Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance

Abstract

Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu 14 cba, Poly-Cu 6 Au 6 cbz and Poly-Cu 6 Ag 4 cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and longterm recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu 14 cba was evaluated as an electrocatalyst for reducing nitrate (NO 3 À ) to ammonia (NH 3 ), which exhibited � 4-fold NH 3 yield rate and � 2-fold Faraday efficiency enhancement compared to that of Cu 14 cba with good durability. Similarly, Poly-Cu 6 Au 6 cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.

Triple-Helical Self-Assembly of Atomically Precise Nanoclusters

“…This packing allowed both the Au 1 S 2 motifs and the S 1 –Au 1 –S 1 unit in the kernels to spiral along the a -axis to form the triple-helical linear structure. Of note, it was observed that other alkynyl-protected Au 6 Cu 6 nanoclusters that lacked intercluster interactions (with only some C–H···π interactions) did not assemble into polymer chains in the crystal lattice (Figure S12), , confirming that the abundant intermolecular interactions between Au 6 Cu 6 (4-MeOBT) 12 nanoclusters played a significant role in its assembly into a triple-helical structure.…”

“…Specifically, as shown in Figure 3A,B, the presence of π−π unit in the kernels to spiral along the a-axis to form the triplehelical linear structure. Of note, it was observed that other alkynyl-protected Au 6 Cu 6 nanoclusters that lacked intercluster interactions (with only some C−H•••π interactions) did not assemble into polymer chains in the crystal lattice (Figure S12), 44,45 S2), indicating that the self-assembly of Au 6 Cu 6 (4-MeOBT) 12 nanoclusters was most thermodynamically favorable. Moreover, Figure 3D shows that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels and the HOMO−LUMO energy gap of the [Au 6 Cu 6 (4-MeOBT) 12 ] 2 dimer were similar to those of the Au 6 Cu 6 (4-MeOBT) 12 monomer, but the distributions of these frontier molecular orbitals (MOs) were different.…”

Asymmetrically Doping a Platinum Atom into a Au38 Nanocluster for Changing the Electron Configuration and Reactivity in Electrocatalysis

“…Both geometric and electronic structures play crucial roles in determining the catalytic properties of nanoparticles [1–14] . However, the two factors are often convoluted, and it is thereby difficult to precisely study the contribution of one factor to the overall catalytic performance at a time.…”

Iron Nanoparticles Protected by Chainmail‐structured Graphene for Durable Electrocatalytic Nitrate Reduction to Nitrogen

“…This is due to the presence of the nitrate reduction reaction and is consistent with previous findings regarding the NO 3 RR of metal-based cathodes. [20] What's more, electrochemical impedance spectroscopy (EIS) shows that Fe@Gnc has a lower resistance than pure graphene, Fe and Fe/G electrocatalytic materials, implying that Fe@Gnc has a higher charge transfer capability (Figure S20b). The growth in the size of Fe nanoparticles in Fe/G leads to a significant increase in the resistance of charge diffusion to reach the active site.…”