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

Abstract

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.

Authors:
 [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  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
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States); McGill Univ., Montreal, QC (Canada)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1501726
Alternate Identifier(s):
OSTI ID: 1508786
Grant/Contract Number:  
SC0016573; RGPIN-2017-06467; SMFSU 507347-17
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Name: ACS Omega Journal Volume: 4 Journal Issue: 3; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; crystal structure; molecular structure

Citation Formats

Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, and Friščić, Tomislav. Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue. United States: N. p., 2019. Web. doi:10.1021/acsomega.9b00295.
Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, & Friščić, Tomislav. Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue. United States. https://doi.org/10.1021/acsomega.9b00295
Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, and Friščić, Tomislav. 2019. "Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue". United States. https://doi.org/10.1021/acsomega.9b00295.
@article{osti_1501726,
title = {Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue},
author = {Li, Shaodi and Huskić, Igor and Novendra, Novendra and Titi, Hatem M. and Navrotsky, Alexandra and Friščić, Tomislav},
abstractNote = {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.},
doi = {10.1021/acsomega.9b00295},
url = {https://www.osti.gov/biblio/1501726}, journal = {ACS Omega},
issn = {2470-1343},
number = 3,
volume = 4,
place = {United States},
year = {Tue Mar 19 00:00:00 EDT 2019},
month = {Tue Mar 19 00:00:00 EDT 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acsomega.9b00295

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Cited by: 10 works
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Works referencing / citing this record:

Mechanochemistry for Synthesis
journal, January 2020