CARBON NANOTUBES DECORATED WITH

NICKEL AS CATALYST FOR AMMONIA ELECTROCHEMICAL OXIDATION

Marlen A. González-Reyna, Maria Selene Luna-Martínez, Juan F. Pérez-Robles
Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Querétaro, Qro. CP 76230
Universidad Autónoma de Querétaro, Santiago de Querétaro, CP 76010, Querétaro
Email: marlen.gonzalez@cinvestav.mx

Abstract: The FTIR spectra of CNT-P (3a) did not show any band, after the acid
Electrochemical and structural characterizations were performed, to treatment (3b) appears those related with functional groups (shown in the
demonstrate that CNT-Ni composite could be used as a cheaper catalyst table). After the impregnation process, CNT present a different spectra (3c)
alternative to the commonly Pt electrodes. where the bands associated with functional groups are reduced and some
new arise due to the present of Ni in the surface.

3000
without ammonia
Current density (µA/cm²)

with 200 ppm ammonia

2000 Group Frequency Range (cm-1) c)
Intermolecular H Bonds 3200-3550 (broad)

Intensity (u.a.)
CH2 2843-2863,2916-2936
, 1000
CO2 2360 b) 645
Nonconjugated C=C 997 440
0 1620-1680
Stretching Vibrations
,
CH3 1355-1395 a) 2360
1636 1120
-1000 3440
-1000 -500 0 500 1000 C-O stretching 1120
Potential (mV)
Figure 1: Graphical abstract 4000 3000 2000 1000

Wavenumber (cm -1)

Figure 3: FTIR spectra of CNTs and CNSs before and after the oxidation process. a
Introduction: CNT-P, b CNT-O, c) CNT-Ni
Ammonia is constantly generated as domestic, agricultural and industrial
The oxidation state on the catalyst surface determines its performance. Then,
wastewater, where the electrochemical oxidation of this compound has
by continues cyclic voltammetry its stability an oxidation state was analyzed
attracted attention for hydrogen generation and water remediation.
(4a). The anodic peak correspond to the oxidation of Ni(OH)2 to NiOOH which
overlaps with ammonia oxidation. The cathodic peak is assigned to the
Despite the fact that nickel is an effective and cheap catalyst for the oxidation
reduction of NiOOH to Ni(OH)2. Also, the current densities increase
of small organic compounds such as amines, alcohols, amino acids, urea, etc.
progressively and present a slight shift caused by Ni recrystallization [1,4].
[1-4], there is limited previous research on the electro-oxidation of ammonia;
instead, Pt, Ru, Pd, and Ir are used [5,6], where the lack of affordability limits
their application on an industrial scale. In the present work, is proposed a a) 3000 b)
nickel electro-catalyst supported in carbon nanotubes as an alternative to Pt
10th cycle 200 ppm
3000

Current density (µA/cm²)

Current density (µA/cm²)

100th cycle 400 ppm

electrodes.
200th cycle 600 ppm
2000 300th cycle
2000
𝛼𝛼 − 𝑁𝑁𝑁𝑁(𝑂𝑂𝑂𝑂)2 𝛾𝛾 − 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁
𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 ↑
1000 ↓
𝑖𝑖𝑖𝑖 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜
𝛽𝛽 − 𝑁𝑁𝑁𝑁(𝑂𝑂𝑂𝑂)2 𝛽𝛽 − 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁
1000

Methodology: , 0000000 0

Multiwalled carbon nanotubes (CNT) were synthesized by chemical vapor

deposition process (CVD), to increase the chemical reactivity and specificity of
-1000 -1000
-1000 -500 0 500 1000 -1.0 -0.5 0.0 0.5 1.0

the CNTs functional groups were added to their surface using an acid
treatment. Then, were dispersed into 0.1M aqueous solution of
Ni(NO3)2*6H2O to add Ni on the surface. Carbon nanostructures were
characterized to confirm the addition of functional groups and the posterior
Ni immobilization by means of scanning electron microscopy (SEM) and
infrared spectroscopy (FTIR). Finally, their catalytic activity was evaluated with
cyclic voltammetry in ammonium solution.
Results:
Potential (mV) Potential (V)
Figure 4: Cyclic voltammograms of CNT-Ni, a) Stability test performed with 200ppm
(NH4)2SO4 and b) effect of the ammonia concentration. Supporting electrolyte 0.1M
K2SO4, scan rate of 100mV/s and pH 11 at 25°C.
The electrochemical activity of Ni was evaluated under different
concentrations of ammonia. In (4b) the current density increase proportional
to ammonia concentration but the reduction peak does not. This decrease
can be explained by the fact that the applied potential is now being split
between two oxidation reactions (nickel and NH3), in addition, ammonia
tends to reduce more NiOOH to β-Ni(OH)2 in the forward scan; hence, the
amount of NiOOH available for reduction in the cathodic region decreases.

a) b) c)

Conclusions:
The results showed that CNT-Ni composite could be used as electrode for
, ammonia oxidation. This process caused in the cyclic voltammetry an
increment in the anodic current density and a decrease in the reduction side.
The decrease in cathodic charge is explained due to ammonia reacts and
reduce NiOOH to Ni(OH)2 and by the fact that the applied potential is now
Figure 2: SEM images of a) as they grown (CNT-P), b) after acid treatment (CNT-O)
and c) when nickel nanoparticles are attached onto their surface (CNT-Ni) being split between two oxidation reactions.

SEM micrographs (Figure 2) show that after the acid treatment, CNT are Acknoledgements:
cleaned from amorphous carbon residues and been covered by carboxyl Authors show their gratitude to CINVESTAV to give financial support to be
groups, the presence of these groups would be used for ion exchange, able to present in this congress. M. A. Gonzalez-Reyna and Maria Selene
replacing the proton with a nickel ion with a very uniform coverage (2c). Luna-Martínez’s scholarships were supported by CONACYT.

References: [4] Catal. Commun. 8 (2007) 1017–1022. doi:10.1016/j.catcom.2006.10.009.

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