Tuning photoelectron dynamic behavior of thiolate-protected MAu₂₄ nanoclusters via heteroatom substitution

Abstract

Heteroatom substitution of gold nanoclusters enables precise tuning of their physicochemical properties at single-atom level, which has importance impact on the applications related to excited states including photovoltaic, photocatalysis and...

Correlating Heteroatoms Doping, Electronic Structures, and Photocatalytic Activities of Single‐Atom‐Doped Ag25(SR)18 Nanoclusters

“…The participation of Ag(sp) and M(sp) orbitals in the PtAg 24 NCs is obviously less pronounced than that in PdAg 24 and AuAg 24 NCs, this result is in accordance with the relatively shorter M-Ag bond lengths among the doped NCs (Table 1). [46] A similar phenomenon could also be found in the LUMOs of the NCs, the contribution of Pt(5d) is less pronounced than the other two doped NCs, which indicates weaker d-d hybridization between Pt and the Ag atoms in PtAg 24 NCs. Ag 25 , PdAg 24 , and AuAg 24 exhibit similar band structures with closed HOMO and LUMO positions.…”

“…Moreover, the LUMO + 1 orbital of Ag 25 NCs exhibits diffuse superatomic d‐type orbitals, where strong hybridization would occur among the interfacial atoms and thus facilitate the transfer of photoinduced electrons in space, further contributing to the electron–hole pairs separation. [ 46 ] Therefore, it could be concluded that the improved charge separation in Ag 25 /TiO 2 leads to greatly enhanced photocatalytic activities compared to the bare TiO 2 .…”

“…There are mainly three excited-state species included in MAg 24 NCs: 1) the higher excited-states; 2) surface-states; 3) a state consisting of low-lying LUMOs centered on the metal core. [46,47] According to the energy evolution and the above-mentioned relaxation process, the MAg 24 NCs could be readily sorted into two types-type A (PtAg 24 ) and type B (Ag 25 , PdAg 24 , and AuAg 24 ), where the orbital coupling is stronger between LUMO þ 1 and the other high-lying LUMOs in type B. Compared to type B NCs, type A NCs present narrower HOMO-LUMO gaps and wider energy gap between LUMO þ 1 and the other high-lying LUMO orbitals, which leads to slower electron relaxation from high exited-states to low-lying LUMO orbitals.…”

Recent developments in the investigation of driving forces for transforming coinage metal nanoclusters

“…[11][12][13][14][15][16][17][18] Based on the new knowledge acquired, researchers can customize nanomaterials more rationally, and cluster-based nanomaterials will find new opportunities in a wide range of applications, such as catalysis, chemical sensing, biological imaging, chirality, two-photon absorption, energy storage, and nanoelectronics. [19][20][21][22][23][24][25][26][27][28][29] Nanoresearch is designed to employ nanoparticles/nanoclusters or their aggregates as complex entities to realize certain functions. Bulk metals are chemically inert and antioxidized, while metal nanoclusters such as Au nanoclusters, 30,31 Ag nanoclusters, [32][33][34][35] and alloy nanoclusters [36][37][38] are relatively unstable and chemically reactive.…”

Photoinduced Carrier Transfer Dynamics in MoSSe/WSSe Vertical and Lateral Heterostructures

“…Despite these preliminary achievements, the fundamental understanding of these fascinating Janus heterostructures, especially for the underlying mechanisms of excited-carrier relaxation and recombination, remains unknown. In recent years, based on time-dependent ab initio nonadiabatic molecular dynamics (NAMD), , it has become possible to achieve valuable insights into the photogenerated carrier dynamics in many structures, including 2D monolayer semiconductors, heterostructure interfaces, and halide perovskites. − ,− Inspired by this, we chose Janus TMDs heterostructures including vertical and lateral heterostructures formed by MoSSe and WSSe monolayers (see Figure ), as templates to explore the photoinduced excited-dynamic behavior of Janus heterostructures. The photoinduced carrier transfer pathways, hot carrier relaxation, and electron–hole recombination dynamics at MoSSe/WSSe interfaces reveal important insights that could provide a detailed atomistic understanding of ultrafast charge carrier dynamics, proving integral for the optimal design of high-performance heterostructures for nanoelectronics, optoelectronics, and photocatalytic devices in the future.…”