Minyuan Tan, Tong Liu, Yuanhua Sun, Dan Wu, Xiaokang Liu, Xue Zhang, Ming Ni, Qiquan Luo, Haiwei Du*, Linlin Cao* and Tao Yao*,
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引用次数: 0
摘要
在工业电流密度下实现5-羟甲基糠醛（HMF）到2,5-呋喃二羧酸（FDCA）的连续转化为塑料制造带来了巨大的希望，但在保持长期稳定性方面提出了重大挑战。在此，我们引入了具有刘易斯酸性的单原子Ru位点，通过缺陷介导的锚定和强共价金属-支持相互作用稳定在镍-铁层双氢氧化物（Ru@NiFe）上，专门为有效的生物质升级设计。在实际的电解槽中，Ru@NiFe实现了159.3 mg cm-2 h - 1的FDCA转化率和90%的法拉第效率，在接近270 mA cm-2的工业密度下保持500小时以上的稳定运行，而没有明显的活性损失。Operando光谱和理论研究表明亲电性单原子Ru位点建立了强的Lewis酸碱相互作用，促进了活性Ni3+δ (0 <；δ& lt;1)增强对HMF的吸附。这种促进使HMF在电氧化还原过程中Ni2+和Ni3+δ之间的动态振荡增强，通过优先捕获释放的质子，有效防止Ni3+δ的过度氧化，从而确保长期运行。
Lewis Acid–Base Interactions in Ru-Stabilized NiFe (Oxy)Hydroxide Promoting Biomass Upgrading at Industrial Currents
Achieving the continuous conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at industrial current densities holds great promise for plastic manufacturing but poses significant challenges in maintaining long-term stability. Herein, we introduce single-atom Ru sites exhibiting Lewis acidic properties stabilized on nickel–iron-layered double hydroxide (Ru@NiFe) through defect-mediated anchoring and strong covalent metal–support interactions, specifically designed for efficient biomass upgrading. In a practical electrolyzer, Ru@NiFe achieves a robust FDCA conversion rate of 159.3 mg cm–2 h–1 with 90% Faradaic efficiency, maintaining stable operation for over 500 h at an industrial density close to 270 mA cm–2 without significant activity loss. Operando spectroscopies and theoretical investigations reveal that electrophilic single-atom Ru sites establish strong Lewis acid–base interactions, promoting the formation of active Ni3+δ (0 < δ < 1) species and enhancing adsorption toward HMF. This promotion enables an enhanced dynamic oscillation between Ni2+ and Ni3+δ during the electrooxidation–reduction of HMF, effectively preventing overoxidation of Ni3+δ by preferentially capturing released protons, thus ensuring long-term operation.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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