Mravak Antonija, Vajda Stefan, Bonačić-Koutecký Vlasta
Center of Excellence for Science and Technology-Integration of Mediterranean Region (STIM), Faculty of Science, University of Split, Rud̵era Boškovića 33, Split 21000, Croatia.
Department of Nanocatalysis, Czech Academy of Sciences, J. Heyrovský Institute of Physical Chemistry, Dolejškova 3, Prague 8 18223, Czech Republic.
J Phys Chem C Nanomater Interfaces. 2022 Nov 3;126(43):18306-18312. doi: 10.1021/acs.jpcc.2c04921. Epub 2022 Oct 24.
For very small nanocluster-based catalysts, the exploration of the influence of the particle size, composition, and support offers precisely variable parameters in a wide material search space to control catalysts' performance. We present the mechanism of the CO methanation reaction on the oxidized bimetallic CuPd tetramer (CuPdO) supported on a zirconia model support represented by ZrO based on the energy profile obtained from density functional theory calculations on the reaction of CO and H. In order to determine the role of the Pd atom, the performance of CuPdO with monometallic CuO at the same support has been compared. Parallel to methane formation, the alternative path of methanol formation at this catalyst has also been investigated. The results show that the exchange of a single atom in Cu with a single Pd atom improves catalyst/s performance via lowering the barriers associated with hydrogen dissociation steps that occur on the Pd atom. The above-mentioned results suggest that the doping strategy at the level of single atoms can offer a precise control knob for designing new catalysts with desired performance.
对于基于非常小的纳米团簇的催化剂，在广泛的材料搜索空间中探索粒径、组成和载体的影响，可提供精确可变的参数来控制催化剂的性能。基于对CO与H反应进行密度泛函理论计算得到的能量分布，我们阐述了负载在以ZrO为代表的氧化锆模型载体上的氧化态双金属CuPd四聚体（CuPdO）上的CO甲烷化反应机理。为了确定Pd原子的作用，我们比较了在相同载体上的单金属CuO与CuPdO的性能。与甲烷生成平行，还研究了该催化剂上甲醇生成的替代路径。结果表明，用单个Pd原子取代Cu中的单个原子，通过降低与Pd原子上发生的氢解离步骤相关的势垒，提高了催化剂的性能。上述结果表明，单原子水平的掺杂策略可为设计具有所需性能的新型催化剂提供精确的控制旋钮。
