交换关联泛函近似方法对Ru催化剂上甲烷和乙烷形成的影响

密度泛函理论作为多相催化研究中的一个强有力工具，常被用于获得催化过程中关键的热力学及动力学参数，如吸附能、反应焓、活化能垒和速率常数等. 理解密度泛函交换关联近似方法对于揭示催化剂的催化性能及机理至关重要. 本文报道了六种不同的交换关联泛函近似方法，包括PBE、RPBE、BEEF+vdW、optB86b+vdW、SCAN和SCAN+rVV10，对金属Ru(0001)和Ru(1011)表面上甲烷和乙烷形成过程中涉及到的中间体的吸附能、反应能和活化能垒的影响. 当基元反应中反应物和产物与表面的配位数不同时，理论计算的反应能大小强烈依赖于交换关联密度泛函的选择. 对于涉及多个基元步骤的总反应，反应能的计算偏差会逐渐累积，从而导致不同的交换关联泛函近似方法之间的巨大差异. 由于不同泛函对反应涉及到的中间体吸附能之间存在差异，交换关联泛函近似方法的选择显著地影响Ru(0001)表面上甲烷、乙烯和乙烷的选择性. 然而，不同泛函近似方法对于Ru(0001) 和Ru(1011)表面上基元反应的能垒以及结构敏感性影响不大. 本工作不仅揭示了交换关联密度泛函近似方法在理论计算研究催化领域的局限性，也强调了选择合适的交换关联泛函方法对于正确评估催化剂活性和选择性的重要性.

Understanding the Effect of the Exchange-Correlation Functionals on Methane and Ethane Formation over Ruthenium Catalysts

Density functional theory (DFT) has been established as a powerful research tool for heterogeneous catalysis research in obtaining key thermodynamic and/or kinetic parameters like adsorption energies, enthalpies of reaction, activation barriers, and rate constants. Understanding of density functional exchangecorrelation approximations is essential to reveal the mechanism and performance of a catalyst. In the present work, we reported the influence of six exchange-correlation density functionals, including PBE, RPBE, BEEF+vdW, optB86b+vdW, SCAN, and SCAN+rVV10, on the adsorption energies, reaction energies and activation barriers of carbon hydrogenation and carbon-carbon couplings during the formation of methane and ethane over Ru(0001) and Ru(1011) surfaces. We found the calculated reaction energies are strongly dependent on exchange-correlation density functionals due to the difference in coordination number between reactants and products on surfaces. The deviation of the calculated elementary reaction energies can be accumulated to a large value for chemical reaction involving multiple steps and vary considerably with different exchange-correlation density functionals calculations. The different exchange-correlation density functionals are found to influence considerably the selectivity of Ru(0001) surface for methane, ethylene, and ethane formation determined by the adsorption energies of intermediates involved. However, the influence on the barriers of the elementary surface reactions and the structural sensitivity of Ru(0001) and Ru(1011) are modest. Our work highlights the limitation of exchange-correlation density functionals on computational catalysis and the importance of choosing a proper exchange-correlation density functional in correctly evaluating the activity and selectivity of a catalyst.