Novel Three-Dimensional Semiconducting Materials Based on Hybrid d¹⁰ Transition Metal Halogenides as Visible Light-Driven Photocatalysts

Abstract

The development of new visible light-driven photocatalysts based on semiconducting materials remains a greatly interesting and challenging task for the purpose of solving the energy crisis and environmental issues. By using photosensitive [(Me)-2,2'-bipy] (1,1'-dimethyl-2,2'-bipyridinium) cation as template, we synthesized one new type of inorganic-organic hybrid cuprous and silver halogenides of [(Me)-2,2'-bipy]MX (M = Cu, Ag, X = Br, I). The compounds feature a three-dimensional anionic [MX] network composed of a one-dimensional [MX] chain based on MX tetrahedral units. The photosensitization of organic cationic templates results in narrow band gaps of hybrid compounds (1.66-2.06 eV), which feature stable visible light-driven photodegradation activities for organic pollutants. A detailed study of the photocatalytic mechanism, including the photoelectric response, photoluminescence spectra, and theoretical calculations, shows that the organic cationic template effectively inhibits the recombination of photoinduced electron-hole pairs leading to excellent photocatalytic activities and photochemical stabilities.

A 3D Iodoplumbate Semiconducting Open Framework with Visible‐light‐induced Photocatalytic Performance

“…Herein, Ammonium oxalate (AO), tert ‐butyl alcohol (TBA) and Benzoquinone (BQ) were chosen as hole (h + ), hydroxyl radical ( . OH) and the superoxide (O 2 .− ) scavengers, respectively . The AO and BQ have more obvious influence on the photocatalytic activity, which indicating that h + and O 2 .− are the main active species in the photodegradation process (Figure c).…”

“…[16,43,[52][53][54][55][56][57] The AO and BQ have more obviousi nfluence on the photocatalytic activity,w hich indicating that h + and O 2 C À are the main active speciesint he photodegradation process (Figure 3c).Compound 1,a sw ell as the reportedh ybrid halometallates containing conjugatedo rganic cations, such as [N-ethyl-4-cyanopyridinium][Ag 2 I 3 ], [9] [N-benzylpyridinium] 2 [Cu 6 I 8 ], [58] [(Me) 2 -2,2'-bipy][Cu 8 I 10 ], [55] [Ni(2,2'-bipy)(THF) 2 (H 2 O) 2 ](Ag 10 I 12 )·2DMF (THF = tetrahydrofuran, DMF = N,N'-dimethylformamide, 2,2'bipy = 2,2'-bipyridine), [59] and [Pb 5 Cu 2 I 16 ][(Me) 2 (4-TPT)] 2 (4-TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), [45] possess narrow band gaps of 1.35-2.74 eV.R eportedly, on the basis of electronic band structuralc alculation, the conductionb ands of most conjugated organic cations directed halometallates are primarily occupied by the conjugatedo rganic moieties, while the valence bandsa re mainly made up by anionic inorganic networks. [46,55] The contribution of conjugated organic moieties to conduction bands decreasing the energy position and leading to the small band gaps. Therefore, it is speculated that the [Me 2 (bpanth)] 2 + moietiesg reatly contribute to the conduction band, decreasing the energy position and resulting in an arrow band gap, accordingly increasing visible-light absorption and making 1 a good visible-light driven photocatalyst.Additionally,t oc onfirm the thermostability of the solid samples, the TG study was performed ( Figure S5).…”

A new two-dimensional CoII coordination polymer based on bis[4-(2-methyl-1H-imidazol-1-yl)phenyl] ether and biphenyl-4,4′-diyldicarboxylic acid: synthesis, crystal structure and photocatalytic degradation activity

“…while the HOMO strongly demands one electron to return to its stable state (Yue et al, 2017). Therefore, electrons are captured from water molecules to produce OH active species (hydroxyl radicals), which can destroy the organic dye efficiently to complete the photocatalysis process (Jennifer et al, 2017;Wu et al, 2017).…”

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

“…For the efficient use of solar energy, the exploration of photocatalysts that is sensitive to visible‐light is of great significance. Metal halide‐based hybrids have attracted considerable attention due to their distinctive photoelectric properties . Particularly, the good performance in semiconducting properties make halides ideal candidates as efficient photocatalysts.…”

“…Lei and Yue et al. systematically investigated halogenides in the presence of transition metal‐complexes, which display efficient photocatalytic properties . Zhang, Fu, and co‐workers.…”