Interrupted Chalcogenide‐Based Zeolite‐Analogue Semiconductor: Atomically Precise Doping for Tunable Electro‐/Photoelectrochemical Properties

Abstract

Incorporation of semiconductor property into zeolite materials is a plausible approach to graft oxide zeolites with multifunctionality in which both electronic/optoelectronic functions and high porosity are integrated. However, creating such semiconductor zeolites, especially the ones with controllable function regulation still remains as a great synthetic challenge over the years. Hereby, we reported the first case of an interrupted chalcogenide-based zeolite-analog semiconductor with an entirely new boracite-related framework and specific sites at the interrupted section. The semiconducting nature and band structure of this open-framework n-type semiconductor material were characterized with solid-state UV/Vis diffuse reflectance spectroscopy and Mott-Schottky measurements. More importantly, the In-Se chalcogenide zeolite analog was for the first time explored as an effective electrocatalyst for the oxygen reduction reaction (ORR). The specific indium sites served as active centers and proved to be responsible for a superior ORR activity. Meanwhile, these specific sites could be precisely replaced by bismuth(III) ions, leading to facile manipulation in their electro-/photoelectrochemical properties. Such atomically precise doping successfully implemented at the semiconductor zeolite material with specifically interrupted sites presents a very promising route for accurately regulating electronic structure and photoelectrical properties of other open-framework semiconductor materials.

Supramolecular Organization in Confined Nanospaces

“…The material was then selectively doped with bismuth at the interruption sites, thus allowing for an atomically precise fine tuning of its electronic structure . In spite of the synthetic challenges posed by the fabrication of chalcogenide frameworks, this route seems thus worth pursuing – not only because the incorporation of semiconductor property into zeolite materials has proved to be possible but also because the electronic properties of these materials are tunable from metal to insulator by chemical design, as predicted by a recent modeling study . Furthermore, beside their intrinsic relevance as transparent nanoporous semiconductors, these zeolite frameworks could also open totally new application prospects to the confinement of quantum dots, and chromophores (Figure ) .…”

“…Such semiconducting zeolite behaved as an effective catalyst for the oxygen reduction reaction, with the In interrupted sites functioning as active centers. The material was then selectively doped with bismuth at the interruption sites, thus allowing for an atomically precise fine tuning of its electronic structure . In spite of the synthetic challenges posed by the fabrication of chalcogenide frameworks, this route seems thus worth pursuing – not only because the incorporation of semiconductor property into zeolite materials has proved to be possible but also because the electronic properties of these materials are tunable from metal to insulator by chemical design, as predicted by a recent modeling study .…”

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

“…The positive slope of the linear region on the MS plot, measured at frequency of 1000 Hz, confirms sample 1 to be a n‐type semiconductor, and the flat band potential ( E fb ) is approximately −0.01 eV versus the Normal Hydrogen Electrode (NHE) (Figure b). It is generally accepted that the flat band potential of a n‐type semiconductor equals its Fermi level and the CB edge of such n‐type semiconductor is more negative by about 0.10 V than E fb . In this way, the CB of compound 1 can be approximately estimated to be −0.11 eV and the VB potential should be 1.59 eV combining with the measured energy band gap ( E bg ) from the UV/Vis diffuse reflectance spectrum.…”

“…2017, 23,14547 -14553 www.chemeurj.org semiconductor is more negative by about 0.10 Vt han E fb . [17] In this way,the CB of compound 1 can be approximately estimated to be À0.11eVand the VB potential shouldbe1.59 eV combining with the measured energy band gap (E bg )f rom the UV/ Vis diffuse reflectance spectrum.O bviously,s ample 1 has a suitable energy potential with which to facilitate the transfer of the photo-excited carriers and photocatalytic H 2 production (0 eV vs NHE) throughout the process of photocatalytic reaction.…”

Improved in Situ Synthesis of Heterostructured 2D/2D BiOCl/g-C3N4 with Enhanced Dye Photodegradation under Visible-Light Illumination

“…Nevertheless, the generation of the heterostructure could not change the valence state of Bi, and the distance between two splitting peaks remained approximately 5.3 eV indicating the existence of Bi 3+ . 45 In the O 1s spectra, two peaks appeared on both samples. The peaks at a low BE value were attributed to the lattice oxygen, and the peaks at a high BE value were assigned to the chemisorbed oxygen, such as O 2 – .…”