Selectively Photocatalytic Activity of an Open-Framework Chalcogenide Built from Corner-Sharing T4 Supertetrahedral Clusters

Abstract

The photocatalysis process with high selectivity is a very important research forefront for the semiconductor photocatalytic decomposition of organic pollutants. However, the rational design of efficient photocatalysts with high selectivity is still a challenge. Here, we present an openframework chalcogenide (Heta) 8 [In 14 Sn 2 Zn 4 Se 33 ] (Heta = ethanolamine-H + ) (compound 1) constructed from T4 supertetrahedral clusters [In 14 Sn 2 Zn 4 Se 35 ] 12− with visiblelight-driven selectively photocatalytic degradation activity. Single-crystal XRD analysis shows that compound 1 crystallizes in I4 1 /acd (no. 142) space group, with a = b = 24.3462(2) Å, c = 45.0062(9) Å, V = 26676.9(7) Å 3 , and Z = 8. Under visible-light irradiation, the selectively photocatalytic activities of 1 were evaluated by photodegradation of two kinds of cationic dye molecules, i.e., methylene blue (MB) and rhodamine B (RhB), against two anionic dyes, methyl orange (MO) and Kermes red (KR), with different sizes. We show that the adsorption capability and charge-matching between organic dyes and the supertetrahedral cluster together with a suitable band structure make it an excellent and selective photocatalyst. This is the first example of an open-framework chalcogenide based on supertetrahedral T4 for the selectively semiconductor photocatalytic decomposition of organic dyes.

Discrete Supertetrahedral Tn Chalcogenido Clusters Synthesized in Ionic Liquids: Crystal Structures and Photocatalytic Activity

“…Although the photocatalytic activities of these Tn clusters are some poorer than that of classical metal sulfides nanomaterials, such as, CdS and ZnS, [105][106][107][108] the exploration of the relationship between structure and photocatalytic properties by single-crystal X-ray diffraction might have a guiding significance to optimize the structure of crystalline compounds and corresponding nanomaterials for gaining better photocatalytic performances. In comparison to previous reports of Tn cluster-based chalcogenide crystals, [11,82,[109][110][111][112][113][114][115][116][117][118][119][120] our discrete supertetrahedral Tn clusters normally show higher photocatalytic H 2 production activities, and especially, the dispersed Tn clusters exhibit the remarkably superior performance, while their performance of photocatalytic degradation of organic compounds needs to be further optimized. To a great extent, preparing stable and highly-dispersible chalcogenides will play a critical role in developing high-efficiency photocatalysts.…”

A wheel-shaped gallium-sulfide molecular ring with enhanced photocatalytic activity via indium alloying

“…Consequently, such superior photocatalytic activity should be related to the suitable band structure and high charge carrier separation efficiency of WSC-1-In as demonstrated above. 6,8,65,69,71…”

“…5c, WSC-1-In exhibits the best photocatalytic performance among all catalysts as 98.1% of MB was decomposed within 5 min, whereas only 58.2% MB and 33.8% MB were degraded within the same time for WSC-1 and commercial TiO 2 . Assuming that the dye degradation is a pseudo-first-order reaction, 10,34,[69][70][71][72] the apparent rate constant (K a ) was calculated to be 0.8144 min −1 for WSC-1-In, which is ca. 4 times faster than that of WSC-1 (K a = 0.2000 min −1 ) (Fig.…”

All-Inorganic Open-Framework Chalcogenides, A3Ga5S9·xH2O (A = Rb and Cs), Exhibiting Ultrafast Uranyl Remediation and Illustrating a Novel Post-Synthetic Preparation of Open-Framework Oxychalcogenides

“…Materials that can effectively extract and bind uranium will soon be needed to achieve advanced uranium recovery and may even enable future possible uranium extraction from seawater. The oceans contain 3.3 ppb of uranium and thus hold 1000 times more uranium than is recoverable from mining. − Consequently, the development of advanced uranium sorbents is a growing research field that targets uranium recovery and has led already to an impressive diversity of sorbents that include functionalized polymers and silica, porous materials, such as metal–organic frameworks and zeolites, as well as ion-exchange materials. − Recently, layered chalcogenide-based ion-exchange materials have demonstrated great potential for uranium recovery due to their fast kinetics, unprecedented uranium exchange capacity, and overall extremely strong affinity between uranyl ions and the chalcogenide layers. − Layered materials can undergo structural transformations during ion intercalation/deintercalation often upon high cation uptake, while three-dimensional chalcogenide ion-exchange materials can avoid this due to having a rigid framework structure and likely providing selective cavities for trapping radioactive species. , Open-framework chalcogenides, consisting of clusters connected through metal or chalcogen bridges creating pores that are typically occupied by organic cations, are therefore attractive. − Such open chalcogenide frameworks received attention recently as their combination of porosity and chalcogenide-based clusters make them attractive as potential materials for applications in photocatalysis, photoluminescence, X-ray detection, ionic conductors, and semiconductors. − To date, investigations of open-framework chalcogenide materials for their ion-exchange properties are limited to several reports focusing on Cs + and heavy metal (Cd 2+ , Hg 2+ , and Pb 2+ ) ion exchange; ,,− interestingly, the direct synthesis of an all-inorganic open-framework chalcogenide and its use for uranyl ion exchange have not yet been explored.…”

“…Solvothermal reactions in amine-based solvents have demonstrated great potential for yielding novel organic–inorganic chalcogenide-based hybrid materials when starting from Ti-, Fe-, Ga-, Ge-, In-, Sn-, and Sb-based reagents. ,,− ,,− Typically, the organic cations act as spacers between chalcogenide layers or as a structure-directing agent promoting the formation of different M x Q y clusters ( M = Ga, In, Sn, and Sb; Q = S and Se) as well as diverse topologies of frameworks. While the use of organic cations is beneficial to promote structural diversity, they can ultimately become problematic for ion-exchange applications where the release of the organic cations can lead to water pollution.…”