Ag₁₀Ti₂₈‐Oxo Cluster Containing Single‐Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties

Abstract

Supported single‐atom catalysts have been emerging as promising materials in a variety of energy catalysis applications. However, studying the role of metal–support interactions at the molecular level remains a major challenge, primarily due to the lack of precise atomic structures. In this work, by replacing the frequently used TiO2 support with its molecular analogue, titanium‐oxo cluster (TOC), we successfully produced a new kind of Ti‐O material doped with single silver sites. The as‐obtained Ag10Ti28 cluster, containing four exposed and six embedded Ag sites, is the largest noble‐metal‐doped Ti‐O cluster reported to date. Density functional theory (DFT) calculations show that the Ag10Ti28 core exhibits properties distinct from those of metallic Ag‐based materials. This Ti‐O material doped with single Ag sites presents a high ϵd and moderate CO binding capacity comparable to that of metallic Cu‐based catalysts, suggesting that it might display different catalytic performance from the common Ag‐based catalysts, for example, for CO2 reduction. These results prove that the synergism of active surface metal atoms and the Ti‐O cluster support result in unique physical properties, which might open a new direction for single‐atom‐included catalysts.

Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization

“…[13][14][15][16][17][18][19] More importantly,o rganoaluminium with highly tailorable shape,c omposition, and surface properties represents an excellent platform for significant atomistic understanding.H owever, the fast hydrolysis of aluminum salts/alkoxides usually results in the formation of ametal oxide/hydroxide.Inthis regard, it is important to slow down its hydrolysis process to promote crystallization and simultaneously enable condensation occurs.R ecently,w eh ave applied organic ligands to delay the hydrolysis process of Ti IV ions through coordination interactions (denoted as coordination delayed hydrolysis (CDH)). [20][21][22][23][24] Therefore,w eb elieve the strategy can be used to understand the hydrolysis and condensation of Al III precursors,w hich remained relatively unexplored before. Considering the similar hydrolysis process between Ti IV and Al III ions,i ti sp redictable that the CDH strategy may bring an ew blueprint for constructing atomically-precise Almolecular architectures.…”

Efficient Dynamic Computational Strategy for Heterogeneous Catalysis Based on Neural Network Potential Energy Surface: A Case Study of Temperature-Dependent Thermodynamics and Kinetics for the Chemisorbed on-surface CO

“…Actually, some limited NN PES MD simulations have appeared in the material and catalysis science. 41 The adsorption and activation of CO molecule on a transition metal surface is often a critical elementary step for the catalytic conversion of CO into the high added-value chemicals, such as Fischer-Tropsch reaction, [42][43][44] CO 2 reduction, [45][46][47] and coal to ethylene glycol, [48][49][50] etc. Given the fact that there exist many active sites on the surface, presumably with different binding affinity to the substrates, intermediates, as well as transition states, a proper description of the adsorbate adsorption and movement between different sites on surface is thus clearly important for a correct understanding of the catalytic process.…”

Lead‐Doped Titanium‐Oxo Clusters as Molecular Models of Perovskite‐Type PbTiO3 and Electron‐Transport Material in Solar Cells

“…[15][16][17][18][19] In addition, the molecular characteristics of metal-oxo clusters allow convenient chemical functionalizationt hrough metal doping and ligand decoration. [20][21][22][23][24][25][26] From as tructural pointo f view,t he constructiono fP bTiO 3 can be attributed to the introductiono fl ead ions into titaniumo xides. Therefore, if lead ions could be dopedi nto the structure of titanium-oxo clusters, the molecular structure of PbTiO 3 might be prepared.I n the past decades, considerable efforts have been devoted to this area or research and as eries of lead-doped polyoxo-titanium clusters (Pb-PTCs) have been reported by Jagner,H ubert-Pfalzgraf,S chubert, and others.…”