Dataset Information

Excitonic Au4Ru2(PPh3)2(SC2H4Ph)8 cluster for light-driven dinitrogen fixation† † Electronic supplementary information (ESI) available. CCDC 1972938. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc06424a

ABSTRACT: The surface plasmon resonance of metal nanoparticles has been widely used to improve photochemical transformations by plasmon-induced charge transfer. However, it remains elusive for the molecular-like metal clusters with non-metallic or excitonic behavior to enable light harvesting including electron/hole pair production and separation. Here we report a paradigm for solar energy conversion on an atomically precise Au4Ru2 cluster supported on TiO2 with oxygen vacancies, in which the electron–hole pairs can be directly generated from the excited Au4Ru2 cluster and the TiO2 support, and the photogenerated electrons can transfer to the Ru atoms. Importantly, the Ru atoms in the Au4Ru2 cluster are capable of injecting the electrons into adsorbed N2 to activate N2 molecules. The cooperative effect in the supported Au4Ru2 catalyst efficiently boosts the photocatalytic activity for N2 fixation in comparison with homogold (Aun) clusters. A molecular-like Au4Ru2 cluster supported on TiO2 with oxygen vacancies enables light harvesting to drive the fixation of N2.

SUBMITTER: Sun Y

PROVIDER: S-EPMC8157179 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:In order to increase the understanding of the recently synthesized Au70S20(PPh3)12 cluster, we used the divide and protect concept and superatom network model (SAN) to study the electronic and geometric of the cluster. According to the experimental coordinates of the cluster, the study of Au70S20(PPh3)12 cluster was carried out using density functional theory calculations. Based on the superatom complex (SAC) model, the number of the valence electrons of the cluster is 30. It is not the number of valence electrons satisfied for a magic cluster. According to the concept of divide and protect, Au70S20(PPh3)12 cluster can be viewed as Au-core protected by various staple motifs. On the basis of SAN model, the Au-core is composed of a union of 2e-superatoms, and 2e-superatoms can be Au3, Au4, Au5, or Au6. Au70S20(PPh3)12 cluster should contain fifteen 2e-superatoms on the basis of SAN model. On analyzing the chemical bonding features of Au70S20(PPh3)12, we showed that the electronic structure of it has a network of fifteen 2e-superatoms, abbreviated as 15 × 2e SAN. On the basis of the divide and protect concept, Au70S20(PPh3)12 cluster can be viewed as Au4616+[Au12(µ3-S)108-]2[PPh3]12. The Au4616+ core is composed of one Au2212+ innermost core and ten surrounding 2e-Au4 superatoms. The Au2212+ innermost core can either be viewed as a network of five 2e-Au6 superatoms, or be considered as a 10e-superatomic molecule. This new segmentation method can properly explain the structure and stability of Au70S20(PPh3)12 cluster. A novel extended staple motif [Au12(µ3-S)10]8- was discovered, which is a half-cage with ten µ3-S units and six teeth. The six teeth staple motif enriches the family of staple motifs in ligand-protected Au clusters. Au70S20(PPh3)12 cluster derives its stability from SAN model and aurophilic interactions. Inspired by the half-cage motif, we design three core-in-cage clusters with cage staple motifs, Cu6@Au12(?3-S)8, Ag6@Au12(?3-S)8 and Au6@Au12(?3-S)8, which exhibit high thermostability and may be synthesized in future.

Dataset Information

Excitonic Au4Ru2(PPh3)2(SC2H4Ph)8 cluster for light-driven dinitrogen fixation† † Electronic supplementary information (ESI) available. CCDC 1972938. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc06424a

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets