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6CCVD Research

Lanthanum Ferrite Ceramic Powders - Synthesis, Characterization and Electrochemical Detection Application

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2020-04-29
JournalMaterials
AuthorsRaluca Dumitru, Sorina Negrea, Adelina Ianculescu, Cornelia Păcurariu, Bogdan ƞtefan Vasile
InstitutionsUniversity of Bucharest, Polytechnic University of TimiƟoara
Citations22
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”

The research details the synthesis, characterization, and electrochemical application of nanometric Lanthanum Ferrite (LaFeO3) ceramic powders, focusing on the detection of the cytostatic drug capecitabine (CCB).

  • Novel Synthesis Route: LaFeO3 perovskite powders were prepared via the thermal decomposition of a novel in situ synthesized lanthanum ferrioxalate precursor (LaFe(C2O4)3·3H2O).
  • Nanostructure Control: The calcination process yielded highly crystalline LaFeO3 nanoparticles, with average crystallite sizes ranging from 17.5 nm (at 550 °C) to 36.7 nm (at 800 °C), forming porous aggregates.
  • Electrocatalytic Performance: The LaFeO3-modified Boron-Doped Diamond (BDD) electrode exhibited strong electrocatalytic activity, driven by intrinsic Fe2+/Fe3+ and Fe3+/Fe4+ redox systems.
  • Dual Detection Capability: The modified electrode successfully detected CCB through both oxidation (+0.4 V/SCE) and reduction (-1.1 V/SCE) processes in alkaline aqueous solution.
  • Superior Sensitivity: Using Multiple-Pulsed Amperometry (MPA), the electrode achieved a very low Limit of Detection (LOD) of 0.017 ”M for CCB reduction, demonstrating superior sensitivity compared to existing literature methods.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Precursor FormulaLaFe(C2O4)3·3H2ON/ALanthanum ferrioxalate precursor
Calcination Temperature Range550 to 800°CSynthesis of crystalline LaFeO3
Heating Rate10°C min-1Calcination process
LaFeO3 Crystal StructureOrthorhombic (Pbnm)N/ADetermined by XRD Rietveld analysis
Average Crystallite Size (550 °C)17.5nmDetermined from XRD data
Average Crystallite Size (800 °C)36.7nmDetermined from XRD data
Unit Cell Volume (V)242.9 to 242.8Angstrom3Contraction observed with increasing temperature
Supporting Electrolyte0.1 M NaOHN/AElectrochemical testing medium
BDD Boron Content~0.1N/ACommercial electrode specification
CCB Oxidation Potential (CV/DPV)+0.4V/SCEAnodic peak potential
CCB Reduction Potential (DPV)-1.02V/SCECathodic peak potential
LOD (Limit of Detection) - DPV0.038”MCCB reduction (high concentration range)
LOD (Limit of Detection) - MPA0.017”MCCB reduction at -1.1 V/SCE
Linear Range (MPA, Reduction)2.5 to 20”MR2 = 0.985 at -1.1 V/SCE

Key Methodologies

Section titled “Key Methodologies”

The LaFeO3 powders and the modified electrode were prepared and tested using the following sequence:

  1. Precursor Synthesis:
    • Reagents (La(NO3)3·6H2O, Fe(NO3)3·9H2O, 1,2-ethanediol, 2 M HNO3) were mixed in a 1:1:3:2 molar ratio, resulting in a solution pH of 3.
    • The solution was heated at approximately 100 °C for 20 minutes to drive the redox reaction, forming the LaFe(C2O4)3·3H2O precursor.
  2. Thermal Decomposition and Crystallization:
    • The precursor was calcinated in air at a heating rate of 10 °C min-1, with temperatures ranging from 550 °C to 800 °C, to yield the crystalline LaFeO3 perovskite phase.
  3. Structural Characterization:
    • X-ray Diffraction (XRD) with Rietveld refinement was used to confirm the orthorhombic Pbnm structure and determine crystallite size (17.5-36.7 nm).
    • FE-SEM and TEM/HRTEM confirmed the formation of porous aggregates composed of nano-sized particles (10-50 nm).
  4. Electrode Modification:
    • A commercial Boron-Doped Diamond (BDD) electrode was modified by simple immersion in a 5 mg mL-1 suspension of LaFeO3 powder (calcined at 550 °C).
  5. Electrochemical Testing:
    • The electrode was stabilized using 10 repetitive Cyclic Voltammetry (CV) scans in 0.1 M NaOH.
    • Capecitabine (CCB) detection was performed using CV, Differential-Pulsed Voltammetry (DPV), and Multiple-Pulsed Amperometry (MPA).
    • MPA utilized three potential levels (-1.1 V/SCE, -0.4 V/SCE, and 0.4 V/SCE) applied for 50 ms durations to capture both reduction and oxidation signals.

Commercial Applications

Section titled “Commercial Applications”

The synthesized LaFeO3 material, particularly when integrated with BDD electrodes, is highly relevant for several high-value engineering and environmental sectors:

  • Environmental Monitoring and Remediation:
    • Emerging Pollutant Detection: High-sensitivity electrochemical sensors for trace detection of pharmaceuticals (like CCB) and other persistent organic pollutants in drinking water and wastewater treatment plant effluents.
  • Electrochemical Energy Systems:
    • Electrocatalysis: Use as a robust, non-precious metal electrocatalyst for key reactions in energy conversion, including the Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), due to its high oxidation-reduction characteristics.
    • Solid Oxide Fuel Cells (SOFCs): Application as cathode material, leveraging its electrical conductivity and structural stability.
  • Chemical and Gas Sensing:
    • Industrial Safety: Development of high-performance chemical sensors for industrial gases (e.g., SO2, ethanol, formaldehyde), benefiting from the material’s porous nanostructure and high surface area.
  • Biosensing and Diagnostics:
    • Biomolecule Detection: Voltammetric/amperometric detection of critical biomolecules (e.g., guanine, uric acid) in biological samples, offering a simple and cost-effective alternative to HPLC/LC-MS.
View Original Abstract

The perovskite-type lanthanum ferrite, LaFeO3, has been prepared by thermal decomposition of in situ obtained lanthanum ferrioxalate compound precursor, LaFe(C2O4)3·3H2O. The oxalate precursor was synthesized through the redox reaction between 1,2-ethanediol and nitrate ion and characterized by chemical analysis, infrared spectroscopy, and thermal analysis. LaFeO3 obtained after the calcination of the precursor for at least 550-800 °C/1 h have been investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). A boron-doped diamond electrode (BDD) modified with LaFeO3 ceramic powders at 550 °C (LaFeO3/BDD) by simple immersion was characterized by cyclic voltammetry and tested for the voltammetric and amperometric detection of capecitabine (CCB), which is a cytostatic drug considered as an emerging pollutant in water. The modified electrode exhibited a complex electrochemical behaviour by several redox systems in direct relation to the electrode potential range. The results obtained by cyclic voltammetry (CV), differential-pulsed voltammetry (DPV), and multiple-pulsed amperometry proved the electrocatalytic effect to capecitabine oxidation and reduction and allowed its electrochemical detection in alkaline aqueous solution.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2015 - Gas sensing properties and modeling of YCoO3 based perovskite materials [Crossref]
  2. 2014 - Chemical tuning versus microstructure features in solid-state gas sensors: LaFe1−xGaxO3, a case study [Crossref]
  3. 2001 - Microstructural and surface characterization of solid state sensor based on LaFeO3−σ oxide for detection of NO [Crossref]
  4. 2019 - Facile fabrication of perovskite-incorporated hierarchically mesoporous/macroporous silica for efficient photoassisted-Fenton degradation of dye [Crossref]
  5. 2019 - Combustion synthesized A0.5Sr0.5MnO3−ή perovskites (where, A = La, Nd, Sm, Gd, Tb, Pr, Dy and Y) as redox materials for thermochemical splitting of CO2 [Crossref]
  6. 2009 - Simultaneous determination of dopamine, uric acid and ascorbic acid with LaFeO3 nanoparticles modified electrode [Crossref]
  7. 2014 - Facile hydrothermal synthesis and characterization of LaFeO3 nanospheres for visible light photocatalytic applications [Crossref]
  8. 2009 - Synthesis of LaFeO3 catalytic materials and their sensing properties [Crossref]
  9. 2001 - AFeO3 (A = La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: Structural, redox and catalytic properties [Crossref]
  10. 1996 - Some characteristics of Al2O3− and CaO-modified LaFeO3-based cathode materials for solid oxide fuel cells [Crossref]

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