RESUMO
Detection of oxygen though color change is highly desirable for rapid qualitative analysis like the case of pH test papers. This work demonstrates 3O2-assisted photoinduced color change of a new photochromic coordination compound [Zn(4-aminopyridine)2Cl2] (ZnaPyCl), which represents the first photochromic compound with a selective 3O2 detection ability. The compound underwent photoinduced intraligand charge separation and formed a stable diradical-like triplet species in the solid state or in frozen solution, accompanied by conversion of triplet oxygen to singlet oxygen.
RESUMO
Photoresponse ranges of commercially prevailing photoelectric semiconductors, typically Si and InGaAs, are far from fully covering the whole solar spectrum (â¼295-2500 nm), resulting in insufficient solar energy conversion or narrow wave bands for photoelectric detection. Recent studies have shown that infinite π-aggregation of viologen radicals can provide semiconductors with a photoelectric response range covering the solar spectrum. However, controlled assembly of an infinite π-aggregate is still a great challenge in material design. Through directional self-assembly of electron-transfer photoactive polycyclic ligands, two crystalline inorganic-organic hybrid photochromic viologen-based bismuth halide semiconductors, ((Me)3pytpy)[BiCl6]·2H2O [1; (Me)3pytpy = N,N',Nâ³-trimethyl-2,4,6-tris(4-pyridyl)pyridine] and ((Me)3pytpy)[Bi2Cl9]·H2O (2), have been synthesized. They represent the first series of pytpy-based photochromic compounds. After photoinduced coloration, the conductivities of both 1 and 2 increased. The radical products have electron absorption bands in the range of 200-1600 nm, exceeding that of Si. Both the conductivity and the photocurrent intensity of 2 are stronger than those of 1, due to better planarity, tighter π-stacking, and higher degrees of overlap of ((Me)3pytpy)3+ cations. This study not only provides a new design idea for synthesizing radical-based multispectral photoelectric semiconductors but also enriches the family of electron-transfer photochromic compounds.
RESUMO
The effects of strong interactions between Ti and ceria on the structures of Ti/CeO2(111) are systematically investigated by density functional theory calculation. To our best knowledge, the adsorption energy of a Ti atom at the hollow site of CeO2 is the highest value (-7.99 eV) reported in the literature compared with those of Au (-0.88--1.26 eV), Ag (-1.42 eV), Cu (-2.69 eV), Pd (-1.75 eV), Pt (-2.62 eV) and Sn (-3.68 eV). It is very interesting to find that Ti adatoms disperse at the hollow site of CeO2(111) to form surface TiOx species, instead of aggregating to form Ti metal clusters for the Ti-CeO2 interactions that are much stronger than those of Ti-Ti ones. Ti adatoms are completely oxidized to Ti4+ ions if they are monatomically dispersed on the next near hollow sites of CeO2(111) (xTi-NN-hollow); while Ti3+ ions are observed when they locate at the near hollow sites (xTi-N-hollow). Due to the electronic repulsive effects among Ti3+ ions, the adsorption energies of xTi-N-hollow are slightly weaker than those of xTi-NN-hollow. Simultaneously, the existence of unstable Ti3+ ions on xTi-N-hollow also leads to the restructuring of xTi-N-hollow by surface O atoms of ceria transferring to the top of Ti3+ ions, or oxidation by O2 adsorption and dissociation. Both processes improve the stability of the xTi/CeO2 system by Ti3+ oxidation. Correspondingly, surface TiO2-like species form. This work sheds light into the structures of metal/CeO2 catalysts with strong interactions between the metal and the ceria support.
RESUMO
A new design strategy through the synergy of Mo(vi)-Mo(v) intervalence charge transfer and π(radical)-π(radical/cation) interactions is proposed to obtain semiconductors with photoresponsive ranges covering the whole UV-SWIR (ultraviolet-shortwave near-infrared; ca. 250-3000 nm) region. With this strategy, a viologen-based molybdate semiconductor with a UV-SWIR photoresponsive range was obtained through UV/X-ray irradiation or thermal annealing. The thermally annealed semiconductor has the highest conversion and the best photocurrent response in the range of 355-2400 nm.