Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Nanopore facilitated monohydrocalcitic amorphous calcium carbonate precipitation

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d2cp00446a· OSTI ID:1899030
Predicting the precipitation of solids is important in both natural systems and subsurface energy applications. The factors controlling reaction mechanisms, phase selection and conversion between phases are particularly important. In this contribution the precipitation and growth of an amorphous calcium carbonate species from flowing aqueous solution in a nanoporous controlled pore glass is followed in situ with differential X-ray pair distribution function analysis. It is discovered that the local atomic structure of this phase indicates monohydrocalcite-like pair–pair correlations, yet is functionally amorphous because it lacks long-range structure. The unexpected occurrence of synthetic proto-monohydrocalcite amorphous calcium carbonate, precipitated from a solution undersaturated with respect to published solubilities, suggests that nanopore confinement facilitates formation of an amorphous phase at the expense of more favorable crystalline ones. Finally, this result illustrates that confinement and interface effects are physical factors exerting control on mineral nucleation behavior in natural and geological systems.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-06CH11357; AC05-00OR22725
OSTI ID:
1899030
Alternate ID(s):
OSTI ID: 1877940
OSTI ID: 1900798
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 30 Vol. 24; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

Amorphous Calcium Carbonate is Stabilized in Confinement journal June 2010
The Crystallization of Amorphous Calcium Carbonate is Kinetically Governed by Ion Impurities and Water journal February 2018
Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates journal October 2010
Calcium Carbonate Polyamorphism and Its Role in Biomineralization: How Many Amorphous Calcium Carbonates Are There? journal November 2012
Pressure-Induced Polyamorphism and Formation of ‘Aragonitic’ Amorphous Calcium Carbonate journal July 2013
Next generation models of carbonate mineral growth and dissolution: Modeling and Analysis: Next generation models of carbonate mineral growth and dissolution journal January 2014
A thermochemical study of monohydrocalcite journal March 1973
The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O journal June 1982
The formation and transformation mechanism of calcium carbonate in water journal October 1987
Solubility of amorphous calcium carbonate journal November 1989
Monohydrocalcite in calcareous corpuscles of Mesocestoides corti journal January 2008
The role of Mg in the crystallization of monohydrocalcite journal February 2014
Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs journal January 2017
Ab Initio Molecular Dynamics Simulations of Amorphous Calcium Carbonate: Interpretation of Pair Distribution Function and X-ray Absorption Spectroscopy Data journal March 2021
Solution and Interface Structure and Dynamics in Geochemistry: Gateway to Link Elementary Processes to Mineral Nucleation and Growth journal December 2021
Effect of pH on Amorphous Calcium Carbonate Structure and Transformation journal July 2016
Role of Impurities in the Kinetic Persistence of Amorphous Calcium Carbonate: A Nanoscopic Dynamics View journal July 2018
Amorphous Calcium Carbonate Constructed from Nanoparticle Aggregates with Unprecedented Surface Area and Mesoporosity journal June 2018
Resolving Single-layer Nanosheets as Short-lived Intermediates in the Solution Synthesis of FeS journal April 2021
Ultrafast, Scale-Up Synthesis of Pure and Stable Amorphous Carbonate Mineral Nanoparticles journal May 2017
Nanoporous Structure and Medium-Range Order in Synthetic Amorphous Calcium Carbonate journal May 2010
Structural Characteristics of Synthetic Amorphous Calcium Carbonate journal July 2008
Biomimetic Model Systems for Investigating the Amorphous Precursor Pathway and Its Role in Biomineralization journal November 2008
Pore-Size-Dependent Calcium Carbonate Precipitation Controlled by Surface Chemistry journal May 2014
Watching Nanoparticles Grow:  The Mechanism and Kinetics for the Formation of TiO 2 -Supported Platinum Nanoparticles journal November 2007
The Stabilizing Effect of Silicate on Biogenic and Synthetic Amorphous Calcium Carbonate journal September 2010
Stabilization of Amorphous Calcium Carbonate in Inorganic Silica-Rich Environments journal December 2010
Water Is the Key to Nonclassical Nucleation of Amorphous Calcium Carbonate journal December 2010
Revealing the Mechanisms behind SnO 2 Nanoparticle Formation and Growth during Hydrothermal Synthesis: An In Situ Total Scattering Study journal April 2012
Structure and Stability of SnO 2 Nanocrystals and Surface-Bound Water Species journal April 2013
Phosphate–Water Interplay Tunes Amorphous Calcium Carbonate Metastability: Spontaneous Phase Separation and Crystallization vs Stabilization Viewed by Solid State NMR journal January 2015
Determination of Structure and Phase Transition of Light Element Nanocomposites in Mesoporous Silica: Case study of NH 3 BH 3 in MCM-41 journal September 2009
Trapping Amorphous Intermediates of Carbonates – A Combined Total Scattering and NMR Study journal October 2018
Designing Solid Materials from Their Solute State: A Shift in Paradigms toward a Holistic Approach in Functional Materials Chemistry journal February 2019
Nanosized Amorphous Calcium Carbonate Stabilized by Poly(ethylene oxide)- b -poly(acrylic acid) Block Copolymers journal January 2006
Dehydration and crystallization of amorphous calcium carbonate in solution and in air journal January 2014
Disordered amorphous calcium carbonate from direct precipitation journal January 2015
Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates journal January 2017
Synthesis-dependant structural variations in amorphous calcium carbonate journal January 2007
In vitro synthesis and stabilization of amorphous calcium carbonate (ACC) nanoparticles within liposomes journal January 2011
Freeze-drying yields stable and pure amorphous calcium carbonate (ACC) journal January 2013
Ethanol assisted synthesis of pure and stable amorphous calcium carbonate nanoparticles journal January 2013
Organic–mineral interfacial chemistry drives heterogeneous nucleation of Sr-rich (Ba x , Sr 1− x )SO 4 from undersaturated solution journal May 2019
Biologically Formed Amorphous Calcium Carbonate journal January 2003
The Solubility and Stabilization of Ikaite (CaCO 3 ·6H 2 O) from 0° to 25°C: Environmental and Paleoclimatic Implications for Thinolite Tufa journal January 1993
Rapid-acquisition pair distribution function (RA-PDF) analysis journal November 2003
Stable Prenucleation Calcium Carbonate Clusters journal December 2008
The Initial Stages of Template-Controlled CaCO3 Formation Revealed by Cryo-TEM journal March 2009
Hydrocalcite (CaCO 3 ⋅ H 2 O) and Nesquehonite (MgCO 3 ⋅ 3H 2 O) in Carbonate Scales journal September 1969
Transformation of amorphous calcium carbonate into monohydrocalcite in aqueous solution: a biomimetic mineralization study [Transformation of amorphous calcium carbonate into monohydrocalcite in aqueous solution: a biomimetic mineralization study] journal December 2015
The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+partitioning journal January 2012
Monohydrocalcite in the Arctic Ikka Fjord, SW Greenland: First Reported Marine Occurrence journal March 2006
Principles of Crystal Nucleation and Growth journal January 2003
Decay-induced biomineralization of the saguaro cactus ( Carnegiea gigantea ) journal November 2003
Precipitation in Pores: A Geochemical Frontier journal January 2015

Similar Records

Disordered amorphous calcium carbonate from direct precipitation
Journal Article · Sun May 31 20:00:00 EDT 2015 · CrystEngComm · OSTI ID:1214327

Structural analyses of amorphous calcium carbonate before and after removing strontium ions from an aqueous solution
Journal Article · Mon Jan 31 19:00:00 EST 2022 · Journal of the Ceramic Society of Japan · OSTI ID:1845760