Department of Chemistry, Middle East Technical University, 06800 Ankara, Turkey.
ACS Appl Mater Interfaces. 2012 Nov;4(11):6302-10. doi: 10.1021/am3019146. Epub 2012 Nov 8.
Ruthenium(0) nanoparticles supported on multiwalled carbon nanotubes (Ru(0)@MWCNT) were in situ formed during the hydrolysis of ammonia-borane (AB) and could be isolated from the reaction solution by filtration and characterized by ICP-OES, XRD, TEM, SEM, EDX, and XPS techniques. The results reveal that ruthenium(0) nanoparticles of size in the range 1.4-3.0 nm are well-dispersed on multiwalled carbon nanotubes. They were found to be highly active catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value of 329 min⁻¹. The reusability experiments show that Ru(0)@MWCNTs are isolable and redispersible in aqueous solution; when redispersed they are still active catalyst in the hydrolysis of AB exhibiting a release of 3.0 equivalents of H₂ per mole of NH₃BH₃ and preserving 41% of the initial catalytic activity even after the fourth run of hydrolysis. The lifetime of Ru(0)@MWCNTs was measured as 26400 turnovers over 29 h in the hydrolysis of AB at 25.0 ± 0.1 °C before deactivation. The work reported here also includes the kinetic studies depending on the temperature to determine the activation energy of the reaction (E(a) = 33 ± 2 kJ/mol) and the effect of catalyst concentration on the rate of the catalytic hydrolysis of AB, respectively.
负载在多壁碳纳米管上的钌(0)纳米颗粒(Ru(0)@MWCNT)在氨硼烷(AB)水解过程中原位形成,可以通过过滤从反应溶液中分离出来,并通过 ICP-OES、XRD、TEM、SEM、EDX 和 XPS 技术进行表征。结果表明,尺寸在 1.4-3.0nm 范围内的钌(0)纳米颗粒均匀分散在多壁碳纳米管上。它们被发现是 AB 水解制氢的高活性催化剂,其周转频率值为 329min⁻¹。重复使用实验表明,Ru(0)@MWCNTs 可在水溶液中分离和再分散;当再分散时,它们仍然是 AB 水解的活性催化剂,每摩尔 NH₃BH₃释放 3.0 当量的 H₂,并保持 41%的初始催化活性,即使在第四次水解循环后也是如此。在 25.0±0.1°C 下,AB 水解的半衰期为 26400 次循环,在失活前为 29 小时。这里报道的工作还包括依赖于温度的动力学研究,以确定反应的活化能(E(a)=33±2kJ/mol)和催化剂浓度对 AB 催化水解速率的影响。