Totarella Giorgio, Beerthuis Rolf, Masoud Nazila, Louis Catherine, Delannoy Laurent, de Jongh Petra E
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands.
Biobased Chemistry and Technology, Wageningen University & Research, Wageningen, The Netherlands.
J Phys Chem C Nanomater Interfaces. 2021 Jan 14;125(1):366-375. doi: 10.1021/acs.jpcc.0c08077. Epub 2020 Dec 23.
Supported copper nanoparticles are a promising alternative to supported noble metal catalysts, in particular for the selective gas phase hydrogenation of polyunsaturated molecules. In this article, the catalytic performance of copper nanoparticles (3 and 7 nm) supported on either silica gel or graphitic carbon is discussed in the selective hydrogenation of 1,3-butadiene in the presence of a 100-fold excess of propene. We demonstrate that the routinely used temperature ramp-up method is not suitable in this case to reliably measure catalyst activity, and we present an alternative measurement method. The catalysts exhibited selectivity to butenes as high as 99% at nearly complete 1,3-butadiene conversion (95%). Kinetic analysis showed that the high selectivity can be explained by considering H activation as the rate-limiting step and the occurrence of a strong adsorption of 1,3-butadiene with respect to mono-olefins on the Cu surface. The 7 nm Cu nanoparticles on SiO were found to be a very stable catalyst, with almost full retention of its initial activity over 60 h of time on stream at 140 °C. This remarkable long-term stability and high selectivity toward alkenes indicate that Cu nanoparticles are a promising alternative to replace precious-metal-based catalysts in selective hydrogenation.
负载型铜纳米颗粒是负载型贵金属催化剂的一种有前途的替代品，尤其适用于多不饱和分子的选择性气相加氢。在本文中，讨论了负载在硅胶或石墨碳上的铜纳米颗粒（3纳米和7纳米）在丙烯过量100倍的情况下对1,3-丁二烯进行选择性加氢的催化性能。我们证明，常规使用的升温方法在这种情况下不适用于可靠地测量催化剂活性，并且我们提出了一种替代测量方法。在1,3-丁二烯几乎完全转化（95%）时，催化剂对丁烯的选择性高达99%。动力学分析表明，通过将氢活化视为限速步骤以及1,3-丁二烯相对于单烯烃在铜表面发生强吸附，可以解释这种高选择性。发现SiO上的7纳米铜纳米颗粒是一种非常稳定的催化剂，在140℃下连续运行60小时后，其初始活性几乎完全保留。这种显著的长期稳定性和对烯烃的高选择性表明，铜纳米颗粒是在选择性加氢中替代贵金属基催化剂的有前途的替代品。
