van IJzendoorn Bono, Albawardi Saad F, Jobbins William D, Whitehead George F S, McGrady John E, Mehta Meera
Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3QR, UK.
Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Nat Commun. 2024 Nov 19;15(1):10030. doi: 10.1038/s41467-024-54277-z.
Although not the only greenhouse gas, CO is the poster child. Unsurprisingly, therefore, there is global interest across industrial and academic research in its removal and subsequent valorisation, including to methanol and its surrogates. Although difficult to study, the heterogenous pnictogens represent one important category of catalytic materials for these conversions; their high crustal abundance and low cost offers advantages in terms of sustainability. Here, Zintl clusters based on these elements are studied as homogenous atom-precise models in CO reduction. A family of group 13 functionalized pnictogen clusters with the general formula [(RE)Pn] (E = B, Al, In; Pn = P, As) is synthesized and their catalytic competency in the reduction of CO probed. Trends in both turnover numbers and frequencies are compared across this series, and [(iBuAl)P] found to be very high-performing and recyclable. Electronic structures across the series are compared using density functional theory to provide mechanistic insights.
尽管一氧化碳并非唯一的温室气体，但它却是典型代表。因此，毫不奇怪，全球工业界和学术界都对其去除及后续增值利用感兴趣，包括转化为甲醇及其替代物。尽管研究起来颇具难度，但异质的氮族元素是这些转化反应的一类重要催化材料；它们在地壳中的丰度高且成本低，在可持续性方面具有优势。在此，基于这些元素的津特耳簇被作为均相原子精确模型用于一氧化碳还原研究。合成了一系列通式为[(RE)Pn]（E = B、Al、In；Pn = P、As）的13族功能化氮族元素簇，并探究了它们在一氧化碳还原反应中的催化能力。比较了该系列中各簇的周转数和频率趋势，发现[(iBuAl)P]表现非常出色且可循环使用。利用密度泛函理论比较了该系列的电子结构，以提供机理见解。
