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恒电流锌电沉积过程中从致密结构到苔藓状结构的转变分析及其对CO电还原的影响

Analysis of Transition from Compact to Mossy Structures During Galvanostatic Zinc Electrodeposition and Its Implications for CO Electroreduction.

作者信息

Altimari Pietro, Iacobelli Silvia, Schiavi Pier Giorgio, Zanellato Gianluca, Amato Francesco, Marrani Andrea Giacomo, Russina Olga, Sanna Alessia, Pagnanelli Francesca

机构信息

Department of Chemistry, Sapienza University of Rome, Piazzale Aldo Moro 5, 00185 Rome, Italy.

Department of Basic and Applied Sciences for Engineering, Sapienza University of Rome Via Antonio Scarpa 16, 00161 Rome, Italy.

出版信息

Nanomaterials (Basel). 2025 Jul 2;15(13):1025. doi: 10.3390/nano15131025.

Abstract

The galvanostatic electrodeposition of zinc on carbon paper from mildly acidic solutions (ZnCl: 0.05-0.1 M; HBO: 0.05 M) was investigated. The deposits' growth mechanisms were analyzed through the study of the electrodeposition potential transients and the physical characterization of the electrodes synthesized by varying the current density, transferred charge, and zinc precursor concentration. The analysis reveals that the transition from crystalline to amorphous mossy deposits takes place via the electrodeposition of metallic zinc followed by the formation of oxidized zinc structures. The time required for this transition can be controlled by varying the zinc precursor concentration and electrodeposition current density, allowing for the synthesis of composite zinc/oxidized zinc electrodes with varying ratios of the oxidized to underlying metallic phases. The impact of this ratio on the electrode activity for CO electroreduction is analyzed, highlighting that composite zinc/oxidized zinc electrodes can achieve a faradaic efficiency to CO equal to 82% at -1.8 V vs. Ag/AgCl. The mechanisms behind the variations in the catalytic activity with varying morphologies and structures are discussed, providing guidelines for the synthesis of composite zinc/oxidized zinc electrodes for CO electroreduction.

摘要

研究了在弱酸性溶液(ZnCl₂:0.05 - 0.1 M;H₃BO₃:0.05 M)中锌在碳纸上的恒电流电沉积。通过研究电沉积电位瞬变以及对通过改变电流密度、转移电荷和锌前驱体浓度合成的电极进行物理表征,分析了沉积物的生长机制。分析表明,从结晶态到非晶态苔藓状沉积物的转变是通过金属锌的电沉积,随后形成氧化锌结构来实现的。这种转变所需的时间可以通过改变锌前驱体浓度和电沉积电流密度来控制,从而能够合成具有不同氧化态与底层金属相比例的复合锌/氧化锌电极。分析了该比例对CO电还原电极活性的影响,突出了复合锌/氧化锌电极在相对于Ag/AgCl为 -1.8 V时可实现高达82%的CO法拉第效率。讨论了随着形态和结构变化催化活性变化背后的机制,为合成用于CO电还原的复合锌/氧化锌电极提供了指导。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3040/12251542/d1e54eddacf4/nanomaterials-15-01025-g001.jpg

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