Effective CO x Suppression by a Na 4 Mg(WO 4 ) 3 Promoter in Chemical Looping Oxidative Dehydrogenation of Ethane
- Award ID(s):
- 1923468
- PAR ID:
- 10595361
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- ACS Catalysis
- Volume:
- 15
- Issue:
- 5
- ISSN:
- 2155-5435
- Page Range / eLocation ID:
- 3992 to 4006
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Five novel heterometallic bismuth-bearing cluster salts within two structural families, monoclinic P21/c α-[M2Bi14Cl4][TrCl4]4 and triclinic P1̅ [M2Bi14Cl2][AlCl4]6 (M = Ru, Os; Tr = Al, Ga), have been discovered via Lewis acidic ionic liquid (LAIL)-assisted synthesis at 180 °C. At the center of both structures is the binuclear inorganic [(Bi5)M(Bi4Clx)M(Bi5)](4,6)+ cluster cation (x = 2, 4), where the inner-sphere chloride content within the median [Bi4Clx] ring determines the charge of the unit, its symmetry, and the number of outer-sphere [AlCl4]− anions required for charge balance. Detailed characterization of the structural relationships, coupled with a comprehensive study of the electronic structure and bonding, indicates the basal–basal Bi–Bi strengthening, apical-basal weakening within [Bi5]+ upon chloride loss, and only minor influence of the transition metal origin on the symmetry of the cluster, besides relatively stronger Os–Os interactions of the two cluster types. These findings indicate inner-outer-sphere chloride exchange in LAILs, controlled by the amount of AlCl3, and periodic substitutions as viable approaches to control symmetry, bonding, and interconversion in Bi-rich clusters.more » « less
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