Silver(I)‐Based Complexes Used as High‐Performance Photocatalysts for the Degradation of Organic Dyes in Water

Abstract

Coordination compounds have been used as efficient photocatalysts for the degradation of pollutive organic dyes due to their semiconductive nature and diverse structures that may be adjusted by the central metals and ligands. Herein we prepared N′,N′‐2,2‐tetrakis(diphenylphosphanylmethyl)thiocarbohydrazide (tpptch) and utilized it to react with AgX (X = Br, I, CN) in different solvent systems. These reactions afforded two dicationic tetranuclear complexes {[Ag4X2(tpptch)2]X2 (1: X = Br; 2: X = I)}, one 1D coordination polymer [Ag2I2(tpptch)]n (3) and one neutral tetranuclear complex [Ag4(CN)2(dptpptch)2] (4, dptpptch is the anion of deprotonated tpptch after an enolization). In 1–4, the S atom of the C=S group binds at one AgI atom in 1 or 2, or remains uncoordinated in 3, or connects with two AgI atoms after transforming into the C–S– end in 4. The catalytic activities of these compounds toward the photodegradation of nine organic dyes under UV irradiation were examined, among which 3 showed the best performance. Their anodic photocurrent responses and HOMO–LUMO energy gaps derived from density functional theory (DFT) calculations correlated well with the photocatalytic activities. The different bindings of the S end of tpptch and dptpptch ligands with AgI centers in 2–4 may be contributed to the discrepancy in their catalytic activities. The results provide a ready route to design and prepare highly stable and efficient photocatalysts for treating dye‐polluted water.

Solution-State Studies, X-ray Structure Determination and Luminescence Properties of an Ag(I) Heteroleptic Complex Containing 2,9-Bis(styryl)-1,10-phenanthroline Derivative and Triphenylphosphine

“…The broad spectral pattern ranging from 240 to 480 nm is commonly found in such complexes. Electronic transitions associated with ligand-centered (LC) π → π* and n → π* transitions are expected within the 240-350 nm range, while lower-energy bands (above 350 nm) can be ascribed to LLCT and MLCT transitions [46][47][48].…”

A Novel Tetranuclear Silver Compound with bis(3,5-dimethylpyrazol-1-yl)acetate: a Simple Synthesis Yielding Complex Crystal Structure

“…16,17 Furthermore, the silver(I) complexes have found different applications in material science for their structural diversity originating from a d 10 electron configuration which allows the formation of different coordination geometries and represent a foundation for construction of supramolecular frameworks. 18,19,20 Herein we report the crystal structure of first silver coordination compound with bdmpza ligands. The compound was also characterized by Hirshfeld surface analysis, coupled thermogravimetric-mass spectrometry analysis and infrared spectroscopy.…”

1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study

“…These properties include antibacterial activity, , gas sensing, proton conductivity, high capacitance and good cycling ability, , and chemical sensing. , Moreover, Ag-CPs might play a significant role in environmental remediation, − as they have been tailored to achieve a particular mechanism of oxoanion exchange to maximize their effectiveness . Most recently, there have been several reports on Ag-CPs manifesting excellent catalytic and photocatalytic properties. − Environmentally friendly and recyclable Ag-CP with 9,10-anthraquinone-1,4-dicarboxylate acid catalyzed the reaction of the visible-light-driven aerobic oxidation of alkynes into 1,2-diketones under ambient conditions . 1D Ag-CPs with N ′, N ′-2,2-tetrakis­(diphenylphosphanylmethyl)­thiocarbohydrazide showed exceptional performance as a photocatalyst for the degradation of organic dyes in water, while generating higher photocurrent response in comparison to molecular complexes with the same ligand .…”

“…Most recently, there have been several reports on Ag-CPs manifesting excellent catalytic and photocatalytic properties. − Environmentally friendly and recyclable Ag-CP with 9,10-anthraquinone-1,4-dicarboxylate acid catalyzed the reaction of the visible-light-driven aerobic oxidation of alkynes into 1,2-diketones under ambient conditions . 1D Ag-CPs with N ′, N ′-2,2-tetrakis­(diphenylphosphanylmethyl)­thiocarbohydrazide showed exceptional performance as a photocatalyst for the degradation of organic dyes in water, while generating higher photocurrent response in comparison to molecular complexes with the same ligand . Nanomicrostructured Ag-CPs offer performance at a level competitive with known semiconductors in photocatalytic water splitting and the degradation of organic pollutants and dyes .…”

“…6 1 1D Ag-CPs with N′,N′-2,2-tetrakis-(diphenylphosphanylmethyl)thiocarbohydrazide showed exceptional performance as a photocatalyst for the degradation of organic dyes in water, while generating higher photocurrent response in comparison to molecular complexes with the same ligand. 62 Nanomicrostructured Ag-CPs offer performance at a level competitive with known semiconductors in photocatalytic water splitting and the degradation of organic pollutants and dyes. 63 They exhibit a highly reactive valence band potential and can be readily recycled, maintaining high activity after four uses.…”