In continuation of our previous DFT calculations on the possibility of using the earlier transition metal nitrides for catalyzing hydrogen evolution reaction, this work analyzes the (111) facets of these surfaces which are as dominant as the (100) when a polycrystalline catalyst is manufactured. Various hydrogen coverage on these surfaces is considered, the free energy diagram and overpotentials are predicted as well as the kinetics of hydrogen recombination and hydrogen evolution reaction. The outcome of this comprehensive investigation and comparison of activity between the (100) and (111) facets reveal that TaN is the most active surface in both facets with the (100) being more promising with regards to both thermodynamics and kinetics. This study suggests that for optimizing the efficiency in the experiments, surface engineering needs to be considered towards the synthesis of single-crystal structured catalysts rather than utilizing polycrystallines. All the results are also compared with the Pt (111) which is the most active hydrogen evolution catalyst.

继续我们之前关于使用早期过渡金属氮化物催化析氢反应的可能性的 DFT 计算，这项工作分析了这些表面的 (111) 面，当制造多晶催化剂时，这些面与 (100) 面一样占主导地位。考虑了这些表面上的各种氢覆盖，预测了自由能图和过电位，以及氢复合和析氢反应的动力学。(100) 和 (111) 晶面之间的综合研究和活性比较结果表明，TaN 是两个晶面中最活跃的表面，而 (100) 在热力学和动力学方面都更有前景。这项研究表明，为了优化实验效率，需要考虑表面工程来合成单晶结构的催化剂，而不是利用多晶。所有结果还与作为最活跃的析氢催化剂的 Pt (111) 进行了比较。