jinpeng Feng , Yang Chen , Rongzhi Chen
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引用次数: 0

摘要

金属六氰高铁酸盐(MHCF)中的n端氰基(CN)已被确定为钯(Pd)的特定亲和力位点,但c端CN由于与金属配体(M)的强键而不能有效地作为Pd的吸附位点,从而降低了CN的活性和密度。本文研究了通过调节MHCF中M (FeII, CoII和NiII)的电子结构来优化氰基C/ n末端的定向配位,以增强Pd的恢复。光谱分析和DFT计算表明,NiHCF表现为n位单配位,而CoHCF由于自旋交换相互作用表现为c位单配位,导致N-CoIII键增强,fei -c键减弱。有趣的是,FeHCF保持了n配位性质,并表现出c配位,因为d波段中心的移动削弱了feii -c键。CN的双配位比单配位具有更高的吸附量和吸附速率,这分别与CN含量和吸附亲和力有关。此外,所有三种mhcf,特别是双配位FeHCF,在贵金属/贱金属体系中表现出优异的选择性,良好的抗阴离子干扰能力和可重复使用性。该研究强调了M的电子结构在CN配位环境中的关键作用,为吸附位点的定向设计提供了一种新的策略。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Directed coordination of C/N-termini of cyano group in metal hexacyanoferrates to efficient palladium recovery: Enhanced adsorption affinity and selectivity

Directed coordination of C/N-termini of cyano group in metal hexacyanoferrates to efficient palladium recovery: Enhanced adsorption affinity and selectivity
N-termini Cyano group (CN) in metal hexacyanoferrates (MHCF) have been identified as specific-affinity sites for palladium (Pd), but C-termini CN do not effectively serve as Pd adsorption sites due to their stronger bonds with the metal ligands (M), which reduces the activity and density of CN. Herein, the optimization of directional coordination of cyano group C/N-termini by modulating the electronic structure of the M (FeII, CoII, and NiII) in MHCF was investigated to reinforce the Pd recovery. Spectroscopic analyses and DFT calculations revealed that NiHCF exhibited N-site mono-coordination, whereas CoHCF displayed C-site mono-coordination due to spin-exchange interactions, leading to the strengthened N-CoIII bonds and weakened FeII-C bonds. Interestingly, FeHCF maintained N-coordination properties and showed C-coordination as the shift of the d-band center weakened the FeIII-C bonds. Double-coordination of CN resulted in a higher adsorption-capacity and -rate than mono-coordination, which were attributed to its greater CN content and adsorption affinity, respectively. Additionally, all three MHCFs, particularly double-coordination FeHCF, demonstrated excellent selectivity in noble/base metal systems, good resistance to anionic interference, and reusability. The study underscores the pivotal role of M's electronic structure in the CN coordination environment, offering a novel strategy for the directional design of adsorbent sites.
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来源期刊
Environmental Research
Environmental Research 环境科学-公共卫生、环境卫生与职业卫生
CiteScore
12.60
自引率
8.40%
发文量
2480
审稿时长
4.7 months
期刊介绍: The Environmental Research journal presents a broad range of interdisciplinary research, focused on addressing worldwide environmental concerns and featuring innovative findings. Our publication strives to explore relevant anthropogenic issues across various environmental sectors, showcasing practical applications in real-life settings.
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