Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides

Massimo Rosa, Debora Marani, Giovanni Perin, Søren Bredmose Simonsen, Philipp Zielke, Antonella Glisenti, Ragnar Kiebach, Andreas Lesch, Vincenzo Esposito*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Continuous hydrothermal flow synthesis (CHFS) is a facile, upscalable and cost-efficient synthetic method enabling the nanostructuring of advanced functional materials in steady conditions, i.e. not in batch synthesis. In this paper, we use CHFS to crystallize NiCo- and NiFe-hydroxides in water solution with 2D nanofeatures. By tuning the synthetic parameters, we disclose the key role of the cation redox chemistry in the transition between two competitive phases: from 2D-nanoplatelets of brucite to layered double hydroxides (LDH). For controlling the precipitation of different Ni, Fe, Co-hydroxide phases, we propose the combined use of an oxidizing (H2O2) and a complexing (NH3) agent. At temperatures as low as 80 °C, the presence of H2O2 and a low concentration of NH3 favour the Ni2+/Co3+ over Ni2+/Co2+ oxidation states, shifting the product structure from brucite phase (temperatures > 80 °C) to LDH. Conversely, for the NiFe-hydroxides the transition from LDH (temperatures ≤ 80 °C) to brucite phase (temperatures > 80 °C) is controlled by the reaction temperature only. Due to the high stability of Fe3+, the synthesis of NiFe products by CHFS does not require oxidizing and complexing agents, resulting in a robust process for large-scale production.
Original languageEnglish
JournalReaction Chemistry & Engineering
Volume4
Issue number12
Pages (from-to)2060-2073
Number of pages43
ISSN2058-9883
DOIs
Publication statusPublished - 2019

Cite this

Rosa, Massimo ; Marani, Debora ; Perin, Giovanni ; Simonsen, Søren Bredmose ; Zielke, Philipp ; Glisenti, Antonella ; Kiebach, Ragnar ; Lesch, Andreas ; Esposito, Vincenzo. / Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides. In: Reaction Chemistry & Engineering. 2019 ; Vol. 4, No. 12. pp. 2060-2073.
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title = "Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides",
abstract = "Continuous hydrothermal flow synthesis (CHFS) is a facile, upscalable and cost-efficient synthetic method enabling the nanostructuring of advanced functional materials in steady conditions, i.e. not in batch synthesis. In this paper, we use CHFS to crystallize NiCo- and NiFe-hydroxides in water solution with 2D nanofeatures. By tuning the synthetic parameters, we disclose the key role of the cation redox chemistry in the transition between two competitive phases: from 2D-nanoplatelets of brucite to layered double hydroxides (LDH). For controlling the precipitation of different Ni, Fe, Co-hydroxide phases, we propose the combined use of an oxidizing (H2O2) and a complexing (NH3) agent. At temperatures as low as 80 °C, the presence of H2O2 and a low concentration of NH3 favour the Ni2+/Co3+ over Ni2+/Co2+ oxidation states, shifting the product structure from brucite phase (temperatures > 80 °C) to LDH. Conversely, for the NiFe-hydroxides the transition from LDH (temperatures ≤ 80 °C) to brucite phase (temperatures > 80 °C) is controlled by the reaction temperature only. Due to the high stability of Fe3+, the synthesis of NiFe products by CHFS does not require oxidizing and complexing agents, resulting in a robust process for large-scale production.",
author = "Massimo Rosa and Debora Marani and Giovanni Perin and Simonsen, {S{\o}ren Bredmose} and Philipp Zielke and Antonella Glisenti and Ragnar Kiebach and Andreas Lesch and Vincenzo Esposito",
year = "2019",
doi = "10.1039/C9RE00334G",
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pages = "2060--2073",
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issn = "2058-9883",
publisher = "Royal Society of Chemistry",
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Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides. / Rosa, Massimo; Marani, Debora; Perin, Giovanni; Simonsen, Søren Bredmose; Zielke, Philipp; Glisenti, Antonella; Kiebach, Ragnar; Lesch, Andreas; Esposito, Vincenzo.

In: Reaction Chemistry & Engineering, Vol. 4, No. 12, 2019, p. 2060-2073.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides

AU - Rosa, Massimo

AU - Marani, Debora

AU - Perin, Giovanni

AU - Simonsen, Søren Bredmose

AU - Zielke, Philipp

AU - Glisenti, Antonella

AU - Kiebach, Ragnar

AU - Lesch, Andreas

AU - Esposito, Vincenzo

PY - 2019

Y1 - 2019

N2 - Continuous hydrothermal flow synthesis (CHFS) is a facile, upscalable and cost-efficient synthetic method enabling the nanostructuring of advanced functional materials in steady conditions, i.e. not in batch synthesis. In this paper, we use CHFS to crystallize NiCo- and NiFe-hydroxides in water solution with 2D nanofeatures. By tuning the synthetic parameters, we disclose the key role of the cation redox chemistry in the transition between two competitive phases: from 2D-nanoplatelets of brucite to layered double hydroxides (LDH). For controlling the precipitation of different Ni, Fe, Co-hydroxide phases, we propose the combined use of an oxidizing (H2O2) and a complexing (NH3) agent. At temperatures as low as 80 °C, the presence of H2O2 and a low concentration of NH3 favour the Ni2+/Co3+ over Ni2+/Co2+ oxidation states, shifting the product structure from brucite phase (temperatures > 80 °C) to LDH. Conversely, for the NiFe-hydroxides the transition from LDH (temperatures ≤ 80 °C) to brucite phase (temperatures > 80 °C) is controlled by the reaction temperature only. Due to the high stability of Fe3+, the synthesis of NiFe products by CHFS does not require oxidizing and complexing agents, resulting in a robust process for large-scale production.

AB - Continuous hydrothermal flow synthesis (CHFS) is a facile, upscalable and cost-efficient synthetic method enabling the nanostructuring of advanced functional materials in steady conditions, i.e. not in batch synthesis. In this paper, we use CHFS to crystallize NiCo- and NiFe-hydroxides in water solution with 2D nanofeatures. By tuning the synthetic parameters, we disclose the key role of the cation redox chemistry in the transition between two competitive phases: from 2D-nanoplatelets of brucite to layered double hydroxides (LDH). For controlling the precipitation of different Ni, Fe, Co-hydroxide phases, we propose the combined use of an oxidizing (H2O2) and a complexing (NH3) agent. At temperatures as low as 80 °C, the presence of H2O2 and a low concentration of NH3 favour the Ni2+/Co3+ over Ni2+/Co2+ oxidation states, shifting the product structure from brucite phase (temperatures > 80 °C) to LDH. Conversely, for the NiFe-hydroxides the transition from LDH (temperatures ≤ 80 °C) to brucite phase (temperatures > 80 °C) is controlled by the reaction temperature only. Due to the high stability of Fe3+, the synthesis of NiFe products by CHFS does not require oxidizing and complexing agents, resulting in a robust process for large-scale production.

U2 - 10.1039/C9RE00334G

DO - 10.1039/C9RE00334G

M3 - Journal article

VL - 4

SP - 2060

EP - 2073

JO - Reaction Chemistry & Engineering

JF - Reaction Chemistry & Engineering

SN - 2058-9883

IS - 12

ER -