One-step facile preparation of ZnO

nanorods as high-performance
photoanodes for photoelectrochemical
cathodic protection - eBook PDF
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 Electrochimica Acta 276 (2018) 311e318

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

One-step facile preparation of ZnO nanorods as high-performance

photoanodes for photoelectrochemical cathodic protection
Yao Yang, Y. Frank Cheng*
Department of Mechanical and Manufacturing Engineering, University of Calgary, Calgary, AB, T2N 1N4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: In this work, ZnO nanorod photoanodes were fabricated by electrodeposition on a conductive indium tin
Received 6 March 2018 oxide glass substrate, enabling photoelectrochemical cathodic protection (CP) of both stainless and
Received in revised form carbon steels in a chloride solution. The surface morphology, composition, crystalline structure and
13 April 2018
optical absorption property of the prepared ZnO photoanodes were characterized by scanning electron
Accepted 26 April 2018
microscopy, energy dispersive X-ray spectrum, X-ray diffraction and UVeVisible diffuse reflection ab-
Available online 28 April 2018
sorption spectrometry, respectively. Electrochemical and photoelectrochemical properties of the pho-
toanodes were measured. Results demonstrate that the ZnO nanorod photoanodes are able to achieve
Keywords:
Photoanodes
sufficient cathodic polarization to 304 stainless steel and X52 carbon steel in 3.5 wt.% NaCl solution
ZnO nanorods under light illumination. Compared to previously reported ZnO photoanodes, the mass activity of the
Photoelectrochemical cathodic protection prepared ZnO nanorod photoanodes in this work is improved nearly 10 times and 3e6 times when
Stainless steel coupled with stainless steel and carbon steel, respectively. The unique surface nanostructure of the
Carbon steel generated ZnO nanorods contributes to the high photoelectrochemical activity of the photoanodes.
Particularly, the ZnO nanorod photoanode prepared at the depositing potential of
0.9 V (SCE) possesses
the higher photoelectrochemical activity of 19.5 mA/mg than those fabricated at more negative potentials.
Under identical illuminating conditions, the ZnO nanorod photoanode can cathodically polarize the
stainless steel much more substantially than carbon steel, causing negative potential shifts of 306.6 mV
and 39.1 mV, respectively.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
Steels have been the most commonly used engineering mate-
rials due to their excellent mechanical properties, machinability
and availability. However, the steels are prone to degradation and
corrosion in industrial environments, resulting in structural failures
and serious consequences. For example, the oil/gas pipelines made
of carbon steels suffer from corrosion and cracking in the service
environments, resulting in energy loss, adverse impact to envi-
ronment and even lethal threats [1].
Cathodic protection (CP) is an effective electrochemical tech-
nique to control corrosion of steel structures by cathodically
polarizing the steels to a potential more negative than their
corrosion potentials in the environment. Conventional CP systems
require either a consumable sacrificial anode or an external power
* Corresponding author.
E-mail address: fcheng@ucalgary.ca (Y.F. Cheng).
supply to impress current for cathodic polarization of the steels [2].
However, both CP methods suffer from limitations. The sacrificial
anodes have a limited service lifetime and need regular replace-
ment to maintain the functionality. In remote areas, the unavail-
ability of power supplies makes the impressed current CP
impossible. In recent years, novel photoelectrochemical CP systems
that use solar light as the power source to enable CP have attracted
much attention [3,4].
A photoelectrochemical CP system consists of a photoanode that
is made of photosensitive material and generates photoinduced
hole-electron pairs under light illumination. The electrons in the
valence band (VB) are excited into the conduction band (CB) by
absorption of photons, leaving photoinduced holes in the VB. The
photoelectrons flow to the steel, and polarize it to a potential more
negative than its corrosion potential in the environment. It has
been reported that photosensitive semiconductors, such as TiO2,
SrTiO3, etc., can be used in photoelectrochemical CP [5e7]. The
conventional method to fabricate photoanodes is to physically coat
nanoparticle doped semiconductor on the substrate to be protected

https://doi.org/10.1016/j.electacta.2018.04.206
0013-4686/© 2018 Elsevier Ltd. All rights reserved.
312 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318
[8e10]. The obtained semiconductor coating is usually thick
compared to the size of the nanoparticles. As a result, only the
nanoparticles located on the coating surface absorb light and
generate photoelectrons, while those beneath the surface do not
participate in photoelectrochemical reactions. This undermines the
performance of the photoanode, and reduces the efficiency of the
photosensitive materials. Moreover, it was reported that some
types of nanoparticles were toxic to a variety of creatures in envi-
ronments [11e14]. Therefore, it is of great importance to develop
innovative photoanodes with improved photoelectrochemical ac-
tivity and reduced environmental impact.
Electrodeposition technique can achieve template-free, in-situ
growth of hierarchical nanostructures on a conductive substrate.
The surface nanostructure achieves a large, electrochemically active
area. The growth of the hierarchical nanostructure requires no
additives, and avoid introduction of impurities that could reduce or
even poison the activity of the nanostructure [15e17]. These ad-
vantages make electrodeposition a promising facile method to
fabricate high-performance photoanodes for photoelectrochemical
CP. Particularly, ZnO is a widely used photosensitive material, with
an energy gap of about 3.3 eV [18], which corresponds to an optical
absorption wavelength of 375 nm. Thus, ZnO is able to harvest
energy from solar light. Moreover, ZnO can grow rapidly along
certain crystalline directions. It is thus feasible to prepare hierar-
chical ZnO nanostructures by electrodeposition via tuning the ZnO
growth directions. It was reported that ZnO nanorods were elec-
trodeposited on a variety of conductive substrates in electrolytes
containing zinc ions [19e21]. Compared to nanoparticles, nanorods
render the photoanode possess more active area for photo-
electrochemical reactions to improve its performance. A
throughout literature review shows that, up to date, there has been
no report to use ZnO nanorods as photoanodes for photo-
electrochemical CP of carbon steels. The effect of the electro-
depositing conditions, such as depositing potential, on the
photoelectrochemical activity of ZnO nanorods has remained
unclear.
In this study, ZnO nanorods were prepared by electrodeposition
on a conductive indium tin oxide (ITO) substrate to fabricate pho-
toanodes under varied electrodepositing potentials. Various anal-
ysis techniques, including scanning electron microscopy (SEM),
energy-dispersive X-ray spectrum (EDS) and X-ray diffraction
(XRD) were used to characterize the morphology, composition and
structure of the prepared ZnO nanorod photoanodes. The optical
absorption property of the photoanodes was measured by
UVeVisible diffuse reflection absorption spectrometry. Electro-
chemical impedance spectroscopy (EIS) was used to investigate the
electrochemical behavior of the ZnO nanorode photoanodes. The
photo potential and photo current density were measured to
determine the performance of ZnO photoanodes for cathodic pro-
tection of a 304 stainless steel and an X52 carbon steel in 3.5 wt.%
NaCl solution under light illumination.
2. Experimental
2.1. Fabrication of ZnO nanorod photoanodes
ZnO nanorod photoanodes were fabricated by electrodeposition
in a three-electrode cell containing 5  10
4 M ZnCl2 þ 0.1 M KCl
electrolyte using a Gamry Reference 600 potentiostat. Commercial
ITO conductive glass (Sigma Aldrich), a graphite rod and a saturated
calomel electrode (SCE) were used as working electrode (WE),
counter electrode (CE) and reference electrode (RE), respectively.
The ITO glass with a surface resistivity of 70e100 U/sq was cut into
specimens with a dimension of 1.0 cm  2.5 cm, cleaned by acetone
and deionized water ultrasonically, and dried by high-purity
nitrogen (99.999%). The processed ITO glass specimens were sealed
with a silicon rubber sealant, leaving a working area of
1.0 cm  1.0 cm. The electrolyte was preheated to 80  C and purged
with pure oxygen gas (99.9%) continuously for 1 h to achieve a
saturation of dissolved oxygen, with the oxygen content of
0.8  10
3 M in the solution. The electrodeposition was performed
at the potentiostatic mode with depositing potentials of
0.9 V
(SCE),
1.0 V (SCE) and
1.1 V (SCE), respectively. The electro-
depositing temperature was maintained at 80  C through a water
bath. The oxygen gas purging was maintained during electrode-
position. The fabricated ZnO nanorod photoanodes were rinsed
with deionized water, and dried with high-purity nitrogen.
To ensure the reproducibility of the obtained photoanodes in
this work, three to five specimens were made under identical
conditions as parallel specimens for various characterization and
measurements.
2.2. Morphological, compositional, structural and optical
characterization of the prepared ZnO nanorod photoanodes
The surface morphology of the prepared ZnO nanorod photo-
anodes was characterized by a SEM (FEI XL30). Prior to SEM
observation, a layer of Pt-Pd alloy coating with 0.5 mm in thickness
was applied on the specimens to improve the electric conductivity.
To measure the diameter of the ZnO nanorods, a number of SEM
images with a high magnification (  100,000) were used, and the
average diameter was calculated. For measurements of the length
of the ZnO nanorods, the top view of SEM images for detached ZnO
nanorods, as shown in Fig. 1d, was used.
The elemental composition of the photoanodes was analyzed by
EDS (Bruker XFlash 6130). The crystalline structure of the prepared
ZnO nanorods was measured by XRD (Rigaku Multiflex X-ray
Diffractometer), where the Cu Ka radiation (l ¼ 0.154 nm) was used
as the X-ray source under an operation condition of 40 kV and
20 mA. The scanner was set to scan from 20 to 90 with a scan rate
of 3 per minute. The optical absorption edge of the ZnO photo-
anodes was measured by UVeVisible diffuse reflection absorption
spectrometry (Agilent, Cary 4000), with a wavelength scan range
from 200 nm to 800 nm.
It is noted that, in this work, the prepared ZnO nanorods were
characterized by XRD first, and then by SEM for morphological
observation. The orientations of obtained nanorods at varied
depositing potentials were confirmed by multiple specimens in
parallel tests. Although TEM is powerful for characterization of the
nanorod orientation, the deposited ZnO nanorods would be
removed from the ITO substrate. This could change the orientation
of the deposited nanorods.
2.3. Electrochemical and photoelectrochemical measurements
The prepared ZnO nanorod photoanodes were coupled with 304
stainless steel and X52 carbon steel, respectively, for photo-
electrochemical measurements. Prior to measurements, the steel
electrodes were prepared by embedding in epoxy, leaving a
working area of 1.0 cm  1.0 cm. The working face of the steel
electrodes was ground sequentially up to #1200 emery paper and
rinsed by acetone. The detailed setup of the testing rig was
described in authors' previous work [22,23]. The ZnO nanorod
photoanode was immersed into a photoelectrode cell containing
0.1 M Na2S þ 0.2 M NaOH solution as hole scavenger, while the steel
electrode was placed in a corrosion cell containing 3.5 wt.% NaCl
solution. Both cells were connected by a salt bridge (i.e., saturated
KCl in agar gel). The ZnO nanorod photoanode and the steel elec-
trode were connected to the WE and CE poles of the potentiostat,
respectively. A SCE was placed in the corrosion cell and connected
 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318
Fig. 1. SEM images of the ZnO nanorods photoanodes prepared at various electro-
depositing potentials (a)
0.9 V (SCE), (b)
1.0 V (SCE), (c)
1.1 V (SCE). (d) View of the
detached ZnO nanorods.
313
to the RE pole. The potentiostat was set as the zero-resistance
amperemeter (ZRA) mode to measure the potential of the steel
electrode vs. SCE, and the current flowing between the photoanode
and the steel electrode. A 100 W Xe arc lamp (PTI LPS-250) with a
light intensity of 125 mW/cm2 was used as the light source. A
transparent quartz cell filled with deionized water was placed be-
tween the Xe arc lamp and the photoanode cell to absorb the heat
generated by the light, avoiding heating of the solution.
EIS measurements were conducted on the prepared ZnO
nanorode photoanodes in a three-electrode cell, where the ZnO
photoanode, a graphite rod and SCE were used as WE, CE and RE,
respectively. The used electrolyte was 0.1 M Na2S þ 0.2 M NaOH
solution. The EIS was measured under a potential perturbation of
±10 mV with a frequency range from 50 mHz to 10 kHz.
All measurements were conducted at room temperature
(25 ± 2  C). For statistical analysis of the measurement results, each
test was repeated at least three times.
3. Results and discussion
3.1. Morphology and composition of the prepared ZnO nanorod
photoanodes
The surface morphology of the fabricated ZnO nanorod photo-
anodes at various electrodepositing potentials are shown in Fig. 1. It
is seen that the prepared ZnO is shaped of rods. The average
diameter of the nanorods is about 250 nm and their average length
is 1.5 mm. The dimensions of the ZnO nanorods is almost inde-
pendent of the depositing potential. The density of the ZnO nano-
rods over the unit area of the ITO substrate decreases with the
negative shift of the depositing potential, which is more apparent at
the potential of
1.1 V (SCE). Generally, the ZnO nanorods orient
perpendicularly to the substrate when they are prepared at less
negative depositing potentials such as
0.9 and
1.0 V (SCE), as
seen in Fig. 1a and b. At the potential of
1.1 V (SCE), the ZnO
nanorods are randomly tilted on the ITO substrate (Fig. 1c). During
electrodeposition of ZnO nanorods, the reduction of dissolved ox-
ygen would occur at the same time. As it is a mass-transfer
controlled step, the electrodeposition of ZnO is actually affected
by mass transfer. A depletion layer of zinc and hydroxide ions can
be generated near the substrate/electrolyte interface due to the
formation of Zn(OH)2 and limited supply of zinc ions. The thickness
of the depletion layer increases with the negative shift of the
depositing potential. The density of ZnO nanorods decreases and
their orientation becomes more irregular with the increasing
thickness of the depletion layer. This phenomenon was also re-
ported in electrodeposition of metallic nanoparticles under diffu-
sion control [24].
The EDS spectrum measured on the prepared ZnO nanorod
photoanodes is shown in Fig. 2. The peaks of Zn and O indicate the
deposition of ZnO on the ITO glass. Other peaks such as Si, Pt, Pd, In
and Sn, are from the ITO substrate and the conductive Pt-Pd alloy
coating applied on the specimen for SEM characterization.
3.2. Structural characterization of the fabricated ZnO nanorod
photoanodes
Fig. 3 shows the XRD spectra of the ZnO nanorod photoanodes
prepared at various depositing potentials. The diffraction peaks
coincide with the standard diffraction pattern of ZnO (JCPDS XRD
file number 36e1451), confirming the preparation of ZnO nanorods
on ITO glass. Moreover, the specific peaks confirm that the crys-
talline structure of ZnO nanorods is hexagonal wurtzite-type. The
ZnO nanorods prepared at
0.9 V (SCE) and
1.0 V (SCE) are pref-
erentially (002) oriented, while that fabricated at
1.1 V (SCE) is
314 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318
Fig. 2. EDS spectrum of the fabricated ZnO nanorod photoanodes.
Fig. 3. XRD spectra of the ZnO nanorods photoanodes fabricated at various depositing
potentials.
preferentially (202) oriented. The results indicate that the ZnO
nanorods prepared at the less negative potentials are mostly
vertically oriented compared to that prepared at
1.1 V (SCE). This
is well consistent with the SEM views in Fig. 1.
3.3. Optical absorption properties of the ZnO nanorod photoanodes
The UVeVisible diffuse reflection absorption spectra of the
fabricated ZnO nanorod photoanodes are shown in Fig. 4a. It is seen
that an apparent light absorption is observed between 350 nm and
400 nm for all the prepared photoanodes. This is attributed to the
instinct absorption of ZnO [25]. Since most of the UV irradiation
from solar light have a wavelength range from 315 to 400 nm at
ground level, the prepared ZnO nanorod photoanodes are thus
Fig. 4. (a) UVeVisible reflectance absorption spectra of the ZnO nanorod photoanodes
prepared at various depositing potentials. (b) (ahn)2 vs. hn plots of the fabricated ZnO
nanorod photoanodes.
capable of harvesting solar energy on the ground.
To obtain the optical bandgap, Eg, of the prepared photoanodes,
the Tauc plot is plotted by Refs. [26,27]:

h
ahn ¼ A hn
Eg (1)
where a is the optical absorption coefficient, which is calculated by
a ¼ 2.303(Absorption)/t [28], h is Plank constant, n is the frequency
of photons, A is a constant, and h is the quantum efficiency. Since
the photo-induced excitation of electrons from VB to CB is the
direct excitation for ZnO, the value of quantum efficiency is 0.5 [29].
The plots of (ahn)2 vs. hn for the fabricated photoanodes are shown
in Fig. 4b. A linear part is seen in the plots between the photo en-
ergy of 3.0 eVe3.5 eV, which is attributed to the instinct absorption
of ZnO. The optical bandgap can be obtained by extrapolating the
linear part to a ¼ 0. The measured bandgaps of the photoanodes
fabricated at the depositing potentials of
0.9 V (SCE),
1.0 V (SCE)
and
1.1 V (SCE) are 3.25 eV, 3.18 eV and 3.21 eV, respectively. The
values are similar to the reported bandgap of undoped ZnO in
 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318 315

literature [18]. Table 1

Fitted electrochemical impedance parameters for the ZnO nanorod photoanodes
fabricated at various depositing potentials.

3.4. Electrochemical and photoelectrochemical measurements of Depositing potential Rs (U cm2) Rct (U cm2) Y0 (sn U cm
2) n
the prepared ZnO nanorod photoanodes Light OFF

0.9 V (SCE) 148.9 2.51  105 4.35  10
5 0.82
The electrochemical properties of the prepared ZnO nanorod
1.0 V (SCE) 179.0 1.95  105 5.04  10
5 0.87
photoanodes at the ZnO/solution interface 0.1 M Na2S þ 0.2 M
1.1 V(SCE) 170.7 4.01  105 3.38  10
5 0.92
Light ON
NaOH solution are measured by EIS in the absence and presence of

0.9 V (SCE) 128.1 1.13  104 2.53  10
4 0.85
light illumination, as shown in Fig. 5. In the electrochemical
1.0 V (SCE) 182.5 6.16  103 2.16  10
4 0.87
equivalent circuit used, Rs is solution resistance, Rct is charge-
1.1 V (SCE) 199.8 2.08  104 7.70  10
5 0.91
transfer resistance, and CPE is a constant phase element to repre-
sent the double-charge layer. The impedance of the CPE is calcu-
lated by ZCPE ¼ 1/[Y0(ju)n], where Y0 is the admittance magnitude of
the CPE, u is angular frequency, and n is the exponential term. For a
pure capacitor, n is equal to 1. The fitted electrochemical impedance
parameters are listed in Table 1. The difference in Rct for the pre-
pared ZnO nanorod photoanodes at varied potentials is attributed
to the charge carrier density of the photoanodes, in addition to the
spacing of the nanorods. The n-type ZnO semiconductors prepared
in this work are undoped, giving them a high resistivity and similar
band gaps. The various depositing potentials can make the stoi-
chiometric ratio of Zn and O atoms slightly deviate from the ideal
1:1 in the crystalline lattice, resulting in varied concentrations of
defects and charge carriers in ZnO and different Rct values [30]. The
Rct values decrease by a factor of 10 upon light illumination. The
generation and accumulation of photoinduced electron-hole pairs
at the ZnO/solution interface contribute to the decreased charge-
transfer resistance, resulting in acceleration of S2
oxidation on
the ZnO surface.
To further investigate the photoelectrochemical CP performance
of the fabricated ZnO nanorod photoanodes, the ZnO nanorod
photoanodes are coupled with 304 stainless steel and X52 carbon
steel electrodes, respectively, to measure the photoinduced current
density and potential. Fig. 6a shows the photoinduced current
density between the ZnO photoanodes and the 304 stainless steel
and X52 carbon steel electrodes, respectively, where a positive
current density indicates the flow of electrons from the photoanode
to the steel electrode. For 304 stainless steel coupled with the ZnO
photoanodes, a positive background current is measured even in
the darkness, which is due to the galvanic coupling effect of the two

Fig. 6. (a) The photoinduced current density between the ZnO nanorod photoanodes
and the 304 stainless steel and X52 carbon steel electrodes, respectively. (b) The po-
tential of the 304 stainless steel and X52 carbon steel electrodes coupled with the ZnO
photoanodes, respectively.

electrodes [22]. Since the corrosion potential of X52 carbon steel in

Fig. 5. Nyquist diagrams of the ZnO nanorod photoanodes in 0.1 M Na2S þ 0.2 M NaOH
solution with and without light illumination, where the electrochemical equivalent
circuit used to fit the measured impedance data is included.
3.5 wt.% NaCl solution, i.e.,
712 mV (SCE) [23], is close to the po-
tential of ZnO photoanode in 0.1 M Na2S þ 0.2 M NaOH solution, the
measured background current density of X52 steel is negligible
when it is coupled with the ZnO photoanode. Under light illumi-
nation, the photocurrent density increases remarkably due to
generation of photoelectrons on the ZnO photoanodes. Meanwhile,
the photoelectrons transfer to the steel electrode, resulting in a
316 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318

negative shift of potential of the steel electrode, as shown in Fig. 6b. protection performance.
It is noted that the potential shift of the prepared photoanodes The potential shift and the photocurrent density, which is
applying for 304 stainless steel is not identical to that for X52 determined by subtracting the background current density from
carbon steel. For example, there is the largest potential shift for the measured value, of the ZnO nanorod photoanodes are shown in
the
0.9 V (SCE) deposited photoanode when it is coupled with 304 Table 2. It is seen that the ZnO nanorod photoanode fabricated at
stainless steel, but this phenomenon is observed for
1.0 V (SCE) the depositing potential of
0.9 V (SCE) generates the largest
deposited photoanode when coupled with the carbon steel. This is photocurrent density, while the one prepared at
1.1 V (SCE) gen-
primarily attributed to the different electrochemical activities of erates the smallest photocurrent density. Although the ZnO pho-
stainless and carbon steels in the solution. For 304 stainless steel, a toanode prepared at
1.0 V (SCE) has the smallest Rct under
potential shift of about 50 mV is sufficient to make the steel under a illumination, which is associated with the largest current density, it
full cathodic polarization. According to Butler-Volmer equation, the also has the smallest Rct in darkness. Thus, the background current
anodic reaction is negligible under this condition. However, for density in the darkness of the photoanode is also the largest, which
carbon steel, due to its high electrochemical activity and negative reduces its photocurrent density.
corrosion potential in the solution, the photocurrent density is not In authors' previous work, it was determined that the current
sufficient to polarize the steel cathodically so that the anodic re- densities required to negatively shift the potential of 304 stainless
action cannot be neglected. Thus, the potential shift of carbon steel steel and X52 carbon steel by 100 mV in 3.5 wt.% NaCl solution are
depends not only on the photocurrent density, but also on the 0.5 mA/cm2 and 20 mA/cm2, respectively [23]. Therefore, the 304
polarization condition of the steel. As a result, the potential shift stainless steel is cathodically polarized much more substantially
under a given photocurrent density measured for stainless steel than X52 carbon steel when coupled with the ZnO photoanode
would be different from that when coupled with carbon steel. under identical illuminating conditions.
The photoelectrochemical process is schematically illustrated in
Fig. 7, where a mechanistic model is proposed for the photo-
electrochemical CP system based on the prepared ZnO nanorod
photoanode coupled with either a 304 stainless steel or an X52 Table 2
Photoinduced current density and potential shift of the prepared ZnO nanorod
carbon steel in 3.5 wt.% NaCl solution. The light is absorbed by ZnO photoanodes coupled with a 304 stainless steel and an X52 carbon steel electrode,
photoanodes, generating hole-electron pairs. The holes are respectively.
consumed by oxidation of S2
into S. Since the photoinduced holes
Photoanodes Photocurrent density (mA/cm2) Potential shift (mV)
are scavenged by S2
, the photoelectrons can transfer to the steel,
and are consumed by cathodic reaction (e.g., the reduction of dis- Coupled with 304 stainless steel electrode

0.9 V (SCE) 15.9 ± 0.6
306.6 ± 8.1
solved oxygen). As a result, the steel is cathodically protected from

1.0 V (SCE) 15.0 ± 0.3
195.9 ± 6.5
corrosion. It is noted that the prepared ZnO photoanode in this
1.1 V (SCE) 13.1 ± 0.9
157.1 ± 7.3
work is an n-type semiconductor, where holes are the minority Coupled with an X52 carbon steel electrode
charge carriers. A fast electron transfer kinetics of hole scavengers
0.9 V (SCE) 17.2 ± 1.4
39.1 ± 4.1

1.0 V (SCE) 15.4 ± 1.0
59.6 ± 7.5
can increase the photocurrent, resulting in an improved cathodic

1.1 V (SCE) 8.9 ± 1.5
16.4 ± 4.7

Fig. 7. Schematic diagram of the mechanistic aspect of photoelectrochemical CP system based on the prepared ZnO nanorod photoanode coupled with either a 304 stainless steel or
an X52 carbon steel in 3.5 wt.% NaCl solution.
 Y. Yang, Y.F. Cheng / Electrochimica Acta 276 (2018) 311e318
Table 3
Effect of depositing potential on mass activity (MA) of ZnO nanorod photoanodes and other photoanodes reported in literature.
Photoanodes Time (s) Charge used (C) Mass (mg)

0.9 V (SCE) 5400 2.089 0.881

1.0 V (SCE) 9700 2.098 0.885

1.1 V (SCE) 4600 2.170 0.915
ZnO on ITO7 50
SrTiO3 on ITO23 5 1.3
3.5. Photoelectrochemical activity of ZnO nanorod photoanodes
Generally, the electrodeposition of ZnO nanorods in an elec-
trolyte containing dissolved oxygen are described by Refs. [20,31]:
1 recombination rate, and enhance the CP performance. The effect of
O þH2 O þ 2e
/2OH

2 2
Zn2þ þ2OH
/ZnO þ H2 O
ZnO possesses a hexagonal crystalline structure. The direction of
±[0001] is one of the fastest growing ones. Thus, the deposited ZnO
exhibits a rod-like structure [32]. The amount of deposited ZnO can
be calculated by Faraday's law, assuming the depositing current is
100% of Faradic current. To characterize the photoelectrochemical
activity of the fabricated ZnO nanorod photoanodes, the mass ac-
tivities (MA) of the ZnO photoanodes prepared at various depos-
iting potentials are calculated by subtracting the background
current density, and the results are shown in Table 3. It is seen that
the MA of the prepared ZnO photoanodes decreases with the
negative shift of the depositing potential for both stainless steel and
carbon steel. Generally, the inter nanorod space of the photoanode
provides active surface areas for photoelectrochemical reaction. In
this work, the inter space between nanorods of the prepared ZnO
photoanode increases as the depositing potential is less negative, as
shown in Fig. 1. Thus, the increasing inner nanorod space of the
photoanode is able to enhance its mass activity for photo-
electrochemical reaction. For example, the ZnO nanorod photo-
anode prepared at
0.9 V (SCE) has the highest mass activity, which
is attributed to its high density of the generated ZnO nanorods and
the large surface area of the nanostructured photoanode.
For comparison, the MA of other types of photoanode reported
in literature [7,23] is listed in the table. To make these photoanodes,
nanoparticles of photosensitive materials were physically loaded
on the substrate material, and the photoinduced current density
was measured under similar conditions used in this work. It is seen
that the MA of the ZnO nanorod photoanodes prepared in this work
is much higher than that of the reported photoanodes. Particularly,
the MA of the photoanodes prepared herein is nearly 10 times of
those photoanodes when coupled with 304 stainless steel. For X52
carbon steel, the MA of the ZnO nanorod photoanodes is also 3e6
times of the ZnO photoanode made in Ref. 7. For the photoanodes
made by physical methods [7,23], the majority of photosensitive
materials are located in the bulk photoanodes, and serve as the
electron conductors only due to the thick (~50 mm) semiconductor
layers. However, the electrical resistivity of semiconductors, i.e.,
ZnO, is usually around 105 U cm [33], resulting in a poor conduction
of photoelectrons and a high recombination rate. For the ZnO
nanorod photoanodes prepared electrochemically in this work, the
thickness of the photosensitive material is reduced to about 1 mm so
that the photoelectrons can be collected by substrate easily.
Moreover, the ZnO nanorod photoanodes possess a surface nano-
structure and thus a large surface area, achieving a sufficiently high
electrochemical activity. Therefore, the prepared ZnO nanorod
photoanodes possess a high photoelectrochemical response.
317
MA with 304 stainless steel (mA/mg) MA with X52 carbon steel (mA/mg)
18.1 19.5
16.9 17.4
14.3 9.4
1.8 3.3
0.9
Furthermore, it is worthy of noting that, if surface states exist on
the ZnO nanorod photoanode and possess an energy level between
valence band and conductance band, a sub-band gap absorption of
light and trapping of photoelectrons in the surface states are
possible. The photoelectron trapping can reduce the surface
(2)
surface states on photoelectrode performance in photo-
electrochemical CP systems will be conducted in authors' further
research.
(3)
4. Conclusions
ZnO nanorod photoanodes prepared by electrodeposition at
various depositing potentials enable photoelectrochemical CP for
304 stainless steel and X52 carbon steel in 3.5 wt.% NaCl solution
under light illumination. Compared to previously reported ZnO
photoanodes, the mass activity of the ZnO nanorod photoanodes
prepared in this work is much higher under similar lighting con-
ditions. For 304 stainless steel and X52 carbon steel, the mass ac-
tivity of the photoanodes prepared herein is nearly 10 times and
3e6 times of that of the report photoanodes, respectively. The
unique surface nanostructure of the generated ZnO nanorods re-
sults in the high photoelectrochemical activity of the photoanodes.
Particularly, the ZnO nanorod photoanode prepared at the depos-
iting potential of
0.9 V (SCE) possesses the highest photo-
electrochemical activity of 19.5 mA/mg compared to those prepared
at
1.0 V (SCE) and
1.1 V (SCE). As the depositing potential is
shifted negatively, the density of the generated ZnO nanorods re-
duces, resulting in decreased surface area and thus the photo-
electrochemical activity. Under identical illuminating conditions,
the ZnO nanorod photoanodes can cathodically polarize the
stainless steel much more substantially than carbon steel. For
example, the ZnO photoanode prepared at the potential of
0.9 V
(SCE) is able to cause negative potential shifts of 306.6 mV and
39.1 mV for 304 stainless steel and X52 carbon steel, respectively.
Acknowledgements
The authors thank Dr. Cooper Harold Langford in the Depart-
ment of Chemistry at the University of Calgary for permitting the
use of photochemical facilities in his lab. This work was supported
by the University of Calgary International Doctoral Student
Recruitment Scholarship.
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Another random document with
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course, with considerable elaborations which by no means promote the
correctness, however much the beauty of aspect is improved.

Ancient Mexico. Taken from an Edition of the Letters of Cortés

Published at Luxemburg A.D. m.d.xx.viii.
Very similar to this is the view given in some of Solis’ editions, that of Antwerp,
1704, for instance, wherein is also found a view of Mexico with its surrounding
towns, as Cuitlahuac, Iztapalapan, and others, all grouped closely together within
the main lake! A native plan of the capital, said to have been given by Montezuma
to Cortés, accords little with Spanish descriptions, and is difficult to understand
from its peculiar outline, illustrated with Aztec hieroglyphics. Alaman doubts its
origin and correctness. See Prescott’s Mex. (Mex. ed. 1844), ii. 157. A good copy
of it is given in Carbajal Espinosa, Hist. Mex., ii. 221.
The view in Libro di Benedetto Bordone, Nel qual si ragiona de tutte l’Isole del
mondo, Vinegia, 1528, 73 leaves, is accompanied by an interesting description of
La gran citta di Temistitan, remarkable from being perhaps the first sketch of any
value given in a cosmographic work. It occupies the greater part of folios vi. to x.,
devoted to the terra da Ferdinando Cortese. Five more folios describe the West
Indies and Venezuela region, the only portions of America known to Bordone
when he wrote his book. It was completed in 1521, according to its pontifical
license, although not issued till 1528. The versatile author, who figured both as
artist and professor, died in 1531, and the later issues of the Libro, henceforth
called Isolario, are by editors whose endeavor to keep apace with the demands of
the times is instanced by the edition of 1537, wherein appears a letter on the
conquest of Peru. In the mappemonde of the first edition before me, the smaller
northern part of the new continent is called terra del laboratore, while the southern
part bears the inscription ponẽti môdo nouo. The two are separated at the
Isthmus, in about the latitude of the Mediterranean, by a long strait, at the eastern
mouth of which, on the sectional map of folio vi., is written, stretto pte del mõdo
nouo. Farther east lie the islands Astores, Asmaide, and Brasil. The numerous
sectional wood-cut maps and plans bear the conventional outline of a series of
concave segments, and of the ten referring to different parts of the new world,
seven apply to the Antilles.
The clearest account of Mexico given by any of the conquerors is to be found
in Relatione d’alcvne cose della Nuoua Spagna, & della gran città di Temistitan
Messico, fatta per vn gentil’huomo del Signor Fernando Cortese, wherein the
description of the natives, their manners and customs, their towns, the resources
of the country, and above all, the capital city, is to be found in concise form,
arranged in paragraphs with appropriate headings, and illustrated by a cut of the
great temple, which appears far more correct than those given by most
subsequent writers. A view of the capital is also appended, showing the
surrounding country, and according very nearly with those of the Nuremberg type,
except in the faulty relative position to the neighborhood. Nothing is known of the
author, who is generally referred to as the Anonymous Conqueror, but the opinion
has been hazarded that he was Francisco de Terrazas, mayordomo of Cortés. His
account was evidently written in Spanish, but did not see the light till Ramusio
issued it in Italian under the above title. It forms one of the most valuable
documents for the history of Mexico to be found in this prized collection of voyages
and travels, the first large work of its class. No branch of literature obtained a
greater stimulus from the discovery of Columbus. He it was who broke the barrier
which had confined the ardor of voyagers, and who led the revival of maritime
enterprise, creating a curiosity among the stayers-at-home that could be satiated
only with repeated editions of narratives relating to expeditions and conquests.
The number of these narratives became, within a few years, so large as to require
their grouping into special collections for the sake of cheapness and convenience.
The earliest is probably the Paesi Nouamente retrouati, Et Nouo Mondo da
Alberico Vesputio; By Fracanzo or Fracanzano da Montalboddo, Vicenza, 1507,
mentioned by Tiraboschi, Storia della literatura italiana. This was reproduced in
1508 by Madrignani, at Milan. According to Panzer, Ruchamer issued the same
year a somewhat fuller collection at Nuremberg, under the title of Newe
Unbekanthe landte Und eine Newe weldte, with eight pieces, among them the
voyages of Columbus, Ojeda, Pinzon, and Vespucci. A similar work was issued by
the Italian Angiolelo, in 1519.
The best known of these early collections, and by many regarded as the first
issued in German, is the Novus Orbis Regionvm ac Insolarvm Veteribvs
Incognitarvm; Basileæ apvd Io Hervagivm, Mense Martio, anno M.D.XXXII., 4to,
584 pages, beside unnumbered leaves. ‘La plus ancienne de ces (Latin)
collections,’ says Boucher, Bibl. Univ., i. 55. Although prepared by John Huttich,
the canon of Strasbourg, it is better known under the name of Simon Grynæus,
who wrote the introductory and revised it at the request of Hervagius, the
publisher, a well known bookman, greatly esteemed by Erasmus. Meusel, Bibl.
Hist., iii. pt. i. 221, gives it with punctilious fairness the title of Collectio Huttichio-
Grynæo-Hervagiana, while others apply only the middle name or the last two. The
attribution to Grynæus is greatly due to his fame as a reformer, as the personal
friend of Luther and Calvin, as the discoverer of Livy’s lost books, and as the first
of a long line of scholars celebrated under that name. It is an excellently printed
volume, with quaint head-pieces, and containing as it does so many papers of
which the original editions are now lost, the collection must be esteemed of great
value. The nineteen pieces of original contributions, journals, and borrowed
accounts, include the voyages of Columbus, Alonso, and Pinzon from Madrignani;
Alberici Vesputij nauigationum epitome, and nauigationes IIII.; and Petri Martyris
de insulis. The other narratives relate to Asia, to the Levant, and to Russia. With
some copies is found a mappemonde, but the only genuine one, according to
Harrisse, 294, bears the inscription Terra de Cuba, in the northern part of the new
world, and in the south, Parias, Canibali America Terra Nova, Prisilia, with the
word Asia in large type. Among the several editions the German of 1534, by Herr,
is rarer than the above original, while the Dutch of 1563, by Ablijn, is the most
complete.
After Huttich the voyage collections increased rapidly in number and size, till
they reached the fine specimen of Ramusio, forming not only the first large work of
this class, but, for a long time, the most extensive which bears on America.
Harrisse, 457, very justly observes that ‘the publication of Ramusio’s Raccolta
may be said to open an era in the literary history of Voyages and Navigation.
Instead of accounts carelessly copied and translated from previous collections,
perpetuating errors and anachronisms, we find in this work original narrations
judiciously selected, carefully printed, and enriched with notices which betray the
hand of a scholar of great critical acumen.’ The first issue appeared as Primo
Volvme Delle Navigationi et Viaggi. In Venetia appresso gli heredi di Lvcantonio
Givnti, 1550, folio, 405 leaves. ‘Les Juntes (le) publièrent ... sous la direction de
Jean-Baptiste Ramusio.’ Camus, Mém. Coll. Voy., 7. Neither in this, nor in the third
volume, issued in 1553, nor in the second edition of the first volume, 1554, does
the name of Giambatista Ramusio, Rannusio, or Rhamusio, appear as author, and
it is only in the second volume that the publisher, Tommaso Giunti, resolves to set
aside the modesty of his friend, and to place his name upon the title-page. The
publication of this volume had been delayed till 1559, owing to the death of the
author and to the burning of the printing establishment.
In the preface Giunti refers to the close friendship between them, and extols
Ramusio as a learned man, who had served in foreign countries, acquiring in this
way a perfect knowledge of French and Spanish. He had long been a devoted
student of history and geography, inspired to some extent by the travels of his
uncle, the celebrated Doctor Girolamo Ramusio. As secretary to the powerful
Venetian Council ‘de Signori Dieci,’ he was in a position to maintain
correspondence with such men as Oviedo, Cabot, Cardinal Bembo, and others,
part of which is to be found in Lettere di XIII. Huomini illustri, Venetia, 1565. All this
served him in the formation of the great work upon which he labored during the
last 34 years of his life. He died at Padua, July 10, 1557, 72 years of age.
The first volume relates chiefly to Asia and Africa, but contains Lettere due
and Sommario by Vespucci, and four papers on Spanish and Portuguese
circumnavigation. The contents of the set have been somewhat changed and
increased during the several republications, but the best editions are those of
1588, 1583, and 1565, for the first, second, and third volume respectively. Vol. ii.
of this set relates chiefly to Asia, but is of interest to American students for its
narrative of the much doubted voyages of the brothers Zeno. Its small size
indicates the loss it sustained by the events above referred to. ‘Et nõ vi
marauigliate, se riguardando gli altri due, non uedrete questo Secõdo volume, si
pieno & copioso di scrittori, come il Ramusio già s’haueua pposto di fare, che la
morte ui s’interpose.’ ii. 2.
The third volume is entirely devoted to America, and contains all the most
valuable documents known up to the time of its first issue, such as the relations of
Martyr, Oviedo, Cortés, and his contemporaries in Mexico, Pizarro, Verazzano,
Carthier, the Relation di Nvnno di Gvsman, in several parts, and the valuable
Relatione per vn gentil’huomo del Signor Fernando Cortese. The volume begins
with a learned discourse by Ramusio on ancient knowledge of a land to the west,
and of causes leading to the discovery. At the end of the 1565 edition is a map of
America, showing Lower California as a wide peninsula, and Terra del Fuego
joined to the land of the Circolo Antartico. The comparative crudeness of the
wood-cuts and maps has not made the work much esteemed by collectors, but its
value even now, for reference, is unquestioned. The set was dedicated to
Hieronimo Fracastoro, the great poet and physician, born mouthless, yet so
eloquent. Scaliger, Aræ Fracastoreæ. At the end of the Discorso sopra Perv, iii.
371, Ramusio says: ‘Et questa narratione con breuità habbiamo voluto discorrere
per satisfattione de i lettori, laquale piu distintamente legeranno nel quarto
volume.’ According to Fontanini, Bibl., 274, the material for this volume lay
prepared in manuscript, only to perish in the disastrous fire of November, 1557.
[459] It is still one of the main roads, known under Spanish dominion as Calzada
de Iztapalapan, now as S. Antonio Abad.

[460] Cortés names the well built Mexicaltzinco, Niciaca, and Huchilohuchico (now
Churubusco), to which he gives respectively 3000, 6000, and 4000 to 5000
families. Cartas, 83-4. Gomara, Hist. Mex., 99, names Coioacan instead of
Niciaca, and this change is generally accepted, for the latter name is probably a
mistake by the copyist or printer. Peter Martyr, dec. v. cap. iii.

[461] ‘Mandò que vn Indio en lengua Mexicana, fuesse pregonando que nadie se
atrauessasse por el camino, sino queria ser luego muerto.’ Herrera, dec. ii. lib. vii.
cap. v.

[462] Also referred to as Fort Xoloc. ‘En donde hoy la garita de San Antonio Abad,’
says Ramirez, in Prescott (ed. Mex. 1845), ii. 104.

[463] Herrera, who is usually moderate, swells the figure to 4000.

[464] The avenue is now called el Rastro. The suburb here bore the name of
Huitzitlan. ‘Vitzillan que es cabe el hospital de la Concepcion.’ Sahagun, Hist.
Conq., 23. At Tocititlan, says Duran, Hist. Ind., MS., ii. 439. ‘Junto de la Hermita de
San Anton.’ Torquemada, i. 450. ‘Segun una antigua tradicion conservada en el
hospital de Jesus, el punto en que le encontró fué frente á éste, y por recuerdo del
suceso se hizo la fundacion en aquel parage.’ Alaman, Disert., i. 103; and
Ramirez, note in Prescott (ed. Mex. 1845), ii. 103. The previous authorities
indicate, however, that the meeting took place farther from the centre of the city.

[465] Chimalpain mentions among others Tetlepanquezatl, king of Tlacopan,

Yzquauhtzin Tlacochcalcatl, lord or lieutenant of Tlatelulco, captain-general
Atlixcatzin, son of Ahuitzatl, and Tepehuatzin, son of Titotzin. Hist. Conq., 125.
Sahagun differs slightly in the names. Hist. Conq., 24-5.

[466] For dress, see Native Races, ii. 178 et seq. Cortés gives sandals only to
Montezuma, but it appears that persons of royal blood were allowed to retain them
before the emperor, as Ixtlilxochitl also affirms. Hist. Chich., 295; Oviedo, iii. 500;
Purchas, His Pilgrimes, iv. 1121.

[467] ‘Cenzeño ... y el rostro algo largo, è alegre.’ Bernal Diaz, Hist. Verdad., 67.
‘Motecçuma quiere dezir hõbre sañudo y graue.’ Gomara, Hist. Mex., 103; Acosta,
Hist. Ind., 502-3. It is from this, probably, that so many describe him as serious in
expression. A number of portraits have been given of the monarch, differing
greatly from one another. The best known is Prescott’s, taken from the painting for
a long time owned by the Condes de Miravalle, the descendants of Montezuma;
but this lacks the Indian type, and partakes too much of the ideal. Clavigero’s,
Storia Mess., iii. 8, appears more like him, though it is too small and too roughly
sketched to convey a clear outline. Far better is the half-size representation
prefixed to Linati, Costumes, which indeed corresponds very well with the text
description. The face in Armin, Alte Mex., 104, indicates a coarse Aztec warrior,
and that in Montanus, Nieuwe Weereld, 244-5, an African prince, while the native
picture, as given in Carbajal Espinosa, Hist. Mex., ii. 6, is purely conventional. The
text description, based chiefly on Bernal Diaz, is not inappropriate to the weak,
vacillating character of the monarch. Clavigero makes him nearly 54 years old,
and Brasseur de Bourbourg 51; but 40, as Bernal Diaz calls him, appears to be
more correct.

[468] ‘Ellos y él ficieron asimismo ceremonia de besar la tierra.’ Cortés, Cartas,

85.

[469] ‘De margaritas y diamantes de vidrio.’ Id. ‘Que se dizen margagitas.’ Bernal
Diaz, Hist. Verdad., 65.

[470] Solis assumes that Cortés was repelled when he sought to place the
necklace on Montezuma. The latter chides the jealous princes, and permits him.
Hist. Mex., i. 370. ‘Pareceme que el Cortès ... le daua la mano derecha, y el
Monteçuma no la quiso, è se la diò â Cortès.’ Bernal Diaz, Hist. Verdad., 65. This
phrase, which applies equally to offering the right hand, has been so understood
by those who notice it; but as this would be confusing, Vetancurt, for instance,
assumes improbably that Marina offers her right hand to Montezuma, which he
disregards, giving his instead to Cortés. Teatro Mex., pt. iii. 129.

[471] Cortés, Cartas, 85. Ixtlilxochitl has it that Cacama was left with him; and
Bernal Diaz, that the lord of Coyuhuacan also remained. According to Cortés,
Montezuma accompanied him all the way to the quarters in the city, keeping a few
steps before. Gomara and Herrera follow this version. But Bernal Diaz states
explicitly that he left the Spaniards to follow, allowing the people an opportunity to
gaze; and Ixtlilxochitl assumes that he goes in order to be ready to receive him at
the quarters. Hist. Chich., 295. It is not probable that Montezuma would expose
himself to the inconvenience of walking so far back, since this involved
troublesome ceremonies, as we have seen, not only to himself but to the
procession, and interfered with the people who had come forth to gaze. The native
records state that Montezuma at once surrendered to Cortés the throne and city.
‘Y se fueron ambos juntos á la par para las casas reales.’ Sahagun, Hist. Conq.,
23-4. Leading Cortés into the Tozi hermitage, at the place of meeting, he made the
nobles bring presents and tender allegiance, while he accepted also the faith.
Duran, Hist. Ind., MS., ii. 440-1.

[472] About 6000 in all. ‘Nosotros aun no llegauamos á 450 soldados.’ Bernal
Diaz, Hist. Verdad., 65. Prescott places the number at about 350.
[473] According to Sahagun not a soul was to be seen, either upon the causeway
or along the streets, the people having taken this manner to express their
indignation at the semi-forcible entry of the Spaniards. Montezuma came to
receive them purely out of a feeling of humanity. Startled at this solitude, Cortés
fears dangers, and vows, if all goes well, to build a church. This was the origin,
says Bustamante, of the Hospital de Jesus. Sahagun, Hist. Conq. (ed. Mex. 1840),
79-84. See note 12, this chapter. Brasseur de Bourbourg accepts this view. Hist.
Nat. Civ., iv. 212-13. Still Sahagun describes the interview with Cortés as most
cordial. He is in fact contradictory, and it is evident that the order issued to the
people to keep the narrow causeway clear, and the etiquette which required them
to give way to the emperor, have been hastily interpreted by the chronicler into
‘deserted streets’ and ‘popular indignation.’ Had the citizens objected to receive
the strangers, the bridges could have been raised against them.

[474] ‘Au coin de la rue del Indio triste et de celle de Tacuba,’ says Humboldt,
Vues, i. 58, prudently, without attempting to give its extent. Ramirez and Carbajal
do so, however, and in allowing it about the same length as the temple inclosure,
they place it right across the eastern avenue of the city, which like the other three
is admitted to have terminated at one of the temple gates. Carbajal Espinosa, Hist.
Mex., ii. 222; Ramirez, notes in Prescott’s Mex. (ed. Mex. 1845), ii. app. 103.
‘Donde hoy las Casas de el Marqués del Valle,’ says Lorenzana, in Cortés, Hist.
N. Esp., 86, a statement disputed by later writers. Prescott quotes Humboldt, but
evidently does not understand him, for he places the palace ‘facing the western
gate,’ which is not only on the wrong side, but across the western avenue. Mex., ii.
79. ‘Adonde ... tenia el gran Monteçuma sus grandes adoratorios de idolos ... nos
lleuaron á aposentar á aquella casa por causa, que como nos llamauã Teules, é
por tales nos tenian, que estuuiessemos entre sus idolos.’ Bernal Diaz, Hist.
Verdad., 66. The idea of being regarded as a god seems to have pleased the old
soldier immensely.

[475] They doubtless formed a double necklace, with gold setting and pendants.
Cortés writes that on the way to the palace Montezuma halted to place them round
his neck. Cartas, 85; Gomara, Hist. Mex., 100-1; Sahagun, Hist. Conq., 23.

[476] ‘A throne of gold,’ is Peter Martyr’s briefer yet grander term. dec. v. cap. iii.

[477] Hist. Verdad., 65-6; Herrera, dec. ii. lib. vii. cap. v.; Sahagun, Hist. Conq., 25-
6.

[478] Bernal Diaz states that the emperor always addressed him as Malinche, and,
indeed, it was common among Mexicans to address persons by a name given
them in later life in connection with some peculiarity, deed, or incident. Hence
Cortés, as master of the prominent female interpreter, received a name implying
that relationship.
[479] For which see Native Races.

[480] Cortés, Cartas, 86. This is in substance the speech of Montezuma, as given
by native as well as Spanish records; yet it appears improbable that the emperor
should have been so ready, at the first interview, and in presence of his courtiers,
to humble himself so completely before a few strangers whom he regarded as
mortals. See note 19. ‘Myself, my wife and children, my house, and all that I
possess, are at your disposal,’ says the Spaniard, even in our day, to the guest
whom he wishes to impress with his hospitality. Perhaps Montezuma was equally
profuse with hollow words, which have been recorded as veritable offers.

[481] Cortés, Cartas, 86-7. Bernal Diaz introduces this paragraph during the next
interview.

[482] Id. ‘Á cada vno de nuestros Capitanes diò cositas de oro, y tres cargas de
mantas de labores ricas de plumas, y entre todos los soldados tambien nos diò á
cada vno á dos cargas de mantas.’ Bernal Diaz, Hist. Verdad., 66; Gomara, Hist.
Mex., 101-2; Peter Martyr, dec. v. cap. iii.; Duran, Hist. Ind., MS., ii. 441-2;
Herrera, dec. ii. lib. vii. cap. vi.; Torquemada, i. 452-3; Ixtlilxochitl, Hist. Chich.,
296; Peralta, Not. Hist., 107-8. Acosta implies that Cortés now reconciled the
Tlascaltecs with the Aztecs. Hist. Ind., 521.

[483] ‘Eramos hermanos en el amor, y amistad, é personas mui principales,’ is the

way Bernal Diaz expresses it. Hist. Verdad., 66.

[484] Gomara, Hist. Mex., 102-3. ‘Los haçia proveer luego, assi de mugeres de
serviçio, como de cama, é les daba á cada uno una joya que pessaba hasta diez
pessos de oro.’ Oviedo, iii. 500-1.

[485] Vetancvrt, Teatro Mex., pt. iii. 129. Sahagun, followed by Acosta, Brasseur
de Bourbourg, and others, states that the artillery was discharged at night to
startle the natives. Hist. Conq. (ed. 1840), 85.

[486] It is so depicted in the old Nuremberg view of the city, already referred to.
Ramirez, Carbajal Espinosa, and Alaman give the extent, and the latter enters into
quite a lengthy account of its situation with respect to present and former outlines
of the quarter. Disert., ii. 202, etc.; Carbajal Espinosa, Hist. Mex., ii. 221-2;
Ramirez, notes in Prescott’s Mex. (ed. Mex. 1845), ii. app. 103. Humboldt places it
opposite the southern half of the western temple side, Essai Pol., i. 190, but that
site is assigned by all the above historians to the old palace of Montezuma, so
called—not the Axayacatl where Cortés was quartered. The mistake is probably
owing to his ignorance of the fact that the residence of the Cortés family stood first
on the site of the new palace of Montezuma, whence it was moved to that of the
old palace when the government bought the former.
[487] The Spaniards were also ‘costretti a scalzarsi, ed a coprirsi gli abiti sfarzosi
con vesti grossolane,’ says Clavigero, Storia Mess., iii. 83, but that is unlikely.

[488] ‘Con esto cumplimos, por ser el primer toque.’ Bernal Diaz, Hist. Verdad.,
67.

[489] ‘Â nosotros los soldados nos diò á cada vno dos collares de oro, que valdria
cada collar diez pesos, è dos cargas de mantas.’ The rest went to their officers. Id.
 CHAPTER XVII.
CAPTURE OF THE EMPEROR.

November, 1519.

Cortés Inspects the City—Visits the Temple with Montezuma—Discovery

of Buried Treasure—Pretended Evidences of Treachery—Cortés
Plans a Dark Deed—Preparations for the Seizure of Montezuma—With
a Few Men Cortés Enters the Audience-Chamber of the King—
Persuasive Discourse—With Gentle Force Montezuma is Induced to
Enter the Lion’s Den.

Cortés failed not to make diligent inquiries and examinations into

the approaches, strength, and topography of the city, but he longed
for a view from one of the great temples which, rising high above all
other edifices, would enable him to verify his observations. He also
desired to obtain a closer insight into the resources of the place.
With these objects he sent to Montezuma for permission to make a
tour through the town to the Tlatelulco market and temple.[490] This
was granted; and attended by the cavalry and most of the soldiers,
all fully armed, Cortés set out for that suburb, guided by a number of
caciques. It was here that the largest market-place in the city was
situated.[491]
From this centre of trade the Spaniards proceeded to the lofty
temple, which occupied one end of the Tlatelulco market-place,[492]
and whither Montezuma had already gone to prepare for their
reception, and to propitiate the idols for the intrusion by prayers and
sacrifices. He hoped, no doubt, that his presence would prove a
check upon the impulsive hands and tongues of the guests.
Dismounting at the gate, the riders advanced with most of the
soldiers through the temple court, and climbed the one hundred and
more steps which led to the summit. Some priests and chiefs had
been sent by Montezuma to assist Cortés to ascend, but he
preferred to trust to himself. This pyramid, unlike that in Mexico
proper, appears to have had but one continuous stair-way leading up
the western slope.[493] The first sight which met the Spaniards on
reaching the summit was the sacrificial cage for holding victims, and
a large snake-skin drum, whose sombre tones gave appropriate
effect to the horrible rites enacted around it.
Montezuma came out of one of the chapels to welcome them,
expressing a fear that they must have been fatigued by the ascent,
but Cortés hastened to assure him that Spaniards never tired.
Calling their attention to the view here afforded of the city and its
surroundings, he stood silent for a while to let the beauteous vision
work its own enchantment. Around on every side spread the lake
and its connecting waters, bordered with prairies and fields. Forests
and towns intermingled on the green carpet, and extended far away
till they disappeared in the shadows of the hills. The soldiers
recognized the settlements and towns which they had passed, and
saw the causeways which on three sides connected with the
mainland. Beneath them lay a vast expanse of terraced roofs,
intersected by streets and canals teeming with passengers and
canoes. Here and there rose palatial edifices and towering temples,
interspersed with open squares, and with gardens shaded by trees
and relieved by the silvery jets of the fountain. At their feet lay the
market through which they had just passed, alive with busy
Lilliputians, whose talk and cries reached their ears in a confused
murmur. Cortés could not fail to be impressed by scenes so varied
and so attractive, but the æsthetic aspect was in him speedily
overshadowed by the practical sense of the military leader. Then
rose on high his soul as he thought to secure for Spain so rich an
inheritance as the great city with its vast population, and turning to
Father Olmedo he suggested that the site ought to be obtained for a
church; but the prudent friar remonstrated that the emperor
appeared to be in no mood to listen to such a proposal.
Cortés accordingly contented himself with asking to see the
idols, and after consulting the priests Montezuma led them past the
piscina with the vestal fire into the chapel. Withdrawing a tasselled
curtain he displayed the images, glittering with ornaments of gold
and precious stones, which at first drew the attention of the
beholders from the hideous form and features. Before them stood
the stone of sacrifice, still reeking with gore, and around lay the
instruments for securing the human victim and for tearing open the
breast. On one altar could be seen three hearts, and on the other
five, offered to the idols, and even now warm and palpitating with life.
The interior walls were so smeared with human blood as to obscure
their original color, and to emit a fetid odor which made the
Spaniards glad to reach the open air again.
Forgetting his prudence, Cortés expressed his wonder to
Montezuma that so great and wise a prince should worship
abominable demons like these. “Let me but plant a cross on this
summit,” he said, “and within the chapel place an image of the virgin,
and you shall behold the fear of the idols.” The eyes of the priests
were at this aflame with anger, and the emperor could hardly
suppress his indignation as he replied, “Malinche, had I suspected
that such insults were to be offered, I would not have shown you my
gods. They are good; they give us health, sustenance, victory, and
whatever we require. We adore them, and to them make our
sacrifices. I entreat you say not another word against them.”
Observing the effect his remarks had produced, Cortés thought it
best to restrain himself, and to express regrets at his hastiness.
Then with a forced smile he said that it was time to depart.
Montezuma bade them farewell. As for himself, he must remain to
appease the idols for the insult offered.[494]
Not at all abashed by his rebuff at the temple, Cortés asked
Montezuma to let him erect a church in his own quarters. Glad
probably at finding the Spanish pretensions in this respect so
modified, he not only assented, but gave artisans to aid in the work.
This was concluded within three days, and services henceforth held
therein, at which the Indians were always welcomed. A cross was
also erected before the entrance, so that the natives might be
impressed by the devotion of their visitors.
This effort in behalf of the faith was not to go unrequited. While
looking for the best site for the altar, says Bernal Diaz, Yañez, the
carpenter, discovered signs of a door-way recently closed and
plastered over. Cortés was told of this, and ever on the guard against
plots, he ordered the wall to be opened. Aladdin on entering the cave
could not have been more surprised than the Spaniards were on
stepping into the chamber there revealed. The interior fairly blazed
with treasures; bars of gold were there, nuggets large and small,
figures, implements, and jewelry of the same metal; and then the
silver, the rare bejewelled and embroidered fabrics, the prized
chalchiuite and other precious stones! Cortés allowed the favored
beholders to revel in the ecstasy created by the sight, but to their
greed he set a check. He had reasons for not disturbing the
treasures at this time, and gave orders to restore the wall, so that no
suspicions might be aroused that the deposit had been discovered.
[495]

One reason with Cortés for not touching the treasures was to
hold out an alluring bait to those who, more prone to listen to the
warnings of timid allies than to the ambitious promptings of their
leader, were ever ready to take alarm and urge withdrawal from a
position which they regarded as dangerous. Unbending in his
resolution, the general had nevertheless grasped all the perils of
their position. Hitherto no firm ground existed for alarm. They had
been a week in the capital, and were still receiving from all hands the
kindest treatment and the most generous hospitality. Cortés was
aware, however, that this depended on the favor of the emperor,
whose power over the submissive people resembled that of a god,
and whose person appeared to them as sacred as his will was
absolute. He had also learned that this monarch was a man
affrighted by his superstitions, and often influenced by trifling
circumstances; ready to strike where he had fawned the moment
before, and little bound by words or pledges, particularly when they
involved his own sovereignty. One misstep by the Spanish leader or
any of his men, ill-behaved and importunate as they were, according
to his own statement, might precipitate the change. The presence of
the hated Tlascaltecs was itself a burden, and the drain for
supporting the self-invited guests would soon be felt. The religious
topic had already created a momentary irritation, which might rankle
and grow under the promptings of the priests, who must naturally
object to rival interference.
Emperor and subjects were evidently restrained only by the
military prestige of the Spaniards, and to some extent by the belief in
their divine mission; but they were also aware that, whatever might
be the prowess of the visitors and the power of their weapons and
steeds, they were mortals, for this had been proved quite lately by
the unfortunate defeat of Escalante, and in the Nautla campaign.
The soldiers of Montezuma had but to raise the bridges of the
causeways and cut off retreat, then stop supplies and reduce them
by starvation. True, there was the fate of Cholula before the
Mexicans; but they had gained experience, and could mass vastly
more warriors and arms, while the Spaniards would have no allies in
reserve to operate in the rear. Besides, what mattered the
destruction of a part, or even of the entire city, when thereupon
depended the safety of the throne, menaced by a horde of cruel,
avaricious monsters!
Cortés had considered all these points, and knew the
expediency of resolute action. He had undertaken an enterprise
wherein one bold move must be supported by another, and to these
all means had to be subordinate. He had not come all this way to
place himself within the power of a suspicious and vacillating despot,
nor to waste his time in waiting for what events might bring forth,
while his enemies, headed by Velazquez, were arranging for his
overthrow. He had formed his plans long beforehand, as indicated in
his first letter to the king, wherein he promised to have the great
Montezuma “a prisoner, a corpse, or a subject to the royal crown of
your Majesty.”[496] Conquest, followed by settlement and conversion,
was his aim. It would not pay him to play for a smaller stake.
Just now rumors began to circulate tending to stir anew the fears
which Montezuma’s friendly and hospitable demeanor had soothed.
One was that the nobles had actually prevailed on the emperor to
break the bridges, to arm the whole city, and to fall on the Spaniards
with all available strength.[497] Soldiers were readily found who
fancied that the mayordomo was less obsequious than formerly, and
that he gave scantier supplies. It was also understood from
Tlascaltecs that the populace appeared less friendly during the last
day or two. These reports may have sprung wholly from timid minds
still agitated by the warnings uttered by Tlascaltecs before the
departure from Cholula, or they may have been promoted by Cortés
himself in furtherance of his plans. He at any rate seized the
pretence to hold a council, composed of Alvarado, Leon, Ordaz, and
Sandoval, together with twelve soldiers whose advice he most
valued, “including myself,” says Bernal Diaz. His chief reason was to
persuade them of the necessity for the measure he had resolved on,
and to win their hearty coöperation. Laying before them the current
rumors which confirmed the warnings formerly received, and
representing the unreliable and suspicious character of Montezuma,
his great power, and the peculiar position and strength of the city, he
concluded by proposing the daring venture of seizing the emperor
and holding him a hostage.[498]
Here was folly run mad! Four hundred men, after penetrating
formidable barriers and gaining the very heart of a great empire,
whose vast armies could oppose a thousand warriors to every
Spaniard there, coolly propose to take captive the worshipped
monarch of this vast realm, and then to defy its millions of subjects!
The wildest tales of mediæval knights hardly equal this project.
Reckless as was the conception, it was the fruit of yet greater
audacity. Cortés reared his structure of folly insensate upon the
platform of still greater insensate folly. If it was true that he had
practically placed himself in the position of a captive, then he would
cut the knot by capturing the captor. And yet, foolhardy as might
appear the scheme when coolly viewed from the isle of Cuba,
situated as the Spaniards were, it was doubtless the best they could
do; it was doubtless all they could do. The efficiency of hostages had
been frequently tried by the conquerors in the Antilles, and the
opportune seizure of the Cempoalan lord had not been forgotten; but
this had been effected under the impulse of the moment, while the
chieftain was surrounded by Spaniards. Here was required not only
a calm resolution, unflinching to the end, but a well laid stratagem.
Cortés stood prepared with both.
Producing the letter from Villa Rica, which had been kept secret
all this time, he gave an account of the unfortunate successes at
Almería, describing in exaggerated terms the treachery of
Quauhpopoca, and consequently of Montezuma as his master, and
stirring the feelings of the council by an appeal to avenge their
comrades.[499] Here was a pretence[500] which served also to set
aside the suggestion that the emperor would be only too glad to let
them depart in peace, for it was argued that a retreat now, since the
Spaniards stood revealed as mortals, would draw upon them not
only the contempt of allies and countrymen, but a general uprising,
with the most fatal results. Retreat meant also the surrender of all
hopes of wealth, preferment, and honor, to be followed by
punishment and disgrace for their irregular proceedings so far. With
Montezuma in their power, they possessed a hostage whose
sacredness in the eyes of his subjects insured their safety, and made
the people pliable to their will, while disaffected vassals could be
secured by alliances, or by the promise of reforms. Should the
seizure result in the monarch’s death, the succession would
doubtless become the cause of division and dissension, in the midst
of which the Spaniards might influence affairs in their own interest.
Thus were answered the various objections raised.
As for the manner of seizure, the safest plan would doubtless be
to inveigle Montezuma to their quarters and there detain him; but this
would cause delay, and might arouse suspicion,[501] and, since
prompt action was considered necessary, the best way would be to
seize him in his own palace. This was agreed upon, and the same
evening the facts and arguments were effectively presented to the
men and preparations made.
“All night,” writes Bernal Diaz, “we passed in earnest prayer, the
priests devoutly imploring God to so direct the undertaking that it
might redound to his holy service.”[502]
In the morning Cortés sent to announce that he would visit the
emperor. He then despatched a number of small parties as if for a
stroll, with orders to keep themselves in and near the palace, and on
the way to it, ready for any emergency. Twenty-five soldiers were
told to follow him, by twos and threes, into the audience-chamber,
whither he preceded them with Alvarado, Sandoval, Velazquez de
Leon, Francisco de Lugo, and Ávila.[503] All were armed to the teeth,
[504]and as the Mexicans had been accustomed to see them thus
equipped no suspicions were aroused. Montezuma proved on this
occasion to be particularly gracious, and after a brief chat he offered
several presents of finely wrought gold, and to Cortés he presented
one of his daughters, the captains being given women of rank from
his own harem, which was a mark of great favor.[505] Cortés sought
to decline for himself the favor, on the ground that he could not
marry. Montezuma nevertheless insisted, and he yielded not
unwillingly.[506]
Assuming a serious tone, the latter now produced the letter from
Villa Rica, and informed the emperor that he had received an
account of the outrageous conduct of Quauhpopoca, resulting in the
death of some of his men, and that he, the sovereign, had been
accused of being the instigator. Montezuma gave an indignant
denial,[507] and Cortés hastened to assure him that he believed the
charge to be false, but as commander of a party he had to account
for the men to his king, and must ascertain the truth. In this
Montezuma said he would aid him; and calling a trusted officer, he
gave him a bracelet from his wrist bearing the imperial signet—a
precious stone graven with his likeness[508]—bidding him to bring
Quauhpopoca and his accomplices, by force, if necessary.[509]
Cortés expressed himself pleased, but added that, in order to cover
his responsibility as commander, and to convince his men that the
emperor was indeed as innocent as Cortés believed him to be, it
would be advisable for him to come and stay at their quarters till the
guilty parties had been punished.[510]
Montezuma was dumfounded at this unhallowed impudence. He,
the august sovereign, before whom even princes prostrated
themselves, at whose word armies sprang into existence, and at
whose name mighty rulers trembled, he to be thus treated by a score
of men whom he had received as guests and loaded with presents,
and this in his own palace! For a moment he stood mute, but the
changing aspect of his countenance revealed the agitation within. At
last he exclaimed that he was not the person to be thus treated. He
would not go. They could always find him at his palace.
Cortés pleaded that his presence among the soldiers was
necessary, not merely as a declaration of his innocence, but to allay
the rumors which had reached them that he and his people were
plotting for their destruction. Montezuma again made an indignant
denial; but added that, even if he consented to go, his people would
never allow it. His refusal, insisted the general, would rouse the
worst suspicions of his men, and he could not answer for their acts.
Mexico might meet the fate of Cholula, and he with it.[511]
Montezuma now began to implore, and offered to surrender his
legitimate children as hostages if he were but spared the disgrace of
being made a prisoner. This could not be, was the reply. The
Spanish quarter was his own palace, and he could readily persuade
his subjects that he went there for a short time of his own accord, or
at the command of the gods.[512] He would be treated with every
consideration, and should enjoy his usual comfort, surrounded by
favorites and councillors. The plan involved no change beyond that
of residence, to a place where he would be under secret
surveillance.

Montezuma still objected, and time was passing.[513] The

companions of Cortés becoming nervous at this delay, Velazquez de
Leon exclaimed in his stentorian voice: “Why so many words, your
worship? Let us either carry him off or despatch him. Tell him that if
he calls out or creates a disturbance we shall kill him!”[514] Turning in
alarm to Marina, Montezuma inquired what was meant. Full of pity
for the troubled monarch, she told him that the men were becoming
impatient at his delay. She besought him, as he valued his life, to
accede to their wishes and go with them. He would be treated with
all the honor due to his rank. A glance at the frowning faces of the
Spaniards confirmed the mysterious words of the interpreter, and
chilled him to the heart. He had heard too many accounts of the
resolution and cruelty of these men not to believe them capable of
anything. Were he to call for aid they would no doubt kill him and
destroy the city; for few as they were they had proved themselves
equal to hosts of natives.
The unhappy monarch yielded, since it was so decreed—by the
sublime audacity of this score of adventurers. The spirit of Axayacatl
had evidently not survived in the son, and the prestige of his early
career as military leader had dwindled to a mere shadow in the
effeminate lap of court-life.[515] Summoning his attendants, he
ordered a litter brought. Everything had been quietly conducted, and
since none ventured to question the emperor, his command was
silently obeyed; but the mysterious interview and his agitation roused
their suspicions, and the rumor spread that something extraordinary
was about to happen. Wondering and murmuring crowds had
already collected along the route between the two palaces when the
emperor appeared. On seeing the sorrowing faces of the favorites
who bore him, and observing how closely it was surrounded by the
Spanish soldiers who acted as guard of honor, their fears became
confirmed. The distance to the quarters was too short, however, and
the news had not yet travelled far enough, to allow a serious
demonstration.[516] But not long after the plaza in front of it was
blocked with an excited multitude, and a number of leading
personages and relatives made their way into the presence of their
sovereign, asking with tearful eyes and knitted brows how they might
serve him. They were ready to lay down their lives to rescue him. He
assured them with a forced smile that there was no cause for alarm.
Too proud to disclose his pusillanimity, he readily echoed the words