Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue

Journal Article · Tue Mar 19 00:00:00 EDT 2019 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.9b00295· OSTI ID:1501726

Li, Shaodi ^[1]; Huskić, Igor ^[1]; Novendra, Novendra ^[2]; Titi, Hatem M.  ^[1]; Navrotsky, Alexandra  ^[2]; Friščić, Tomislav  ^[1]

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1. Department of Chemistry, McGill University, 801 Sherbrooke St. W., H3A 0B8 Montreal, Canada
2. Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, One Shields Avenue, Davis, California 95616, United States

We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc)₄·6H₂O (where OAc^– is the acetate ion), composed of coordination polymer chains containing alternating Ca²⁺ and Cu²⁺ ions, as well as its cadmium-based analogue CaCd(OAc)₄·6H₂O. While the synthesis of paceite in aqueous solutions requires a high excess of the copper precursor, mechanochemistry permits the use of stoichiometric amounts of reagents, as well as the use of poorly soluble and readily accessible calcium carbonate or hydroxide reactants. As established by thermochemical measurements, enthalpies of formation of both synthetic paceite and its cadmium analogue relevant to the mechanochemical reactions are highly exothermic. Reactions can also be conducted using accelerated aging, a synthetic technique that mimics geological processes of mineral weathering. Accelerated aging reactivity involving copper(II) acetate monohydrate (hoganite) and calcium carbonate (calcite) provides a potential explanation of how complex organic minerals like paceite could form in a geological environment.

• Research Organization: Univ. of California, Davis, CA (United States); McGill Univ., Montreal, QC (Canada)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); Natural Sciences and Engineering Research Council of Canada (NSERC)
• Grant/Contract Number: SC0016573; RGPIN-2017-06467; SMFSU 507347-17
• OSTI ID: 1501726
• Alternate ID(s): OSTI ID: 1508786
• Journal Information: ACS Omega, Journal Name: ACS Omega Vol. 4 Journal Issue: 3; ISSN 2470-1343
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
58 GEOSCIENCES
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molecular structure