Efremov Vladimir, Choi Minji, Choi Myeongjin, Yoo Jong Suk
Department of Chemical Engineering, University of Seoul, Seoul, 02504, Republic of Korea.
Center for Innovative Chemical Processes, Institute of Engineering, University of Seoul, Seoul, 02504, Republic of Korea.
ChemSusChem. 2025 Apr 14;18(8):e202401620. doi: 10.1002/cssc.202401620. Epub 2024 Dec 10.
Density functional theory calculations are employed to investigate the effects of various metal dopants on thiolates-protected transition metal nanoclusters (NCs) for CO reduction, focusing on deviations from the linear scaling relation between COOH* and CO* for high CO selectivity. We first explore the most favorable positions for different dopants in several M (M=parent metal) NCs and assess the potential for ligand removal under reducing conditions. Furthermore, we construct an activity volcano for CO production in DM (D=dopant) NCs, revealing that NCs composed of coinage parent metals with group 12 metal dopants exhibit the most significant deviation from the scaling relation. This behavior is attributed to the tendency of these NCs to bind COOH* in a bidentate form, which stabilizes the O atom of COOH* through interactions with the oxyphilic dopants. As a result, several group 12 metal doped coinage metal NCs are identified as new promising candidates for syngas production due to their high activity towards both CO and H production.
采用密度泛函理论计算来研究各种金属掺杂剂对用于CO还原的硫醇盐保护的过渡金属纳米团簇（NCs）的影响，重点关注高CO选择性下COOH和CO之间线性标度关系的偏差。我们首先探索了几种M（M =母体金属）NCs中不同掺杂剂的最有利位置，并评估了还原条件下配体去除的可能性。此外，我们构建了DM（D =掺杂剂）NCs中CO生成的活性火山图，发现由第12族金属掺杂的货币金属母体组成的NCs与标度关系的偏差最为显著。这种行为归因于这些NCs以双齿形式结合COOH的倾向，通过与亲氧掺杂剂的相互作用稳定了COOH的O原子。因此，几种第12族金属掺杂的货币金属NCs因其对CO和H生成的高活性而被确定为合成气生产的新的有前途的候选物。
