Hierarchical NiCo2O4/CuO-C

nanocomposite derived from

copper-based metal organic framework
and Ni/Co hydroxides_ Excellent
electrocatalytic activity towards
methanol oxidation Sara Sheikhi &
Fahimeh Jalali
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 Journal of Alloys and Compounds 907 (2022) 164510

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Hierarchical NiCo2O4/CuO-C nanocomposite derived from copper-based

metal organic framework and Ni/Co hydroxides: Excellent ]]
]]]]]]
]]

electrocatalytic activity towards methanol oxidation

⁎
Sara Sheikhi, Fahimeh Jalali
Department of Analytical Chemistry, Razi University, Kermanshah, Iran

a r t i cl e i nfo a bstr ac t

Article history: In this work, a metal-organic framework (Cu-MOF) and two none-precious metals (Ni and Co) are used for
Received 27 December 2021 preparation of a highly efficient electrocatalyst for methanol oxidation reaction. Nickel/cobalt hydroxides
Received in revised form 5 March 2022 are coprecipitated on Cu-MOF in alkaline solution. The composite is then calcinated at 350 °C to obtain a
Accepted 7 March 2022
carbonaceous framework and flower-like NiCo2O4 deposits (CuO-C/NiCo2O4). The obtained composite is
Available online 9 March 2022
characterized by several methods (XRD, XPS, FT-IR, SEM, TEM, and electrochemical techniques). The pre­
sence of metal oxides CuO and NiCo2O4 in the prepared electrocatalyst is confirmed by XRD and XPS
Keywords:
Electrocatalyst methods. CuO-C/NiCo2O4 shows excellent catalytic activity towards MOR in alkaline solution (NaOH, 1 M).
Metal-organic framework The electrocatalytic activity of CuO-C/NiCo2O4 is compared to stepwise composites (CuO-C/NiO, CuO/CoO,
Metal oxides NiCo2O4) and commercial Pt/C, which confirms the superiority of the proposed catalyst in terms of current
Copper density (208.1 mA cm−2) and amperometric stability (7000 s) in methanol oxidation reaction. The observed
Nickel benefits are attributed to synergistic effects between the porous conductive carbonaceous material and
Cobalt multi transition-metal oxides (CuO and NiCo2O4).
Methanol oxidation © 2022 Elsevier B.V. All rights reserved.
Fuel cell

1. Introduction alternatives for noble-metal catalysts, have recently attracted con­

The worldwide demand for new energy resources has been the
basis of numerous researches exploring new sustainable and eco-
friendly energy-production systems. Fuel cells, which convert che­
mical energy to electricity, are in the core of many research activ­
ities. Various fuel cells have been proposed to overcome the energy
crisis and environmental issues. Significant progress in using in­
expensive and abundant fuels with the least environmental pollu­
tion, such as hydrogen and small alcohols, has been achieved.
However, their oxidation reaction is sluggish and needs efficient
catalysts to proceed. Nobel metals (such as Pt and Pd), known as
highly efficient catalysts, have been widely used in fuel cells. But
they are scarce metals in the earth-crust and are largely poisoned by
intermediates (such as CO) in the reaction course. Therefore, de­
veloping new more efficient, robust and more abundant catalysts
was focused as a main challenge in fuel cells researches [1–4].
Transition metal oxides, such as Co3O4 [5], Co(OH)2 [6], NiO [7],
MoO3 [8], ZnCo2O4 [9] and NiCo2O4 [10], as highly efficient
⁎
Corresponding author.
E-mail addresses: fjalali@razi.ac.ir, fahimeh41@gmail.com (F. Jalali).
siderable attention. In addition, mixed-metal oxide, NiCo2O4, has
been introduced as a useful catalyst for methanol oxidation reaction
(MOR) [11,12]. Its efficiency was attributed to its much higher con­
ductivity, larger specific surface area and high-density defects, as
compared to NiO and Co3O4. Three-dimensional hierarchical struc­
ture of NiCo2O4 facilitates the electrolyte permeability and ion dif­
fusion, leading to improved catalytic activity towards MOR [13,14].
Another class of useful materials in designing efficient electro­
catalysts are metal-organic frameworks (MOFs), which are porous
crystalline structures with widely adjustable morphologies. MOF's
porous structure provides large surface area, as well as, numerous
active metallic sites. In addition, they have several channels for ion
diffusion, an important requirement in catalysis [15]. They have been
used as highly ordered materials in many applications, such as
electrochemical sensors [16], fuel cells [17], supercapacitors [18] and
solar cells [19]. The main drawback of most MOFs in electrochemical
methods is their low electrical conductivity [20]. Many efforts have
been made to increase their conductivity, such as making compo­
sites with conductive nanomaterials or proper polymers, and calci­
nation at high temperatures [17,21]. Calcination converts the organic
skeleton of MOFs to highly conductive porous carbon in which
metal/metal oxides are embedded. The highly-ordered carbonaceous

https://doi.org/10.1016/j.jallcom.2022.164510
0925-8388/© 2022 Elsevier B.V. All rights reserved.
S. Sheikhi and F. Jalali
framework containing numerous accessible metal/metal oxide cen­
ters exhibited excellent electrocatalytic properties in various elec­
trochemical applications [17,22,23]. Cu-MOF has received
prominence as a precursor of various Cu-containing electrocatalysts,
e.g., in oxygen evolution reaction (OER) [24], hydrogen evolution
reaction (HER) [25], water splitting [26], supercapacitors [27], and
MOR [28].
In the present study, a highly efficient, noble-metal-free elec­
trocatalyst was prepared by a simple procedure. HKUST-1 (Cu-MOF)
was used as a new platform for deposition of Ni-Co hydroxides.
Then, by calcination at 350 °C, the composite was converted to a
carbonaceous structure containing metal oxides (CuO-C/NiCo2O4).
The resulted composite offered outstanding electrocatalytic activity
towards MOR. Increased current density, anti-poisoning property,
longer lifetime and stability were observed for CuO-C/NiCo2O4
compared to other studied catalysts (such as, CuO, NiCo2O4, etc.).
2. Experimental section
2.1. Chemicals
All chemicals were of analytical reagent grade and used without
further purification. Double distilled water was used as the solvent
for preparation of the solutions. Nitrate salts of nickel (Ni
(NO3)2.6 H2O), copper (Cu (NO3)2.3 H2O) and cobalt (Co
(NO3)2∙6 H2O), trimesic acid (benzene-1,3,5-tricarboxylic acid,
H3BTC), ammonia, and Nafion solution (5 w/v%) were purchased
from Sigma-Aldrich. All other chemicals such as methanol (chro­
matography grade), sodium hydroxide, ethanol, and N,N-di­
methylformamide (DMF) were from Merck (Darmstadt, Germany).
2.2. Characterization methods
Morphological studies were conducted by field emission scan­
ning electron microscopy (FESEM, Czech Republic, TESCAN mirra3),
transmission electron microscopy (TEM, Philips CM30, Netherlands),
and X-Ray diffractometry (XRD, Rigakuultima iv, Japan). XRD spectra
were collected at 2θ values ranging from 5 to 80 degrees. Fourier
transform IR (FT-IR) spectra were recorded by using a Bruker spec­
trometer. X-ray photoelectron microscopy (XPS) measurements
were made on Specs Lab Prodigy (Version 4.43.2-r73078) by using Al
Kα line (1486.6 eV). Inductively coupled plasma-optical emission
spectroscopy (ICP-OES) was carried out by Varian Vista-Pro instru­
ment, Australia.
2.3. Preparation of CuO-C/NiCo2O4 nanocomposite
A previously reported procedure was used for synthesis of Cu-
MOF (HKUST-1) [29]. Briefly, H3BTC (0.63 g, 3 mmol) and Cu
(NO3)2.3 H2O (1.25 g, 5.2 mmol) were stirred for 15 min in 31.5 mL of
solvent (equal volumes of DMF, ethanol and deionized water), to
obtain a clear solution. The mixture was then transferred into a
50 mL Teflon-lined stainless-steel autoclave. The autoclave was
sealed and placed in an oven at 85 °C for 20 h. After cooling at room
temperature, the resulted blue solid was collected and dried at 120
°C (12 h) to obtain crystalline Cu-MOF.
The nanocomposite (CuO-C/NiCo2O4) was synthesized by a co-
precipitation method in alkaline aqueous solution followed by an
annealing treatment. In a typical experiment, Ni(NO3)2.6 H2O (0.18 g,
1 mmol) and Co(NO3)2.6 H2O (0.36 g, 2 mmol) were dissolved in
deionized water (30 mL). Then, the prepared Cu-MOF (0.50 g) was
added to the mixture and homogenized by ultrasonication for
20 min. In the next step, pH was adjusted to 10 by dropwise addition
of ammonia solution. The obtained solution was then stirred under
reflux conditions (5 h at 80 °C). Cu-MOF/NiCo2(OH)x, formed in this
step, was washed with deionized water and ethanol several times
2
Journal of Alloys and Compounds 907 (2022) 164510
and then dried in an oven (12 h at 60 °C). Finally, Cu-MOF/
NiCo2(OH)x was calcinated at 350 °C (2 h) with a heating rate of 1 °C
min−1 in air to obtain CuO-C/NiCo2O4 composite [30,31]. In order to
study the effect of each component on electrocatalytic activity, the
procedure was repeated by omitting one of the constituents each
time. Therefore, CuO-C/NiO, CuO-C/CoO, and pure NiCo2O4 were also
synthesized by the same procedure.
2.4. Electrochemical measurements
Glassy carbon electrode (GCE, d = 2.0 mm, geometric surface area
= 0.0314 cm2) was polished on smooth alumina slurry to a mirror-
like appearance and rinsed with a plenty of distilled water. A
homogeneous suspension of the synthesized catalyst, i.e., mixture of
CuO-C/NiCo2O4 (5 mg in 1 mL H2O) and Nafion (6 μL of 5 w/v%) was
prepared by ultrasonication. The suspension (4 μL) was drop cast on
GCE surface and dried in air at room temperature. Electrochemical
measurements including cyclic voltammetry (CV), electrochemical
impedance spectroscopy (EIS), and chronoamperometry were car­
ried out on the modified electrode by using an electrochemical in­
strument (Autolab PGSTAT 204, Utrecht, The Netherlands) equipped
with NOVA 2.1.2 software. All electrochemical experiments were
performed in NaOH aqueous solution (1 M), in the absence and
presence of methanol. In all experiments, Ag/AgCl (KCl, 3 M) was
used as the reference electrode, a platinum wire as the counter and
CuO-C/NiCo2O4/GCE as the working electrode. All measured poten­
tials were reported relative to RHE (reference hydrogen electrode) by
using the following relationship: ERHE = EAg/AgCl + 0.198 + 0.059 × pH
[32], where EAg/AgCl is the experimental potential vs. Ag/AgCl (KCl,
3 M), E° Ag/AgCl = 0.198 V at room temperature, and pH value is ~ 14 for
the electrolyte (NaOH 1 M). CV plots were recorded within the po­
tential range of + 1.0 to + 1.8 V (vs. RHE) at scan rate of 100 mV s−1.
EIS measurements were performed by using a voltage amplitude of
10 mV and frequencies from 0.1 Hz to 105 Hz.
3. Results and discussion
3.1. Characterization of the proposed electrocatalyst (CuO-C/NiCo2O4)
3.1.1. Thermal gravimetry (TGA)
The weight-loss profile of Cu-MOF in TGA showed three stages
(Fig. 1A). The initial slight weight-loss (up to 90 °C) can be assigned
to the removal of the solvent (ethanol). The second weight-loss
observed in the temperature range from 100° to 330°C was attrib­
uted to the elimination of coordinated or residual water molecules
and DMF, and the subsequent significant weight-loss occurred about
350 °C was due to combustion of the organic framework in Cu-MOF,
with the residue being mainly copper oxide [24].
3.1.2. XRD spectra
XRD is a useful method for studying crystalline structures con­
taining heavy metals. Herein, XRD spectra of three species were
compared. The powder diffraction spectrum of the prepared Cu-MOF
and its simulated XRD pattern are compared in Fig. 1B. The results
showed that the prepared Cu-MOF had the characteristic diffraction
peaks of simulated spectrum at 2θ= 6.68°, 9.48°, 11.64° and 13.43°,
evidenced successful synthesis of Cu-MOF [33]. XRD diffraction
spectra of NiCo2O4 and CuO-C/NiCo2O4 are shown in Fig. 1C. The XRD
spectrum of prepared NiCo2O4 showed diffraction peaks (2θ = 18.9°,
31.1°, 36.7°, 38.4°, 44.6°, 55.4°, 59.0°,and 65°) similar to NiCo2O4
cubic spinel crystalline phase (JCPDS No.20–0781) [34,35]. After
calcination of Cu-MOF/NiCo2(OH)x at 350 °C in air, it showed a large
change compared to Cu-MOF spectrum. In addition, characteristic
peaks of NiCo2O4 and CuO were observed. Standard spectrum of
cubic CuO (JCPDS No. 48–1548) was similar to that we obtained after
calcination of the composite (2θ = 32.5°, 35.5°, 38.7°, 46.3°, 48.7°,
S. Sheikhi and F. Jalali
Fig. 1. (A) Thermal gravimetric analysis of Cu-MOF, (B) Comparison of powder-XRD
spectrum of the prepared Cu-MOF and its simulated spectrum. (C) Powder XRD
spectra of NiCo2O4 and CuO-C/NiCo2O4. Standard XRD spectra of CuO (JCPDS No.
48–1548) and NiCo2O4 (JCPDS No.20–0781) are shown as vertical lines at corre­
sponding 2θ values (D) FTIR spectra of Cu-MOF, CuO-C and CuO-C/NiCo2O4.
3
Journal of Alloys and Compounds 907 (2022) 164510
53.4°, 58.2°, 61.5°, 66.2°, 68.1°, 72.3° and 74.9°) [36]. Therefore, it
seems that, after calcination procedure, crystalline structures of
NiCo2O4 and CuO were formed in the final composite.
3.1.3. FT-IR spectroscopy
FT-IR spectra of Cu-MOF, CuO-C and the final nanocomposite
(CuO-C/NiCo2O4) are shown in Fig. 1D. In the case of Cu-MOF, two
sharp absorption peaks about 1647 and 1380 cm−1 were due to the
asymmetric and symmetric C=O stretching vibrations of carboxylate
groups, respectively. In addition, the absorption peaks appeared at
1563 and 1443 cm−1 were attributed to C=C stretching vibrations,
while absorption around 1712 cm−1 was related to stretching vibra­
tion of C=O present in the organic framework (BTC). Coordination of
Cu(II) to the carboxylate groups of BTC was confirmed by observing
Cu-O vibration peak at 728 cm−1[16]. In the case of CuO-C (obtained
from calcination of Cu-MOF), the existence of a carbonized network
was ensured by absorption peaks at 1121 and 1625 cm−1, which
originated from C-C and C=O stretching vibrations, respectively. The
absorption peaks at 480 and 618 cm−1 were ascribed to the
stretching vibrations of Cu-O bond in CuO/C [37]. Compared to Cu-
MOF, in CuO-C and CuO-C/NiCo2O4 spectra, the peaks corresponding
to C=C and metal coordinated carboxylate groups have disappeared
due to the carbonization process. The peaks at 621, 552 and 480 cm−1
were attributed to Ni-O, Co-O and Cu-O in CuO-C/NiCo2O4, respec­
tively [38], while the remained spectrum was nearly intact, com­
pared to CuO-C. Therefore, FT-IR spectra confirmed the results of
XRD experiments.
3.1.4. Nitrogen adsorption/desorption studies
The surface area and porosity of a catalyst are important factors
for evaluating its efficiency. Therefore, BET specific surface areas of
the synthesized Cu-MOF, NiCo2O4, and CuO-C/NiCo2O4 were de­
termined by N2 adsorption-desorption isotherms, and pore size
distribution plot obtained from Barrett-Joyner-Halenda (BJH)
method (Fig. S1 and Table S1, supporting file). The observed ad­
sorption-desorption isotherm type (I) reflects the microporous net­
work of the Cu-MOF. In the case of CuO-C/NiCo2O4, a typical type IV
isotherm was recorded with a noticeable hysteresis loop in the re­
lative pressure range of 0.4–1.0, indicating a mesoporous structure of
the catalyst. The calculated BET specific surface area (SBET) and the
mean pore diameter for CuO-C/NiCo2O4 were about 424.6 m2 g−1
(much larger than that for NiCo2O4, 170.3 m2 g−1) and 6.8 nm, re­
spectively.
3.1.5. XPS analysis
In order to obtain more structural information about the pre­
pared electrocatalyst (CuO-C/NiCo2O4), X-ray photoelectron spec­
troscopy (XPS) was used. The survey scan spectrum of CuO-C/
NiCo2O4 (Fig. 2A) revealed the coexistence of C 1 s, O 1 s, Cu 2p, Ni
2p and Co 2p elements. In Fig. 2A, the peaks marked KLL and LMM
corresponded to electronic energy levels of atoms that involved in
the process, i.e., KLL means the initial photoelectron ejection from
K level, followed by filling the created hole by a L electron, and
finally ejection of a L electron (an auger electron) from the excited
ion (a same explanation applies to LMM). According to XPS de­
convoluted results for Cu (Fig. 2B), two typical peaks centered at
binding energies (B.E.) 934.5 and 954.5 eV were related to spin-
orbit peaks of Cu 2p3/2 and Cu 2p1/2, respectively (energy separa­
tion of 20.0 eV), endorsing the presence of Cu (II) in the CuO phase.
Moreover, the shake-up satellite peaks found at 942.5 and 962.5 eV
(denoted as Sat.) were also related to Cu 2p3/2 and Cu 2p1/2, re­
spectively [16,39]. In the case of Ni (Fig. 2C), characteristic peaks of
Ni 2p3/2 and Ni 2p1/2 appeared at B.E. values 855.4 and 873.3 eV,
respectively, with the spin−orbit energy difference of 17.9 eV, which
S. Sheikhi and F. Jalali
Fig. 2. (A) XPS survey, and deconvoluted spectra of (B) Cu 2p, (C) Ni 2p, (D) Co 2p, (E) O 1 s, and (F) C 1 s for CuO-C/NiCo2O4.
were indexed to Ni (II) [16,40]. Meanwhile, two shake-up satellites
related to Ni 2p3/2 and Ni 2p1/2 at 861.3 and 880.3 eV can be ob­
served [40]. The energy difference of 15.4 eV (Fig. 2D) is commonly
assigned to major Co 2p peaks (Co 2p3/2 and Co 2p1/2). In detailed
spectrum of Co 2p, Co 2p3/2 and Co 2p1/2 were distinguished by the
major peaks at 779.8 and 795.2 eV, respectively, which were as­
cribed to Co (III) [40]. Finally, in XPS core level spectrum of O 1 s,
three oxygen contributions (O1, O2, and O3) could be distinguished
(Fig. 2E). The peak at 530.2 eV (O1) was attributed to the metal
oxygen bond, O2 at 531.1 eV to the defective sites with low oxygen
coordination and oxygen deficient regions in the metal oxide pre­
parations, and O3 at 532.8 eV to physico/chemically adsorbed water
on the surface of the samples [17,40]. The peaks centered at 283.3,
284.4, and 286.4 eV (Fig. 2F), are attributed to C−C/C=C, C−O, and
C=O bonds, respectively.
4
Journal of Alloys and Compounds 907 (2022) 164510
3.1.5.1. Morphological studies. SEM images of Cu-MOF, CuO-C and
CuO-C/NiCo2O4 were compared. Fig. 3A shows uniform octahedral-
like morphology with smooth surfaces for Cu-MOF, similar to
previous reports [41]. Octahedral-like morphology was observed
after direct carbonization of Cu-MOF to CuO-C (Fig. 3B).
Carbonization process converts organic ligands into a carbon
matrix with rough surfaces [16]. After calcination of Cu-MOF/
NiCo2(OH)x in air, SEM and TEM images (C and D) were recorded.
Flower-like microstructure of NiCo2O4 was clearly observed in the
final composite. TEM images of CuO-C/NiCo2O4, however, showed
octahedrons of CuO-C and interconnected NiCo2O4 structures
(image D).
The presence of Cu, Co and Ni elements was also confirmed by
energy-dispersive X-ray (EDX) spectroscopy (Fig. 4). EDX elemental
analysis and mapping results showed the homogeneous distribution
S. Sheikhi and F. Jalali
Fig. 3. SEM images of (A) Cu-MOF, (B) CuO-C, (C) CuO-C/NiCo2O4 composites; (D) TEM images of CuO-C/NiCo2O4. Insets: Zoom-in images.
of Cu (18.16%), O (50.04%), Co (10.13%) and Ni (5.10%) in CuO-C/
NiCo2O4. Interestingly, the obtained atomic ratio of about 0.5 for
Ni:Co is similar to their stoichiometry in NiCo2O4. Moreover, ICP-OES
analysis was carried out for precise measuring Ni/Co ratio (Table S2).
The obtained mole ratio of Ni/Co in the composite was about 0.5,
which was in agreement with the obtained results from EDX ana­
lysis.
3.2. Electrochemical properties of CuO-C/NiCo2O4
Prior to the investigation of electrocatalytic properties of CuO-C/
NiCo2O4, its electrochemical behavior in alkaline solution (NaOH,
1 M) was studied by cyclic voltammetry (CV). Stepwise composites
were also prepared and their electrochemical properties compared
to CuO-C/NiCo2O4 (Fig. 5A). In all cases, voltammetric measurements
were performed after activation of the modified electrode by po­
tential cycling in the range of + 1.0 to + 1.6 V (vs. RHE, 20 cycles).
Despite the presence of Cu(II) in Cu-MOF, no obvious redox peak was
observed (Fig. 5A inset), which may be attributed to the en­
capsulation of copper ions in a nonconductive organic framework.
Therefore, restricted electron transfer among metal species on one
hand, and with the electrode surface, on the other hand, prevented a
faradaic current to flow [16]. Carbonization of Cu-MOF showed lar­
gely increased current, due to increased conductivity brought about
by carbonaceous framework and copper oxide centers.
5
Journal of Alloys and Compounds 907 (2022) 164510
In order to study the effect of Co and Ni oxides, separately, on the
electrochemical properties, two additional composites were pre­
pared by the same coprecipitation and calcination procedures, i.e.,
Cu-MOF (a) with Co salt to obtain CuO-C/CoO, and (b) with Ni salt for
producing CuO-C/NiO. These additional composites were not char­
acterized in detail and used only for comparison purposes. Anodic
and cathodic peaks appeared in CVs of both composites in alkaline
solution. The redox peaks at 1.49/1.40 V (vs. RHE), in the case of CuO-
C/ CoO, were attributed to Co(III)/Co(II) couple, and those for CuO-C/
NiO (1.49/1.21 V vs. RHE) to Ni(III)/Ni(II) redox couple [42] (ob­
viously, anodic peak potentials for Co and Ni overlapped in Fig. 5A).
In the next experiment, mixed-metal oxides NiCo2O4 (in the absence
of Cu-MOF) was deposited on the electrode surface, which showed
increased peak currents, due to the contribution of both Ni and Co
oxides in current flow (Eq. 1). The anodic peak was broadened due to
the overlapped oxidation potentials of Ni(II) and Co(II) [11,14,43,44].
In the reverse scan, both cathodic peaks were observable. Finally, the
composite CuO-C/NiCo2O4 exhibited the largest current densities
and the least onset potential (faster charge-transfer) due to the sy­
nergistic effect of its components, i.e., three redox active metallic
centers (Cu, Ni, Co) and highly conductive carbonaceous framework.
The effect of scan rate (20–200 mV s−1) on CuO-C/NiCo2O4
-modified electrode was studied in NaOH (1 M) (Fig. 5B). Linear
correlation between peak currents and scan rates (ʋ), as well as, the
slope of approximately 0.9 in the plot of log jp vs. log ʋ (inset) de­
monstrated a typical surface-confined electron-transfer process.
S. Sheikhi and F. Jalali
Fig. 4. EDX spectrum and corresponding elemental mapping images of CuO-C/NiCo2O4 nanocomposite.
Increased ∆Ep (Epa – Epc) with scan rate was mainly due to sluggish
kinetics of the quasi-reversible electron-transfer (Eq. 1) at higher
sweep rates [45].
NiCo2O4 + 3OH- ⇄ NiOOH + 2CoOOH + H2O + 3e- (1)
3.2.1. Electrocatalytic behavior of the proposed composite towards MOR
Electrocatalytic behavior of the prepared composites towards
methanol oxidation was studied (Fig. 5C). Both Cu-MOF and CuO-C
showed weak catalytic activities in methanol oxidation (inset). It
was proposed that CuO species that have been oxidized to CuOOH
6
Journal of Alloys and Compounds 907 (2022) 164510
before methanol oxidation were involved in the observed catalytic
current [43]. The comparison showed better catalytic effect after
carbonization of Cu-MOF to CuO-C, due to increased conductivity of
the carbonous framework, and more activity of CuO centers com­
pared to Cu(II) in Cu-MOF.
The presence of multi- metal oxides improved the catalytic
properties, significantly. The best result was obtained for CuO-C/
NiCo2O4 which may be attributed to the synergy between three
redox couples, i.e., Cu(III)/Cu(II), Co(III)/Co(II), and Ni(III)/Ni(II) to­
wards electrocatalytic oxidation of methanol. The following elec­
trocatalytic mechanism (Eq. 2-5) was proposed to be responsible for
methanol oxidation:
S. Sheikhi and F. Jalali Journal of Alloys and Compounds 907 (2022) 164510

Fig. 5. (A) CVs on a glassy carbon electrode (GCE) modified with different composites in NaOH (1 M), scan rate = 100 mVs−1; inset: comparison between CVs of CuO-MOF and CuO-
C. (B) Scan rate effect (20–200 mV s−1) on CuO-C/NiCo2O4/GCE in NaOH (1 M); inset: linear relationship between peak currents and scan rates and the plot of log jp vs. log ʋ. (C) CVs
of different composites in methanol solution (1 M); inset: comparison of CuO-MOF, and CuO-C modified electrodes. (D) Scan rate effect on CuO-C/NiCo2O4 in methanol (1.0 M) and
NaOH (1 M); inset: Normalized CVs.

oxidation peak on CuO-C/NiCo2O4 was 3.63 times higher than that

M(II) ⇄ M(III) + e M(III): CuOOH, NiOOH, CoOOH
M(III) + CH3OH + O2 → M(OH)2 + CO2 + H2O
Maximum current density for methanol oxidation was observed
at the surface of CuO-C/NiCo2O4 (208 mA cm2- at +1.6 V and scan rate
100 mV s−1), while Cu-MOF and CuO-C showed the least responses.
The multi-metal oxide catalyst, porous flower-like surface and in­
creased conductivity presented by carbonaceous framework greatly
increased the current response on CuO-C/NiCo2O4 [46]. One of the
most important characteristics of electrocatalysts is lowering the
required overpotential. The lowest onset potential for MOR was
observed in the case of CuO-C/NiCo2O4, emphasizing kinetics im­
provement of methanol oxidation on this composite compared to
other surfaces.
The effect of calcination at high temperatures (350 °C) on elec­
trocatalytic activity was studied on calcinated and non-calcinated
composites (Fig. S2, supporting file). A large increase in current
density was observed after calcination so that the methanol
(2)
on NiCo2(OH)x, and 2.94 times larger than Cu-MOF/NiCo2(OH)x. This
(3) result confirmed the great effect of calcination on catalyst efficiency,
i.e., increased conductivity and activity of the electrocatalyst.
By increasing potential scan rates (Fig. 5D), a gradual increase
was observed in the electrocatalytic oxidation current (in methanol
1.0 M, NaOH 1.0 M). Normalized CVs (j/ʋ1/2 vs. E) were plotted (inset)
which showed decreased current function with scan rate, confirming
electrocatalytic mechanism (EC’).
It is known that surface adsorption of MOR intermediates (e.g.,
CO) is the main reason for poisoning of precious metal-based cata­
lysts which limits their lifetime. Some non-precious metal oxides
have shown good anti-poisoning properties, i.e., they adsorb oxygen-
containing species on their surface (e.g., OH-ads), which facilitates
oxidation of adsorbed intermediates (such as oxidation of COads to
CO2) to clean the catalyst surface (Eq. 4).
MOOH-(CO)ads + 2 OH-ads → MOOH + CO2 + H2O + e- M: Cu, Ni, or Co
(4)

7
S. Sheikhi and F. Jalali Journal of Alloys and Compounds 907 (2022) 164510

Fig. 6. (A) LSV curves of CuO-C/NiCo2O4 in NaOH (1 M) in the presence (a) and absence (b) of methanol (1 M). (B) Nyquist plots of methanol electrooxidation on different
composites; in methanol (1.0 M) + NaOH (1 M); insets (a) magnified Nyquist plots for CuO-C/NiCo2O4 and NiCo2O4 (b) best fitted equivalent circuits. Rs, Q, Rct and Rads represent
the solution resistance, constant phase element (related to capacitance), charge-transfer resistance, and the adsorption resistance of reaction intermediates, respectively. (C) Effect
of methanol concentration (0.0–1.5 M) on CVs recorded on CuO-C/NiCo2O4 in NaOH (1 M).

8
S. Sheikhi and F. Jalali
Table 1
Charge-transfer and adsorption resistances (from EIS), ECSA and Cdl values (from CV)
for the prepared catalysts.
Catalysts Rct (Ω.cm2) Rads (Ω.cm2) ECSA Cdl (mF cm−2)
CuO-C/NiCo2O4 0.189 0.7 413.5 16.54
NiCo2O4 0.316 1.5 331.5 13.26
CuO-C/NiO 0.442 7.0 65 2.60
CuO-C/CoO 0.455 12.3 52 2.08
Rct: Charge-transfer resistance; Rads: Charge-transfer resistance due to adsorbed
species (e.g., CO); ECSA: Electrochemically active surface area; Cdl: Double-layer ca­
pacitance.
Theoretical studies have shown the preference binding to Ni by
methanol, while CO-like intermediates have more tendency to ad­
sorb on cobalt species in the composite [47]. In addition, the efficient
adsorption of CO on CuO has also been reported [48]. Therefore, the
simultaneous presence of Ni, Co, and Cu oxides in CuO-C/NiCo2O4 is
beneficial for both MOR catalysis and cleaning electrode surface
from poisonous intermediates.
In order to differentiate between MOR and water oxidation (be­
yond +1.6 V vs. RHE), linear sweep voltammograms (LSV) on CuO-C/
NiCo2O4 were compared in the absence and presence of methanol
(Fig. 6A). The onset potential for water oxidation is apparently far
from MOR (about 242 mV apart at 20 mA cm−2), thus, they are easily
distinguishable. LSV plots for other prepared composites are com­
pared in Fig S3 (Supporting file).
Electrochemical impedance spectroscopy (EIS) was applied to
obtain more information about electrical resistance and methanol
oxidation kinetics on different surfaces. In Nyquist plots (Fig. 6B),
experimental points were well-fitted to proper functions (solid
curves) and electrical equivalent circuits (inset), in which Rs is the
solution resistance, Q is the constant phase element (related to ca­
pacitive behavior), and Rct and Rads are charge transfer resistances
for oxidation of methanol and adsorbed intermediates, respectively
(directly proportional to the diameter of the semicircles in Nyquist
plots). Two merged semicircles appeared, revealing two electron-
transfer reactions during MOR process. The semicircle in the higher
frequency region (low Z′) can be assigned to the catalytic oxidation
of methanol, and the bigger semicircle in low frequency region (high
Z′) arises due to the adsorption of MOR intermediates (e.g., CO) on
the electrode surface and their further oxidation (Eq. 4) [49,50].
From the calculated Rct and Rads (Table 1), it was concluded that
CuO-C/NiCo2O4 exhibited the largest conductivity and electron
transfer kinetics, compared to other prepared catalysts, which are in
accordance with CV results.
The electrochemically active surface area (ECSA) is an important
parameter in catalyst performance; which represents the available
active sites. Double-layer capacitance (Cdl), proportional to ECSA,
was calculated [51]. In order to estimate Cdl, CVs in NaOH (1 M) were
obtained in response to different scan rates (10 – 60 mVs−1). Ac­
cording to the equation: ic = ʋ × Cdl, double layer charging current (ic)
at a constant potential (1.25 V in this study) increased linearly with
scan rate (ʋ) (Fig. S4, Supporting file) with a slope equal Cdl. ECSA
was then estimated by dividing Cdl to Ce (specific capacitance of the
alkaline electrolyte was reported as 0.04 mF cm−2 for 1.0 M NaOH
[52,53]). The calculated ECSA and Cdl values (Table 1) showed su­
periority of CuO-C/NiCo2O4 compared to other composites, i.e., the
accessibility to more active sites on this electrocatalyst. The reason is
the high surface to volume ratio provided by MOF-derived CuO-C for
9
Journal of Alloys and Compounds 907 (2022) 164510
deposition of a large amount of hierarchical flower-like structure of
NiCo2O4. This special structure allowed more diffusion of methanol
and ions to inner active sites of the catalyst.
Methanol concentration had high impact on current density, as
was expected (Fig. 6C). A steady increase in current density was
observed with alcohol concentration up to 1 M, which leveled off in
more concentrated solutions. The observation was explained on the
basis of limited number of active sites on the catalyst surface which
would be saturated at high methanol concentrations. In addition,
adsorption of CO-like intermediates on catalyst surface increases at
higher alcohol concentration which diminishes the number of ac­
cessible active sites [54,55].
A proper MOR electrocatalyst should have long-term stability,
i.e., tolerance against blockage by intermediates during prolonged
exposure to methanol. Application of hybrid metal oxides in catalyst
structure has been shown to accelerate further oxidation of poiso­
nous CO-like intermediates to CO2 through adsorption of OH- ions.
To confirm the long-term stability of the catalyst, two methods
(chronoamperometry and potential cycling experiments) were used.
Chronoamperometry (at +1.45 V vs. RHE) was applied to a glassy
carbon electrode modified with each of the prepared composites in
alkaline methanol solution (Fig. 7A). A relatively stable current
density was observed for each composite during a long time period
(about 2 h), but CuO-C/NiCo2O4 exhibited the highest current den­
sity (20.27 mA cm−2), as well as, the least decay (~12.3%) in the time
interval. A comparison with the commercial Pt/C (20%) electrode was
also carried out (Fig. S5, supporting file) which showed much better
stability of the proposed catalyst after ~2 h. Amperometric stability
was attributed to the better tolerance of the proposed electrocatalyst
against CO-like intermediates during MOR.
In order to study potential cycling stability, CVs were recorded
during successive potential cyclings to the prepared electro­
catalysts in methanol solution (200 cycles). The resulted CVs for
CuO-C/NiCo2O4 are shown in Fig. 7B and those for other catalysts
are presented in Supporting file (Fig. S6). The current response of
CuO-C/NiCo2O4 toward methanol electro-oxidation showed a loss
of only 12.67% after 200 cycles (inset), much better than that for
other studied surfaces, NiCo2O4 (50.91%), CuO-C/CoO (50.3%) and
CuO-C/NiO (45.62%). This result showed the fast recovery of CuO-
C/NiCo2O4 after exposure to repeated potential cycling during
methanol oxidation. It may be due to mixed-metal oxide structure
of CuO-C/NiCo2O4 and high tendency of the metal oxides for ad­
sorbing OH- and further oxidation of CO-like intermediates, thus,
refreshing the catalyst surface [54,55]. The electrode surface was
observed by SEM and EDX elemental analysis after cycling stabi­
lity test in methanol solution (Fig. 7C and D). The morphology and
elemental composition of the catalyst were nearly preserved after
200 consecutive potential cycles.
Comparison between the proposed electrocatalyst and some
recently reported Ni/Co – based catalysts for MOR (Table 2) re­
vealed better performance of CuO-C/NiCo2O4 than many of the
previous works. Therefore, application of Cu-MOF as a platform
for growing NiCo2O4 had a great effect on the electrocatalytic
properties of the final composite. After carbonization, CuO-C/
NiCo2O4 provided several metallic centers for catalytic methanol
oxidation, and due to its porous hierarchical flower-like mor­
phology, exhibited efficient pathways for diffusion of ions and
electrons in the course of MOR. Thus, large current density, as well
as, high stability was obtained for methanol oxidation on the
proposed electrocatalyst.
S. Sheikhi and F. Jalali Journal of Alloys and Compounds 907 (2022) 164510

Fig. 7. (A) Chronoamperometry on different electrocatalysts at a potential of 1.45 V vs. RHE recorded for 7000 s (B) Consecutive potential cycling (200 cycles) on CuO-C/NiCo2O4;
inset comparison of the 1st and 200th cycles. NaOH (1 M) + methanol (1.0 M). (C) SEM image and (D) EDX spectrum after 200 consecutive potential cycles.

10
S. Sheikhi and F. Jalali Journal of Alloys and Compounds 907 (2022) 164510

Table 2
Electrocatalytic performance of CuO-C/NiCo2O4 towards MOR compared to Ni/Co-based electrocatalysts.

Catalysts Loading (mg cm−2) Electrolyte Applied Voltage Activiy Stability Time, Scan Rate Ref.
(vs. RHE) (mA cm−2) s Decay% (mV s−1)

Ni1Co2Px 0.35/GCE 1.0 M CH3OH 1.7 155 7200 18.5 50 [56]

1.0 M KOH
Ni2Co2 Alloys 0.5/Ti electrode 0.5 M CH3OH 1.7 58 1200 3 50 [57]
1.0 M NaOH
Urchin-like NiCo2O4 Hollow 1.43/GCE 0.5 M CH3OH 1.6 33.8 1000 10 10 [58]
Microspheres 1.0 M KOH
Petal-like NiCo/NiO-CoO/Nanoporous 0.16/GCE 0.5 M CH3OH 1.61 178 2000 40 50 [17]
Carbon 0.5 M NaOH
NiCo2O4-rGO 0.24/GCE 0.5 M CH3OH 1.66 16.6 3500 6 50 [59]
1.0 M KOH
Ultrathin Nickel Oxide 0.28/GCE 0.5 M CH3OH 1.7 85.3 30,000 50 [60]
Nanosheets 1.0 M KOH Negligible
Drops
Co-MOF/GO 3.57/GCE 3.0 M CH3OH 1.1 29.1 4000 38 50 [61]
1.0 M KOH
NiO/Ni-P Tube 0.06/GCE 1.0 M CH3OH 1.55 28.56 20,000 50 [62]
0.5 M KOH Negligible
Drops
Ni0.75Cu0.25 0.5/Ti electrode 0.5 M CH3OH 1.83 140 1200 11 50 [63]
1.0 M NaOH
Ni-NPs/ZrO2-PCs/rGO 0.38/GCE 1.0 M CH3OH 1.75 240 5000 11.53 50 [23]
1.0 M NaOH
Au-NiCo2O4 nanoflower 1.43/GCE 0.5 M CH3OH 1.67 135.9 500 cycles 45 50 [11]
1 M KOH
NiCo2O4 Nanoparticles 6/GCE 0.5 M CH3OH 1.52 125 1000 28 10 [42]
1 M KOH
Coral-like NiCo2O4 0.72/GCE 0.5 M CH3OH 1.72 21 1000 27.47 10 [14]
1 M KOH
Co3O4/NiCo2O4 Direct growth/ 0.5 M CH3OH 1.52 140 1200 0 10 [64]
Ni foam 1 M KOH
Flower-like NiCo2O4 0.68/GCE 0.5 M CH3OH 1.52 148 1200 Negligible 50 [53]
1 M KOH Drops
CuO-C/NiCo2O4 0.63/GCE 1.0 M CH3OH 1.6 194.6 7000 12.29 50 This work
1.0 M NaOH

4. Conclusions Declaration of Competing Interest

Metal-organic framework (Cu-MOF) and non-precious metals (Ni,
Co) were used in synthesis of a new electrocatalyst. To improve elec­
trochemical properties and stability of the composite, it was calcinated
at 350 °C in air. The resulted composite ((CuO-C/NiCo2O4) showed
excellent electrocatalytic activity in methanol oxidation reaction
(MOR). The presence of three metal oxides in the composite (Ni, Co, Cu)
caused improved performance in the electro-oxidation of methanol
through bifunctional mechanism, i.e., adsorbing hydroxyl ions from
alkaline solution to promote methanol oxidation, and further oxidation
of blocking intermediates such as carbon monoxide. Comparison be­
tween the proposed catalyst (CuO-C/NiCo2O4) with CuO-C, NiCo2O4,
CuO-C/NiO and CuO-C/CoO revealed the significant improvement of
electrocatalytic properties by using Cu-MOF other than NiCo2O4 in the
catalyst structure. The flower-like hierarchical structure of NiCo2O4 on
CuO-C platform exhibited highest ECSA in comparison with the pre­
pared stepwise composites. As a result, highly increased current den­
sity (~ 194.6 mA cm−2 at scan rate 50 mVs−1) for methanol oxidation
was obtained. In addition, high current preservation (7000 s in chron­
oamperometry) and stability towards potential cycling (200 cycles) in
alkaline solution of methanol revealed its suitability as an anodic cat­
alyst in direct methanol fuel cells.
CRediT authorship contribution statement
Sara Sheikhi: Conceptualization, Methodology, Validation,
Software, Formal analysis, Investigation, Writing – original draft,
Writing – review & editing. Fahimeh Jalali: Conceptualization,
Investigation, Writing – review & editing, Supervision, Project ad­
ministration.
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the financial support of Razi
University, Kermanshah, Iran. We are thankful to Mr. Hamed
Mohtasham (PhD candidate in Kurdistan University, Sanandaj, Iran)
for interpreting XPS results.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.jallcom.2022.164510.
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Another random document with
no related content on Scribd:
que solo el hidalgo se podia en
aquella tierra mantener, que el
labrador pechero era neçesario
morir de hanbre.
Miçilo.—¿Pues porque no se iba
tu padre á vibir a otra tierra?
Gallo.—Son tan acobardados
para en eso los labradores, que
nunca se atreuen a hazer
mudança de la tierra donde
naçen: porque vna legua de sus
lugares les pareçe que son las
Indias: y imaginan que ay alla
gentes que comen los honbres
biuos. Y por tanto muere cada
vno en el pajar donde naçio,
avnque sea de hanbre. Y deste
padre naçimos dos hijos varones,
de los quales yo fue el mayor,
llamado por nonbre Alexandro. Y
como vimos tanta miseria como
passauan con el señor los
labradores, pensauamos que si
tomauamos offiçios que por
entonçes nos libertassen se
oluidaria nuestra vileza, y
nuestros hijos serian tenidos y
estimados por hydalgos y viuirian
en libertad. Y ansi yo elegi ser
saçerdote, que es gente sin ley; y
mi hermano fue herrero, que en
aquella tierra son los herreros
exentos de los pedidos, pechos y
velas del lugar donde siruen la
ferreria. Y ansi yo demandé
liçencia a mi padre para aprender
a leer: y avn se le hizo de mal
porque le seruia de guardar vnos
patos. y ojear los pajaros que no
comiessen la simiente de vn linar.
En conclusion mi padre me
encomendo[362] por criado y
monaçino de vn capellan que
seruia vn beneffiçio tres leguas de
alli. ¡O Dios omnipotente, quien te
dixera las bajezas y poquedades
deste honbre! Por cierto si yo no
huuiera tomado la mano oy para
te contar[363] de mi y no de otros,
yo te dixera cosas de gran
donayre. Pero quierote hazer
saber que ninguno dellos sabe
más leer que deletrear y lo que
escriben aslo de sacar por
discreçion. En ninguna cosa estos
capellanes muestran ser
auentajados, sino en comer y
beber: en lo qual no guardan
tiempo ni medida ni razon. Con
este estuue dos años que no me
enseñó sino a mal hazer, y mal
dezir, y mal pensar y mal
perseuerar. A leer me enseñó lo
que el sabia, que era harto poco,
y á escreuir vna letra que no
pareçia sino que era arado el
papel con pies de escarabajos. Ya
yo era buen moço de quinze
años, y entendia que para yo no
ser tan asno como mi amo que
deuia de saber algun latin. Y ansi
me fue á Zamora a estudiar
alguna gramatica: donde llegado
me presenté ante el bachiller y le
dixe mi necesidad, y el me
preguntó si traya libro: y yo le
mostré vn arte de gramatica que
auia hurtado a mi amo, que fue de
los de Pastrana que auia mas de
mil años que se inprimió. Y el me
mostró en el los nominatiuos que
auia de estudiar.
Miçilo.—¿De qué te mantenias?
Gallo.—Dauame el bachiller los
domingos vna çedula suya para
vn cura, o capellan de vna aldea
comarcana el qual me daua el
çetre del agua bendita los
domingos y andaua por todas las
casas a la hora del comer
echando a todos agua: y en cada
casa me dauan vn pedaço de
pan, con los quales mendrugos
me mantenia en el estudio toda la
semana. Aqui estube dos años:
en los quales aprendi
declinaciones y conjugaçiones:
genero, preteritos y supinos. Y
porque semejantes honbres
que[364] yo luego nos
enhastiamos de saber cosas
buenas, y porque nuestra
intinçion no es saber más: sino
tener alguna noticia de las cosas
y mostrar que emos entendido en
ello quando al tomar de las
ordenes nos quisieren examinar.
Porque si nuestra intinçion fuesse
saber algo perseuerariamos en el
estudio. Pero en ordenandonos
començamos a oluidar y damonos
tan buena priesa que si llegamos
a las ordenes neçios, dentro de
vn mes somos confirmados
asnos. Y ansi me sali de Çamora,
donde estudiaua harto de mi
espaçio, y por estar ya enseñado
á mendigar con el çetre sabiame
como miel el pedir: y por tanto me
bolui a ello[365]. Y ansi acordé de
yrme por el mundo en compañia
de otros perdidos como yo, que
luego nos hallamos vnos a otros.
Y en esta compañia fue gran
tiempo zarlo, ó espinel: y alcançe
en esta arte de la zarleria todo lo
que se pudo alcançar.
Miçilo.—Nunca esa arte á mi
noticia llegó: declarate me mas.
Gallo.—Pues quiero
descubrirtelo todo de raiz. Tu
sabras que yo tenia la persona de
estatura creçida y andaua vestido
en diuersas prouinçias de
diuersos atauios, porque ninguno
pudiesse con mala intinçion
aferrar en mi. Pero mas á la
contina traya vna vestidura de
vuriel algo leonado obscuro,
honesta, larga y con vna barua
espesa y muy prolixa, de grande
autoridad y un manteo encima,
puesto á los pechos vn boton[366].
Otras vezes mudando las tierras
mudaua el vestido: y con la
mesma barua vsaua de vn habito
que en muchas prouinçias llaman
veguino: con vna saya y vn
escapulario de Religioso que
hazia vida en la soledad de la
montaña; vna cayada y vn rosario
largo, de vnas cuentas muy
gruesas en la mano, que cada
vez que la vna cuenta caya sobre
la otra lo oyan todos quantos en
vn gran templo estuuiessen.
Publiqué adiuinar lo que estaua
por venir, hallar los perdidos,
reconçiliar enamorados, descubrir
los ladrones, manifestar los
thesoros, dar remedio façil á los
enfermos y avn resuçitar los
muertos. Y como de mí los
honbres tenian noticia venian
luego prostrados con mucha
humildad a me adorar y bessar
los pies y a ofreçerme todas sus
haziendas, llamandome todos
propheta y diçipulo y sieruo de
Dios, y luego les ponia en las
manos vno versos que en vna
tabla yo traya scriptos con letras
de oro sobre vn barniz negro; que
dezian de esta manera:

Muneribus decorare meum

vatem atque ministrum
precipio: nec opum mihi cura,
at maxima vatis.
Estos versos dezia yo auermelos
enbiado Dios con vn angel del
çielo, para que por[367] su
mandado fuesse yo de todos
honrrado y agradeçido como
ministro y sieruo de su diuina
magestad. Hallé por el reyno de
Portogal y Castilla infinitos
honbres y mugeres los quales
avnque fuessen muy ricos y de
los más prinçipales de su
republica, pero eran tan tímidos
superstiçiosos que no alçauan los
ojos del suelo sin escrupulizar.
Eran tan façiles en el credito que
con vna piedra[368] arrebuxada en
unos trapos ó vn pergamino con
vnos plomos ó sellos colgando,
en las manos de vn hombre
desnudo y descalço luego se
arrojauan y humillauan al suelo, y
venian adorando y ofreciendose a
Dios sin se leuantar de alli hasta
que el prestigioso questor los
leuantasse con su propria mano;
y ansi estos como me vian con
aquella mi santidad vulpina
façilmente se me rendian sin
poder resistir. Venian á consultar
en sus cosas conmigo todo lo que
deuian, ó querian hazer y yo les
dezia, que lo consultaria con Dios,
y que yo les responderia su diuina
determinacion, y ansi a sus
preguntas procuraua yo
responder con gran miramiento
porque no fuesse tomado en
palabras por falso y perdiesse el
credito. Sienpre daua las
respuestas dubdosas, ó con
diuersos entendimientos, sin
nunca responder absolutamente a
su intinçion. Como a vno que me
preguntó; qué preçeptor daria a
vn hijo suyo que le queria poner al
estudio de las letras. Respondi
que le diesse por preçeptores al
Antonio de Nebrija y a Sancto
Thomas. Dando á entender que le
hiziesse estudiar aquellos dos
auctores, el vno en la gramatica y
el otro en la theología; y suçedió
morirse el mochacho dentro de
ocho dias; y como sus amigos
burlasen del padre porque daua
credito a mis desuarios y de mis
juizios llamandolos falsos,
respondió que muy bien me auia
yo dicho: porque sabiendo yo que
se auia de morir, di a entender
que auia de tener por preçeptores
aquellos allá. Y a otro que auia de
hacer vn camino y temiasse de
vnos enemigos que tenia, que me
preguntó si le estaua bien yr
aquel camino. Respondi que más
seguro se estaua en su casa si le
podia escusar; y caminó por
burlar[369] de mi juizio, y sucedió
que salieron sus enemigos y
hirieronle mal. Despues como
aquel juizio se publicó me valio
muchos dineros a mi: porque
desde allí adelante no auian de
hazer cosa que no la viniessen
comigo á consultar pagandomelo
bien. En fin en esta manera dy
muchos y diuersos juizios que te
quisiera agora contar, sino fuera
porque me queda mucho por
dezir. Deziamos yo ser Juan de
vota Dios[370].
Miçilo.—¿Qué hombre es ese?
Gallo.—Este fingen los zarlos
superstiçiosos vagabundos que
era vn zapatero que estaua en la
calle de amargura en Hierusalen,
y que al tiempo que passauan a
Cristo presso por aquella calle,
salió dando golpes con vna horma
sobre el tablero diziendo: vaya,
vaya el hijo de María; y que Cristo
le auia respondido: yo yré y tú
quedarás para sienpre jamas para
dar testimonio de mi; y para en fe
desto mostraua yo vna horma
señalada en el braço, que yo
hazia con cierto artifiçio muy
façilmente, que pareçia estar
naturalmente empremida allí: y a
la contina traya vn compañero del
mesmo offiçio y perdiçion que
fuesse mas viejo que yo, porque
descubriendonos el vno al otro lo
que en secreto y confession con
las gentes tratauamos,
pareçiendo vn dia el vno y otro dia
el otro les mostrauamos tener
speçie de divinaçion y spiritu de
profeçia, lo qual sienpre nosotros
queriamos dar á entender. Y
haziamos se lo façilmente creer
por variarnos cada dia en la
representaçion; y deziales yo que
en viendome viejo me yba a
bañar al rio Xordan y luego boluia
de edad de treynta y tres años
que era la edad en que Cristo
murio. Otras vezes dezia que era
vn peregrino de Hierusalen,
honbre de Dios, enviado por él
para declarar y absoluer los
muchos pecados que auia[371]
secretos en el mundo, que por
verguença los honbres no los
osan descubrir ni confesar a
ningun confessor.
Miçilo.—¿Pues para qué era
eso?
Gallo.—Porque luego en
auiendoles hecho creer que yo
era qualquiera destos dos
façilmente los podia abunir a
qualquiera cosa que los quisiesse
sacar. Luego como los tenia en
este estado començaua la zarleria
cantandoles el espinela, que es
vn genero de diuinança, a manera
de dezir la buenauentura. Es vna
agudeça y desenboltura de
hablar, con la qual los que
estamos platicos en ello sacamos
façilmente qualesquier genero de
scollos (que son los pecados) que
nunca por abominables se
confessaron a saçerdote. En
començando yo a escantar con
esta arte luego ellos se
descubren.
Miçilo.—Yo querria saber qué
genero de pecados son los que
se descubren a ti por esta arte, y
no al saçerdote?
Gallo.—Hallaua mugeres que
tuuieron açeso con sus padres,
hijos y con muy çercanos
parientes, y vnas mugeres con
otras con instrumentos hechos
para effectuar este viçio; y otras
maneras que es verguença de las
dezir; y hallaua honbres que se
me confessauan auer cometido
grandes inçestos, y con animales
brutos, que por no infiçionar el
ayre no te los quiero contar. Son
estos pecados tan abominables
que de pura verguença y miedo
honbres ni mugeres no los osan
fiar ny descubrir a sus curas ni
confessores; y ansi aconteçe
muchos[372] destos neçios
morirse sin nunca los confessar.
Miçilo.—Pues de presumir es
que muchos destos honbres y
mugeres, pensando bastar
confessarlos a ti se quedaron sin
nunca á sacerdote los confessar.
Gallo.—Pues ese es vn daño
que trae consigo esta peruersa
manera de vibir, el qual no es
daño qualquiera sino de gran
caudal.
Miçilo.—Querria saber de ti, qué
virtud, o fuerça tiene esa arte que
se los hazeis vosotros confessar,
y qué palabras les dezis?
Gallo.—Fuerça de virtud no es:
pero antes industria de Sathanas.
La manera de palabras era: que
luego les dezia yo que por auer
aquella persona naçido en vn dia
de vna gran fiesta en çinco puntos
de Mercurio y otros çinco de
Mars, por esta causa su ventura
estaua en dos puntos de gran
peligro, y que el vn punto era
vibo, y el otro era muerto, y que
este punto vibo conuenia que se
cortasse, porque era vn gran
pecado que nunca confessó, por
el qual corria gran peligro en la
vida. En tanta manera que si no
fuera porque Dios le quiso
guardar por los ruegos del
bienauenturado San Pedro, que
era mucho su abogado ante Dios,
que muchas vezes le ha cometido
el demonio en grandes, afrentas
donde le quiso auer traydo a la
muerte; y que agora era enbiado
por Dios este su peregrino de
Hierusalen y santo profeta; que
soy vno de los doze peregrinos
que residen á la contina en el
sancto sepulcro de Hierusalen en
lugar de los doze apostoles de
Cristo; y que yo soy su abogado
San Pedro que conuiene que el
me le aya de descubrir y
confessar para que yo se le
absuelua, y avn pagarle[373] por
el, y asegurarle que no penará ni
peligrará por el[374] pecado más.
Y ansi él luego me descubre su
pecado por graue y inorme que
sea; y prostrado por el suelo
llorando me pide misericordia y
remedio y le mande quanto yo
quisiere que haga para ser
absuelto, que en todo me
obedeçerá y avn me dará quanto
yo le pidiere y el tuuiere para su
neçesidad; y ansi quando yo veo
a la tal persona tan obediente y
rendida digola. Pues mira,
hermana, que este pecado se ha
de absoluer con tres signos y tres
cruzes y tres psalmos y tres
misas solenes: las quales se han
de dezir en el templo del Santo
Sepulcro de Hierusalen, y que
son misas de mucha costa y
trabajo, porque las han de dezir
tres cardenales y rebestirse con
ellos al altar tres obispos; y
hanlas de offiçiar tres patriarcas
vestidos de pontifical, y han de
arder alli tres çirios a cada misa,
que pesse cada vno seys libras
de cera; y luego dize el tal
penitente:
Pues vos mi padre y santo señor
vays allá hazedlas dezir, y yo al
presente daré los dineros y
limosna que pudiere y boluiendo
vos por aqui lo acabaré de pagar;
y yo respondo: que a mi me
conuiene forçado estar en
Hierusalen la Semana Santa, y
que en llegando se las haré dezir,
y ansi luego el penitente me da
diez y veinte[375] ducados y más,
o menos como cada qual tiene la
facultad, y yo la doy vna señal por
la qual quedo de boluer a la visitar
dentro de vn año o dos, sin
pensarla mas ver; y otras vezes
para auctoriçar esta mi mala arte
digoles: que yo le daré parte del
gran trabajo que tengo de reçebir
en el camino que emos de hazer
los escolares peregrinos de
Hierusalen quando todos juntos
vamos la Santa pasqua de
Resureçion por el olio y crisma a
la torre de Babilonia, como lo
tenemos por costunbre y promesa
traerlo nosotros doze para la
iglesia de Dios; lo qual se trae en
doze cauallos yendo nosotros a
pie. Que van luego los siete y
quedan los çinco aguardando; y
aquellos siete que van lleuan
siete ropas ricas y siete armas,
con las quales peleamos con
siete gigantes que guardan el
santo crisma y el olio de noche y
de dia, y como son mas fuertes
que nosotros dannos grandes
palos y bofetadas, hasta que
vienen del çielo siete donzellas en
siete nubes y en su fabor siete
estrellas; las quales peleando con
los gigantes los vencen y ansi las
damos las siete ropas, y nos
cargan los cauallos del Santo olio
y crisma y nos venimos con ello á
Hierusalen para que en la Santa
pascua de Resurreçion se
distribuya por toda la cristiandad;
y ansi por la misericordia de Dios
nuestro señor, por esta tu limosna
te haré parçionera deste trabajo
que en este viaje tengo de lleuar
por la iglesia de Dios; y demas
desto porque quedes más
purgada deste pecado me vañaré
por ti en la fuente y rio Xordan
vna vez. Y con este fingimiento y
enbaymiento, fiçiones y engaños
las hazia tan obedientes a mi
mandado, que despues de
auerme dado su hazienda si
queria tenia açesso con ellas a
medida de mi voluntad, y ellas se
preçiaban auer tenido açesso con
el profeta diçipulo de Dios y
peregrino[376] santo de
Hierusalen, sieruo de Jesu-
Cristo[377]. Y se tenian por muy
dichosos los maridos por auer
querido yo ansi bendezir a su
muger; y ellas se piensan quedar
benditas para sienpre jamas con
semejantes bendiçiones. En estas
maldades querria yo mucho que
el mundo estuviesse auisado, y
que no diesse lugar ninguno a se
dexar engañar de semejantes
honbres malos, pues todo esto es
manifiesta mentira y fiçion.
Y sé yo que al presente andan
muchos por el mundo, los quales
tienen engañada la mayor parte
de los cristianos, y se debria
procurar que los juezes los
vuscassen, y hallados los
castigassen en las vidas, porque
es vna speçie de superstiçion y
hurto el mas nefando que entre
infieles nunca se vsó, ni se sufrió.
Y porque veas quanta es la
desverguença y poquedad de los
semejantes hombres te quiero
contar vn passo que passé,
porque entiendas que los tales
ninguna vellaqueria ni poquedad
dexan de acometer y executar.
Sabras que vn dia yuamos tres
compañeros del offiçio del zarlo y
espinela, que andauamos
vuscando nuestra ventura por el
mundo. Y como llegamos acaso
en vna çiudad á la hora del
comer, nos entramos en vn
bodegon, donde comimos y
bebimos muy a pasto todos tres, y
acordamos que se saliesse el vno
á vuscar çierto menester, y como
se tardasse algo fuele el otro
vuscar: y ansi me dexaron solo a
mi por gran pieza de tiempo, y
dixome la bodegonera: hermano,
pagad, ¿que aguardais?
Respondi yo: aguardo aquellos
compañeros que fueron á vuscar
çierta cosa para nuestra
necesidad; y ella me dixo: pagad
que por demas los esperais: por
neçios los ternia si ellos
boluiessen acá; y yo le pregunté
quanta costa estaua hecha, para
pagarla; y ella contando á su
voluntad y sin contradiçion dixo
que quatro reales auiamos
comido y bebido; y luego me
leuanté de la mesa viniendome
para la puerta de la casa
mostrando vuscar la bolsa para la
pagar, y dixela: señora echadme
en vna copa vna vez de vino, que
todo junto lo pagaré: y diziendo
esto nos fuemos llegando a vn
cuero de vino que sobre vna
mesa tenia junto a la[378] puerta, y
la buena dueña, avnque no era
menos curial en semejantes
maldades que yo, descuydose: y
desató luego el cuero echando la
cuerda sobre el hombro por tener
con la vna mano el piezgo y con
la otra la medida, y começando
ella a medir le tomé yo la cuerda
del ombro y fueme lo mas
solapadamente que yo pude por
la calle adelante y avnque ella me
llamaua no le respondia: ni ella
por no dexar el cuero desatado
me vio mas hasta oy. Cansado ya
desta miserable y trabajada vida
fueme a ordenar para clerigo.
Miçilo.—¿Con que letras te yuas
al examen?
Gallo.—Con seys conejos y
otras tantas perdiçes que lleué al
prouisor, y ansi maxcando vn
euangelio que me dio a leer, y
declinando al reues vn nominatiuo
me passó, y al escrivano que le
dixo que no me deuia de ordenar
respondio: andad que es pobre y
no tiene de qué viuir.
Miçilo.—Por çierto que todo va
ansi. Que yo conozco clerigos tan
neçios y tan desuenturados que
no les fiaria la tauerna del lugar.
No saben sino coger la pitança y
andar, y si les preguntais, ¿donde
vays tan apriesa? Responde él
con el mesmo desasosiego: a
dezir misa. ¿Que no ay mas? Por
vn miserable estipendio, que si no
fuesse por él no la diria.
Gallo.—La cosa que más
lastimado me tiene el coraçon en
las cosas de la cristiandad es
esta: el poco acatamiento que
tienen estos capellanes en el
dezir misa. Que de todas las
naçiones del mundo no ay
ninguna que más bienes aya
reçebido de su Dios que los
cristianos: que los de los otros no
son dioses: no los pueden dar
nada; y con tantas merçedes
como los ha hecho, que avn asi
mesmo se les dio, y no ay naçion
en el mundo que menos
acatamiento tenga á su Dios que
los cristianos: y por eso les da
Dios enfermedades, pestelençias,
hambres, guerras, herejes. Que
en vn rincon de la cristiandad ay
todos estos males y justamente
los mereçen. Que como ellos
tratan a Dios ansi los trata él a
ellos a osadas. Que vno que para
tauernero no es sufiçiente se
haze saçerdote por ganar de
comer: y tanbien tienen desto
gran culpa los seglares, por el
trato que anda de misas y varatos
malos: que si esto no huuiesse no
se ordenaria tanto perdido y
oçioso como se ordenan con
confiança desto. Escriben los
historiadores por gran cosa, que
vn papa ordenó tres saçerdotes y
çinco diaconos, y ocho
subdiaconos. Y agora no hay
obispo de anillo que cada año no
aya ordenado quinientos desos
ydiotas y mal comedidos asnos.
Por eso determinó la iglesia que
los saçerdotes no se pudiessen
ordenar sino en qvatro temporas:
porque entonçes ayunasse el
pueblo aquellos dias, y rogassen
á Dios que les diesse buenos
saçerdotes, y por yr en ello tanta
parte del bien de la republica.
Pues y crees tú que se haze esto
alguna vez? Yo confio que nunca
le passa por pensamiento mirar
en esto a honbre de toda la
cristiandad: ni avn creo que nunca
tú oyste esto hasta agora.
Miçilo.—No por çierto.
Gallo.—Pues sabete que es la
verdad. Aveis de rogar a Dios que
os dé buenos saçerdotes: porque
algunos saçerdotes ay que no os
los dio Dios, sino el demonio, la
simonia y avariçia. Como a mí
que en la verdad yo me ordené
por auariçia de tener de comer: y
simoniacamente me dieron las
ordenes por seys conejos y otras
tantas[379] perdiçes, y permitelo
Dios, Quia qualis populus talis est
sacerdos. Quiere Dios daros
ruynes saçerdotes por los
pecados del pueblo: porque qual
es el pueblo tales son sus[380]
sacerdotes.
Miçilo.—Por çierto que en quanto
dizes has dicho verdad, y que me
he holgado mucho en oyrte.
Boluamos, pues, a donde
dexaste: porque quiero saber tú
que tal saçerdote heziste.
Gallo.—Por çierto dese mesmo
jaez: y avn peor que todos los
otros de que emos hablado.
Luego como fue saçerdote el
primer año mostré gran santidad:
y çertificote que yo mudé muy
poquito de mi vida passada: pero
mostraua gran religion: y ansi vibi
dos años aqui en esta villa: y
como me viessen la bondad que
yo representaua, que siempre
andaua en compañía de vna trulla
de clerigos santos que ha auido
de pocos tiempos en ella,
andando a la cortina visitando los
hospitales y corrales donde
auia[381] pobres, en compañía de
vnas mugerçillas andariegas y
vagarosas, callegeras que no
sufren estar vn momento en sus
casas quedas, que estas con todo
desassosiego tratauan en la
mesma santidad.
Miçilo.—Mayor santidad tuuieran
estando en sus casas en oraçion
y recogimiento.
Gallo.—-De las quales[382]
teniamos nuestras çiertas
granjerias, como camisas,
pañizuelos de narizes: y la ropa
blanca labada cada semana: y
algunas ollas y otros guisadillos
regalados[383] y algunoe
vizcochos y rosquillas: y como
vian todos la bondad que
representaua hablome vn letrado
rico si queria enseñarle vnos
niños pequeños que tenia, sus
hijos.