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 Surface & Coatings Technology 403 (2020) 126407

Contents lists available at ScienceDirect

Surface & Coatings Technology

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

A highly efficient α-Fe2O3/NiFe(OH)x photoelectrode for photocathodic T

protection of 304 stainless steel under visible light
Liya Fana,b, Xiao Zhanga, Chuanqun Zhanga, Jiangshan Lia, Chenglin Wua, , Yuxiao Chua,
⁎

Fangqi Gea, Yiyuan Liua, Xianqiang Xionga,c,

⁎⁎

a
School of Pharmaceutical and Materials Engineering, Taizhou University, Jiaojiang 318000, China
b
College of Chemistry, Liaoning University, Shenyang 110136, China
c
Department of Chemistry, Zhejiang University, Hangzhou 310027, China

ARTICLE INFO ABSTRACT

Keywords: Developing highly stable and broad spectrum responsive semiconductor photoelectrode materials without the
Photocathodic protection use of hole scavengers is challenging for photoelectrochemical protection application. In this study, α-Fe2O3/
Hematite photoelectrode NiFe(OH)x electrodes were successfully prepared by combining hydrothermal method and simple drop-casting
NiFe(OH)x technique. The morphology, structure, composition and optical property of the obtained electrodes were well
304 stainless steel
characterized by SEM, XRD, XPS and UV–vis DRS. α-Fe2O3/NiFe(OH)x electrode exhibited enhanced photo­
cathodic protection performance as compared to hematite (α-Fe2O3) electrode, and greatly shift photo potential
and self-corrosion potential of the coupled 304 stainless steel into a more negative region. Remarkably, under
visible light illumination, the prepared electrodes can protect the 304 stainless steel without the use of hole
scavengers. Meanwhile, the photoanodes can maintain a better photo-stability without losing its activity. The
possible mechanism for the enhanced photocathodic protection performance is proposed, which is involved with
the fast hole transfer from hematite to NiFe(OH)x cocatalyst and generates high valence state Ni species to drive
the water oxidation reaction. The reduced charge recombination will result in the effective electron transfer from
the α-Fe2O3/NiFe(OH)x electrode to the 304 stainless steel and realize the effective protection.

1. Introduction Fermi level of the metal.

Stainless steels are widely used in various corrosive environments due to
their excellent corrosion resistance among numerous metallic materials.
However, in a salt-rich marine environment, stainless steel would suffer
from corrosion such as pitting corrosion, which is not beneficial for the long-
term use of this material [1]. Thus, different methods have been developed
to protect the stainless steels from corrosion, such as impressed current
cathodic protection and sacrificial anode protection. Unfortunately, im­
pressed current cathodic protection technique needs a high electric energy
input, and the sacrificial anode protection will result in environmental
pollution and material consumption [2]. In recent years, photoelec­
trochemical cathodic protection has attracted great attention since it can
protect the metal materials by only using solar energy and water as the
input sources. Under light illumination, the photoelectrode will generate
photo-electrons after absorbing the photons with energy larger than the
band gap, and then the excited electrons will transfer to the protected metal
if the conduction band potential of the photoelectrode is higher than the
The development of semiconductor photoelectrodes with suitable band
structure is the key to realize the wide application of photocathodic pro­
tection technique. Up to now, many semiconductors have been developed
such as TiO2 [3], SnO2 [4], ZnO [5], α-Fe2O3/Fe3O4 [6], WO3 [7] and
SrTiO3 [8]. However, it should be pointed out that most of these semi­
conductors have wide bandgap, which can only absorb UV-light accounting
for 3–5% of the solar spectrum. To our knowledge, there are few narrow
band gap semiconductors exhibiting photocathodic protection performance
except for those such as C3N4, BiVO4 and α-Fe2O3. This is mainly ascribed to
the many factors, including the positive conduction band position, small
photovoltage and weak stability of many narrow band semiconductor. In
addition, due to the quick charge recombination and slow water oxidation
kinetics occurring on the electrode/electrolyte interface, most of photo­
electrochemical protection systems have to use hole scavengers. Although
the usage of hole scavengers could shift the OCP of the photoanode to lower
levels, it's difficult to realize large-scale employment because the photo­
electrode will gradually lose its protection ability as the scavengers are

⁎
Corresponding author.
⁎⁎
Correspondence to: X. Xiong, Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
E-mail addresses: polyclwu@126.com (C. Wu), 11337061@zju.edu.cn (X. Xiong).

https://doi.org/10.1016/j.surfcoat.2020.126407
Received 6 July 2020; Received in revised form 5 September 2020; Accepted 9 September 2020
Available online 11 September 2020
0257-8972/ © 2020 Elsevier B.V. All rights reserved.
L. Fan, et al.
gradually consumed. To address these problems, it is necessary to develop
semiconductor materials with visible-light response, high stability and
meanwhile avoid the use of hole scavengers.
Recently, α-Fe2O3 has attracted much attention in the field of photo
(electro)catalytic water splitting or organic degradation [9–11] due to its
high solar-to-chemical energy conversion efficiency, suitable bandgap
(2.1 eV) allowing for visible light absorption, high valence band potential
for driving the water oxidation reaction, good photostability in alkaline
solution and great elemental abundance. Moreover, the conduction band
potential of hematite was estimated to be −0.62 V vs. SCE at pH 13.6 [12],
which is more negative than the self-corrosion potential of 304 stainless
steel (304SS). Therefore, hematite can be considered as a promising pho­
toelectrode material for photocathodic protection of 304SS. However, lim­
ited by the short holes diffusion length of α-Fe2O3 and its poor conductivity,
the photoelectrocatalytic water splitting activity is still very low and usually
a higher overpotential is needed. Therefore, optimizing hematite photo­
electrode for photocathodic protection is worthy of further exploration,
especially for the case without the use of hole scavengers. To realize this, it
is obvious that the water oxidation reaction needs to be accelerated. Cur­
rently, numerous strategies have been proposed to accelerate surface water
oxidation reaction for hematite photoanode, such as doping with metal or
non-metal element [13,14], morphology modulation [15], constructing
heterojunction [16], passivation of surface states [17], or modification of
cocatalyst [18,19]. Among these methods, the integration of electrocatalysts
with hematite photoanode has been confirmed to be a very efficient method
for the enhancement of water oxidation activity. For example, Wang and co-
workers reported a dramatic enhancement of photocurrent and photo­
voltage by spin-coating NiFeOx onto hematite films, which is ascribed to the
increase on the number of trapped holes at the electrode surface and the
decrease of the surface recombination rate [20]. Li Yat's group found that
the uniform deposition of NieFe hydroxide overlayer on hematite nanowire
photoanodes can significantly enhance the surface hole transfer kinetics and
passivate the surface states, and thus exhibit the lowest onset potential
among the NieFe based electrocatalysts [21,22]. However, to our knowl­
edge, the loading of NieFe hydroxide on α-Fe2O3 for the photocathodic
protection application has never been reported, and the underlying effect of
NieFe electrocatalysts on the photocathodic protection performance is also
unclear. Therefore, attempts to develop α-Fe2O3/NiFe(OH)x photoanode for
photoelectrochemical cathodic protection application in sacrificial-agent-
free environment and understanding the role of NiFe(OH)x for the possible
enhancement on the photocathodic protection performance is worth of in-
depth study.
In this work, α-Fe2O3 was synthesized by hydrothermal method, fol­
lowed by decoration of NiFe(OH)x overlayer by drop-casting technique. The
prepared films were well characterized by X-ray diffraction, UV–vis diffuse
reflectance spectroscopy, X-ray photo-electronic spectroscopy and scanning
electron microscopy to reveal the crystal structure, light absorption, valence
state and surface morphology. The photocathodic protection performance of
304SS coupled with α-Fe2O3 photoelectrode was evaluated by open circuit
potential (OCP) technique and Tafel polarization curve. The effect of cal­
cination temperature on the OCP variation of α-Fe2O3 was well analyzed. As
the increase of calcination temperature, the OCP under visible light illu­
mination was negatively shifted. Moreover, the effect of NiFe(OH)x de­
position on the OCP, self-corrosion potential, water oxidation activity,
charge transfer and energy band bending of α-Fe2O3 photoelectrode was
systematically investigated. Finally, a possible mechanism for elucidating
the enhanced photocathodic protection performance of α-Fe2O3/NiFe(OH)x
is proposed.
2. Experimental section
2.1. Materials
FeCl3 (99%), Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, KCl, NaOH and urea
in AR grade were all purchased from Aladdin and used without further
purification. Fluorine-doped tin oxide (FTO) glasses (14 Ω sq.−1,
2
Surface & Coatings Technology 403 (2020) 126407
2.2 mm thick) were obtained from Nippon Sheet Glass Co Ltd., Japan,
and successively cleaned by deionized water, acetone, and ethanol for
15 min respectively, followed by drying under N2 stream at room
temperature. The 304SS was machined into rectangular block with an
area of 2.5 cm × 1 cm, thickness of 2 mm, and then ground with 1000-
grit SiC papers, polished with alumina powder, and finally ultra­
sonically cleaned in absolute pure water and ethanol for 10 min, re­
spectively. The absolute pure water (resistivity 18.2 MΩ/cm2) was
purified by a Millipore Ultrapure water system.
2.2. Synthesis of α-Fe2O3 films
Hematite nanorods were prepared on FTO glasses substrate by hy­
drothermal method reported in the literature [23]. Firstly, FTO sub­
strate with an area of 3 cm × 2 cm was vertically placed in the staining
jar containing 0.1 M FeCl3 and 0.15 M urea. Then it was sealed and
placed in the oven at 100 °C for 4 h. After that, the FTO glasses with
uniform β-FeOOH layer on the surface were washed with ultrapure
water and dried in the air. Finally, the electrodes were first annealed at
500 °C for 3 h, followed by another heat treatment for 20 min at 500 °C,
600 °C, 650 °C, and 750 °C, respectively. The morphological changes of
the hematite samples calcinated at different temperature are shown in
Fig. S1. As the increase of annealing temperature, the rod-like α-Fe2O3
become more rounded, smoother and compact. If no other specified, α-
Fe2O3 sintered at 750 °C for the second heat treatment was used
throughout the whole text.
2.3. Synthesis of α-Fe2O3/NiFe(OH)x films
Precursor solution containing 5 mM Fe(NO3)3 and 5 mM Ni(NO3)2
for the synthesis of NiFe(OH)x overlayer was first prepared. Then, 20 μL
precursor solution was drop-casted on the surface of α-Fe2O3 film,
followed by drying at 60 °C for 1 h in air. The treated electrode was
finally immersed in a 1 M KOH aqueous solution for 5 min and washed
with deionized water for several times. The obtained composite films
are denoted as α-Fe2O3/NiFe(OH)x.
2.4. Characterization
The crystalline structures of the prepared films were examined with
power X-ray diffraction (XRD) with a D8/Advance diffractometer using
Cu Kα radiation (λ = 0.15418 nm) with a scan range of 20°-70°. The
surface morphologies of the prepared photoelectrodes were measured
by field-emission scanning electron microscope (Hitachi S-4800, Tokyo,
Japan). The optical absorption properties of all the samples were ob­
tained by using UV–Vis absorption spectroscopy (Hitachi U-4100
UV–VIS-NIR spectrophotometer) with BaSO4 as background. The com­
position of NiFe(OH)x on the surface of α-Fe2O3 was determined using a
PSP Vacuum Technology X-ray source operating with an Al Kα X-rays at
144 W and a PSP Vacuum Technology Electron Energy Analyzer CHA.
2.5. Photoelectrochemical and electrochemical measurements
The typical experimental setup used for photocathodic protection
measurement contained a photoanode cell and a corrosion cell, see Fig.
S2. The photoelectrode was placed in the photoanode cell, and 1 M
NaOH aqueous solution was used as the electrolyte. The corrosion cell
was consisted of three-electrode system, in which Pt sheet, saturated
calomel electrode (SCE) and 304SS connected with the α-Fe2O3 or α-
Fe2O3/NiFe(OH)x photoelectrode through a Cu wire were used as the
counter electrode, reference electrode and working electrode, respec­
tively. And the corrosion cell was filled with 3.5 wt% NaCl solution and
connected with photoanode cell with a salt bridge. 300 W xenon lamp
(CEL-HXF300) was selected as the light source to simulate the sunlight
(power density = 100 mW/cm2), and a 420 nm filter was chosen to
obtain visible light.
L. Fan, et al.
The open circuit potential (OCP) of the 304SS coupled with α-Fe2O3
or α-Fe2O3/NiFe(OH)x electrodes were measured under turn-on illu­
mination, and the Tafel curves were measured with the scan rate of
5 mV/s. Upon light illumination, the Fermi level of photoelectrode
splits into quasi-Fermi level of electrons and holes, due to the genera­
tion of nonequilibrium electron/hole pairs. The photovoltage is given
by the difference between the quasi-Fermi level of electrons and holes,
which acts as the thermodynamic driving force for injecting the pho­
togenerated holes into the electrolyte for oxygen evolution reaction
[24]. Experimentally, the photovoltage can be calculated by the dif­
ference between the open circuit potential in the dark (dark-potential)
and the open circuit potential under illumination (photo-potential). The
linear sweep voltammetry (LSV) curves of α-Fe2O3 and α-Fe2O3/NiFe
(OH)x films were measured on a CHI660E Electrochemical Workstation
(CHI Co, Shanghai, China) with photoelectrode as the working elec­
trode, Pt as the counter electrode and saturated calomel electrode (SCE)
as the reference electrode. All the experiments were performed under
one sun illumination (100 mW/cm2) with a scan rate of 10 mV/s. The
electrochemical impedance spectroscopy (EIS) was measured using an
electrochemical analyzer (Zennium, Zahner) in a frequency range of
10−2 Hz–105 Hz and at an AC amplitude of 10 mV. The corresponding
data was analyzed using ZView2 software. The Mott-Schottky experi­
ments were operated in 1 M NaOH aqueous solution by applying a
range of potential varied from −0.5 to 0.2 V vs. SCE with a potential
step of 50 mV, and the frequency was set as 1 kHz.
3. Results and discussion
3.1. Materials characterization
Fig. 1A shows the XRD pattern of α-Fe2O3 and α-Fe2O3/NiFe(OH)x
film, where the α-Fe2O3 films were treated at 750 °C. The asterisks
corresponding to the diffraction peaks at 2θ = 35.6°, 54.1°, and 64.0°
were indexed to the α-Fe2O3 (JCPDS No.33-0664), whereas the masks
of other triangle well matched to the FTO substrate (JCPDS No.46-
1088). No diffraction peaks corresponding to NiFe(OH)x overlayer were
observed with the α-Fe2O3/NiFe(OH)x films. It may be ascribed to the
low loading or the amorphous nature of NiFe(OH)x overlayer. To verify
the presence of NiFe(OH)x, the XPS spectra of Fe and Ni elements were
measured, and the results are shown in Fig. S3. The binding energy
located at 712.4 eV and 726.1 eV are ascribed to the Fe 2p3/2 and 2p1/2
of Fe3+ [25]. Besides, the XPS peaks located at 856.88 and 874.58 eV
are ascribed to the Ni 2p3/2 and Ni 2p1/2 of Ni2+, and two satellite
peaks at 862.1 and 880.8 eV are related to Ni LMM Auger peaks [26]. It
was noted that the optical absorption of α-Fe2O3 and α-Fe2O3/NiFe
(OH)x film were nearly identical, see Fig. 1B. For pure α-Fe2O3 film, it
exhibits an absorption edge starting at 581 nm, which corresponding to
a band gap value of 2.13 eV. The morphology of α-Fe2O3 and α-Fe2O3/
NiFe(OH)x electrodes was characterized with SEM, see Fig. 1C and D.
Notably, α-Fe2O3 nanorod arrays with a diameter of ̴ 30 nm were grew
on the FTO substrate. After being loaded with the NiFe(OH)x overlayer,
the surface of α-Fe2O3 nanorod became more coarser and the diameter
was increased. This indicates that NiFe(OH)x overlayer has been suc­
cessfully loaded on the outer surface of α-Fe2O3 nanorods. The uniform
loading of NiFe(OH)x cocatalyst is crucial for the effective photo­
cathodic protection of 304SS because the overlayer can effectively re­
duce the void on the α-Fe2O3/NiFe(OH)x interface and thus improve the
photoelectrode/catalyst interface quality. It will be beneficial for the
interfacial charge transfer and the surface passivation of α-Fe2O3
electrode.
3.2. Photocathodic protection performance
It was well documented that the photoelectrocatalytic water oxi­
dation activity of α-Fe2O3 film increased as the increase of sintering
temperature [27,28], which is ascribed to the improved electrical
3
Surface & Coatings Technology 403 (2020) 126407
conductivity induced by Sn doping from the FTO conducting substrate.
Therefore, it is highly possible that the sintering temperature of α-
Fe2O3 may also have effect on the photocathodic protection perfor­
mance of 304SS. Based on this, we attempt to evaluate the relative
performance of α-Fe2O3 treated at different sintering temperature by
using open circuit technique, and the results are shown in Fig. 2. In the
absence of light illumination, the measured open circuit potentials
(dark-potential) for the coupled α-Fe2O3-304SS electrodes were nega­
tively shifted as the increase of sintering temperature up to 650 °C. The
negative shift is ascribed to the partial Fermi level pinning caused by
surface states originating from the Sn doping [29,30]. Upon steady-
state light illumination, the obtained open circuit potentials, namely
photo-potential, were also shifted toward a more negative value with
increasing the sintering temperature. This is in consistent with the re­
sult observed under white light illumination, see Fig. S4. These results
indicate that the photogenerated electrons produced on all the irra­
diated α-Fe2O3 photoanodes are able to transfer to the 304SS and po­
larize it into a more negative value. In general, the more negative the
photo-potential, the better the anticorrosion ability [4,31]. Therefore, a
higher photocathodic protection performance is accompanied with a
higher sintering temperature of α-Fe2O3 photoanode. It has been ver­
ified that the Sn ions will diffuse into the α-Fe2O3 when the sintering
temperature was increased [30]. The Sn dopant will incorporate elec­
tron energy level close to the conduction band of α-Fe2O3, and thus the
Sn ions act as the electron donors and increase the electrical con­
ductivity [32]. This will increase the charge separation and charge
collection efficiency, and hence enhance the electron concentration as
verified by the negative shift of photo-potential. However, as the in­
crease of sintering temperature, the voltage drop (or photovoltage)
between the dark potential and the photo-potential is decreased. This is
mainly ascribed to the significant negative shift of dark-potential.
Clearly, the incorporated Sn ions increase the concentration of surface
states and thus result in severe Fermi level pinning. This will increase
the potential drop within the Helmholtz layer [33], and therefore shift
the dark-potential into a more negative value, which is detrimental for
the generation of high photovoltage. Luckily, the Sn doping can also
contribute to the negative shift of photo-potential. This will enhance the
concentration of photogenerated electrons, thereby enhancing the
photocathodic protection performance for 304SS.
In the following text, we will use the α-Fe2O3 film calcinated at
750 °C for photocathodic protection measurements due to its better
performance. To evaluate the photocathodic protection properties of α-
Fe2O3 and α-Fe2O3/NiFe(OH)x electrodes, the OCPs variations of 304SS
coupled with α-Fe2O3 and α-Fe2O3/NiFe(OH)x electrodes under inter­
rupted illumination of visible light were measured, and the result is
shown in Fig. 3A. In this experiment, the photoelectrodes were im­
mersed in 1 M NaOH solution in the photoanode cell, and the 304SS
was placed in the 3.5 wt% NaCl solution in the corrosion cell. In the
dark, the OCPs for the coupled α-Fe2O3 and α-Fe2O3/NiFe(OH)x elec­
trodes were −0.188 V and −0.143 V, respectively. When the visible
light was switched on, the photo potentials were quickly shifted to
−0.291 V and −0.374 V vs. SCE for these two electrodes, respectively.
Under white light illumination, the photo potentials moved to a more
negative direction due to the enhanced light intensity, which are
−0.316 V for the coupled α-Fe2O3 electrode and −0.392 V for the
coupled α-Fe2O3/NiFe(OH)x electrodes, see Fig. S5. Clearly, as ex­
pected, the composite photoelectrode presented higher potential drop
and better photocathodic protection compared with bare α-Fe2O3
photoelectrode. These results suggest that the loading of NiFe(OH)x
cocatalyst on the surface of α-Fe2O3 can indeed reduce the re­
combination of photogenerated charge carriers, and increase the elec­
tron transfer from the irradiate α-Fe2O3 to 304SS, and thus result in a
more negative photo-potential and better photocathodic protection
performance. In addition, to better simulate the actual working en­
vironment, we also attempted to measure the photocathodic protection
performance of the α-Fe2O3 and α-Fe2O3/NiFe(OH)x electrodes in the
L. Fan, et al.
Fig. 1. (A) XRD patterns, (B) UV–vis absorption spectrum of (a) α-Fe2O3 and (b) α-Fe2O3/NiFe(OH)x films. The SEM images of (C) α-Fe2O3 and (D) α-Fe2O3/NiFe
(OH)x films respectively.
Fig. 2. Photo-induced OCPs variation of Fe2O3 films coupled with 304SS. The
α-Fe2O3 films were first sintered at 500 °C for 3 h, followed by additional
calcination at 500 °C, 600 °C, 650 °C or 750 °C for 20 min, respectively. The α-
Fe2O3 films were immersed into 1 M NaOH solution in the photoanode cell, and
the 304SS in the corrosion cell.
3.5 wt% NaCl solution under interrupted illumination of visible light,
and the result is shown in Fig. S6. Upon light illumination, the OCP for
the coupled α-Fe2O3-304SS and α-Fe2O3/NiFe(OH)x-304SS electrodes
are both negatively shifted, but the photo-potential of the α-Fe2O3/NiFe
(OH)x-304SS electrode is more negative than that of α-Fe2O3-304SS
electrode. These results illustrate that α-Fe2O3 and α-Fe2O3/NiFe(OH)x
4
Surface & Coatings Technology 403 (2020) 126407
photoelectrodes can both protect the 304SS from corrosion even in the
seawater environment, but the NiFe(OH)x-decorated α-Fe2O3 possess
the better protection performance. Similar result was also observed
when 3.5 wt% NaCl +0.1 M Na2S was used as the electrolyte in the
photoanode cell, see Fig. S7. However, the OCPs of the coupled elec­
trodes measured in the presence of Na2S was more negative than that
without Na2S, no matter in the dark or under illumination. This is be­
cause the redox potential of S2−/S (−0.71 V) is much smaller than that
of H2O/O2 (1.23 V) [34], and thus result in a significant negative shift
on the Fermi level of α-Fe2O3 and α-Fe2O3/NiFe(OH)x photoelectrodes.
Therefore, the addition of Na2S as the hole scavenger agent is a good
route to realize the effective protection of 304SS in the NaCl solution.
However, we also noted that the photo-potentials obtained in Na2S-
containing solution are very close to those obtained in 1 M NaOH so­
lution, and the potential drop in 1 M NaOH solution is even higher than
of Na2S-containing solution, see Figs. 3A and S7. Therefore, the NaOH
solution can be chosen as a feasible electrolyte used in the photoanode
cell to protect the 304SS immersed in the 3.5 wt% NaCl solution. This
will help us to prevent the use of chemical scavengers.
In addition, Tafel polarization curves were also selected to further
evaluate the photoelectrochemical protection performance. Fig. 3B
shows the results of the Tafel curves examined with bare 304SS elec­
trode uncoupled and coupled with α-Fe2O3 or α-Fe2O3/NiFe(OH)x
electrodes illuminated with visible light. It can be seen that the corro­
sion potential (Ecorr) of 304SS is −0.219 V vs. SCE, whereas it was
negatively shifted to −0.322 and −0.383 V vs. SCE when the 304SS
were coupled with the irradiated α-Fe2O3 and α-Fe2O3/NiFe(OH)x
electrodes under visible light, respectively. The tendency is in good
agreement with those observed in the OCPs variation (Fig. 3A). These
results further confirm that the photogenerated electrons on the
L. Fan, et al.
Fig. 3. (A) Variation of the open circuit potential of 304SS coupled with (a) α-Fe2O3 and (b) α-Fe2O3/NiFe(OH)x electrodes in 1 M NaOH solution under visible light
illumination. (B) Tafel curves of (a) bare 304SS in the dark, 304SS coupled with (b) α-Fe2O3 and (c) α-Fe2O3/NiFe(OH)x photoelectrode. The photoelectrodes were
immersed into 1 M NaOH solution in photoanode cell and the coupled 304SS was placed in 3.5 wt% NaCl solution in the corrosion cell.
irradiated photoelectrodes are capable of transferring to the 304SS and
shift the self-corrosion potential to a more negative value. Meanwhile,
the α-Fe2O3/NiFe(OH)x electrode possesses the higher photocathodic
protection performance than α-Fe2O3 electrode. Furthermore, it is
highlighted that no hole scavengers were used in all the photocathodic
protection measurements shown in this work. This means that the
photoelectrodes developed in this study can provide a completely green
and sustainable protection to the 304SS without the sacrifice of the
photoanode and use of hole scavengers.
The photostability of photoanode materials is very important for the
practical application of photocathodic protection technique [35]. Fig. 4
shows that the OCP-time curves of α-Fe2O3/NiFe(OH)x electrodes
coupled with 304SS under interrupted white or visible light illumina­
tion. In this experiment, the α-Fe2O3/NiFe(OH)x electrode was im­
mersed in 1 M NaOH solution in the photoanode cell, and the 304SS
was immersed in 3.5 wt% NaCl solution in the corrosion cell. When the
visible light was on, the OCP of α-Fe2O3/NiFe(OH)x electrode was ne­
gatively shifted and gradually stable at −0.38 V, and it increased to
−0.46 V under white light illumination. Interestingly, the composite
electrodes exhibited highly stable photo potential with negligible decay
within 4 h illumination, and no obvious differences were observed on
the surface morphology of α-Fe2O3/NiFe(OH)x film before and after the
Fig. 4. Photo-induced OCPs variation of α-Fe2O3/NiFe(OH)x electrodes under
(a) visible light and (b) white light illumination. The photoelectrodes were
immersed into 1 M NaOH solution in photoanode cell and the coupled 304SS
was placed in 3.5 wt% NaCl solution in the corrosion cell.
5
Surface & Coatings Technology 403 (2020) 126407
photostability test, see Fig. S8. It indicates that the α-Fe2O3/NiFe(OH)x
is rather stable in alkaline solution. In addition, we also examine the
photo-stability of coupled α-Fe2O3/NiFe(OH)x-304SS electrodes with
3.5 wt% NaCl or 3.5 wt% NaCl +0.1 M Na2S solution filling into the
photoanode cell, and the result is shown in Fig. S9. In both cases, the
OCPs within 5 h illumination under white light or visible light are more
negative than that observed in the dark. Furthermore, the photo-po­
tentials show minor decay under the continuous illumination. This
further illustrates that the α-Fe2O3/NiFe(OH)x photoanodes are stable
enough and can be used at a wide range of electrolytes.
3.3. Possible mechanism for the enhanced photocathodic protection
performance
We next want to understand why the loading of NiFe(OH)x can
enhance the photocathodic protection performance of hematite. In
general, the photocathodic protection performance of semiconductor
materials depend on many physical and chemical factors, such as the
crystal structure, surface area, light absorption, charge separation and
interfacial charge transfer. However, the deposition of NiFe(OH)x on
the surface of α-Fe2O3 by drop-casting technique has little effect on the
physical property of α-Fe2O3, such as the crystal structure and optical
absorption (Fig. 1A and B). Therefore, it is highly possible that the NiFe
(OH)x modification improves the charge kinetics since the NiFe(OH)x
cocatalyst is a well-known electrocatalyst which can effectively catalyze
the oxidation of water to O2 [26,36]. Fig. S10 shows the electro­
chemical characterization of NiFe(OH)x film prepared on the FTO
substrate, measured by cyclic voltammograms curve in 1 M NaOH
aqueous solution. It was noted that the electrocatalytic activity of
parent FTO was fairly poor, indicating the water oxidation is a slow
process. However, after the deposition of NiFe(OH)x, the electrode
displayed distinct oxygen evolution activity at potential higher than
0.375 V vs. SCE. This illustrates that the NiFe(OH)x is an efficient water
oxidation electrocatalyst. In addition, two distinct redox peaks located
at around ~0.46 and 0.35 V vs. SCE are well assigned to the oxidation
of Ni(II) to Ni(III) and the reduction of Ni(III) to Ni(II), respectively
[37]. The oxidation state change is very similar to (de)protonation in
the Ni(OH)2/NiOOH redox process in the voltammograms reported in
the literature [38].
To verify the positive effect of NiFe(OH)x on the photoelec­
trocatalytic water oxidation for α-Fe2O3 photoanode, the linear sweep
voltammogram (LSV) curves of the α-Fe2O3 and α-Fe2O3/NiFe(OH)x
electrodes were measured to evaluate the oxygen evolution activity, see
Fig. 5. The electrolyte used for the LSV measurement is 1 M NaOH
aqueous solution. In the dark, the current density for two electrodes is
L. Fan, et al.
Fig. 5. Linear sweep voltammogram curves of α-Fe2O3 and α-Fe2O3/NiFe(OH)x
electrodes measured in the dark (dotted lines) or under simulated solar light
(solid line) in 1 M NaOH solution (pH = 13.6) with a scan rate of 20 mV/s.
very small. When the light was turned on, the α-Fe2O3 photoanode
exhibited initial current for water oxidation starting at about −0.38 V
(vs. SCE). However, upon the loading of NiFe(OH)x overlay, the pho­
tocurrent density was significantly enhanced, which is about 1.5 times
higher than the bare α-Fe2O3 electrode at 0 V vs. SCE. In addition, the
onset potential for water oxidation was also reduced by 50 mV for the
composite electrode. This means that the NiFe(OH)x cocatalyst can
reduce the kinetic barrier for water oxidation and low the charge re­
combination of electron-hole pairs [39].
Additionally, electrochemical impedance spectroscopy was used to
extract the kinetic information for charge transfer at the electrode/
electrolyte interface. The impedance experiments were performed at
open circuit potential to simulate the real experiment condition oc­
curring on the photocathodic protection process, and the corresponding
Nyquist and Bode plots are shown in Fig. 6A and B. The charge transfer
resistances (Rct) are obtained by fitting the Nyquist plots with equiva­
lent circuit shown in Fig. 7. Fig. 7A is the equivalent circuit model for
bare 304SS as Rs (CPE-Rct), where Rs stands for electrolyte resistance,
CPE stands for constant phase element, and Rct stands for charge
transfer resistance. Whereas, the coupled 304SS with α-Fe2O3 or α-
Fe2O3/NiFe(OH)x films were fitted with the equivalent circuit shown in
Fig. 7B as Rs(CPE-Rf)(Cdl-Rct). In particular, under high frequencies, we
can obtain the information of space charge layer and passivation oxide
Fig. 6. Nyquist (A) and Bode (B) plots of 304SS, and 304SS coupled with α-Fe2O3 and α-Fe2O3/NiFe(OH)x electrodes under simulated solar light illumination at open
circuit potential measured with 1 M NaOH solution.
6
Surface & Coatings Technology 403 (2020) 126407
layer resistance from CPE and Rf, respectively [7]. The double-layer
capacitance and charge transfer resistance can be obtained from Cdl and
Rct under low frequencies. Table 1 summaries the fitting results of the
circuit models. Obviously, the coupled α-Fe2O3/NiFe(OH)x electrodes
show a lower Rct value (14.5 kΩ) than that of the coupled α-Fe2O3
electrodes (27.5 kΩ), which means a faster charge transfer rates.
Therefore, the loading of NiFe(OH)x can promote the interfacial hole
transfer for water oxidation, and thus the long-lived and high-energy
electrons on the conduction band of α-Fe2O3/NiFe(OH)x electrodes are
able to transfer to the 304SS and polarize it into a more negative po­
tential to prevent corrosion.
It has been suggested that the negative shift of flat band potential
could increase the band bending of the photoanodes, and then promote
interfacial charge transfer [40]. To examine the possible effect of NiFe
(OH)x on the band bending of α-Fe2O3 photoanode, Mott-Schottky
curves of these two electrodes at different potentials were measured in
1 M NaOH solution with 1 kHz frequency, see Fig. 8. It was found that
the NiFe(OH)x overlayer has negligible effect on the flat band potential
of α-Fe2O3 photoanode, which could determine from the intercept of
Mott-Schottky plots with the x-axis. It suggests that the increased water
oxidation rate mainly depend on the electrocatalytic activity of NiFe
(OH)x overlayer, rather than the band bending. However, we can find
that the effective carrier densities Nd of the two films have been
changed due to the different slope of the Mott-Schottky curves. The Nd
value can be calculated through Eq. (1), from which the Nd values are
deduced to be 7.4 × 1019 and 1.2 × 1020 cm−3 for α-Fe2O3 and α-
Fe2O3/NiFe(OH)x films, respectively. It can be seen that the carrier
densities of α-Fe2O3 electrodes was increased by 0.6 times after being
modified with NiFe(OH)x cocatalyst, which might be ascribed to the
change of surface states [41]. Although the enhancement might not
have a significant effect on improving the electrical conductivity of the
photoelectrode, the gentle improvement of the majority carrier den­
sities after the NiFe(OH)x modification could be a possible additional
advantage to enhance the photoelectrochemical activity of α-Fe2O3
electrode. Moreover, the band edge potential of α-Fe2O3 can be calcu­
lated by using the obtained Efb and ND values following a relationship
described in Eq. (2). Thus, the conduction band potential (ECB) of α-
Fe2O3 is estimated to be −0.42 V vs. SCE, and then the valence band
potential (EVB) is calculated to be 1.71 V vs. SCE through a relationship
of EVB = Eg + ECB, where Eg is the band gap value of α-Fe2O3.
2
Nd = (dC 2/ dV ) 1
e0 0 r (1)
ECB = Efb + kT ln(NC /ND ) (2)
L. Fan, et al. Surface & Coatings Technology 403 (2020) 126407

Fig. 7. Schematic of the equivalent circuit obtained by EIS result fitting: (A) 304SS and (B) α-Fe2O3-304SS or α-Fe2O3/NiFe(OH)x-304SS. Rs: solution resistant, Rf:
film resistant, CPE: constant phase element corresponding to film, Cdl: double-layer capacitance, Rct: charge transfer resistance.

Table 1
Electrochemical impedance parameters for 304SS and α-Fe2O3-304SS and α-
Fe2O3/NiFe(OH)x-304SS in 3.5 wt% NaCl solution under simulated solar light
illumination.
Samples Rs (Ω) CPE Rf (kΩ) Cdl (uF) Rct (kΩ)

CPE-T CPE-P

304SS 12.4 5.4 0.9 – – 2576.4

α-Fe2O3-304SS 25 20.3 0.8 100.6 75.2 27.5
α-Fe2O3/NiFe(OH)x- 10.1 16.9 0.8 21.4 72.2 14.5
304SS

Fig. 9. Scheme illustrating the photocathodic protection mechanism in the α-

Fe2O3/NiFe(OH)x electrode when coupled with 304SS under visible light.

and 6A). Thus, the rate of interfacial charge recombination will be

greatly inhibited. Hence, more electrons will accumulate on the con­
duction band of α-Fe2O3 electrodes, and lead to the negative shift of the
OCP. In addition, it is noted that the conduction band potential of α-
Fe2O3 (−0.42 V vs. SCE) is more negative than the self-corrosion po­
tential of 304SS (−0.219 V vs. SCE). Therefore, the accumulated
electrons on the conduction band of α-Fe2O3 will promote the electron
transfer from α-Fe2O3 to 304SS and thus better protect the 304SS.

4. Conclusion

In summary, α-Fe2O3/NiFe(OH)x photoelectrodes were successfully

Fig. 8. Mott-Schottky plots of (a) α-Fe2O3 and (b) α-Fe2O3/NiFe(OH)x elec­
trodes measured at 1 kHz in 1 M NaOH solution of pH 13.6.
where e0 is the elemental charge (e0 = 1.6 × 10−19C), ε0 is the per­
mittivity of vacuum (ε0 = 8.85 × 10−14 F m−1), εr is the dielectric
constant of hematite (εr = 80) [42], and C is the capacitance derived
from the electrochemical impedance obtained at each potential. k and T
are the Boltzmann constant and the absolute temperature, respectively.
Nc is the effective density of states in the conduction band of α-Fe2O3,
taken as 4 × 1022 cm−3 [43], ND is the effective charge density, which
has been calculated from the slope of Mott-Schottky. Furthermore, we
can obtain the Efb value from the intercept of Mott-Schottky plot with
the x-axis, which is −0.26 V vs. SCE.
Based on the above analysis, a possible mechanism for the enhanced
photocathodic protection performance is proposed in Fig. 9. Upon light
irradiation, the valence band electrons on α-Fe2O3 will jump to the
conduction band, and leave holes in the valence band. The photo­
generated holes are able to oxidize Ni2+ of Ni(OH)x to high valence
state (Ni3+) since the valence band potential of α-Fe2O3 (1.71 V vs.
SCE) is more positive than the redox potential of Ni2+/3+, see Fig. S10.
The long-lived Ni3+ ions can reduce the activation energy for water
oxidation reaction and accelerate the water oxidation kinetics (Figs. 5
synthesized by combining hydrothermal and drop casting technique.
The prepared photoelectrodes could be used as a green, stable and
visible light responsive material to prevent 304SS from corrosion.
Meanwhile, no hole scavengers are needed in this system. The NiFe
(OH)x decoration could greatly improve the water oxidation kinetics
occurring at the electrode/electrolyte interface, and shift the photo
potential and self-corrosion potential of 304SS into a more negative
value. The enhanced photocathodic protection performance is mainly
ascribed to the electrocatalytic activity of NiFe(OH)x, which promote
the interfacial hole transfer and reduce the charge recombination. The
accumulated electrons will accelerate the electron transfer from the
irradiated α-Fe2O3 photoelectrode and provide a better protection to
304SS. In addition, the enhanced photostability and chemical stability
of the α-Fe2O3/NiFe(OH)x films offer a new option for the development
of anticorrosive materials for stainless steel and a better platform for
practical application.
CRediT authorship contribution statement
Fan Liya: Methodology, Writing-Original draft preparation.
Xiao Zhang: Investigation.
Chuanqun Zhang: Data collection and interpretation.

7
L. Fan, et al.
Jiangshan Li: Performance test.
Chenglin Wu: Supervision, Validation, Provide research funding.
Yuxiao Chu, Fangqi Ge, Yiyuan Liu: Films preparation and char­
acterization.
Xianqiang Xiong: Guide the whole research idea, Supervision and
Reviewing, Provide research funding.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
This work is supported by China Postdoctoral Science Foundation
(2020M671692), National Students' Platform for Innovation and
Entrepreneurship Training Program (201910350032, 201910350015),
Chemical Engineering & Technology of Zhejiang Province First-Class
Discipline (Taizhou University), Science and Technology Innovation
Activity Plan of College Students in Zhejiang Province (2020R468010).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.surfcoat.2020.126407.
References
[1] A.U. Malik, P.C. Mayan Kutty, N.A. Siddiqi, I.N. Andijani, S. Ahmed, The influence
of pH and chloride concentration on the corrision behaviour of AISI 316L steel in
aqueous solutions, Corros. Sci. 33 (1992) 1809–1827.
[2] J.-G. Kim, Y.-W. Kim, Advanced Mg-Mn-Ca sacrificial anode materials for cathodic
protection, Mater. Corros. 52 (2001) 137–139.
[3] J. Li, C.-J. Lin, Y.-K. Lai, R.-G. Du, Photogenerated cathodic protection of flower-
like, nanostructured, N-doped TiO2 film on stainless steel, Surf. Coat. Technol. 205
(2010) 557–564.
[4] W. Liu, K. Yin, F. He, Q. Ru, S. Zuo, C. Yao, A highly efficient reduced graphene
oxide/SnO2/TiO2 composite as photoanode for photocathodic protection of 304
stainless steel, Mater. Res. Bull. 113 (2019) 6–13.
[5] J. Hu, Y.-F. Zhu, Q. Liu, Y.-B. Gao, R.-G. Du, C.-J. Lin, SnO2 nanoparticle films
prepared by pulse current deposition for photocathodic protection of stainless steel,
J. Electrochem. Soc. 162 (2015) C161–C166.
[6] H. Deng, M.-C. Huang, W.-H. Weng, J.-C. Lin, Photocathodic protection of iron
oxide nanotube arrays fabricated on carbon steel, Surf. Coat. Technol. 266 (2015)
183–187.
[7] W. Sun, S. Cui, N. Wei, S. Chen, Y. Liu, D. Wang, Hierarchical WO3/TiO2 nanotube
nanocomposites for efficient photocathodic protection of 304 stainless steel under
visible light, J. Alloys Compd. 749 (2018) 741–749.
[8] Y. Bu, Z. Chen, J. Ao, J. Hou, M. Sun, Study of the photoelectrochemical cathodic
protection mechanism for steel based on the SrTiO3-TiO2 composite, J. Alloys
Compd. 731 (2018) 1214–1224.
[9] Z. Wang, X. Mao, P. Chen, M. Xiao, S.A. Monny, S. Wang, M. Konarova, A. Du,
L. Wang, Understanding the roles of oxygen vacancies in hematite-based photo­
electrochemical processes, Angew. Chem. Int. Ed. 131 (2018) 1042–1046.
[10] K. Sivula, R. Zboril, F. Le Formal, R. Robert, A. Weidenkaff, J. Tucek, J. Frydrych,
M. Grätzel, Photoelectrochemical water splitting with mesoporous hematite pre­
pared by a solution-based colloidal approach, J. Am. Chem. Soc. 132 (2010)
7436–7444.
[11] W. Wu, R. Hao, F. Liu, X. Su, Y. Hou, Single-crystalline α-Fe2O3 nanostructures:
controlled synthesis and high-index plane-enhanced photodegradation by visible
light, J. Mater. Chem. A 1 (2013) 6888–6894.
[12] A. Boudjemaa, S. Boumaza, M. Trari, R. Bouarab, A. Bouguelia, Physical and photo-
electrochemical characterizations of α-Fe2O3. Application for hydrogen production,
Int. J. Hydrog. Energy 34 (2009) 4268–4274.
[13] J. Zhang, S. Eslava, Understanding charge transfer, defects and surface states at
hematite photoanodes, Sustain. Energy Fuels 3 (2019) 1351–1364.
[14] I. Cesar, K. Sivula, A. Kay, R. Zboril, M. Gratzel, Influence of feature size, film
thickness, and silicon doping on the performance of nanostructured hematite
photoanodes for solar water splitting, J. Phys. Chem. C 113 (2009) 772–782.
8
Surface & Coatings Technology 403 (2020) 126407
[15] Z. Luo, T. Wang, J. Zhang, C. Li, H. Li, J. Gong, Dendritic hematite nanoarray
photoanode modified with a conformal titanium dioxide interlayer for effective
charge collection, Angew. Chem. Int. Ed. 56 (2017) 12878–12882.
[16] S.-S. Yi, J.-M. Yan, Q. Jiang, Carbon quantum dot sensitized integrated Fe2O3@g-
C3N4 core-shell nanoarray photoanode towards highly efficient water oxidation, J.
Mater. Chem. A 6 (2018) 9839–9845.
[17] Z. Fan, Z. Xu, S. Yan, Z. Zou, Tuning the ion permeability of an Al2O3 coating layer
on Fe2O3 photoanodes for improved photoelectrochemical water oxidation, J.
Mater. Chem. A 5 (2017) 8402–8407.
[18] R. Boddula, B. Guo, A. Ali, G. Xie, Y. Dai, C. Zhao, Y. Wei, S.U. Jan, J.R. Gong,
Synergetic effects of dual electrocatalysts for high-performance solar-driven water
oxidation, ACS Appl. Energy Mater. 2 (2019) 7256–7262.
[19] J. Qiu, H. Hajibabaei, M.R. Nellist, F.A.L. Laskowski, S.Z. Oener, T.W. Hamann,
S.W. Boettcher, Catalyst deposition on photoanodes: the roles of intrinsic catalytic
activity, catalyst electrical conductivity, and semiconductor morphology, ACS
Energy Lett. 3 (2018) 961–969.
[20] W.Y. Sohn, S. Kuwahara, J.E. Thorne, D. Wang, K. Katayama, Investigation of
photoexcited carrier dynamics in hematite and the efect of surface modifications by
an advanced transient grating technique, ACS Omega 2 (2017) 1031–1035.
[21] J. Deng, Q. Zhang, K. Feng, H. Lan, J. Zhong, M. Chaker, D. Ma, Efficient photo­
electrochemical water oxidation on hematite with fluorine-doped FeOOH and
FeNiOOH as dual cocatalysts, ChemSusChem 11 (2018) 3783–3789.
[22] M. Li, T. Liu, Y. Yang, W. Qiu, C. Liang, Y. Tong, Y. Li, Zipping up NiFe(OH)x-
encapsulated hematite to achieve an ultralow turn-on potential for water oxidation,
ACS Energy Lett. 4 (2019) 1983–1990.
[23] Z. Wang, G. Liu, C. Ding, Z. Chen, F. Zhang, J. Shi, C. Li, Synergetic effect of
conjugated Ni(OH)2/IrO2 cocatalyst on titanium-doped hematite photoanode for
solar water splitting, J. Phys. Chem. C 119 (2015) 19607–19612.
[24] K. Takanabe, Photocatalytic water splitting: quantitative approaches toward pho­
tocatalyst by design, ACS Catal. 7 (2017) 8006–8022.
[25] T. Yamashita, P. Hayes, Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide
materials, Appl. Surf. Sci. 254 (2008) 2441–2449.
[26] D. Wang, J. Zhou, Y. Hu, J. Yang, N. Han, Y. Li, T.-K. Sham, In situ X-ray absorption
near-edge structure study of advanced NiFe(OH)x electrocatalyst on carbon paper
for water oxidation, J. Phys. Chem. C 119 (2015) 19573–19583.
[27] Wang L., Lee C.-Y., Schmuki P., Influence of annealing temperature on photoelec­
trochemical water splitting of α-Fe2O3 films prepared by anodic deposition,
Electrochim. Acta 91 (2013) 307–313.
[28] Y. Ling, G. Wang, D.A. Wheeler, J.Z. Zhang, Y. Li, Sn-doped hematite nanos­
tructures for photoelectrochemical water splitting, Nano Lett. 11 (2011)
2119–2125.
[29] O. Zandi, T.W. Hamann, Enhanced water splitting efficiency through selective
surface state removal, J. Phys. Chem. Lett. 5 (2014) 1522–1526.
[30] P.S. Shinde, S.H. Choi, Y. Kim, J. Ryu, J.S. Jang, Onset potential behavior in α-
Fe2O3 photoanodes: the influence of surface and diffusion Sn doping on the surface
states, Phys. Chem. Chem. Phys. 18 (2016) 2495–2509.
[31] Y. Bu, J.-P. Ao, A review on photoelectrochemical cathodic protection semi­
conductor thin films for metals, Green Energy Environ. 2 (2017) 331–362.
[32] P. Dias, L. Andrade, A. Mendes, Hematite-based photoelectrode for solar water
splitting with very high photovoltage, Nano Energy 38 (2017) 218–231.
[33] C. Du, X. Yang, M.T. Mayer, H. Hoyt, J. Xie, G. McMahon, G. Bischoping, D. Wang,
Hematite-based water splitting with low turn-on voltages, Angew. Chem. Int. Ed. 52
(2013) 12692–12695.
[34] M. Sun, Z. Chen, Y. Bu, J. Yu, B. Hou, Effect of ZnO on the corrosion of zinc, Q235
carbon steel and 304 stainless steel under white light illumination, Corros. Sci. 82
(2014) 77–84.
[35] X. Xiong, L. Fan, Y. Xu, Q. Zhang, J. Li, Y. Wang, G. Chen, C. Wu, T. Li, S. Fu,
G. Zhang, Online corrosion monitoring of photoelectrochemical cathodic protection
of carbon steel using particle video microscope, Optik 208 (2020) 164091.
[36] S. Niu, W.-J. Jiang, T. Tang, L.-P. Yuan, H. Luo, J.-S. Hu, Autogenous growth of
hierarchical NiFe(OH)x/FeS nanosheet-on-microsheet arrays for synergistically en­
hanced high-output water oxidation, Adv. Funct. Mater. 29 (2019) 1902180.
[37] J. Qi, W. Zhang, R. Xiang, K. Liu, H.-Y. Wang, M. Chen, Y. Han, R. Cao, Porous
nickel–iron oxide as a hghly efficient electrocatalyst for oxygen evolution reaction,
Adv. Sci. 2 (2015) 1500199.
[38] F. Dionigi, P. Strasser, NiFe-based (oxy)hydroxide catalysts for oxygen evolution
reaction in non-acidic electrolytes, Adv. Energy Mater. 6 (2016) 1600621.
[39] P.S. Bassi, Gurudayal, L.H. Wong, J. Barber, Iron based photoanodes for solar fuel
production, Phys. Chem. Chem. Phys. 16 (2014) 11834–11842.
[40] C. Wang, X. Long, S. Wei, T. Wang, F. Li, L. Gao, Y. Hu, S. Li, J. Jin, Conformally
coupling CoAl-layered double hydroxides on fluorine-doped hematite: surface and
bulk co-modification for enhanced photoelectrochemical water oxidation, ACS
Appl. Mater. Interfaces 11 (2019) 29799–29806.
[41] S. Zhang, P. Shangguan, S. Tong, Z. Zhang, W. Leng, Enhanced photoelec­
trochemical oxidation of water over Ti-doped α-Fe2O3 electrodes by surface elec­
trodeposition InOOH, J. Phys. Chem. C 123 (2019) 24352–24361.
[42] K. Sivula, F. Le Formal, M. Grätzel, Solar water splitting: progress using hematite
(α-Fe2O3) photoelectrodes, ChemSusChem 4 (2011) 432–449.
[43] F.J. Morin, Electrical properties of α-Fe2O3, Phys. Rev. 93 (1954) 1195–1199.
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The Project Gutenberg eBook of The Devil's
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Title: The Devil's picture-books

Author: Mrs. John King Van Rensselaer

Release date: June 21, 2022 [eBook #68367]

Language: English

Original publication: United States: Dodd Mead and Co, 1890

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 Plate 1.

THE
DEVIL’S PICTURE-BOOKS

A History of Playing-Cards

BY

MRS. JOHN KING VAN RENSSELAER

AUTHOR OF CROCHET LACE, ETC.

ILLUSTRATED

NEW YORK
DODD, MEAD, AND COMPANY
PUBLISHERS

Copyright, 1890
By Dodd, Mead, and Company

All rights reserved

 University Press
John Wilson and Son, Cambridge
 PREFACE.

T he “Devil’s Books” was the name bestowed upon Playing-cards

by the Puritans and other pious souls who were probably in
hopes that this name would alarm timid persons and so prevent their
use. Whether or not his Satanic Majesty originated Playing-cards, we
have no means of discovering; but it is more probable that he only
inspired their invention, and placed them in the hands of mankind,
who have eagerly adopted this simple means of amusing
themselves, and have used it according to the good or evil which
predominated in their own breasts. Many learned men have written
books or treatises on Playing-cards, and I am indebted for a large
part of the information contained in this history to “Les Cartes à
Jouer,” by M. Paul la Croix; “Facts and Speculations about Playing-
cards,” by Mr. Chatto; “The History of Playing-cards,” by the Rev.
Edward Taylor; and “The History of Playing-cards,” by Mr. Singer.
These books are now out of print, and somewhat difficult to obtain;
and I hope, by bringing into a small compass the principal features
set forth in them, I shall be able to place before a number of readers
interesting facts that would be otherwise unobtainable.
Hearty thanks are due to the custodians of the National Museum
in Washington, who have aided me in every way in their power, and
also to the many kind friends who have sought far and wide for
unique and uncommon packs of cards, and helped materially by
gathering facts relating to them for me.
That many nations have cards peculiar to their own country and
almost unknown beyond its boundaries may be a matter of surprise
to some; that such ordinary and familiar objects as Playing-cards
should have a history, will astonish others. My hope is that the
subject will interest my readers as it has done me. Any facts
concerning Playing-cards or any communications relating to rare or
curious packs will be gladly received by the author, who would like to
add to her collection.
M. K. VAN RENSSELAER.
New York, 1890.
 CONTENTS.
PAGE
The Tarots, or the First Cards 11
Chess 21
Engraving 33
Materials 41
Name 49
Classification of Packs of Cards into Suits 55
Cards of Different Countries, viz.:—
China 65
Egypt 69
India 70
Cashmere 74
Persia 77
Italy 80
Germany 83
Spain 88
France 90
England 102
America 112
Japan 131
The King 139
The Queen 151
The Knave 161
Aces and Other Cards 171
Use and Abuse 179
Pips, Suits, and Colours 191
Odds and Ends 201
 LIST OF ILLUSTRATIONS.
PLATE
Persian 1
Tarot 2
Tarot 3
Chinese 4
Cashmere. Cards owned by Lockwood de Forest, Esq. 5, 6
Italian Cards showing the Suits of Swords, Maces, Money, and
7
Cups. Owned by Mrs. J. K. Van Rensselaer
German Cards showing the Aces of Grün, Roth, Schellen, and
8
Herzen. Owned by Mrs. J. K. Van Rensselaer
Remains of the Pack supposed to have been used by Charles VII. of
9
France, date 1425. In the Cabinet des Estampes, Paris, France
Elizabeth of York 10
Cards found by Mr. Chatto in a Black-Letter Volume formerly in
the Cathedral Library, at Peterborough, England. Now in the 11
Print Room of the British Museum
Found in an Old Edition of Claudian, Early English 12
Cards on which Invitations were Written. Owned by Mrs. Ten Eyck
13
and Miss Crowninshield. Date 1763
Geographical Cards. Owned by Richard H. Derby, Esq., M.D. Date
14
1795
North American Indian Cards, Apache Tribe. Cut out of Deerskin and 15, 16,
painted by themselves. National Museum, Washington, D.C., U.S.A. 17
North American Indian Gambling-Sticks, Haida Tribe, Queen
Charlotte Islands. Carved on Cubes of Wood. National Museum, 18, 19
Washington, D.C., U.S.A.
North American Indian Gambling-Sticks, Alaska Tribe. Painted on
20
Cubes of Wood. National Museum, Washington, D.C., U.S.A.
Japanese Cards, each one representing a Week in the Year. Owned 21, 22,
by Mrs. J. K. Van Rensselaer 23, 24
 THE DEVIL’S PICTURE-BOOKS
“The Ladies arm-in-arm in clusters,
As great and gracious a’ as sisters;

On lee-lang nights, wi’ crabbit leuks,

Pore owre the devil’s pictured beuks.”

Burns.
THE DEVIL’S PICTURE-BOOKS.
 THE TAROTS.
A youth of frolic, an old age of cards.

Hone: Every-Day Book, ii. 98.

T HE origin of Playing-cards and their inventor is still a subject of

speculation, and will probably remain forever undiscovered.
Almost every country in Europe has through her scholars laid claim
to having been the first to use cards; and many documentary and
other proofs have been brought forward to substantiate their
assertions, which are based upon ancient laws, common traditions,
or contemporary illustrations.
That cards were brought from the East to Europe about the time of
the Crusades, and probably by the home-returning warriors, who
imported many of the newly acquired customs and habits of the
Orient into their own countries, seems to be a well established fact;
and it does not contradict the statement made by some writers, who
declare that the gypsies—who about that time began to wander over
Europe—brought with them and introduced cards, which they used,
as they do at the present day, for divining the future. Cards may well
have become known by both means, and they spread rapidly over all
of what was then considered the only civilized part of the world; and
the proofs that have been brought forward show that they were
known nearly simultaneously in Italy, Spain, France, Germany, and
England, and point to a common origin not to be found in any one of
these countries.
 Plate 2.

The first cards known in Europe, and which were named Tarots,
Tarocchi, etc., seem to differ in almost every respect from those of
the fifteenth century, although these probably inspired their invention.
The latter resemble much more those of the present day than they
do the original Tarots. The first packs consisted of seventy-eight
cards,—that is, of four suits of numeral cards; and besides these
there were twenty-two emblematical pictured cards, which were
called Atous, or Atouts,—a word which M. Duchesne, a French
writer, declares signifies “above all.” This word used in French has
the same meaning as our word Trump. The marks which distinguish
the Tarot suits are usually Swords, Cups, Sticks, and Money; and
each one consists of fourteen cards, ten of which are “pips” and
three or four “coat” cards,—namely, King, Queen, Knight, and
Knave. The Queen was not always admitted. These suits seem to be
the origin of the modern packs; and the emblems used on them have
been adopted in many countries where the Atout part was discarded
while the rest of the pack with its original symbols was retained.
Mr. Singer gives a graphic description of these cards and the
games to be played with them, and says that “among different
nations the suits [as will be hereafter shown] are distinguished by
marks peculiar to themselves, while only the general features of the
numbered cards headed by figures or court cards have been
retained.”
The second division of the Tarot pack, called Atouts, are
numbered up to twenty-one, each of these having its proper value;
and besides all these there is one, not numbered and not belonging
to the division of the suit cards, which is called a Fou, and in playing
the game is designated Mat, or il Matto. This “Joker,” as we should
term it, has no value of its own, but augments that of any of the
Atouts to which it may be joined, and is sometimes played instead of
a Queen, being then called “her Excuse.”
These Atouts are each represented by a print which is supposed
to resemble some character, and the name is generally placed on
the card. Among them are an Emperor, a Cupid, a Chariot, a Hermit,
a Gallows, Death, The Day of Judgment, a Pope, Fortune,
Temperance, Justice, the Moon, the Sun, etc. The order in which
they are placed is not always the same, and is seemingly
unimportant. The game may be played by two or four persons. “The
one who holds the ‘Fool’ regains his stake; ‘La Force’ (or Strength)
takes twice as much from the pool, while ‘La Mort’ (or Death) most
appropriately sweeps the board.”
It is said that the distribution of the suit cards has a peculiar
signification. Each one is distinguished by an emblem which
represents the four classes into which communities were once
divided. First comes the Churchman, represented by the Chalice (or
Copas); next in rank, the Warrior, whose emblem is the Sword; third,
the Merchant, symbolized by a Coin; and fourth, the Workman with
his Staff. It will be shown hereafter that almost all writers on the
subject allow the possibility of the divisions of the suits being shown
in the cards.
The earliest known specimens of these Tarot cards are now to be
found in the Cabinet des Estampes in Paris, and are supposed to
have formed part of the pack which was painted for King Charles the
Seventh of France in 1393, to cheer and amuse him during an illness
which had been caused by a coup-de-soleil in 1392, and which
made him a melancholy but not a dangerous lunatic. M. Paul la Croix
describes these Tarots as having been most delicately painted and
resembling in treatment the illuminations of manuscripts. They are
on a golden background on which dots forming an ornamental
pattern were impressed. A border of silver surrounded and as it were
framed each picture, through which a dotted line twisted spirally like
a ribbon. M. la Croix points out that this dotted line, in his language
technically termed a tare (which also means a “fault” or “defect”),
was a sort of fluting produced by small holes pricked into the
substance of which the cards were made, and fancies that to these
Tares the Tarots owe their name. Other writers, however, dispute this
derivation of the word, and discover new ones for themselves which
are generally quite as fanciful and far-fetched.
 These well preserved Tarots are eighteen centimetres by nine, and
are painted in water colours on a thin card. The composition of the
figures is ingenious and artistic. The drawing is correct and full of
character, and the colours are still brilliant. A narrow border of black
and white checks surrounds each one. This border is a piece of
checkered paper pasted on the back of the card and neatly folded
over its edge as if to protect it, showing on the face of the card and
forming a frame for the pictures. This fashion of having a checkered
or diapered back was closely followed in many of the countries
where cards have been used; and these backs are still seen,
although this old pattern (which, as will hereafter be seen, had
probably a very interesting origin) has been generally discarded, and
each card-maker adopts a different device with which to decorate the
backs of his cards according to his own fancy. In France the backs
are generally plain, and coloured red, pink, or blue. In Spain the
pattern is dotted on the surface in lines and circles, while in other
countries interlaced and meaningless designs are employed.