SA4-P050

Synthesis of N-doped MWCNT-Fe3O4 by co-precipitation technique for

electrocatalytic applications
Luis Alberto Romero-Orellana1, Mercedes Teresita Oropeza-Guzmán1, Jose Manuel Romo-Herrera2 , Jose Manuel Ruiz-
Marizcal2, Yadira Gochi-Ponce1.
1
Tecnológico Nacional de México, Instituto Tecnológico de Tijuana/Posgrado en Ciencias de la Ingeniería, Blvd. Alberto Limón Padilla s/n, Mesa de Otay, CP 22500 Tijuana, B.C., México
2
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México (CNyN-UNAM), Km 107 Carretera Tijuana-Ensenada, CP 22800 Ensenada, B.C., México.
luis.romero18@tectijuana.edu.mx, mercedes.oropeza@tectijuana.edu.mx, jmromo@ens.cnyn.unam.mx, jrmarizcal@ens.cnyn.unam.mx, yadira.gochi@tectijuana.edu.mx.

Abstract
General Aim
This work presents the synthesis of a smart N-doped MWCNT-Fe3O4, first by chemical vapor
Design a composite with electrocatalytic characteristics for
deposition to obtain N-MWCNT, and then by co-precipitation to prepare the composite using different
the oxygen reduction reaction and electro-Fenton.
amounts of Fe2+ and Fe3+ salts, up to a molar ratio of 1:2. The nanostructured material was
characterized by thermogravimetric analysis, transmission electron microscopy, and X-ray 𝑶 𝟐 +𝟐 𝑯 +¿ +𝟐 𝒆
−
→ 𝑯 𝟐 𝑶𝟐 ¿

photoelectron spectroscopy. The thermogravimetric analysis showed complete thermal

decomposition of the N-MWCNT, while the N-MWCNT-Fe3O4 composites presented significant
weight loss. XPS characterization showed that nitrogen was mainly present in its graphitic form and
in a smaller percentage of pyridinic and oxidized nitrogen. A N-MWCNT-Fe O composite was
−
𝟑+ ¿+ 𝑶𝑯 +• 𝑶𝑯 ¿
+¿ → 𝑭 𝒆 ¿
𝟐+ ¿ + 𝑯 𝟐 𝑶 𝟐 + 𝑯 ¿
𝑭 𝒆
a) 3 4
successfully synthesized using the co-precipitation technique, and the results indicate that the
composite could be a good candidate for electrocatalytic applications, particularly in the oxygen
reduction reaction and electro-Fenton.
Synthesis N-MWCNT-Fe3O4

Synthesis by chemical vapor deposition Methodology Synthesis by co-precipitation

𝑵𝑯 𝟒 𝑶𝑯

−
𝟑+ ¿ +𝟖 𝑶 𝑯 ⟹ 𝑵 − 𝑴𝑾𝑪𝑵𝑻 −𝑭 𝟑 𝑶 +𝟒 𝑯𝟐 𝑶 ¿
𝟐+ ¿ +𝟐 𝑭 𝒆 𝟒
¿
𝑵 − 𝑴𝑾𝑪𝑵𝑻 + 𝑭 𝒆

b)

75 °C Argon
Solution of 10 mL
of benzylamine with
2.5 % ferrocene
900 °C in Argon 100 mg N-MWCNT Drying at 50 °C
Magnetic decantation
atmosphere, 1 hr And Fe2+ y Fe3+ salts

C1s
N-MWCNT
M02 N-MWCN-Fe3O4_2
M03 C1s

Results
Intensidad (CPS)

Intensidad (CPS)

C-C C-C
C-N C-N
C-O C-O

𝟏𝟔 ± 𝟐 𝒏𝒎

292 290 288 286 284 282 280 292 290 288 286 284 282 280
Energía de unión (eV) Energía de unión (eV)
M02
N-MWCNT N1s M03
N-MWCNT-Fe3O4_2
N1s
Intensidad (CPS)

Intensidad (CPS)

C-N=C
O-N
Fig. 3. TGA curves of Fe3O4, N-MWCNT and different O-N C-N=C

amounts of Fe3O4 on N-MWCNT N(N-H)

N(N-H)

410 408 406 404 402 400 398 396 394 410 408 406 404 402 400 398 396 394

𝟏𝟖 ± 𝟑 𝒏𝒎 Energía de unión (eV) Energía de unión (eV)

M03
N-MWCNT-Fe32p
O4_2 Fe2p
M01
Fe3O4 Fe2p
1/2
2p1/2
2p3/2
2p3/2 Fe2+
𝟐 𝑷 𝟏 /𝟐
Intensidad (CPS)

Intensidad (CPS)

Fe2+

Satelite Fe2+
Fe2+
Satelite
Satelite
Satelite

Fe3+
Fe3+

Fe3+
3+
Fe

Fig. 5. TEM images of Fe3O4, and N-MWCNT-Fe3O4 composite and particle size 740 735 730 725 720 715 710 705 740 735 730 725 720 715 710 705

Fig. 4. X-ray powder diffraction patterns for Fe3O4, N-MWCNT Energía de unión (eV) Energía de unión (eV)

and N-MWCNT-Fe3O4 composite Fig. 5. XPS spectra of N-MWCNT, Fe3O4 and N-MWCNT-Fe3O4

Conclusions
The synthesis N-MWCNT-Fe3O4 was achieved using the co-precipitation technique References
obtaining a homogeneous particle size of 16 nm of Fe3O4. The analysis revealed
that this compound presents adequate properties due to the presence of Fe3O4 and Contreras E., Dominguez D., Tiznado H., Guerrero-Sanchez J., Takeuchi N.,
N-graphitic. These results suggest its potential application in electrocatalytic and Alonso-Nunez Gabriel, Contreras O., Oropeza-Guzmán, M. T., Romo-Herrera
electro-Fenton processes. J. M., (2019).. Nanoscale, 11(6), 2829-2839.
Acknowledgments
Song K., Wei J., Dong W., Zou Z., Wang, J, International Journal of Hydrogen
The authors thank the Consejo Nacional de Humanidades, Ciencia y Tecnología
Energy, 47(47), 20529-20539.
(CONAHCYT) for the financial support, Universidad Nacional Autónoma de
México, Centro de Nanociencias y Nanotecnología, Uriel Caudillo Flores, Jaime
Fabian Mendoza López, and the SENER CONACyT-117373 project for their
support.