A Functionalized Heterogeneous Catalyst from Atomically Precise Pd₁Au₈ Clusters Facilitates Carbon–Carbon Bond Construction

Abstract

It has become possible to establish a connection between homogeneous and heterogeneous catalysis with atomically precise metal clusters. Due to their defined coordination geometry, in this work, atomically precise Pd1Au8(PPh3)82+ clusters are exploited to identify the crucial factor that can impact the catalytic efficiency for the Suzuki–Miyaura cross‐coupling process and further gain valuable insight into the exclusive cooperative effect of the central Pd atom and the peripheral Au atoms of the Pd1Au8(PPh3)82+ cluster on controlling the cross‐coupling reaction. Specifically, a heterogeneous catalyst, namely Pd1Au8@Resin, is designed by exchanging positively charged Pd1Au8(PPh3)82+ clusters into the porous resin, thereby not only facilitating catalyst recyclability when performed in a batch reactor, but also realizing time‐on‐stream performance for the Suzuki–Miyaura cross‐coupling reaction carried out in a fixed‐bed reactor. The integrated advantages of homogeneous complexes and heterogeneous catalysts are expected to advance the usability of atomically precise metal clusters as heterogeneous catalysts for important bond constructions in homogeneous systems.

Stability prediction of gold nanoclusters with different ligands and doped metals: deep learning and experimental tests

“…An interesting example is reported by our group on the use of PPh 3 ligand for the synthesis of Pd 1 Au 8 @Resin to realize time-on-stream performance for the Suzuki–Miyaura cross-coupling reaction carried out in a fixed-bed reactor. 60 Furthermore, Au 4 Ru 2 (PET) 8 (PPh 3 ) 2 is synthesized by the combination of PET and PPh 3 ligands, which enables photochemical N 2 reduction to NH 3 . 32…”

Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

“…The determined structural information on nanocluster catalysts imparts advantages in identifying active sites and exploring catalytic mechanisms, which can in turn guide the design and synthesis of high-performance catalysts. More notably, doping foreign metal atoms (i.e., heteroatoms) into a designated nanocluster is an effective strategy for tailoring its catalytic property through modulating the electronic properties, improving the structural robustness, and providing additional active sites for the absorption and activation of reactant molecules. − ,− Given structural characteristic of nanoclusters, the heteroatoms can be introduced into the surface of the parent homometal nanocluster, , in which they can directly act as active sites for improving the catalytic reactivity or cooperatively communicating with organic ligands to form surface multisites to promote the reactions occurring at different sites. The heterometallic atom can also replace the subsurface or kernel atom of the parent nanocluster, in which it can tune the electronic property through the electron transfer of subsurface/kernel heteroatoms to exterior metal atoms or vice versa, thereby imparting a substantial influence on the observed catalytic performance. ,,,, These researches bring about a new conceptual framework for understanding subnanometer-scale catalysis.…”

“…A typical case reported by Yamazoe et al was the [Au 8 Pd 1 (PPh 3 ) 8 ] 2+ cluster, whose stability was obviously improved by the core Pd incorporation in comparison with the counterpart [Au 9 (PPh 3 ) 8 ] 3+ cluster . Cai and co-workers further studied the potential role of the central Pd atom of the [Au 8 Pd 1 (PPh 3 ) 8 ] 2+ cluster in tuning the catalytic property. , Given that [Au 8 Pd 1 (PPh 3 ) 8 ] 2+ was positively charged, an ion-exchange strategy was utilized to intercalate the cluster into the layered montmorillonite (MMT) with counter cations between the layers to make a heterogeneous catalyst (denoted as Au 8 Pd 1 @MMT), as shown in Figure a, while the reference catalyst of the positively charged [Au 9 (PPh 3 ) 8 ] 3+ cluster was designed in the same way (short for Au 9 @MMT). The Au 8 Pd 1 @MMT catalyst exhibited better catalytic performance than the Au 9 @MMT catalyst for the hydrogenation of CO 2 performed in a fixed-bed reactor with a space velocity of 6000 mL/g/h of 2 MPa reaction gas (CO 2 :H 2 = 1:3) at 200 °C (Figure b).…”

Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters

“…Crucial to the application of atomically precise nanoclusters (NCs) is the ability to controllably modify their structural features and, in turn, their physicochemical properties. The search for new configurations is motivated by the diversity of applications, which, inter alia, includes vital renewable energy technologies , and catalysis. − Although creating novel architectures is always essential, synthetic protocols that provide NCs with incremental atomically precise changes (in nuclearity, symmetry, and surface nature) are of significant importance and often a more challenging aspect of NC chemistry. Therefore, it is paramount to understand and control these manipulations from a fundamental point of view and unlock the potential of NCs in future technologies.…”