Mori Kohsuke, Tanaka Hiromasa, Dojo Masahiro, Yoshizawa Kazunari, Yamashita Hiromi
Graduate School of Engineering, Osaka University, 1-2 Yamadaoka, Suita, Osaka 565-0871(Japan).
Elements Strategy Initiative for Catalysts & Batteries ESICB, Kyoto University, Katsura, Kyoto 615-8520 (Japan).
Chemistry. 2015 Aug 17;21(34):12085-92. doi: 10.1002/chem.201501760. Epub 2015 Jul 14.
Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing N(CH3 )2 functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high-purity H2 from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the N(CH3 )2 groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost-effective because of the superior catalytic activity compared with that of well-established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells.
在带有N(CH3 )2官能团的大孔碱性树脂中成功制备了高度分散的钯铜合金纳米颗粒。这种此前未被重视的合金组合首次被证明对通过甲酸(HCOOH)脱氢高效生产高纯度氢气用于化学储氢具有重要作用。通过添加铜,与单金属钯相比,电子促进的钯位点显示出显著更高的催化活性以及对一氧化碳中毒更好的耐受性。实验和密度泛函理论计算研究表明,不仅合金的协同效应,而且树脂中N(CH3 )2基团的协同作用在实现优异的催化性能中起着关键作用。除了制备方法简便、无需添加剂、可回收且活性成分不浸出以及抑制一氧化碳生成量低于3 ppm等优点外,由于与成熟的贵金属钯银或钯金催化剂相比具有优异的催化活性,本催化体系具有成本效益。就燃料电池的潜在工业应用而言,本催化体系特别适合作为理想的氢载体。