Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Siebert, Jan P.; Juelsholt, Mikkel; Günzing, Damian; Wende, Heiko; Ollefs, Katharina; Birkel, Christina S.

doi:10.1039/d2qi00053a

Title: Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Journal Article · 17 February 2022 · Inorganic Chemistry Frontiers (Online)

DOI: https://doi.org/10.1039/d2qi00053a · OSTI ID:1982253

Siebert, Jan P. ^[1];

^[2];

^[3];

^[3]; Ollefs, Katharina ^[3];

^[4]

Arizona State Univ., Tempe, AZ (United States)
Copenhagen Univ. (Denmark)
University of Duisburg-Essen (Germany)
Arizona State Univ., Tempe, AZ (United States); Technische Univ. Darmstadt (Germany)

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr₂GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1982253

Journal Information:: Inorganic Chemistry Frontiers (Online), Journal Name: Inorganic Chemistry Frontiers (Online) Journal Issue: 7 Vol. 9; ISSN 2052-1553

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Structural Evolution of Superconductor Nanowires in Biopolymer Gels Schnepp, Zoe A. C.; Wimbush, Stuart C.; Mann, Stephen Advanced Materials, Vol. 20, Issue 9 https://doi.org/10.1002/adma.200702679	journal	May 2008
Transactions and Communications Ellingham, H. J. T. Journal of the Society of Chemical Industry, Vol. 63, Issue 5, p. 125-160 https://doi.org/10.1002/jctb.5000630501	journal	May 1944
Untersuchungen über die Verbindungen der Borsäure und Kieselsäure mit Aether Annalen der Chemie und Pharmacie, Vol. 57, Issue 3 https://doi.org/10.1002/jlac.18460570303	journal	January 1846
Kohlenstoffhaltige tern�re Verbindungen (V-Ge-C, Nb-Ga-C, Ta-Ga-C, Ta-Ge-C, Cr-Ga-C und Cr-Ge-C) Jeitschko, W.; Nowotny, H.; Benesovsky, F. Monatshefte f�r Chemie, Vol. 94, Issue 5 https://doi.org/10.1007/BF00902358	journal	January 1963
Kohlenstoffhaltige tern�re Verbindungen (H-Phase) Jeitschko, W.; Nowotny, H.; Benesovsky, F. Monatshefte f�r Chemie, Vol. 94, Issue 4 https://doi.org/10.1007/BF00913068	journal	January 1963
Thermal behaviour of citric acid and isomeric aconitic acids Wyrzykowski, D.; Hebanowska, E.; Nowak-Wiczk, G. Journal of Thermal Analysis and Calorimetry, Vol. 104, Issue 2 https://doi.org/10.1007/s10973-010-1015-2	journal	August 2010
Thermal decomposition of citric acid Barbooti, Mahmood M.; Al-Sammerrai, Dhoaib A. Thermochimica Acta, Vol. 98 https://doi.org/10.1016/0040-6031(86)87081-2	journal	February 1986
Vacancy distribution in nonstoichiometric vanadium monoxide Gusev, A. I.; Davydov, D. A.; Valeeva, A. A. Journal of Alloys and Compounds, Vol. 509, Issue 5 https://doi.org/10.1016/j.jallcom.2010.10.095	journal	February 2011
Synthesis of nanosized zirconium carbide by a sol–gel route Dollé, Mickael; Gosset, Dominique; Bogicevic, Christine Journal of the European Ceramic Society, Vol. 27, Issue 4, p. 2061-2067 https://doi.org/10.1016/j.jeurceramsoc.2006.06.005	journal	January 2007
Synthesis of crystalline metal nitride and metal carbide nanostructures by sol–gel chemistry Giordano, Cristina; Antonietti, Markus Nano Today, Vol. 6, Issue 4 https://doi.org/10.1016/j.nantod.2011.06.002	journal	August 2011
Standard X-Ray Diffraction Powder Patterns from The JCPDS Research Associateship McMurdie, Howard F.; Morris, Marlene C.; Evans, Eloise H. Powder Diffraction, Vol. 2, Issue 1 https://doi.org/10.1017/S0885715600012239	journal	March 1987
In Situ Synchrotron X-ray Diffraction Study of the Sol–Gel Synthesis of Fe ₃ N and Fe ₃ C Schnepp, Zoe; Danks, Ashleigh E.; Hollamby, Martin J. Chemistry of Materials, Vol. 27, Issue 14 https://doi.org/10.1021/acs.chemmater.5b01811	journal	July 2015
Mechanistic Insights into the Nonconventional Sol–Gel Synthesis of MAX Phase M₂GeC (M = V, Cr) Siebert, Jan P.; Patarakun, Keene; Birkel, Christina S. Inorganic Chemistry, Vol. 61, Issue 3 https://doi.org/10.1021/acs.inorgchem.1c03415	journal	January 2022
Evolution of Atomic-Level Structure in Sub-10 Nanometer Iron Oxide Nanocrystals: Influence on Cation Occupancy and Growth Rates Cooper, Susan R.; Candler, Randall O.; Cosby, Alexia G. ACS Nano, Vol. 14, Issue 5 https://doi.org/10.1021/acsnano.9b09551	journal	April 2020
Shape Control of MAX Phases by Biopolymer Sol–Gel Synthesis: Cr₂GaC Thick Films, Microspheres, and Hollow Microspheres Siebert, Jan P.; Flores, Matthew; Birkel, Christina S. ACS Organic & Inorganic Au, Vol. 2, Issue 1 https://doi.org/10.1021/acsorginorgau.1c00022	journal	October 2021
In situ x-ray diffraction study of crystallization kinetics in PbZr1-xTixO3, (PZT, x = 0.0, 0.55, 1.0) Wilkinson, Angus P.; Speck, James S.; Cheetham, Anthony K. Chemistry of Materials, Vol. 6, Issue 6 https://doi.org/10.1021/cm00042a009	journal	June 1994
Metal Nitride and Metal Carbide Nanoparticles by a Soft Urea Pathway Giordano, Cristina; Erpen, Christian; Yao, Weitang Chemistry of Materials, Vol. 21, Issue 21 https://doi.org/10.1021/cm9018953	journal	November 2009
In Situ Studies of the Sol−Gel Synthesis of Materials Cheetham, Anthony K.; Mellot, Caroline F. Chemistry of Materials, Vol. 9, Issue 11 https://doi.org/10.1021/cm970497k	journal	November 1997
Study of the Sol−Gel Reaction Mechanism in Supercritical CO₂ for the Formation of SiO₂ Nanocomposites Charpentier, Paul A.; Li, Xinsheng; Sui, Ruohong Langmuir, Vol. 25, Issue 6 https://doi.org/10.1021/la803449z	journal	February 2009
Mechanisms for Iron Oxide Formation under Hydrothermal Conditions: An in Situ Total Scattering Study Jensen, Kirsten M. Ø.; Andersen, Henrik L.; Tyrsted, Christoffer ACS Nano, Vol. 8, Issue 10 https://doi.org/10.1021/nn5044096	journal	October 2014
The evolution of ‘sol–gel’ chemistry as a technique for materials synthesis Danks, A. E.; Hall, S. R.; Schnepp, Z. Materials Horizons, Vol. 3, Issue 2 https://doi.org/10.1039/C5MH00260E	journal	January 2016
Sol–gel based synthesis and enhanced processability of MAX phase Cr ₂ GaC Siebert, Jan Paul; Bischoff, Lothar; Lepple, Maren Journal of Materials Chemistry C, Vol. 7, Issue 20 https://doi.org/10.1039/C9TC01416K	journal	January 2019
Structure determination and magnetic properties of the Mn-doped MAX phase Cr₂GaC Siebert, Jan P.; Mallett, Shayna; Juelsholt, Mikkel Materials Chemistry Frontiers, Vol. 5, Issue 16 https://doi.org/10.1039/D1QM00454A	journal	January 2021
Parameter-free calculations of X-ray spectra with FEFF9 Rehr, John J.; Kas, Joshua J.; Vila, Fernando D. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/b926434e	journal	January 2010
High-resolution electron microscopy studies of non-graphitizing carbons Harris, P. J. F.; Tsang, S. C. Philosophical Magazine A, Vol. 76, Issue 3 https://doi.org/10.1080/01418619708214028	journal	September 1997
Reticulated superconducting YBCO materials of designed macromorphologies with enhanced structural stability through incorporation of lithium Walsh, Dominic; Wimbush, Stuart C.; Hall, Simon R. Superconductor Science and Technology, Vol. 22, Issue 1 https://doi.org/10.1088/0953-2048/22/1/015026	journal	December 2008
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
ADDIE: ADvanced DIffraction Environment – a software environment for analyzing neutron diffraction data McDonnell, M. T.; Olds, D. P.; Page, K. L. Acta Crystallographica Section A Foundations and Advances, Vol. 73, Issue a1 https://doi.org/10.1107/S0108767317096325	journal	December 2017
The interpretation of diffuse X-ray diagrams of carbon Franklin, R. E. Acta Crystallographica, Vol. 3, Issue 2 https://doi.org/10.1107/S0365110X50000264	journal	March 1950
The structure of graphitic carbons Franklin, R. E. Acta Crystallographica, Vol. 4, Issue 3 https://doi.org/10.1107/S0365110X51000842	journal	May 1951
PDFgetN3 : atomic pair distribution functions from neutron powder diffraction data using ad hoc corrections Juhás, Pavol; Louwen, Jaap N.; van Eijck, Lambert Journal of Applied Crystallography, Vol. 51, Issue 5 https://doi.org/10.1107/S1600576718010002	journal	August 2018
Synthesis and Characterization of a Remarkable Ceramic: Ti3SiC2 Barsoum, Michel W.; El-Raghy, Tamer Journal of the American Ceramic Society, Vol. 79, Issue 7 https://doi.org/10.1111/j.1151-2916.1996.tb08018.x	journal	July 1996
Sol-Gel Synthesis and Formation Mechanism of Ultrahigh Temperature Ceramic: HfB₂ Venugopal, Saranya; Boakye, Emmanuel E.; Paul, Anish Journal of the American Ceramic Society, Vol. 97, Issue 1 https://doi.org/10.1111/jace.12654	journal	November 2013
Strukturuntersuchungen an Carbosulfiden von Titan und Zirkon Rohde, Helga; Kudielka, Heinz Zeitschrift für Kristallographie - Crystalline Materials, Vol. 114, Issue 1-6 https://doi.org/10.1524/zkri.1960.114.16.447	journal	December 1960
Crystal data for the spinels MGa₂O₄ (M = Mg, Μn) Casado, P. Garcia; Rasines, I. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 160, Issue 1-4 https://doi.org/10.1524/zkri.1982.160.14.33	journal	November 1982

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