Ghosh Atanu, Sagadevan Arunachalam, Murugesan Kathiravan, Nastase Stefan Adrian F, Maity Bholanath, Bodiuzzaman Mohammad, Shkurenko Aleksander, Hedhili Mohamed Nejib, Yin Jun, Mohammed Omar F, Eddaoudi Mohamed, Cavallo Luigi, Rueping Magnus, Bakr Osman M
KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
Advanced Membranes and Porous Materials Center (AMPMC), Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
Mater Horiz. 2024 May 20;11(10):2494-2505. doi: 10.1039/d4mh00098f.
Atomically precise copper nanoclusters (NCs) are an emerging class of nanomaterials for catalysis. Their versatile core-shell architecture opens the possibility of tailoring their catalytically active sites. Here, we introduce a core-shell copper nanocluster (CuNC), [Cu(SBu)Cl(PPh)H]BuSO (SBu: -butylthiol; PPh: triphenylphosphine), CuNC, with multiple accessible active sites on its shell. We show that this nanocluster is a versatile catalyst for C-heteroatom bond formation (C-O, C-N, and C-S) with several advantages over previous Cu systems. When supported, the cluster can also be reused as a heterogeneous catalyst without losing its efficiency, making it a hybrid homogeneous and heterogeneous catalyst. We elucidated the atomic-level mechanism of the catalysis using density functional theory (DFT) calculations based on the single crystal structure. We found that the cooperative action of multiple neighboring active sites is essential for the catalyst's efficiency. The calculations also revealed that oxidative addition is the rate-limiting step that is facilitated by the neighboring active sites of the CuNC, which highlights a unique advantage of nanoclusters over traditional copper catalysts. Our results demonstrate the potential of nanoclusters for enabling the rational atomically precise design and investigation of multi-site catalysts.
原子精确的铜纳米团簇（NCs）是一类新兴的用于催化的纳米材料。它们通用的核壳结构为定制其催化活性位点提供了可能性。在此，我们介绍一种核壳铜纳米团簇（CuNC），[Cu(SBu)Cl(PPh)H]BuSO（SBu：叔丁硫醇；PPh：三苯基膦），即CuNC，其壳上有多个可及的活性位点。我们表明，这种纳米团簇是用于形成碳 - 杂原子键（C - O、C - N和C - S）的通用催化剂，与先前的铜体系相比具有若干优势。负载后，该团簇还可作为多相催化剂重复使用而不损失其效率，使其成为一种兼具均相和多相性质 的混合催化剂。我们基于单晶结构，利用密度泛函理论（DFT）计算阐明了催化的原子水平机理。我们发现多个相邻活性位点的协同作用对催化剂的效率至关重要。计算还表明，氧化加成是限速步骤，而CuNC的相邻活性位点促进了这一步骤，这突出了纳米团簇相对于传统铜催化剂的独特优势。我们的结果证明了纳米团簇在实现多位点催化剂的合理原子精确设计和研究方面的潜力。
