Two novel donor–acceptor hybrid heterostructures with enhanced visible-light photocatalytic properties

Abstract

The ternary combination of metal cations, CuI and viologen based carboxylate leads to two donor-acceptor hybrid heterostructures with novel cuprous iodide clusters and narrow energy gaps. Thanks to the facilitated electron transfers between both donor and acceptor components, these unique hybrids exhibit enhanced photocatalytic degradation activities towards organic dyes under visible light irradiation in comparison with those of bulk CuI and viologen semiconductors.

Encapsulating Halometallates into 3-D Lanthanide-Viologen Frameworks: Controllable Emissions, Reversible Thermochromism, Photocurrent Responses, and Electrical Bistability Behaviors

“…Clearly, the 0-D iodobismuthate clusters in cationic frameworks are beneficial for the charge transfer compared with the 1-D lead halide chain-containing composites, which have been observed in relative compounds . Finally, compared with bulk PbI 2 and BiI 3 , obvious red-shifts of UV–vis absorptions of 1 – 4 have occurred, which could be ascribed to the intermolecular charge transfer (CT) between lead/bismuth halide anions and the Ln-bpdo MOF. , …”

“…The study about the crystal structures and properties of halometallate@MOF composites might give some hints about this system. So far, limited reports about halometallate@MOF composites have been documented. − …”

“…Lead­(II) and bismuth­(III) halides are the most frequently observed halometallate-base perovskites, whose structural mofits range from 0-D clusters to 3-D networks based on corner-, edge- or face-sharing of MI 6 octahedra. − As far as the choice of host MOF, photoresponsive lanthanide-MOFs are good candidates because of their high sensitivity for external stimuli, − and their functions can be alerted after the encapsulation of halometallates . For example, some electron-deficient organic molecules were incorporated with halometallates to construct donor–acceptor hybrid materials, in which some interesting phenomena such as optical red-shift and effective photo-induced carrier separation can be achieved. − The encapsulation electron-rich halometallates with electron-deficient cationic frameworks will lead to the formation of novel donor–acceptor hybrid materials, which is still in its infancy due to the cation/anion competition. − ,− , Besides, novel photo/electrical properties such as photochromism and photomagnetism have been frequently observed in this kind of hybrid, − which also hint their application in electrical bistability devices . Viologen-like molecules are good photoresponsive species, and more recently, metalloviologen with viologen coordinated to a second metal was emerged because their radical species can be controlled by the metallic centers .…”

Hierarchical Co3(PO4)2/CuI/g-CnH2n–2 S-Scheme Heterojunction for Efficient Photocatalytic Hydrogen Evolution

“…Therefore, it is very important to select a substrate that can act as a catalyst and can be easily removed. Halide-based cuprous materials have many applications in many fields such as photocatalysis and semiconductor optics. , CuI is a wide-band-gap semiconductor in halide-based cuprous materials . CuI has higher hole mobility due to copper vacancies and interface defect bands .…”

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 .…”