He Fei, Xia Nannan, Zheng Yan, Zhang Yixin, Fan Huailin, Ma Delong, Liu Qianhe, Hu Xun
School of Material Science and Engineering, University of Jinan, Jinan 250022, PR China.
State Key Laboratory of Biobased Material and Green Papermaking, Key Laboratory of Pulp & Paper Science and Technology of Shandong Province/Ministry of Education, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, China.
ACS Appl Mater Interfaces. 2021 Feb 24;13(7):8488-8496. doi: 10.1021/acsami.0c22700. Epub 2021 Feb 12.
Ultrasmall Ru nanoparticles is expected as a potential alternative to Pt for efficient hydrazine oxidation (HzOR). However, preparation of ultrasmall and well-distributed Ru nanoparticles usually suffered from the steps of modification of supports, coordination, reduction with strong reducing reagents (e.g., NaBH) or pyrolysis, imposing the complexity. Based on the self-reducibility of C-OH group and physical adsorption ability of commercial Ketjen black (KB), we developed an efficient, stable and robust Ru-based electrocatalyst (-Ru-KB) by coupling impregnation of KB in RuCl solution and simple in situ electrochemical activation strategy, which endowed the formation of ultrasmall and well-distributed Ru nanoparticles. Benefiting from an enhanced exposure of Ru sites and the faster mass transport, -Ru-KB achieved 63.4 and 3.9-fold enhancements of mass activity compared with Pt/C and Ru/C, respectively, accompanied by a ∼144 mV lower onset potential and faster catalytic kinetics than Pt/C. In the hydrazine fuel cell, the open-circuit voltage and maximal mass power density of -Ru-KB was 130 mV and ∼3.8-fold higher than those of Pt/C, respectively, together with the long-term stability. This work would provide a facile and sustainable approach for large-scale production of other robust metal (electro)catalysts with ultrasmall nanosize for various energy conversion and electrochemical organic synthesis.
超小钌纳米颗粒有望成为高效肼氧化(HzOR)中铂的潜在替代品。然而,制备超小且分布均匀的钌纳米颗粒通常需要经过载体改性、配位、用强还原剂(如硼氢化钠)还原或热解等步骤,过程较为复杂。基于C-OH基团的自还原性和商业科琴黑(KB)的物理吸附能力,我们通过将KB浸渍在RuCl溶液中并结合简单的原位电化学活化策略,开发了一种高效、稳定且坚固的钌基电催化剂(-Ru-KB),该策略使得超小且分布均匀的钌纳米颗粒得以形成。得益于钌位点的暴露增加和更快的传质速率,-Ru-KB的质量活性分别比Pt/C和Ru/C提高了63.4倍和3.9倍,同时起始电位比Pt/C低约144 mV,催化动力学更快。在肼燃料电池中,-Ru-KB的开路电压和最大质量功率密度分别比Pt/C高130 mV和约3.8倍,并且具有长期稳定性。这项工作将为大规模生产其他用于各种能量转换和电化学有机合成的具有超小纳米尺寸的坚固金属(电)催化剂提供一种简便且可持续的方法。