Novel 3D Semiconducting Open‐Frameworks based on Cuprous Bromides with Visible Light Driven Photocatalytic Properties

Abstract

Visible light driven photocatalysts based on crystalline microporous metal halogenides received much less attention compared with dense or composite oxide semiconductors. Using the well-known photosensitive transition metal-complexes [TM(2,2-bipy) ] (TM=Fe, Co, Ni, Ru) as templates, a special three-dimensional (3D) metal halogenide framework of [TM(2,2-bipy) ]Cu Br was designed with [Cu Br ] cluster as 4-connected node. These microporous materials feature narrow band gaps and stable visible light driven photocatalytic properties including water reduction to provide H and photodegradation of organic pollutants. The study of electronic band structure shows that the TM complexes effectively prevent the recombination of photo-induced electron/hole pairs leading to excellent photocatalytic activity and photochemical stability. This work represents the first 3D microporous metal halogenides used as visible light driven photocatalyst to provide hydrogen energy.

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( COH) and the superoxide (O 2 C À )s cavengers, respectively. [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).…”

“…It is still ac hallenge to obtain 3D metal-halide-based framework structures. [42,43] Recently,o ur research focusingo nt he systematic exploration of halometallates using the conjugated polypyridine derivatives as SDAs has made some progress. [44][45][46][47] These previous study indicated that N-alkylation conjugated polypyridinec ations as SDAs ande lectron acceptors can effectively decrease the band gap and accordingly increaset he absorption of the visible light of the resultant materials.…”

“…Herein, Ammonium oxalate (AO), tert-butyl alcohol( TBA) and Benzoquinone (BQ) were chosen as hole (h + ), hydroxyl radical( COH) and the superoxide (O 2 C À )s cavengers, respectively. [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.…”

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

“…To get an in-depth understanding the catalytic property and study the possible mechanism, the radical trappinge xperimentsw ere carried out to identify the main reactive species responsible for the degradation.A mmonium oxalate (AO), Benzoquinone (BQ) and tertbutyl alcohol (TBA) weres elected as scavengers for hole (h + ), the superoxide (O 2 C À )a nd hydroxyl radical (COH), respectively. [51,52,68,69] Obviously,f or the MO solutions, the respective inhibition rates of AO, BQ, and TBAa ss cavengers are 95.5 %, 97.1 %a nd 95.4 %, indicating that h + ,O 2 C À and COH all play very important roles for the degradation of MO. For the MV solutions, the inhibition rates of AO, BQ, and TBA as scavengers are 90.0 %, 60.6 %a nd 80.0 %, suggesting that O 2 C À was more activet han h + and COH in decomposition of MV.T of urther study the relationship between the structure and optical property,e lectronic structure calculations were performed based on density functional theory.…”

A Polypyridyl‐Based Layered Complex as Dual‐Functional Co‐catalyst for Photo‐Driven Organic Dyes Degradation and Water Splitting

“…Constructed from diversely π‐delocalized organic ligands and inorganic central metal atoms or metal clusters, coordination polymers (CPs) with semi‐conductive properties have been becoming one of the effective photocatalysts towards the degradation of organic pollutants and water splitting under irradiation of UV and/or visible light . Up to date, lots of Zn II ‐, Cd II ‐, Co II ‐, Ni II ‐, Cu I/II ‐, and Pb II ‐based CPs with bulky π‐conjugated ligands, such as porphyrin‐like subunits, 4,4′‐bis(2‐methylbenzimidazol‐1‐ylmethyl)biphenyl, tetra(3‐imidazoylphenyl)ethylene, 3,5‐diphenyltriazolate, carboxyl derivatives of 1,10‐phenanthrolines, tetrakis(4‐pyridyl)cyclobutane, naphthalenedicarboxylate, bis‐pyridyl‐bis‐amide, and viologen derivatives have been subsequently synthesized and used to degrade Rhodamine B (RhB), methyl orange (MO), methyl blue (MB), methylene blue (MLB), congo red, as well as crystal violet. Remarkably, a microporous 3,5‐diphenyltriazolate (3,5‐Ph 2 ‐tz)‐based cationic framework with a formula of {Cu 8 (3,5‐Ph 2 ‐tz) 6 (HSO 4 ) 2 · (H 2 O) 5.5 } can completely decompose the MLB, MO, RhB, and MB within half an hour resulting from the high efficiency in generating the most active species of • OH .…”