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 Corrosion Science 176 (2020) 108901

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

High-efficiency photoelectrochemical cathodic protection performance of T

the TiO2/AgInSe2/In2Se3 multijunction nanosheet array
Xuhong Jianga,b,d,1, Mengmeng Suna,b,c,1, Zhuoyuan Chena,b,c,*, Jiangping Jinga,b,c,
Chang Fenga,b,d
a
Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, 7 Nanhai Road, Qingdao, 266071, China
b
Center for Ocean Mega-Science, Chinese Academy of Sciences, 7 Nanhai Road, Qingdao, 266071, China
c
Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology (Qingdao), No. 1 Wenhai Road, Qingdao, 266237, China
d
University of Chinese Academy of Sciences, 19 (Jia) Yuquan Road, Beijing, 100049, China

A R T I C LE I N FO A B S T R A C T

Keywords: Optimization of multijunction photoelectric conversion materials with a much negative band potential is very
A. AgInSe2/In2Se3 nanoparticles important for improving the photoelectric conversion and photoelectrochemical cathodic protection perfor-
A. Multijunctions mance because the well-matched multijunction can assist the fast transport of photogenerated electrons. In this
A. TiO2 nanosheet array paper, a “green” AgInSe2/In2Se3 sensitized TiO2 nanosheet array (NSA) photoanode was prepared. Vertically-
C. Photoelectrochemical conversion
grown two-dimensional TiO2 NSA with the multijunction of TiO2 NSA/AgInSe2(7)/In2Se3(3) improves the se-
performance
paration efficiency and the transfer of photoinduced charge carriers compared with single AgInSe2 sensitized
C. Photoelectrochemical cathodic protection
performance TiO2 NSA. The TiO2 NSA/AgInSe2/In2Se3 photoanode achieves highly efficient photoelectrochemical cathodic
protection performance for 316LSS in NaCl solution under AM1.5 light illumination.

1. Introduction high carrier recombination rate, an effective method is to construct

It is vital to control corrosion for the benefit of mankind since
corrosion can cause huge economic losses and catastrophic accidents
[1]. Among all of the corrosion protection methods, the photoelec-
trochemical cathodic protection (PECCP) has attracted wide attentions
owing to its energy-saving, environmentally friendly, and economical
virtues, which mainly utilizes the photoelectric conversion effect of
semiconductors to convert solar energy into electrical energy and then
transports the photogenerated electrons to the coupled metals, thus
achieving the cathodic protection effect [2,3]. The key of this tech-
nology is to choose suitable semiconductor materials and take ad-
vantage of their excellent photoelectrochemical (PEC) conversion
properties. TiO2 has been proved to be the most promising semi-
conductor materials due to its appropriate electronic band structure,
environmental friendliness, high photostability and low cost, playing a
central role in fields of photovoltaic cells [4,5] as well as photocatalytic
pollutants degradation [6]. However, the band gap of TiO2 is 3.2 eV,
which limits its light absorption only to the ultraviolet region [7], and
also the photogenerated carriers are easy to be recombined. Recent
researches have been focusing on overcoming the above defects. For the
direct electrical pathways in order to transport the photoinduced
electrons rapidly and reduce the grain boundaries so as to enhance the
photogenerated carrier collection efficiency. Different morphologies of
well-organized TiO2 nanostructures, such as one-dimensional (1D) na-
norods [8,9] and nanotubes [10–14], two-dimensional (2D) nanosheet
[15,16] and three-dimensional (3D) nanotree, nanoforest and nanolawn
[17–21] etc. have been developed, and the electron-transport efficiency
and PEC conversion performance have been improved to different ex-
tents. Especially, the 2D TiO2 nanosheet array (NSA) is of significance
for improving the performance of the PEC system [22–26], which can
provide sufficient nanoparticles (NPs) loading and light harvesting
area, improve the electron transport and charge separation efficiency,
thus result in achieving excellent PEC properties.
Apart from morphology modification, the construction of suitable
semiconductor heterojunction also plays a substantial role on reducing
the recombination rate of the photogenerated electron-hole pairs by
effectively separating them. And more importantly, coupling TiO2 with
visible light responsive narrow band gap semiconductor materials can
widen the light response to visible light region, and greatly improve the
PEC conversion performance [27–31]. Compared with bulk

⁎
Corresponding author at: Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, 7 Nanhai
Road, Qingdao, 266071, China.
E-mail address: zychen@qdio.ac.cn (Z. Chen).
1
Xuhong Jiang and Mengmeng Sun are the co-first authors.

https://doi.org/10.1016/j.corsci.2020.108901
Received 28 April 2020; Received in revised form 15 July 2020; Accepted 26 July 2020
Available online 29 July 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
X. Jiang, et al.
semiconductor materials, NPs are more sufficiently in heterojunction
with matched energy bands and energy levels, and has been extensively
investigated [32–35]. And, unlike the Cd and Pb elements whose
toxicity has hindered their further applications, the I–III–VI2-group (I:
Cu/Ag, III: Ga/In, VI: S/Se/Te) ternary chalcogenides have attracted
more attention because of their narrow band gaps, solar energy-ab-
sorbing ability, light stability and low toxicity. CuInS2 [36,37], AgInS2
[38], CuInSe2 [39,40], AgInSe2 [41–43] etc. are becoming alternatives
of the Pb- and Cd-based semiconductors for PEC conversion applica-
tions lying in their high absorption coefficient and ability to increase
photoconversion efficiency [44]. Recently, novel nano-photocatalyst of
TiO2-decorated AgInSe2 has been synthesized and was applied to dye
degradation, which showed effective degradation efficiency and stabi-
lity [41]. The band gap of AgInSe2 is around 1.20 eV [41], close to the
optimal band gap for absorbing the solar spectrum. This could be an
ideal PEC material to substitute contaminated substances in the areas of
PEC conversion and PECCP.
Besides, for heterojunction structure, at the interface of semi-
conductor composite, unmatched energy band arrangement and high
surface state density may exist, which results in a chance of charge
recombination at the interface [45]. Therefore, interfacial optimization
of the heterojunction is also necessary to further improve the PEC
conversion efficiency [46]. To solve this problem, a multijunction
heterostructure composite with well-matched band potentials can be
constructed, then the photogenerated electron-hole pairs will be sepa-
rated and transferred more efficiently [47–49]. Chang et al. fabricated a
series of TiO2/CuInS2, TiO2/Cu2S/CuInS2, TiO2/Cu2Se/CuInS2, TiO2/
In2S3/CuInS2, TiO2/In2Se3/CuInS2 configurations, which use Cu2S,
Cu2Se, In2S3, In2Se3 as the buffer layers of the bulk material, and the
PEC conversion efficiencies were 0.58 %, 1.06 %, 1.22 %, 0.89 % and
1.35 %, respectively. This result and other reports have demonstrated
that among all the currently studied “green” co-sensitizers, such as
Cu2S, Cu2Se, In2S3, In2Se3, InP, ZnS, ZnSe and ZnTe, In2Se3 has been
proved to be the most effective one to act as a composite layer of the
multijunction owing to its better PEC performance [50–54]. Therefore,
the studies for designing effective, energy band well-matched multi-
junction systems, especially combining with assist layers, are critical to
further promote the carrier transmission efficiency at the heterointer-
face and thus enhance the PEC activity of photoanodes.
In the present work, an AgInSe2/In2Se3 co-sensitized TiO2 NSA
multijunction photoanode was constructed, and the PEC conversion and
PECCP performance were explored in simulated seawater (3.5 wt%
NaCl solution) under simulated sunlight (AM1.5 light) illumination.
This condition does not contain any added man-made hole-scavengers
and is more closely to the realistic marine environment. The PEC per-
formance of the prepared TiO2 NSA/AgInSe2/In2Se3 was investigated
under intermittent AM1.5 light illumination. Besides, the energy band
potential of the n-type semiconductor of TiO2/AgInSe2/In2Se3 multi-
junction is comparatively negative, therefore, its application in the
PECCP for 316 L stainless steel (SS) was also explored. And, a highly
efficient PECCP performance in NaCl solution under AM1.5 light illu-
mination was obtained. Simultaneously, the relationship between the
multijunction structure and the PEC and PECCP performance as well as
the corresponding mechanism was analyzed. The results obtained in
Scheme 1. The synthesis procedure of the TiO2 NSA, TiO2 NSA/AgInSe2 and TiO2 NSA/AgInSe2/In2Se3 photoanodes.
2
Corrosion Science 176 (2020) 108901
this work will contribute for designing efficient photo-functional
coating to develop the expanded PEC applications in the PECCP field.
2. Experimental
2.1. Preparation of TiO2 NSA and TiO2 NSA/AgInSe2/In2Se3 photoanodes
All reagents used in this study were of analytical grades and were
directly used without further treatments. A fluorine-doped tin oxide
(FTO) glass (1 × 2 cm2) was ultrasonically cleaned with acetone and
ethanol for 10 min, respectively, and then dried in air before growing
TiO2 NSA on it. The 2D TiO2 NSA film was prepared on the cleaned FTO
conductive glass by a simple one-step hydrothermal method. In brief,
15 mL concentrated hydrochloric acid (mass fraction 36.5–38 %) and
15 mL deionized water were mixed together and stirred for 5 min. Then,
0.5 mL titanium butoxide (TBT) was added to the prepared HCl solu-
tion. After stirring for another 5 min, 0.25 g ammonium hexa-
fluorotitanate ((NH4)2TiF6) was added and further stirred for 5 min.
Then, the mixture was transferred to a 50 mL Teflon-lined stainless steel
autoclave. Finally, the FTO substrate was placed at an angle against the
wall of the Teflon liner with the conductive side facing down. The
hydrothermal synthesis was conducted at 170, 180 and 200 °C for 12 h
in an electric oven, respectively. After that, the autoclave was cooled
down, and the FTO substrate was taken out and rinsed with deionized
water thoroughly and dried in the air.
The AgInSe2 NPs were deposited onto the TiO2 substrate by suc-
cessive ion layer absorption and reaction (SILAR) technique. Typically,
the obtained TiO2 NSA film substrate was successively immersed into
three different aqueous solutions for 5 min for four times, firstly in a
0.02 M AgNO3 aqueous solution (cation precursor) and then in a 0.02 M
Na2SeSO3 aqueous solution (anion precursor), thirdly in a 0.02 M
In2(SO4)3 aqueous solution (cation precursor), and finally in a 0.02 M
Na2SeSO3 aqueous solution again. Between each immersion step, the
samples were rinsed thoroughly with deionized water to remove the
excess weakly-bounded ions. The Na2SeSO3 aqueous solution was
synthesized by dissolving elemental selenium powder (99.99 %) in an
aqueous sodium sulfite solution at 90 °C, adjusting pH to 12–14 with
sodium hydroxide, as adopted from previous literature [55,56]. The
Se2+ solution preparation method in the present paper is more stable
than those prepared by reducing the alcohol solution of selenium di-
oxide with sodium borohydride [50,57]. Such 4-times immersion pro-
cedure is termed as one cycle of the deposition process, and several
times of this immersion cycle were repeated until specified amount of
AgInSe2 NPs was compounded. By adjusting the number of deposition
cycles, the amount of deposited AgInSe2 NPs can be controlled.
After that, the In2Se3 layer was incorporated on the TiO2 NSA/
AgInSe2 photoanode by another SILAR deposition. The In2Se3 deposi-
tion cycle is similar to the AgInSe2 deposition procedure but without
immersing into the AgNO3 aqueous solution. Finally, the obtained
sample was denoted as TiO2 NSA/AgInSe2(m)/In2Se3(n), where m and
n represent the number of the deposition cycles of AgInSe2 and In2Se3
NPs, respectively. The preparation procedure of the TiO2/AgInSe2/
In2Se3 multijunction nanosheet array photoanode is schematically il-
lustrated in Scheme 1.
X. Jiang, et al.
The 316 L SS electrode was prepared by embedding a 316 L SS
square in epoxy resin, exposing an area of 10 × 10 mm2 for testing.
After that, the 316 L SS electrode was successively wet ground with SiC
paper to 2000 grits, and then ultrasonically cleaned in analytical grade
ethanol for 5 min and dried.
2.2. Characterizations
The surface morphology and the microstructure of the prepared
photoanodes were examined by a field-emission scanning electron mi-
croscope (SEM) (ULTRA 55, Zeiss Company, Germany) and a high re-
solution transmission electron microscope (HRTEM, Tecnai G20, FEI
Company, USA). The crystalline structures of the prepared materials
were characterized using Ultima IV X-Ray Diffractometer (XRD)
(Rigaku Co., Tokyo, Japan) with Cu Kα radiation. Fourier transform
infrared (FTIR) spectra were tested using a Fourier transform infrared
spectroscopy (FTIR, Thermo-Nicolet 8700, Thermo Electron Scientific
Inc., USA) at room temperature. The elemental compositions and the
bonding information were identified using X-ray photoelectron spec-
troscopy (XPS) on an X-ray spectrometer (Model Thermo ESCALAB 25
XI, Al Kα, hν =1486.6 eV, Mono X-ray source). The optical absorption
properties were measured on a UV/Vis spectrophotometer (SHIMADZU
UV-2600, Japan). The photoluminescence (PL) emission intensities of
the prepared materials were recorded by a fluorescence spectrometer
(Fluoro Max-4, HORIBA Jobin Yvon, France).
2.3. Electrochemical and PEC performance measurements
The PEC performance of the prepared materials was determined by
i-V curves and open circuit potential (OCP) variations as well as the
photoinduced current densities and potentiodynamic polarization
curves under intermittent simulated solar light (AM1.5) illumination.
The i-V curves were conducted at the potential range of −0.8 V to
0.4 V. The potentiodynamic polarization curves were measured from
−250 to 250 mV (vs. OCP). The electrochemical impedance spectro-
scopy (EIS) tests were performed in the dark at open circuit potential
over the frequency range between 105 and 10−2 Hz, with an AC voltage
magnitude of 5 mV. Mott-Schottky plots were conducted in the dark
with the potential range of -0.8 V to 0.4 V and the frequency of 1000 Hz
and the AC voltage magnitude of 10 mV. The abovementioned i-V, EIS,
and Mott-Schottky measurements were all conducted in 0.1 M Na2SO4,
while the OCP, photoinduced current density and polarization curves
were measured in 3.5 wt% NaCl solution. All of the measurements were
performed using a CHI 660D electrochemical workstation (Shanghai
Chenhua Instrument Co., Ltd.), by employing a Pt electrode as the
counter electrode and an Ag/AgCl (saturated KCl) as the reference
electrode, respectively.
2.4. PECCP performance measurements
The photoinduced variations of the current densities of the galvanic
coupling between the 316 L SS electrode and the photoanodes and the
mixed potentials of the 316 L SS electrode coupled with the photo-
anodes were examined to study the PECCP performance of the prepared
samples. All measurements were performed in 3.5 wt% NaCl solution
under intermittent simulated AM1.5 solar light illumination using the
CHI 660D electrochemical workstation (Shanghai Chenhua Instrument
Co., Ltd.). The experimental arrangement is schematically illustrated in
Fig. 1, which is similar to those listed in previous reports. By using this
experimental setup, the current density and potential can be measured
simultaneously [2,58]. The galvanic current densities between the
photoanode and the 316 L SS electrode were measured without any
applied polarization. A 300-W Xe arc lamp (PLS-SXE300, Beijing Per-
fect Light Co. Ltd., China) was used as the light source to generate
AM1.5 light with the power energy density of 100 mW cm−2.
3
Corrosion Science 176 (2020) 108901
3. Results and discussion
3.1. Morphology and structure analyses of the prepared AgInSe2/In2Se3
decorated TiO2 NSA
In order to prepare the photoanodes with best performance, the
influence of hydrothermal temperature on the morphologies and per-
formance of the prepared photoanodes was performed and the results
are shown in Fig. 2. With the increase of hydrothermal temperature
from 170 °C to 200 °C, the shape of each nanosheet is barely changed,
however, the density, size and thickness of the TiO2 NSA increase with
the hydrothermal temperature (Fig. 2a–c). Higher hydrothermal tem-
perature can promote the growth of the TiO2 NSA. Meanwhile, the
nanosheets which are too sparse or too crowded will not benefit the
light harvesting and the electron transport. As confirmed by Fig. 2d, the
photoinduced current density of the TiO2 NSA substrate prepared at
180 °C achieved the highest value, indicating that the TiO2 NSA pre-
pared at 180 °C possesses the best PEC conversion performance. As
shown in Fig. 2b, the prepared plain TiO2 NSA at 180 °C consists of a
series of vertically arranged and staggered nanosheets. The inset in
Fig. 2b shows the partial enlarged view of the formed nanosheets. A
well-faceted crystal structure can be seen, and the junction edge of the
adjacent different crystallographic planes can also be clearly seen. The
nanosheets are interlaced and interconnected with each other. The side
length of these nanosheets is approximately 2 μm, and the thickness of a
single nanosheet is approximately 200 nm. This ordered structure will
facilitate the transport of the photogenerated carriers. Subsequent
analyses were based on the photoanodes prepared under the optimal
hydrothermal temperature of 180 °C.
XRD patterns were recorded to investigate the crystal phases of the
prepared AgInSe2/In2Se3, AgInSe2, In2Se3 decorated TiO2 NSA and pure
TiO2 NSA samples, and the results are shown in Fig. 3. The diffraction
peaks corresponding to anatase TiO2 and FTO glass are clearly shown in
Fig. 3. The diffraction peaks at 2θ = 25.3°, 37.8°, 48.0°, 55.1°and 62.7°
are attributed to (101), (004), (200), (211) and (204) crystal planes of
anatase TiO2 (JPCDS No. 21- 1272) [59,60], respectively. As shown in
Fig. 3, much higher intensity ratios of the diffraction peak of (004)
crystal plane to those of other diffraction peaks are observed in com-
parison with those in the standard pattern of anatase TiO2, demon-
strating that the synthesized TiO2 has a highly exposed (004) crystal
plane. However, no diffraction peaks from AgInSe2 and In2Se3 are de-
tected in Fig. 3, indicating the low amount, well dispersion and/or low
degree of crystallinity of the deposited AgInSe2 and In2Se3 in the syn-
thesized photoanodes. Similar results of loading NPs using the same
SILAR method were also reported in previous literature [38,55,61].
The morphologies of the prepared composite photoanodes and the
combination states of AgInSe2 and In2Se3 on the TiO2 NSA were ana-
lyzed, and Fig. 4a–e show top-view SEM images of the prepared TiO2
NSA/AgInSe2(7), TiO2 NSA/AgInSe2(7)/In2Se3(3), TiO2 NSA/
AgInSe2(3)/In2Se3(3) and TiO2 NSA/AgInSe2(11)/In2Se3(3) photo-
anodes and cross-sectional-view image of TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanode, respectively. As shown in Fig. 4a, for TiO2 NSA/
AgInSe2(7), plenty of fine NPs are distributed uniformly on the surface
of the TiO2 NSA. While, with the further deposition of In2Se3 on TiO2
NSA/AgInSe2(7), the formed NPs on TiO2 NSA/AgInSe2(7)/In2Se3(3)
become larger and easier to be observed, as shown in Fig. 4b. The larger
NPs of AgInSe2(7)/In2Se3(3) distribute uniformly on the surface of TiO2
NSA, and exhibit a well combination onto the sheets. This ensures the
large light-harvesting of both the nanosheets and the large amount of
AgInSe2/In2Se3 NPs. While, in Fig. 4c, for TiO2 NSA/AgInSe2(3)/
In2Se3(3), several scattered NPs deposited on the surface of the TiO2
NSA can be seen. For TiO2 NSA/AgInSe2(11)/In2Se3(3) photoanode
(Fig. 4d), a lot of NPs are deposited onto TiO2 NSA, some of which
aggregate together to form larger particles. This will hinder the electron
transport process. The amount of the NPs on the TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanode is between those of the TiO2 NSA/AgInSe2(3)/
X. Jiang, et al. Corrosion Science 176 (2020) 108901

Fig. 1. Schematic illustrations of the experimental setup for the PECCP measurments: (a) the photoinduced current density between the prepared photoanode and the
316 L SS electrode and (b) the photoinduced mixed potentials of the coupled 316 L SS electrode and the prepared photoanode.

Fig. 2. SEM images of the TiO2 NSA substrates prepared under different hydrothermal reaction temperatures: (a) 170 °C, (b) 180 °C and (c) 200 °C; and (d) the
corresponding photoinduced current densities of the TiO2 NSA photoanodes prepared at different temperature under intermittent AM1.5 light illumination.

In2Se3(3) and TiO2 NSA/AgInSe2(11)/In2Se3(3) photoanodes. On one
hand, proper amount of NPs can guarantee enough light absorption and
generate a largest amount of electrons, on the other hand, compara-
tively small size of NPs can make sure the generated electrons to mi-
grate rapidly at the interfaces of NPs and nanosheets. The cross-sec-
tional view SEM image of the TiO2 NSA/AgInSe2(7)/In2Se3(3) is shown
in Fig. 4e, the thickness of the whole TiO2 NSA film is approximately
2 μm. And, the TiO2 NSA film is nearly perpendicular to the FTO sub-
strate, which is consistent with the top-view SEM image shown in
Fig. 4b.
Fig. 5 shows the SEM image and the corresponding EDS elemental
mapping of TiO2 NSA/AgInSe2(7)/In2Se3(3), from which the Ti, O, Ag,
In and Se elements are clearly observed. The distribution of Ti and O
elements in the EDS mapping is in good agreement with the corre-
sponding SEM image. While, the elements of Ag, In and Se are evenly
distributed, indicating that the AgInSe2(7)/In2Se3(3) NPs are dispersed
evenly on the surface of the TiO2 NSA.
The prepared TiO2 NSA/AgInSe2(7) and TiO2 NSA/AgInSe2(7)/
In2Se3(3) photocatalysts were further investigated by TEM and HRTEM
to confirm the deposited NPs, and the results are shown in Fig. 6. Fig. 6a
and b are the TEM images of TiO2 NSA/AgInSe2(7) and TiO2 NSA/
AgInSe2(7)/In2Se3(3), respectively. Both images illustrate the NPs in
the size of 20−50 nm on a sheet-like structure. The difference between
Fig. 6a and b is that some clusters are observed to surround the NPs in

4
X. Jiang, et al.
Fig. 3. XRD patterns of the prepared samples.
Fig. 6b, while, in Fig. 6a, the boundaries of nanosheets and NPs are
clear and obvious. Further HRTEM analyses help to distinguish the
different lattices and the results are shown in Fig. 6a1, a2, b1 and b2.
Fig. 6a1 and a2 in Fig. 6 are the corresponding HRTEM images of TiO2
Fig. 4. Top-view SEM images of (a) TiO2 NSA/AgInSe2(7), (b) TiO2 NSA/AgInSe2(7)/In2Se3(3), (c) TiO2 NSA/ AgInSe2(3)/In2Se3(3) and (d) TiO2 NSA/AgInSe2(11)/
In2Se3(3) photoanodes; Cross-sectional-view SEM image (e) of TiO2 NSA/ AgInSe2(7)/In2Se3(3) photoanode.
5
Corrosion Science 176 (2020) 108901
NSA/AgInSe2(7) sample in the square areas of Fig. 6a, while Figures
6b1 and 6b2 in Fig. 6 correspond to HRTEM images of TiO2 NSA/
AgInSe2(7)/In2Se3(3) sample in the square areas of Fig. 6b. The lattices
spacing of 0.352 nm and 0.189 nm correspond to the (101) and (200)
planes of anatase TiO2 (JCPDS 12-1272) [62,63], implying the forma-
tion of anatase crystal of TiO2. The observed fringe spacing of 0.211 nm
and 0.327 nm are consistent with the (220) and (111) lattice distances
in cubic AgInSe2 (JCPDS 65-7084) [42,64,65], confirming the prepared
crystalline state of the AgInSe2 NPs. The HRTEM results shown in Fig. 6
confirm the successful deposition of AgInSe2 NPs onto the surface of
TiO2 nanosheets.
Apart from the clearly seen AgInSe2 NPs, the weak crystallinity
layer around the AgInSe2 NPs might be the In2Se3 phase, which is at-
tributed to the low crystallinity of In2Se3 obtained via the SILAR de-
position process [50,61,66]. Moreover, the TEM and HRTEM analyses
of the prepared TiO2 NSA/In2Se3(10) was conducted to study the state
of In2Se3 deposited on TiO2 NSA by the SILAR deposition method. High
concentration of In3+ and Se2− precursor solutions (ten times) were
employed to deposited sufficient amount of In2Se3 onto TiO2 NSA.
Fig. 7a, c and e are the TEM images of the TiO2 NSA/In2Se3 at low
magnifications, Fig. 7b, d and f are the HRTEM images in the corre-
sponding square areas shown in Fig. 7a, c and e. From the TEM image of
TiO2 NSA/In2Se3(10), the TiO2 nanosheets seem to be coated by
something. From all of the HRTEM images, anatase TiO2 nanosheets are
detected, each nanosheet is coated with a layer on the edge, which
X. Jiang, et al. Corrosion Science 176 (2020) 108901

Fig. 5. SEM image and the corresponding EDS elemental mapping results of the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode.

could be In2Se3 with a low crystallinity and obscured morphology
[38,50,55,61,67]. This result is also agreed with the SEM image of TiO2
NSA/AgInSe2(7)/In2Se3(3) shown in Fig. 4e, in which the edge of the
TiO2 nanosheets become obscured compared with those of pure TiO2
NSA in Fig. 2b. As the TEM and HRTEM images of TiO2 NSA/
AgInSe2(7)/In2Se3(3) shown in Fig. 6b, b1, b2, a large amount of ob-
scured particles are observed, which could be the In2Se3 particles de-
posited on the surface of the TiO2 NSA by SILAR process. These In2Se3
layers act as the composite layer of the AgInSe2 NPs sensitized TiO2
NSA, and the formed multijunction structure can help to further

Fig. 6. TEM and HRTEM images of the prepared (a) TiO2 NSA/AgInSe2(7) and (b) TiO2 NSA/AgInSe2(7)/ In2Se3(3) photoanodes. a1 and a2 show the corresponding
HRTEM images of TiO2 NSA/AgInSe2(7) in the square area of (a); b1 and b2 show the corresponding HRTEM images of TiO2 NSA/AgInSe2(7)/ In2Se3(3) in the square
area of (b).

6
X. Jiang, et al.
Fig. 7. TEM and HRTEM images of the prepared TiO2 NSA/In2Se3 photoanode; a, c, e: TEM images; b, d, f: the corresponding HRTEM images in the square areas.
separate the photoinduced electrons and holes efficiently, and also the
NSA architecture can promote the transfer of the photoinduced elec-
trons as a direct electron transmission path.
XPS spectra were used to analyze the states of Ag, In and Se in the
prepared TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode, and the results
are shown in Fig. 8. Fig. 8a illustrates the total survey spectrum, which
reveals the presence of Ti, O, Ag, In, Se as well as C impurity from the
absorption of CO2 gaseous molecules and Si from the FTO glass. High-
resolution XPS spectra of Ag, In, Se core regions are given in Fig. 8b–d.
The binding energies for Ag 3d5/2 and 3d3/2 are observed at 368.3 and
374.3 eV, respectively, which are attributed to the monovalent state of
Ag (Ag+) [68]. In the XPS core level spectra of In 3d, two peaks at the
binding energies of 445.3 eV and 452.9 eV are observed, which corre-
spond to the In 3d5/2 and In 3d3/2 states and confirm the presence of the
trivalent nature of In (In3+) in prepared TiO2 NSA/AgInSe2(7)/
In2Se3(3) [41]. In Se XPS core level spectra, abroad peak at 54.3 eV
corresponds to the Se 3d state and confirms the existence of Se2− in the
prepared TiO2 NSA/AgInSe2(7)/In2Se3(3) [69–73]. All of the detected
Ag+, In3+ and Se2− are in agreement with the previous reports of
AgInSe2 and In2Se3 nanocrystals [69–73], demonstrating that AgInSe2
and In2Se3 were successfully prepared in TiO2 NSA/AgInSe2(7)/
In2Se3(3).
3.2. Analyses of the optical properties of the prepared photoanodes
The optical properties of the prepared AgInSe2/In2Se3, AgInSe2 and
In2Se3 NPs sensitized TiO2 NSA and pure TiO2 NSA nanostructures were
studied using UV–vis diffuse reflection spectroscopy, as shown in
Fig. 9a. Owing to the wide band gap of 3.2 eV, the TiO2 NSA shows its
fundamental absorption sharp edge rising at 387 nm in the UV light
region. For In2Se3 sensitized TiO2 NSA photoanode, the adsorption re-
gion is consistent with that of TiO2 NSA. However, for the AgInSe2 and
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Corrosion Science 176 (2020) 108901
AgInSe2/In2Se3 NPs sensitized TiO2 NSA, the absorption properties in
the visible-light region of 400−800 nm are extremely enhanced, which
is due to the sensitization of AgInSe2 and AgInSe2/In2Se3 NPs. And, the
absorption intensity of TiO2 NSA/AgInSe2(7)/In2Se3(3) is higher than
that of TiO2 NSA/AgInSe2(7), which is relevant to the additional In2Se3
composite layer. Due to the narrow band gap of AgInSe2/In2Se3 NPs
with visible light response capability [41], the light absorption region
of TiO2 NSA/AgInSe2(7)/In2Se3(3) is broadened to visible light region,
which overcomes the shortcoming of narrow photoresponse range of
TiO2.
The PL analyses of the TiO2 NSA/AgInSe2(7)/In2Se3(3), TiO2 NSA/
AgInSe2(7) and TiO2 NSA photoanodes were also conducted to reveal
the efficiency of charge carrier trapping, transfer and separation in
semiconductors, and their PL emission spectra are shown in Fig. 9b. The
lower PL intensity demonstrates the lower recombination rate of the
photoinduced electrons and holes, indicating a higher PEC conversion
activity [74]. For TiO2 NSA/AgInSe2(7) sample, the PL emission peaks
at 614, 688, 712, 732, 764 nm are lower than those of pure TiO2 NSA
photoanode. For TiO2 NSA/AgInSe2(7)/In2Se3(3), the PL intensities are
further reduced compared with those of TiO2 NSA/AgInSe2(7). There-
fore, the heterojunction of TiO2 NSA/AgInSe2(7) will improve the se-
paration of photogenerated electrons and holes compared with pure
TiO2 NSA. And, the multijunction of TiO2 NSA/AgInSe2(7)/In2Se3(3)
will further significantly separate and transfer the photoinduced elec-
trons and holes more efficiently compared with TiO2 NSA/AgInSe2(7).
The PL results confirm the importance of the multijunction of TiO2
NSA/AgInSe2/In2Se3 in preventing the recombination of the photo-
induced carriers.
3.3. PEC conversion performance of the prepared photoanodes
The photoinduced i-V curves of the TiO2 NSA/AgInSe2(7)/In2Se3(3),
X. Jiang, et al.
Fig. 8. (a) XPS survey spectrum and high-resolution XPS spectra of (b) Ag 3d, (c) In 3d and (d) Se 3d of the prepared TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode.
TiO2 NSA/AgInSe2(7), TiO2 NSA/In2Se3(3) and TiO2 NSA photoanodes,
together with the TiO2 NSA/AgInSe2/In2Se3 photoanodes with different
AgInSe2 deposition cycles are depicted in Fig. 10a and b. Among all of
the samples investigated, the TiO2 NSA/AgInSe2(7)/In2Se3(3) photo-
anode exhibits the highest photoinduced current density. This is at-
tributed to the deposited In2Se3 layer around AgInSe2 NPs that further
improves the photo-to-current conversion through the well-matched
energy band and accelerates the transfer of photogenerated electrons as
well as the separation of photoinduced electron-holes in the system.
The multijunction electric field at the interface of TiO2 NSA/AgInSe2/
In2Se3 facilitates the separation of the photogenerated carriers and
hence improves the PEC performance of TiO2 NSA/AgInSe2/In2Se3.
Fig. 10c presents the photoinduced OCP variations of the TiO2 NSA,
TiO2 NSA/In2Se3(3), TiO2 NSA/AgInSe2(7), TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanodes conducted in 3.5 wt% NaCl solution in the dark
and under AM1.5 light illumination. As soon as switching on the light,
Fig. 9. (a) UV/Vis diffuse reflectance spectra of the prepared samples, (b) Photoluminescence spectra of pure TiO2 NSA, AgInSe2 and AgInSe2/In2Se3 NPs sensitized
TiO2 NSA.
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Corrosion Science 176 (2020) 108901
the OCPs of these photoanodes shift negatively as a result of the gen-
eration and accumulation of the photoinduced electrons on the elec-
trode surface. After switching off the light, the OCPs of these photo-
anodes show positive shifts. The TiO2 NSA/AgInSe2(7)/In2Se3(3)
photoanode exhibits the maximum photoinduced potential drop of
approximately 280 mV, indicating that the TiO2/AgInSe2/In2Se3 mul-
tijunction greatly enhances the PEC performance under AM1.5 light
illumination. The more negative the photoinduced OCP is, the more
negative the quasi-Fermi level of the photoanode is, and the better
PECCP performance is.
The potentiodynamic polarization curves of the TiO2 NSA, TiO2
NSA/AgInSe2(7), TiO2 NSA/In2Se3(3) and TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanodes were measured in 3.5 wt% NaCl solution in the
absence and presence of AM1.5 light illumination, and the results are
shown in Fig. 10d. Under light illumination, the OCPs of these photo-
anodes shift to more negative values, which are agreed with those
X. Jiang, et al. Corrosion Science 176 (2020) 108901

Fig. 10. The photoinduced variations of the i-V curves of (a) the AgInSe2/In2Se3, AgInSe2, In2Se3 NPs sensitized TiO2 NSA photoanodes and pure TiO2 NSA
photoanode and (b) TiO2 NSA/AgInSe2/In2Se photoanodes with different AgInSe2 deposition cycles under switching on and off the AM1.5 light in 0.1 M Na2SO4
solution; (c) The photoinduced variations of the OCPs of the AgInSe2/In2Se3, AgInSe2, In2Se3 NPs sensitized TiO2 NSA photoanodes and pure TiO2 NSA photoanode in
3.5 % NaCl solution under AM1.5 light illumination; (d) The potentiodynamic polarization curves of the TiO2 NSA, TiO2 NSA/AgInSe2(7), TiO2 NSA/In2Se3(3) and
TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanodes measured in 3.5 wt% NaCl solution in the absence and presence of AM1.5 light illumination.

observed in Fig. 10c and are due to the generation and accumulation of
photoinduced electrons on the photoanodes. Both the anodic and
cathodic polarization current densities of these photoanodes measured
under light illumination show significant increases compared with
those obtained in the dark, which are caused by the participation of the
photogenerated holes and electrons in the anodic and cathodic reac-
tions of the electrochemical polarization process. Among which, the
TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode possesses the highest
anodic polarization current density and the most negative OCP among
all the prepared photoanodes. This result indicates that the photo-
induced electrons and holes generated by the TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanode are separated to the greatest extent, which makes
it have the most photogenerated holes to participate in the anodic water
oxidation reactions of the electrochemical polarization process and thus
makes its anodic polarization current density being greatly enhanced.
Meanwhile, the largest number of the photoinduced electrons accu-
mulate on the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode due to the
maximum separation of the photoinduced carriers generated by it. This
results in the observation of the most negative OCP of this photoanode
under light illumination. The electrochemical polarization results
shown in Fig. 10d further demonstrate that the TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanode possesses the largest separation efficiency of the
photogenerated electrons and holes among all of the prepared photo-
anodes, which makes it have the best photoelectrochemical cathodic
protection performance. Moreover, for the coupled photoanodes/316 L
SS electrodes, there are major issues for the potentiodynamic polar-
ization curves measured on them because they are galvanic corrosion
systems. When coupling the photoanode with the 316 SS electrode, it
becomes impossible to sort out which electrode the current is coming
from. Therefore, the potentiodynamic polarization curves of the cou-
pled photoanodes/316 SS electrode were not performed in the present
work.
3.4. PECCP performance of the prepared photoanodes
In order to characterize the PECCP performance of the prepared
photoanodes, the photoinduced variations of the current densities of
the galvanic coupling between the 316 L SS electrode and the photo-
anodes without any applied bias potential and the photoinduced var-
iations of the potentials of the 316 L SS electrode coupled with the
photoanodes under intermittent simulated sunlight (AM1.5) illumina-
tion were measured. The results are shown in Fig. 11. During the
measurements, both the photoanode and the 316 L SS electrode were
immersed in 3.5 wt % NaCl solution. Fig. 11a shows the variations in
the current densities between the 316 L SS electrode and the prepared
photoanodes. Positive excitation current densities are obtained under
light illumination, signifying that the photoinduced electrons generated
by the semiconductor transfer from the photoanode to the coupled
316 L SS electrode and thus provide cathodic protection for it. The
variations of the current densities in the absence and presence of light
illumination are the photoinduced current densities. In this work, the
maximum photogenerated current density of approximately 7 μA cm−2
belongs to the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode, which is
much higher than those of the TiO2 NSA/AgInSe2(7) and TiO2 NSA/
In2Se3(3).
As shown in Fig. 11b, the variations of the potentials of the 316 L SS
electrode coupled with the photoanodes exhibit negative shifts when
the light is switched on. With switching off the light, the potentials

9
X. Jiang, et al. Corrosion Science 176 (2020) 108901

Fig. 11. (a) The photoinduced variations of the current densities between the prepared photoanodes and the 316 L SS electrode, (b) the photoinduced variations of
the mixed potentials of the 316 L SS electrode coupled with the photoanodes, (c) the photoinduced variations of the current densities between the 316 L SS electrode
and the AgInSe2/In2Se3 NPs sensitized TiO2 NSA photoanodes prepared by depositing different amount of AgInSe2 NPs, and (d) the photoinduced variations of the
mixed potentials of the 316 L SS electrode coupled with the AgInSe2/In2Se3 NPs sensitized TiO2 NSA photoanodes prepared by depositing different amount of AgInSe2
NPs under intermittent AM1.5 light illumination in 3.5 wt % NaCl solution.

immediately shift towards positive direction and then go slowly back to
their initial potentials. The photoinduced potential drop is the differ-
ence of the potentials in the absence and presence of light illumination.
The negatively shift of the potentials demonstrates that the photo-
induced electrons generated by the photoanode are transferred to the
coupled 316 L SS electrode, thereby providing cathodic protection for
316 L SS. These results are consistent with those of the photoinduced
current densities shown in Fig. 11a. The photoinduced potential drops
of the TiO2 NSA/AgInSe2(7)/In2Se3(3)-316 L SS (approximately
236 mV) are also much higher than those of other photoanodes. The
multijunction TiO2 NSA/AgInSe2/In2Se3 further enhances the separa-
tion efficiency of the photoinduced electrons and holes by the multi-
junction effect, and thus improves the PECCP performance under
AM1.5 light illumination. Because of the difference in the Fermi levels
and energy band structures of AgInSe2, In2Se3 and TiO2, numerous in-
ternal multijunction electrostatic fields can be built at the interfaces of
the prepared TiO2 NSA/AgInSe2(7)/In2Se3(3), thus the separation of
the photoinduced electrons and holes will be greatly promoted under
the excitation of the simulated sunlight. As a consequence, the TiO2
NSA/AgInSe2(7)/In2Se3(3) photoanode exhibits the highest PECCP
performance.
Moreover, the effect of the deposition amount of AgInSe2 NPs on the
PECCP performance of the prepared TiO2 NSA/AgInSe2/In2Se3 photo-
anode for 316 L SS under intermittent AM1.5 light illumination has also
been studied by changing the deposition cycles of AgInSe2, and the
results are shown in Fig. 11c and d. For TiO2 NSA/AgInSe2(3)/In2Se3(3)
photoanode, the photogenerated cathodic protection current density
and the photoinduced potential drop are 2 μA cm−2 and 160 mV,
respectively, demonstrating a low PECCP efficiency due to the in-
sufficient loading amount of AgInSe2 NPs. With the increase of the
loading amount of AgInSe2 NPs, the PECCP performance is enhanced,
and the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode exhibits the lar-
gest photoinduced cathodic protection current density of 7 μA cm−2 in
NaCl solution and the photoinduced potential drop of 236 mV. With the
further increase of the loading amount of AgInSe2 NPs, the decreased
PECCP performance is observed. The excessive deposition of AgInSe2
NPs will lead to the agglomeration of the deposited NPs. This reduces
the effective heterojunction area, thereby reducing the multijunction
effect among AgInSe2, In2Se3 and TiO2 NSA, and causing the re-
combination of the photoinduced electrons and holes. The excessive
deposition of AgInSe2 NPs results in the agglomeration of AgInSe2 NPs
can also be proved by the SEM images (Fig. 3d), from which the NPs
loaded on TiO2 NSA become more and then cluster together with the
increased loading amount of AgInSe2 NPs.
In order to characterize the stability of prepared photoanodes, the
SEM image of the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode after the
PECCP tests and the XRD patterns and the FTIR spectra of the TiO2
NSA/AgInSe2(7)/In2Se3(3) photoanode before and after the PECCP
tests were recorded, and the results are shown in Fig. 12. As shown in
Fig. 12a, the micromorphology of TiO2 NSA/AgInSe2(7)/In2Se3(3)
photoanode after PECCP does not change significantly, maintaining the
same morphology of that before the PECCP tests (Fig. 4b). Besides, the
XRD pattern after PECCP tests shown in Fig. 12b was basically con-
sistent with that before the PECCP tests. Furthermore, the FTIR spec-
trum of the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode after PECCP
tests are highly consistent with those before PECCP tests, as shown in

10
X. Jiang, et al.
Fig. 12. (a) SEM image of the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode after PECCP tests, (b) XRD patterns and (c) FTIR spectra of the TiO2 NSA/AgInSe2(7)/
In2Se3(3) photoanode before and after PECCP tests.
Fig. 12c. The results shown in Fig. 12 indicate that the TiO2 NSA/
AgInSe2(7)/In2Se3(3) photoanode has good PECCP stability.
3.5. Charge transfer property and flat band potential of the prepared
photoanodes
EIS analyses were performed to study the charge transfer property
of the prepared photoanodes, and the results are shown in Fig. 13a. In
general, smaller diameter of the semicircle arc of the Nyquist plot in-
dicates faster interfacial charge transfer capability. As shown in
Fig. 13a, the diameters of the semicircle arc decrease in the order of
TiO2 NSA > TiO2/In2Se3(3) > TiO2/AgInSe2(7) > TiO2/AgInSe2(7)/
In2Se3(3), indicating the highest interface charge transfer efficiency of
TiO2/AgInSe2(7)/In2Se3(3). The Nyquist plots were fitted using the
equivalent circuit shown in the inset in Fig. 13a. In this equivalent
electrical circuit, Rs represents the solution resistance; Q means the
constant phase angle element, whose impedance is equal to
(Y0(jω)n)−1, and ω is the ac-voltage angular frequency (rad s−1), Y0 and
n are the frequency-independent parameters. Rf and Qc represent the
resistance and capacitance of the surface film, respectively. Rct and Qdl
represent the resistance and capacitance of the double layer, respec-
tively, and W represents the Warburg resistance. In Fig. 13a, the mea-
sured data are the dots with different symbols, and the fitted results are
the solid lines. The measured data are fitted very well. The fitted
parameters are listed in Table 1. As shown in Table 1, Rf of TiO2/
AgInSe2(7)/In2Se3(3) and TiO2/AgInSe2(7) are smaller than the other
two photoanodes, suggesting that the resistances of the TiO2/
AgInSe2(7)/In2Se3(3) and TiO2/AgInSe2(7) are decreased with the de-
position of AgInSe2 NPs. And the TiO2 NSA/AgInSe2(7)/In2Se3(3)
photoanode shows the smallest Rf value, revealing that TiO2 NSA/
AgInSe2(7)/In2Se3(3) photoanode possesses the smallest resistance and
Fig. 13. (a) EIS plots of the AgInSe2/In2Se3, AgInSe2, In2Se3 NPs sensitized TiO2 NSA photoanodes, and pure TiO2 NSA photoanode in 0.1 M Na2SO4 solution in the
dark. (b) Mott-Schottky plots of the AgInSe2/In2Se3, AgInSe2, In2Se3 NPs sensitized TiO2 NSA photoanodes, and pure TiO2 NSA photoanode in 0.1 M Na2SO4 solution
in the dark.
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Corrosion Science 176 (2020) 108901
the highest electron transmission performance. This also indicates that
the electron transfer is further accelerated and the interfacial charge
transfer barrier is further reduced after depositing the In2Se3 layer,
leading to the promotion of the PEC and PECCP performance of the
TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode.
Mott-Schottky plot reports on the relation between the capacitance
of the space charge region and the applied potential with the specific
formula for an n-type semiconductor listed as follows [3]:
1 2
= ⎛E − Efb − kT ⎞
2
CSC εε0 eND ⎝ e ⎠ (1)
where Csc is the capacitance of the space charge region in the semi-
conductor, ε is the relative permittivity of the semiconductor, ε0 is the
vacuum permittivity (8.854 × 10−14 F cm−1), e is the electron charge
(1.602189 × 10−19 C), ND is the charge carrier density, E is the applied
potential, Efb is the flat band potential, k is the Boltzmann constant
(1.38066 × 10−23 J K−1) and T is the absolute temperature (298 K).
Mott-Schottky plots of the prepared photoanodes are shown in Fig. 13b.
The slopes of the Mott-Schottky plots of the prepared photoanodes are
positive, indicating the n-type semiconductor characteristics of the
prepared samples. According to Eq. (1), the Efb of the semiconductors
can be obtained from the horizontal intercept. As shown in Fig. 13b, the
Efb of TiO2 NSA is approximately -0.46 V (vs. Ag/AgCl), which equals to
-0.26 V (vs. SHE). Considering the n-type semiconductor characteristics
of the prepared materials, it can be concluded that the CB potential of
pure TiO2 locates at approximately -0.26 V (vs. SHE), which is close to
the reported -0.29 V (vs. SHE) of the CB of TiO2 [17]. After decorated
with AgInSe2 NPs, the Efb negatively shifts to -0.57 V (vs. Ag/AgCl),
revealing that the Fermi level (Ef) of TiO2 was pulled to a more negative
value and form a more negative Eco-f due to the deposited AgInSe2 NPs
with more negative energy band. Furthermore, after In2Se3 decoration,
X. Jiang, et al.
Table 1
Fitted parameters of the EIS equivalent circuit data shown in Fig. 13a.
Rs(Ωcm2) Qc
(Yoc) (Ω−1 cm−2 S−n) n1
−6
TiO2 73.88 7.03 × 10 0.7756
TiO2/AgInSe2(7) 73.17 1.19 × 10−5 0.7021
TiO2/In2Se3(3) 54.07 1.18 × 10−5 0.6989
TiO2/AgInSe2(7)/In2Se3(3) 107.8 8.45 × 10−6 0.7144
the TiO2/AgInSe2(7)/In2Se3(3) photoanode shows the most negative Efb
of -0.63 V (vs. Ag/AgCl). The comparatively negative Efb denotes higher
activity and utilization rate of the photogenerated electrons for reduc-
tion reactions, such as the photocatalytic hydrogen evolution from
water splitting, as well as the PECCP for metallic materials.
Furthermore, the ND of the semiconductors is inversely proportional
to the slope of the Mott-Schottky plots. The smaller slope contributes to
the larger ND and denotes the higher concentration of charge carriers
[3]. From Fig. 13b, the obtained the charge carrier density can be
ranked as ND (TiO2 NSA/AgInSe2(7)/In2Se3(3)) > ND (TiO2 NSA/
AgInSe2(7)) > ND (TiO2 NSA/ In2Se3(3)) > ND (TiO2 NSA). The TiO2
NSA/AgInSe2(7)/In2Se3(3) has the smallest slope, corresponding to the
largest ND and the highest charge carrier density. This will benefit the
generation and transfer of photoinduced electrons in an n-type semi-
conductor photoanode. Therefore, the aforementioned results reveal
that the TiO2 NSA/AgInSe2(7)/In2Se3(3) with comparatively negative
Efb and high charge carrier density possesses superior PEC conversion
capability in the utilization of electrons.
3.6. Promotion mechanism of the PEC and PECCP performance of TiO2
NSA/AgInSe2/In2Se3 photoanode
Fig. 14 schematically describes the mechanism for the improved
PEC conversion and PECCP performance of TiO2 NSA/AgInSe2(7)/
In2Se3(3) under AM1.5 light in NaCl solution. In the prepared TiO2
NSA/AgInSe2/In2Se3 multijunction, AgInSe2 and In2Se3 are visible-
light-responsive semiconductors. The band gap (Eg) of AgInSe2 is
1.57 eV with the CB and VB potentials of -1.64 V and -0.075 V (vs. SHE),
respectively [41]. Besides, the Eg of In2Se3 is 1.35 eV, whose CB and VB
potentials locate at -0.83 V and 0.95 V (vs. SHE), respectively [70,75].
The Eg, CB and VB of TiO2 are 3.2 eV, -0.29 V and 2.91 V (vs. SHE),
respectively [17]. The CB of In2Se3 is located between TiO2 and
Fig. 14. Proposed mechanisms for the enhanced PEC as well as the enhanced PECCP performance of TiO2 NSA/AgInSe2(7)/In2Se3(3) under AM1.5 light illumination.
12
Corrosion Science 176 (2020) 108901
Rf(Ωcm2) Qdl Rct(Ωcm2) W(Ωcm2S−1/2)
(Yodl) (Ω−1 cm−2 S-n) n2
−5
933.4 7.12 × 10 0.9001 2.01 × 106 8.85 × 10−20
121.2 3.75 × 10−5 0.938 2.76 × 105 3.32 × 10−5
231.5 4.57 × 10−5 0.92 3.27 × 105 6.89 × 10−19
101.3 3.48 × 10−5 0.9459 1.53 × 105 3.05 × 10−5
AgInSe2, making it be more efficient in transferring photoinduced
electrons between the AgInSe2/TiO2 heterojunction. Once the TiO2
NSA/AgInSe2(7)/In2Se3(3) is excited by simulated sunlight, the elec-
trons in the VBs of AgInSe2, In2Se3 and TiO2 are excited to their CBs to
produce the photogenerated electrons. Due to the difference in energy
band potentials of AgInSe2, In2Se3 and TiO2, whose CB potentials are in
the order of ECB(AgInSe2) < ECB(In2Se3) < ECB(TiO2), the photoinduced
electrons generated on the CB of AgInSe2 will transfer to the CB of
In2Se3 and then further to the CB of TiO2 to decrease the energy of the
system. Simultaneously, with the VB potentials in the order of EVB
(AgInSe2) < EVB(In2Se3) < EVB(TiO2), the photoinduced holes gener-
ated on the VB of TiO2 can be transferred to the VB of In2Se3 and further
to the VB of AgInSe2 and finally participate in the oxidation reaction
with the ambient NaCl solution. Therefore, constructing an In2Se3
composite layer around AgInSe2 helps the formation of TiO2 NSA/
AgInSe2/In2Se3 multijunction with well-matched energy band struc-
ture. The TiO2 NSA/AgInSe2/In2Se3 multijunction will further facilitate
the transfer of the photogenerated electrons and holes between TiO2
and AgInSe2, as described in Fig. 14. Besides, the NSA structure can
offer a large light-harvesting area and fast electron transmission
channel, and thus increase light absorption area and promote the
transfer of photogenerated electrons towards substrate. Therefore, the
TiO2 NSA/AgInSe2/In2Se3 photoanode exhibits the highest photo-to-
current conversion efficiency.
Since the Fermi levels of AgInSe2 and In2Se3 are relatively negative,
the TiO2 NSA/AgInSe2/In2Se3 multijunction will pull the Fermi level of
TiO2 NSA to a negative direction, as illustrated in the Mott-Schottky
plots. When an n-type semiconductor is exposed to simulated sunlight,
the photoinduced electrons will accumulate on its CB, inducing a ne-
gative shift of the quasi-Fermi level of the photogenerated electrons.
Then, the potential of the system will negatively shift. Hence, for the
TiO2 NSA/AgInSe2(7)/In2Se3(3), a large amount of the photoinduced
X. Jiang, et al.
electrons will push the quasi-Fermi level of the photogenerated elec-
trons to a more negative level than those generated by other photo-
anodes. When coupling the TiO2 NSA/AgInSe2(7)/In2Se3(3) photo-
anode with the 316 L SS electrode, the photogenerated electrons will be
transferred to the coupled 316 L SS electrode and achieve the PECCP
effect for it. Therefore, the TiO2 NSA/AgInSe2(7)/In2Se3(3) exhibits an
excellent PECCP property for 316 L SS under simulated sunlight illu-
mination and shows great application potentials in the field of the
PECCP for metals. The optimization of multijunction photoanode with a
much negative band potential can be beneficial for the PECCP appli-
cation of metals in marine environment.
4. Conclusions
The environment-friendly AgInSe2/In2Se3 NPs decorated TiO2 NSA
photoanode with a multijunction structure was fabricated in this paper.
The TiO2 NSA with numerous vertically-grown two-dimensional na-
nosheets can offer a large light harvest area, and the direct electron
transfer pathways, which benefits the separation of the photogenerated
electrons and holes. Meanwhile, the constructed TiO2 NSA/AgInSe2/
In2Se3 multijunction avoids the unmatched energy band arrangement
between AgInSe2 and TiO2 compared with single AgInSe2 NPs deco-
rated TiO2 NSA, and can lead to the further promotion of the charge
generation/separation efficiency under simulated sunlight illumination.
For the TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode, AgInSe2 and
In2Se3 are prepared at optimal quantity, and distributed evenly on the
surface of TiO2 NSA, forming close interfacial adhesion to TiO2 NSA.
The light response range is broadened due to the visible light response
of narrow band gap of AgInSe2/In2Se3 NPs. The PL results reflect that
the TiO2 NSA/AgInSe2/In2Se3 multijunction photoanode leads to the
swift separation of the photogenerated electrons and holes compared
with the bi-junction of TiO2 NSA/AgInSe2. Moreover, for the TiO2 NSA/
AgInSe2(7)/In2Se3(3) photoanode, EIS and Mott-Schottky analyses in-
dicate that the reduced charge transfer barrier, the more negative Efb as
well as the highest charge carrier density benefit to the transmission of
the photogenerated electrons. Under simulated sunlight illumination,
the multijunction system exhibits enhanced the photon-to-current
conversion activity. This study confirms that the complex of AgInSe2
sensitizer with In2Se3 assist layer can optimize the interfacial micro-
structure of the photoanode, thereby effectively improving the PEC
activity. When coupling the multijunction photoanode with 316 L SS,
the photogenerated electrons on the photoanode can be transported to
the metallic material and provide cathodic protection for it. Finally, the
TiO2 NSA/AgInSe2(7)/In2Se3(3) photoanode with a much more nega-
tive band potential exhibits a further enhanced PECCP performance for
316 L SS by providing the photogenerated cathodic protection current
density of 7 μA cm−2 and the photoinduced potential drop of 236 mV
under simulated sunlight illumination in NaCl solution.
Data availability
The raw/processed data required to reproduce the findings cannot
be shared at this time as the data also forms part of an ongoing study.
CRediT authorship contribution statement
Xuhong Jiang: Investigation, Data curation, Formal analysis,
Validation, Visualization, Methodology, Writing - original draft,
Writing - review & editing. Mengmeng Sun: Funding acquisition,
Resources, Investigation, Data curation, Formal analysis, Validation,
Visualization, Methodology, Writing - original draft, Writing - review &
editing. Zhuoyuan Chen: Funding acquisition, Resources, Project ad-
ministration, Supervision, Methodology, Validation, Conceptualization,
Data curation, Writing - original draft, Writing - review & editing.
Jiangping Jing: Funding acquisition, Investigation, Data curation,
Formal analysis, Validation, Visualization, Methodology. Chang Feng:
13
Corrosion Science 176 (2020) 108901
Investigation, Data curation, Formal analysis, Validation, Visualization,
Methodology.
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 was financially supported by the National Natural Science
Foundation of China (Grant Nos. 41676069, 41976036, 41906034),
Key Research and Development Program of Shandong Province (Grant
No. 2019GHY112085, 2019GHY112066), and Qingdao Applied Basic
Research Plan Program (Grant No. 19-6-2-79-cg).
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acquaintance, near the Bridge. Thus relieved of their anxiety, they
could now listen with interest, to the details of old Sam. “The regulars
will be starved out, by and by,” said he, “if they don’t get scared to
death first. They say that three of their generals, as they were
walking down Beacon Hill, the other night, heard strange noises over
their heads, which they supposed to be some kind of airguns, fired at
them by the Yankee rebels, as they called them, and took to their
heels with such expedition that they nearly fell headlong; but, after
all,” said he, with an explosion of great glee, “it was only the
humming of beetles, and if they run for such imaginations, what will
they do when they stand, face to face, with our brave boys? And,
there is a plan afoot, which will soon settle the business; it is to erect
works on the hill in Charlestown, which overlooks Boston, so that our
men can fire in among them.” He then proceeded to say that the
British would not permit the inhabitants of Boston to leave the town,
or hold any communication with their friends; that it was said
reinforcements from England were daily expected, and that the
Americans were anxious to strike some bold stroke, before their
arrival. More than all, he reported, that George Washington, of
Virginia, was appointed Commander in Chief of the American
Armies, “and a noble commander it is said he will make, being an old
soldier, and, that it will not be long before he will be before Boston.”
The heart of the affectionate mother throbbed with anxiety at these
tidings. Situated as they were, in the very seat of contention, what
would be the result if the enemy were victorious, and succeeded in
dispersing her countrymen, and what would become of her, and her
helpless little family? Anticipating such an emergency, her husband,
in his last letter, had directed her to leave their home, and, with her
little girls, retire to her native place, which was about forty miles in
the interior, there to await his return, or the indications of Providence.
With a heavy heart, after taking the advice of the good Prudy, who,
with disinterested affection, offered to stay at the mansion as long as
it was safe, she determined that the crisis which her husband had
foreseen, had now arrived, and that she would follow his directions.
“If,” said her faithful domestic, “it comes to the worst, Sam and I can
shut up the house, turn out the cattle, and retire over the hill to his
sister’s, where we shall be safe, but, it would not do for you, with
these little ones, to run such a risk. You can now go with safety in the
old chaise; which is roomy enough to hold considerable, and, you
will not be afraid to drive the horse, who, tho’ not swift, is sure.”
Having come to this resolution, no time was to be lost, and they
immediately commenced preparations for the journey.
The morning arrived when she must bid farewell to the scene of so
much peace and quiet domestic joy, perhaps never again to see it,
for she could not conceal from herself that fire and sword were the
accompaniments of modern warfare; but her children, delighted at
the journey, would not suffer a shade to linger upon her brow, and
Prudy, amidst smiles and tears, uttered her affectionate adieu,
echoed by Sam. The day was beautiful, and the wild enthusiasm of
her companions prevented her indulgence in melancholy reflections,
while the road led them away from the scenes of tumult and
confusion, and she trusted they might escape observation. She was
not disappointed; night brought them to the home of her youth,
where a joyous welcome awaited them, and until better times, a
peaceful retreat.
“And now,” said Mrs. Wilson, “I must leave my farther tale untold.
Perhaps at some future time I may continue it, and I think it will
interest you, as the incidents are connected with your family.” “I had
hoped, mother,” said Charles, that you would tell us about Bunker
Hill.” “I should not be a good historian, my son, in tales of war and
bloodshed. Charlestown was burned by the British, as you know, but
their devastations stopped there, at that time, and our old mansion
was left unharmed and safe, till such time as its owners could return
to its peaceful shades.” “And did the Tory uncle never return to
America?” “He did not; he reached England in safety, but did not live
long after that event. I will relate one little circumstance, Charles,
which happened at this time. There was a poor widow, who occupied
a small house in Charlestown, which was destroyed during the
conflagration, and which comprised the whole of her fortune. She
had contrived to support herself and two children by her daily
exertions, but was now left destitute indeed. With the hope of
assistance from some friends, in an adjoining town, she took her
departure from the scene of destruction, carrying one child in her
arms, while the other, an active little boy of four years, closely
followed her footsteps. As he trudged along and employed the little
staff with which his mother had provided him, in tracing lines in the
road, he struck something which, by its brightness, attracted his
attention. Picking it up and delighted with his prize, he soon overtook
his mother and showed her a ring, the value of which was evident by
its costly diamond, and the initials and cypher upon the inside. The
good woman, rather perplexed than pleased with this circumstance,
and tired with her walk, sat down with her children upon some timber
to deliberate upon what she should do with her acquisition. Two
gentlemen, whose dress announced them to be British officers, were
walking slowly by, and as they passed, she heard one say, ‘It must
have been near this spot. It was a last memento, and the loss is to
me irreparable.” Thinking it possible this observation might refer to
the ring, she immediately addressed them, and related the
circumstance of her son’s finding it. It was directly identified, and
claimed by the officer, who had made the remark which had attracted
her attention. He had discovered his loss, and was then retracing his
steps, though almost hopeless of recovering his treasure. He was a
nobleman of high rank in the army, and, after a few words of inquiry,
she received not only present assistance, but assurance that her son
should never want a friend. The promise was faithfully fulfilled, and
through the assistance of their kind benefactor, he received an
education, which has enabled him to take a high stand in his
profession, which was that of a clergyman, and he is now a much
respected minister in this vicinity.”
 Chapter XVI

’Midst the thorns are fragrant roses,

Sunbeams ’midst the shifting clouds.

Many days of open weather now intervened, when winter

appeared to meditate resigning his sovereignty. The snow
disappeared from the hills which surrounded their pleasant retreat,
little sunny nooks were visible where the early violet might shelter,
and the sands on the seashore were becoming bright and sparkling.
Delightful as were these indications of spring, the inmates of Mrs.
Wilson’s abode were not inclined to wish for its rapid approach. The
winter had not only been pleasantly, but they all felt, profitably, spent,
that seed had been sown which might, by careful culture, produce an
abundant harvest. The joyous and lively spirits of Susan still retained
all their buoyancy and she joined them on the sands where they
were watching the white sails of the vessels as they were leaving the
harbor, as the sun shone full upon them.
“They are leaving their homes,” said Elizabeth, “to cross that
ocean, which, though now so serene, we have seen under such
different aspects.” “And,” said Herbert, “they are, no doubt, elated
with the pleasant auspices under which they commence their
voyage. Sailors are a superstitious race; they dread to leave their
port under a lowering sky; and it is almost impossible to induce them
to embark on Friday. You will frequently see them on a land-cruise,
as they call it, to overhaul the log-book of the redoubtable Moll
Pitcher, or some old fortune teller, relative to the success of their
voyage, the constancy of their sweethearts, etc., and the wise old
lady prognosticates so much to their satisfaction that they return in
great glee, after leaving with her a goodly portion of their well-filled
purses.” “It is surely a kind Providence,” said Mary, “which hides from
us the events of futurity. How wretched would be every intervening
moment were we certain of the time of some great calamity!”
 “True, Mary,” said Herbert, “and there are many who, without this
knowledge, suffer a thousand deaths in fearing one. I refer to those
who are ever anticipating evil, who prophesy destroying frost in
every cold wind and blight or blasting mildew in the warm sun or
refreshing rain.” “I am decidedly of the opinion,” said Susan, “that
such persons are worse in society than drones in a hive, for the idle
person generally injures himself more than any one else, but the
discontented one makes others wretched by imparting to them a
portion of his bitterness. It gives me the fidgets to hear poor Mrs.
Flagg complain of this wicked world, protesting that everybody is
governed by selfish motives and, shaking her head, declare that
there is no such thing as happiness on earth, and yet she enjoys, or
seems to enjoy, to perfection a good cup of tea and a warm cake.”
“We are too young, as yet, my cousin,” said Herbert, “and have
seen too few of the trials of life to controvert, positively, the good
woman’s assertion, but, when we look around us and see so much
beauty, so much to love and admire, we may be sure that our
Creator did not place us here to be miserable.”
“Now for a race, Charles,” said Susan; “I shall be at the gate first.”
They met Mrs. Wilson at the door and she greeted them with joyful
news; a letter had arrived from their parents. The health of their
father had so much improved that he wrote of speedy return and
rejoiced in the happiness so apparent in the letters of his children.
There was but one shadow to this pleasant news, the breaking up of
their winter enjoyments, but Herbert reminded them that at any rate
his vacation was nearly at an end; that they could look back upon
this Winter in Retirement with almost unalloyed pleasure and forward
with the cheering hope of future joyous meetings; also with the
certainty that, by the help of Providence, the treasures stored in their
minds through this, at first, dreaded season, would prove precious
and available in all the varying events of their lives. “We will improve
the time yet left us and I will read you this evening some lines written
by a lady born in this town.”
THE OLD HOME

Speed onward, Time! thy dark wings leave

Deep traces on the path they cleave!
Speed onward! for the goal is near,
Backward I mark thy swift career,
And through the hazy past mine eye
Dwells on the scenes of infancy;
For, bright and clear its visions seem,
And sweet, in Memory’s glowing dream,
The broad Atlantic’s waves are bright
Where first my eyes beheld the light;
The broad Atlantic’s shores are fair
Where first I breathed my native air;
They boast of clear Italian skies;
I’ve seen the glorious sun arise
From out his sparkling ocean-bed,
And, o’er my home, his splendors shed,
His beams illumined the swelling sails
That caught the scented morning gales;
Ne’er were Italian skies more fair
Than rested o’er my old Home there.

Thy rocky cliffs, Nahant, gleamed bright

As morning poured her golden light;
And silvery streams of whiteness broke
From the rough seams of old Egg Rock;
Inland arose, ’midst foliage gay,
The Lover’s Leap, with forehead grey;
With haughty front, High Rock would seek
To court the sun’s first rising beam,
And sheltered homes, and meadows rare,
Soon caught the glittering radiance there.
The early sunlight never shone
On brighter than my own old Home.

And romance spread her witching dream

O’er shore and wood and rippling stream,
For here, ’twas said, the pirate Kidd
His ill-got store of treasure hid;
Amidst a wild and craggy waste,
Where straggling pines their shadows cast,
A rocky Cavern, dark and deep,
Stretched inward from its opening steep;
And there, ’twas told, foul deeds were wrought
And gold concealed, by murder bought,
Till, at the Dungeon’s gloomy name
The blood in quicker currents came.

Weird Superstition spread her wing

Of sombre shade, o’er dell and spring;
Once, powers of ill seemed leagued, to bind
In clouds of mist, the human mind;
Dread scenes ensued, and but the name
Of Witchcraft roused the smouldering flame,
The whirlwind spent its mightiest force
On Salem’s heights, but in its course
Its withering breath defiled the scene
Which else would more like Eden seem,
The haze of long past years alone
Casts shadows o’er my own old Home.
We boast, too, of a Sybil’s fame,
Though graced with but a homely name,
But never Sybil had more power,
And Sybil ne’er more honors bore;
No horrid rites she tried to show
A prophet’s skill, no charms to know,
No Sybil of old Rome was she
To give the Books of Destiny;
She knew no Book; but could enthrall
With magic skill the minds of all,
And some may live who once have known
The Sybil of my own old Home.

Here patriot hearts and patriot hands

Were joined to break Oppression’s bands;
Our pleasant homes sent forth their best
To fight, at Freedom’s high behest;
We claim the Puritan’s high birth;
Our fathers left their native hearth,
Their sons on Freedom’s land to rear,
Who, tyrant despots need not fear;
Where they might truly worship God
Without a Bishop’s mitred rod;
And tyrant power has ne’er been known
To hover round my own old Home.

Speed onward, Time! while life remains

And Memory her power retains,
My own old Home! I’ll cherish thee
Amidst the dreams of infancy;
The mists of age may gather round;
The silver cord may be unbound;
Speed onward, Time! for death alone
Can dim the thought of my old Home.

“Though the local scenery of Lynn,” said Mrs. Wilson, “is not
essentially changed since this was written, many of its manners and
customs are. The good old Puritan days have somewhat gone by;
but it is pleasant to read something which refers to the time when
they were reverenced and appreciated.”
 Chapter XVII
Peaceful and calm as Sabbath’s holy eve.

On the ensuing Sabbath evening the conversation turned upon the

public services of the day, which were rendered interesting to
Charles, as well as the others, by their reference to the ancient
history of Palestine. “There is now left,” said Herbert, “but the dust
and ruins of these celebrated countries of antiquity. Were it not for
these, even yet, splendid mementoes of the former greatness of
ancient Syria, we should be lost in wonder and credulity when we
contrast the history of its past grandeur with the accounts of modern
travelers. How puny do the works of our days of boasted superiority
appear, compared with the colossal ruins of Balbec and Palmyra,
where the stones of which their mighty edifices were composed
would seem to require the strength of giants, or such machinery as
the mechanism of these times can hardly imagine, to place them in
their appointed situation. The plains of Syria, from the earliest
records of time, have been the theatre on which the most interesting
scenes have been performed. Embattled legions have here fought to
the death, and the footsteps of the messengers of peace on earth,
preceded by those of their Divine Master, have pressed the favored
soil. Here, too, the wild fanaticism of the Crusades rose to its climax,
here the brave, but imprudent and improvident Richard of England,
and the generous, noble-hearted Saladin figured in their brief
careers. These scenes possess an indescribable charm for the
Christian, while they present inexhaustible themes for poetry and
romance.” “Your enthusiasm, dear Herbert,” said Elizabeth, “would
lead us to suppose that you, too, had taken them for a theme; do not
deny us the pleasure of profiting by the inspiration.” “I will not,” said
he, “though I have only attempted a paraphrase of an incident
related in the Scriptures.”

’Twas noon; on Syria’s sandy plains

The scorching sun pours down his beams:
Where shall the weary traveler rest?
Where shall he slake his burning thirst?
Far in the hazy distance seen,
Rises a grove of palm trees green,
And, to the near approach displays
To the enraptured wanderer’s gaze
A sweet retreat, whose verdure bright
And fountains cool and shaded light
Would seem to promise that no care
Or sorrowing heart could linger there.
Vain thought! for earth contains no spot
Where sin or sorrow enters not.
Mistaken dream! a heaven of bliss
Alone bestows a gift like this.
Amidst these shades a palace rose;
A proud and stately front it shows;
Around, ’tis graced with gardens fair,
Delightful perfumes fill the air;
Sweet music cheers the passing day,
Delicious waters cast their spray;
And, when the soft and gentle breeze
Of peaceful twilight stirs the trees,
The bird of night, with plaintive strains
Soothes to repose and pleasant dreams.
But in this spot, so calm and sweet,
There dwelt sad hearts and sorrows deep;
The Syrian Captain there abode,
Naaman, favorite of his lord;
Riches surround the mighty Chief;
Do they avert a dreaded grief?
Slaves bow before his slightest word,
And splendor decks his plenteous board;
Ah! sad relief for anxious care.
Ah! poor resort against despair.
With saddened brow the warrior stalks
Through stately halls and sheltered walks,
The leper’s curse is on him fixed;
With his best blood the plague is mixed,
And fleeting Time, he knows, full sure,
Will bring fresh misery to endure.
No hope for him; each rising morn
Still sees his heart with anguish torn,
While each returning hour for sleep
But marks his hour for torture deep.
Still, one there is to share his grief
If sympathy could bring relief;
Behind those latticed windows dwells
A form whose heart with sorrow swells;
The wife; whose best affections twine
Around his love; as twines the vine
Round some supporting prop or power
That shields it in the dangerous hour.
Oh! not for them the trusting prayer,
That sure resource against despair;
Thine idol gods are powerless now,
In vain to them, the knee they bow.
But, as the pious man of old
Obtained, by intercession bold,
A promise, that, if ten were found
Within the fated city’s bound,
Who worshiped God with zeal and truth,
They should avert the dreaded wrath.
So, now, the faith of one restored
To health and strength the Syrian Lord,
Amidst the slaves, a Hebrew maid,
Obedience to her mistress paid,
And, sympathizing with her woe,
Sought means to save the dreaded blow;
A holy prophet dwelt, she told,
Where rose Samaria’s turrets bold;
That God, to him, had given the power
This fatal leprosy to cure.

Beneath an Olive’s spreading shade,

The holy prophet knelt and prayed;
The leper, with his pompous train,
Assistance asks, nor asks in vain;
“Go wash in Jordan’s sacred stream,”
The prophet said, “Wash and be clean.”
With proud disdain, the Syrian turned;
Such simple means his nature spurned;
Some mighty deed, he proudly thought.
Was needful, when his cure was wrought,
“Are not our Syrian streams,” he said,
“Better than Jordan’s vaunted tide?
“Is not Arbana’s silver wave,
“Or Pharphar’s flood, fit place to lave?”
But, yielding to affection’s prayer
The haughty leper sought the shore;
Where Jordan’s swelling waters flowed,
And bathed him in the healing flood;
Then, rising from the holy stream,
No loathsome leprosy is seen;
No tainted blood his system knows,
But, pure the healthful current flows;
No sickly scales his flesh deform,
Like the fair child’s, now soft and warm,
With joyful heart, and thankful praise
To Israel’s God, he lifts his eyes;
“There is no God, but Israel’s God;”
The wondering train repeat the word.

’Twas eve; on Syria’s sandy plains

The scorching sun no longer beams;
Athwart the weary traveler’s brow
The chilling night-wind passes now;
The prowling thief, with murderous steel
Each sandy hillock may conceal;
Where shall the wanderer find repose?
How shall he ’scape his secret foes?
On; pilgrim, on; yon glimmering light
That, through the distance, greets thy sight,
Is the bright beacon-ray to guide
Thy toiling footsteps to its side;
Not now does sorrow’s gloomy cloud
That lovely spot in darkness shroud;
No rites, unholy, now are there;
No tainted incense fills the air;
On; pilgrim, on; for Israel’s God
Is worshiped there, by Syria’s lord;
And the rich mercies he receives
With bounteous hand he freely gives.

And now that our “Winter in Retirement” has drawn to a close, let
us hope that the lesson we have tried to inculcate, that a life of
excitement, and scenes of continued gayety are not necessary for
the happiness of the young, may not be unheeded by those for
whose benefit it is written. Life is too precious, too priceless a gift
from our Father in heaven for part of its hours to be spent in trifling
amusements, part in resting after their fatigue, and part in sad
reflections upon their inutility. May this little volume, through His
blessing, carry an antidote for these evils, and lead our youth to try
its efficacy.

Autumn drew near; and, with her magic brush

Had touched the landscape; on the mountain’s slope,
Bright tints were mingling with the evergreens
Crowning its heights; and, as the freshening breeze
Swept onward, in its joyous course it bore
The many colored leaves, the forest’s pride,
Some few were green, and to the thoughtful mind
Recalled the youthful spring, in verdure rich;
Others appeared, touched with bright summer’s ray,
And mingled with the glowing heaps, bring back,
The sunny days of bright July; but more
Displayed deep crimson hues, or, orange, gay,
Or golden yellow; or, perchance, laid clothed
In sombre garb—
I sought, long time,
A title for my Book; Leaves there are here
Of Thought and Memory; some fresh like youth,
And many tinged with Autumn’s varying shades;
While, over all, a brightening light is cast,
The light of Hope.
 Transcriber’s Notes
pg 8 Changed: procurring the contents of his basket
to: procuring the contents of his basket
pg 11 Changed: And the triumphalt Arch
to: And the triumphal Arch
pg 13 Changed: Who can this women be
to: Who can this woman be
pg 20 Changed: these obtinate Christians in view
to: these obstinate Christians in view
pg 21 Changed: and pursuaded her to hear the preaching
to: and persuaded her to hear the preaching
pg 22 Changed: under that, shelter our pulsillanimity
to: under that, shelter our pusillanimity
pg 22 Changed: request of Servius Sulspicus Galba
to: request of Servius Sulpicius Galba
pg 44 Changed: infered that learning was not necessary
to: inferred that learning was not necessary
pg 51 Changed: Rise, dear to memory’e eye
to: Rise, dear to memory’s eye
pg 57 Changed: so reverened and beloved
to: so revered and beloved
pg 59 Changed: trobbing with hope and visions
to: throbbing with hope and visions
pg 61 Changed: silmultaneous burst of triumph around
to: simultaneous burst of triumph around
pg 61 Changed: and the terrible ery of “death”
to: and the terrible cry of “death”
pg 62 Changed: alotted so long a term of life
to: allotted so long a term of life
pg 63 Changed: with speed unparalelled
to: with speed unparalleled
pg 64 Changed: the lofty Appenines still bound
to: the lofty Apennines still bound
pg 73 Changed: He is not destitue of partisans
to: He is not destitute of partisans
pg 75 Changed: rushed upon its point, anad closed
to: rushed upon its point, and closed
pg 75 Changed: in rapid emotion, for the city
to: in rapid motion, for the city
pg 77 Changed: no place for their inuendoes
to: no place for their innuendos
pg 81 Changed: Sagana, the Thessaiian
to: Sagana, the Thessalian
pg 81 Changed: implores a resing place
to: implores a resting place
pg 82 Changed: whose transcendant beauty
to: whose transcendent beauty
pg 94 Changed: took an affecionate interest
to: took an affectionate interest
*** END OF THE PROJECT GUTENBERG EBOOK A WINTER IN
RETIREMENT ***

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