Premium
Speciation of Molybdates under Hydrothermal Conditions
Author(s) -
Noack Johannes,
Rosowski Frank,
Schlögl Robert,
Trunschke Annette
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400439
Subject(s) - hydrothermal circulation , raman spectroscopy , chemistry , aqueous solution , inorganic chemistry , supramolecular chemistry , genetic algorithm , precipitation , crystallography , crystal structure , chemical engineering , physics , optics , engineering , evolutionary biology , meteorology , biology
In situ Raman spectroscopy was applied to investigate the speciation of molybdates under hydrothermal conditions in 0.2 M aqueous solution in the temperature range between 20 °C and 200 °C and at pH values between 7 and 1. The nature and abundance of molecular and supra‐molecular species differs significantly compared to the distribution of species under ambient conditions at the same pH. Whereas heptamolybdate Mo 7 O 24 6– dominates under ambient pressure at 25 °C in the pH range between 6 and 5, at 170–190 °C, chain‐like or molecular structures of dimolybdates Mo 2 O 7 2– and trimolybdates Mo 3 O 10 2– are preferentially formed. In acidic solutions (pH < 2), supramolecular species, like Mo 36 O 112 8– , which generally predominate at 25 °C, do not occur at T > 100 °C. Instead, β‐Mo 8 O 26 4– is the final molecular precursor of precipitation reactions that was detectable by Raman spectroscopy. The structural type of the solid phase formed through addition of vanadyl sulfate under hydrothermal conditions is sensitively controlled by the nature of the molecular precursor, which is adjusted by the pH. In acidic medium, hexagonal MoO 3 (ICSD 80290) is formed, while at pH = 5.8 nano‐crystalline M1 (ICSD 55096) was obtained.