TY - JOUR
T1 - Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue
AU - Li, Shaodi
AU - Huskić, Igor
AU - Novendra, Novendra
AU - Titi, Hatem M.
AU - Navrotsky, Alexandra
AU - Friščić, Tomislav
N1 - Funding Information:
*E-mail: anavrotsky@ucdavis.edu (A.N.). *E-mail: tomislav.friscic@mcgill.ca (T.F.). ORCID Hatem M. Titi: 0000-0002-0654-1292 Alexandra Navrotsky: 0000-0002-3260-0364 Tomislav Frisč ič :́ 0000-0002-3921-7915 Author Contributions †S.L. and I.H. contributed equally. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding NSERC Discovery Grant (RGPIN-2017-06467); E. W. R. Steacie Memorial Fellowship (SMFSU 507347−17); U.S. Department of Energy, Grant DE-SC0016573. Notes The authors declare no competing financial interest.
Funding Information:
We acknowledge the financial support of the NSERC Discovery Grant (RGPIN-2017-06467) and E. W. R. Steacie Memorial Fellowship (SMFSU 507347-17). Support for calorimetry was provided by the U.S. Department of Energy Grant DE-SC0016573.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/3/19
Y1 - 2019/3/19
N2 - We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc) 4 ·6H 2 O (where OAc - is the acetate ion), composed of coordination polymer chains containing alternating Ca 2+ and Cu 2+ ions, as well as its cadmium-based analogue CaCd(OAc) 4 ·6H 2 O. 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.
AB - We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc) 4 ·6H 2 O (where OAc - is the acetate ion), composed of coordination polymer chains containing alternating Ca 2+ and Cu 2+ ions, as well as its cadmium-based analogue CaCd(OAc) 4 ·6H 2 O. 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.
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U2 - 10.1021/acsomega.9b00295
DO - 10.1021/acsomega.9b00295
M3 - Article
AN - SCOPUS:85063228925
SN - 2470-1343
VL - 4
SP - 5486
EP - 5495
JO - ACS Omega
JF - ACS Omega
IS - 3
ER -