Saturated Alcohols Electrocatalytic Oxidations on Ni-Co Bimetal Oxide Featuring Balanced B- and L-Acidic Active Sites

IF 36.3 1区材料科学 Q1 Engineering

Nano-Micro Letters Pub Date : 2025-08-25 DOI:10.1007/s40820-025-01893-z

Junqing Ma, Wenshu Luo, Xunlu Wang, Xu Yu, Jiacheng Jayden Wang, Huashuai Hu, Hanxiao Du, Jianrong Zeng, Wei Chen, Minghui Yang, Jiacheng Wang, Xiangzhi Cui

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引用次数: 0

Abstract

Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols. Herein, we report efficient electrocatalytic oxidations of saturated alcohols (C₁-C₆) to selectively form formate using NiCo hydroxide (NiCo–OH) derived NiCo₂O₄ solid-acid electrocatalysts with balanced Lewis acid (LASs) and Brønsted acid sites (BASs). Thermal treatment transforms BASs-rich (89.6%) NiCo–OH into NiCo₂O₄ with nearly equal distribution of LASs (53.1%) and BASs (46.9%) which synergistically promote adsorption and activation of OH⁻ and alcohol molecules for enhanced oxidation activity. In contrast, BASs-enriched NiCo–OH facilitates formation of higher valence metal sites, beneficial for water oxidation. The combined experimental studies and theoretical calculation imply the oxidation ability of C₁-C₆ alcohols increases as increased number of hydroxyl groups and decreased HOMO–LUMO gaps: methanol (C₁) < ethylene glycol (C₂) < glycerol (C₃) < meso-erythritol (C₄) < xylitol (C₅) < sorbitol (C₆), while the formate selectivity shows the opposite trend from 100 to 80%. This study unveils synergistic roles of LASs and BASs, as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.

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饱和醇电催化氧化Ni-Co双金属氧化物具有平衡的B-和l -酸性活性位点

研究固体酸电催化剂对醇电氧化制高附加值产品的结构和羟基效应对生物质醇的升级至关重要。本文报道了采用平衡Lewis酸（LASs）和Brønsted酸位（BASs）的NiCo2O4固体酸电催化剂，对饱和醇（C1-C6）进行了高效的电催化氧化，选择性地形成甲酸盐。热处理将富BASs（89.6%）的NiCo-OH转化为LASs（53.1%）和BASs（46.9%）分布几乎相等的NiCo2O4，从而协同促进OH -和醇分子的吸附和活化，增强氧化活性。相反，富bass的NiCo-OH有利于形成高价位的金属，有利于水的氧化。结合实验研究和理论计算表明，C1-C6醇的氧化能力随着羟基数目的增加和HOMO-LUMO间隙的减小而增加：甲醇（C1） <、乙二醇（C2） <、甘油（C3） <、中赤藓糖醇（C4） <、木糖醇（C5） <、山梨糖醇（C6），甲酸盐选择性在100 ~ 80%之间呈现相反的趋势。本研究揭示了LASs和BASs的协同作用，以及羟基效应在固体酸电催化醇的电升级中的作用。

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

Nano-Micro Letters NANOSCIENCE & NANOTECHNOLOGY-MATERIALS SCIENCE, MULTIDISCIPLINARY

CiteScore

32.60

自引率

4.90%

发文量

981

审稿时长

1.1 months

期刊介绍： Nano-Micro Letters is a peer-reviewed, international, interdisciplinary, and open-access journal published under the SpringerOpen brand. Nano-Micro Letters focuses on the science, experiments, engineering, technologies, and applications of nano- or microscale structures and systems in various fields such as physics, chemistry, biology, material science, and pharmacy.It also explores the expanding interfaces between these fields. Nano-Micro Letters particularly emphasizes the bottom-up approach in the length scale from nano to micro. This approach is crucial for achieving industrial applications in nanotechnology, as it involves the assembly, modification, and control of nanostructures on a microscale.