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@PHDTHESIS{Schler:908576,
      author       = {Schüßler, Martina Claudia Beate},
      title        = {{O}n the {F}ormation {M}echanism of {A}morphous
                      {C}arbonates: {P}recursors in {N}onclassical
                      {C}rystallization and for {F}unctional {M}etal {O}xides},
      school       = {Erlangen},
      type         = {Dissertation},
      address      = {Erlangen},
      reportid     = {FZJ-2022-02700},
      pages        = {188 p.},
      year         = {2022},
      note         = {Dissertation, Erlangen, 2022},
      abstract     = {This work is dedicated to the highly discussed formation
                      mechanism of amorphous calcium carbonate (ACC), its role in
                      nonclassical crystallization, and amorphous carbonates as a
                      precursor for functional metal oxides. Decrypting the
                      formation mechanism of ACC provides a new environmentally
                      benign synthesis pathway for complex hierarchically
                      structured nanomaterials. Therefore, different ACC synthesis
                      pathways and the corresponding ACC is studied: ACC synthesis
                      via carbonate released by hydrolysis, manual rapid mixing of
                      calcium chloride and sodium carbonate, and controlled
                      turbulent mixing in a stopped-flow device. Particularly
                      three-dimensional nanonetworks of ACC are received, applying
                      the stopped-flow synthesis approach, which indicates a
                      formation mechanism via liquid-liquid phase separation and
                      spinodal decomposition. Moreover, the existence of a
                      liquid-condensed phase in the formation mechanism is
                      emphasized by the break-down of the nanonetwork to
                      energetically favored droplets over time and a pH-dependent
                      hydration rate of ACC. The extraordinary synthesis pathway
                      via liquid-liquid phase separation is further transferred to
                      other alkaline earth and transition metal carbonates.
                      Thereby, three-dimensional highly hydrated amorphous
                      carbonates or hydroxycarbonates, depending on the relevant
                      solubility products, are accessible, demonstrating the
                      potential and applicability of the mechanism studied herein.
                      The cation hydration enthalpy and radius are suggested to
                      limit the ability of liquid phase formation. Amorphous zinc
                      carbonate hydroxide reveals a peculiar pH dependency,
                      regarding its morphology, composition, and hydration.
                      Moreover, it serves as a tuneable precursor for zinc oxide
                      formation. Besides nanostructured zinc oxide offering a high
                      surface area, copper oxide is synthesized via a stable
                      amorphous copper carbonate hydroxide precursor, georgeite.
                      In contrast to the highly structured porous nanonetworks,
                      smooth georgeite thin films are formed by assembly of the
                      liquid-condensed phase at the air-water interface, utilizing
                      the stabilizing effect of the additive polyacrylic acid
                      (PAA) on georgeite. The obtained high surface area is
                      particularly suited for catalytical applications, cobalt
                      oxide, which was synthesized via an amorphous cobalt
                      carbonate hydroxide precursor, shows promising properties as
                      an electrode material in water-splitting. Further, the
                      synthesis approach via a liquid-condensed phase is utilized
                      for coatings. The results clearly demonstrate that liquid-
                      condensed phases are a powerful concept towards new
                      synthesis approaches for functional metal oxides.},
      cin          = {JCNS-FRM-II / MLZ},
      cid          = {I:(DE-Juel1)JCNS-FRM-II-20110218 / I:(DE-588b)4597118-3},
      pnm          = {6G4 - Jülich Centre for Neutron Research (JCNS) (FZJ)
                      (POF4-6G4)},
      pid          = {G:(DE-HGF)POF4-6G4},
      experiment   = {EXP:(DE-MLZ)KWS1-20140101 / EXP:(DE-MLZ)KWS3-20140101},
      typ          = {PUB:(DE-HGF)11},
      url          = {https://juser.fz-juelich.de/record/908576},
}