Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant

Abstract

Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag12(S t Bu)6(CF3COO)3(TPyP)] n (denoted as Ag12TPyP) composed of a Ag12 chalcogenolate cluster core stabilized by porphyrinic ligands. Ag12TPyP showed superior sulfur mustard simulant (2-chloroethyl ethyl sulfide, CEES) degradation efficiency and achieved a half lifetime (t 1/2) of 1.5 min with 100% selectivity. The experimental results demonstrated that synergistic effects between the silver cluster and photosensitizer ligand promote the efficiency of the generation of singlet oxygen (1O2), which accelerates the decontamination rate. Additionally, benefiting from strong affinity between the silver cluster and CEES, Ag12TPyP exhibits a CEES uptake of 74.2 mg g–1. This work demonstrates that SCAMs offer a new route to the rational design of novel materials for the detoxification of mustard gas.

Ambient Chemical Fixation of CO2 Using a Robust Ag27 Cluster‐Based Two‐Dimensional Metal–Organic Framework

“…entries 15,16). Additionally,t he turnover number (TON) study for this model reaction catalyzed by Ag27-MOF revealed the value is up to 1333, which is even higher than that for presently the most efficient heterogeneous catalyst TOS-Ag4 (930).…”

Molecular reactivity of thiolate-protected noble metal nanoclusters: synthesis, self-assembly, and applications

“…It should be noted that a similar solvent-or gasmolecule-sensitive luminescence has been widely recorded in Ag(I) NC-based metal-organic frameworks (MOFs), which are usually bridged by N-containing heterocyclic cross-linkers. [219][220][221] The detection of large biomolecules (e.g., proteins) is another important topic in the sensor development of metal NCs. This detection largely depends on the specic bio-recognition and bio-conjugation interactions.…”

One-, Two-, and Three-Dimensional Self-Assembly of Atomically Precise Metal Nanoclusters

“…Recently, this group also formed a 2D CS with Ag 12 (S t Bu) 6 (CF 3 COO) 3 NCs as nodes by using 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP, Scheme 2 (11)) as a linker ( Figure 24 A) [ 171 ]. TPyP has a photosensitizing effect.…”

“…( B ) Schematic illustration of the capture and photodetoxification of CEES by Ag 12 (S- t Bu) 6 (CF 3 COO) 3 (TPyP). Reproduced with permission from Reference [ 171 ]. Copyright 2019 American Chemical Society.…”