Carbon quantum dots (CQDs) modified

TiO2 nanorods photoelectrode for

enhanced photocathodic protection of
Q235 carbon steel - eBook PDF
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 Corrosion Science 176 (2020) 108919

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

Carbon quantum dots (CQDs) modified TiO2 nanorods photoelectrode for T

enhanced photocathodic protection of Q235 carbon steel
Min Fenga,b, Ying Liub,**, Sainan Zhangb, Yupeng Liua,c,*, Ning Luoc, Daoai Wanga,c,*
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
b
Institute of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China
c
Qingdao Center of Resource Chemistry and New Materials, Qingdao 266100, China

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

Keywords: A new photoanode of Al2O3 anchored carbon quantum dots/TiO2 nanorods (Al/C/TNRs) was constructed for
A. Titanium efficient photocathodic protection of Q235 carbon steel (CS) by hydrothermal treatment and ALD process. The
A. Carbon steel Al/C/TNRs photoanode achieved a photocurrent density of 2.28 mA/cm2 under simulated sunlight (AM 1.5 G),
B. XPS and could maintain for 7 days nearly without decay. Potential of Q235 CS was negatively shifted by 620 mV after
B. EIS
coupling with Al/C/TNRs in 3.5 wt% NaCl solution, and could maintain more than 7 h. The high and stable
C. Cathodic protection
photoelectrochemical performances of Al/C/TNRs indicate potential photocathodic protection for Q235 CS in
marine environment.

1. Introduction However, at present the efficiency of photocathodic protection is still

As a typical engineering material in marine system, carbon steel
(CS) has been widely applied in shipping, oil recovery, offshore plat-
form and mining industries over the years [1,2]. While the corrosion
problem of CS has always been an important challenge, and was usually
inhibited or slowed down by anti-corrosion coating, cathodic protec-
tion, corrosion inhibitor and other technologies [3]. As one of the most
frequently used technologies for metal anticorrosion, cathodic protec-
tion has mainly two types of impressed current cathodic protection and
sacrificial anodic protection [4,5]. The impressed current cathodic
protection needs an external power source to provide electrons to the
protected metal, this undoubtedly increases the electric energy con-
sumption. The sacrificial anode protection introduces an active metal
(mostly Zn, Mg, Al) with the self-corrosion potential more negative than
the protected metal to polarize the protected metal to corrosion stable
region, while usually brings sacrificial metal anode wasting and en-
vironmental pollution. Different from the traditional cathodic protec-
tion, the new photocathodic protection technology utilizes photo-
electric properties of semiconductors and solar energy to provide
electrons to the protected metal, which is environmentally friendly and
will not consume other electric energies during this process [6,7]. It
seems to be an ideal technology that photocathodic protection can
achieve protection of metals simply by consuming sunlight in nature.
relatively low by using only the ultraviolet part of sunlight and there
are only a few suitable materials for photocathode, which highly limits
its practical application [8].
In principle, the photocathodic protection of metals based on a
photocatalyst semiconductor material occurs in three steps, similar to
the photoelectrochemical (PEC) processes [9]. Firstly, the photoelec-
trode semiconductor material absorbs light energy greater than its band
gap to generate electron and hole pairs (hν ≥ Eg). Then, the photo-
excited charges separate and transmit to the external circuit without
recombination. Lastly, the photogenerated electrons enriched on the
surface of the protected metal, which makes the potential of the pro-
tected metal more negative than its self-corrosion potential to form
photocathodic protection. Therefore, the photoelectrode semiconductor
material is the key factor, which determines the following efficiency of
photocathodic protection. Take TiO2 photoelectric semiconductor ma-
terial as an example, it was the first and the most widely studied ma-
terial in the field of photocathodic protection, while the low efficiency
of photocathode protection still limits its practical application at pre-
sent [10]. Generally, the applications of pure TiO2 in photocathodic
protection are usually hindered by the following three factors. Firstly,
the intrinsic wide bandgap confines its light absorption range within
ultraviolet light (UV) region of the solar spectrum [11]. Secondly, the
surface defect structures and other impurities in TiO2 cause high

⁎
Corresponding authors at: State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000,
China.
⁎⁎
Corresponding author.
E-mail addresses: liuyingwda@ouc.edu.cn (Y. Liu), yupengliu@licp.cas.cn (Y. Liu), wangda@licp.cas.cn (D. Wang).

https://doi.org/10.1016/j.corsci.2020.108919
Received 24 March 2020; Received in revised form 29 July 2020; Accepted 30 July 2020
Available online 03 August 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
M. Feng, et al.
photoinduced charge recombination rate and bring low quantum effi-
ciency in PEC measurements [12]. In addition, no electrons are pro-
duced under dark conditions, accompanied by swift photogenerated
electrons annihilation, make it hard to provide valid all-weather pro-
tection of metals [6,13].
To solve the above problems, numerous methods have been carried
out to enhance the photoelectric activity of TiO2 materials.
Constructing highly pure TiO2 with ordered structure is an effective
way to facilitate the separation and transportation of photogenerated
electrons and holes [9], such as TiO2 nanowires, nanotubes and nano-
belts. Moreover, if these one-dimensional materials assemble to more
ordered nanoarray structure, the efficiency of charge separation and
transportation can be further improved, which has been widely used in
photocatalytic water splitting, solar cells and chemical sensors [14,15].
Band modulation is another frequently-used strategy to improve the
photoelectric activity of TiO2 materials by broadening the absorption
range of TiO2, such as doping of other elements (C, N, F, Ag, etc)
[16–19], coupling with narrow band-gap semiconductors (CeO2, V2O5,
WO3, etc) [20–22] and absorbing organic dyes [23] to extend the ab-
sorption edge from ultraviolet light to visible light region. In these
strategies, the stability of the new doped or composite materials, the
short life span of sensitizers under illumination and the instability of
nanocomposites often decrease the efficiency and restrict practical ap-
plication in photocatalysis and photocathode protection [24,25]. Re-
cently, as a new type of photocatalytic and photoelectric materials, the
quantum dots (QDs) have also attracted attention for its quantum
confinement effect defined that band gap and optical properties of QDs
can be tuned by changing their sizes [13]. Given that QDs can be uti-
lized to absorb hot electrons and generate plentiful electron-hole pairs
with a single photon under light irradiation [26], carbon quantum dot
(CQD) has been used as a new kind of efficient and green sensitizer to
enhance the photocatalytic properties of TiO2 in photocatalysis and PEC
water splitting fields owing to its strong absorption band within UV
region with a long streaking under visible light [27]. Meanwhile, the
lowest unoccupied molecular orbital (LUMO) energy level of CQDs lies
higher than the conduction band (CB) of TiO2, so the electrons excited
by visible light can be easily transferred from LUMO energy level to CB
of TiO2, and then greatly broaden the optical absorption range of TiO2
[28]. However, CQDs are easy to fall off from photoanodes due to the
flow and vibration of the solution during measurements, which highly
limits the applications of the composite materials. New technology is
required to anchor carbon quantum dots on the surface of photoelec-
trodes. Therefore, design and preparation of a stable electrode material
with highly ordered structure and visible light absorption performance
is the key to achieve high efficiency photocathode protection.
Herein, a new Al2O3 layer-anchored CQDs-loaded TiO2 nanorods
array (Al/C/TNRs) photoanode was constructed for efficient photo-
cathodic protection of Q235 carbon steel (CS) by hydrothermal and
atomic layer deposition (ALD) methods. The Al/C/TNRs electrode was
obtained by loading CQDs on ordered rutile TNRs through impregna-
tion method and depositing ultrathin Al2O3 film on C/TNRs through
thermal ALD technique. The modification of CQDs highly extends the
light absorption array of TiO2 from ultraviolet region to visible region.
Moreover, the CQDs could also act as an electron trap that stores
photoinduced electrons and releases them to the surface of metals to
maintain photocathodic protection performances in the absence of
sunlight illumination [29]. The high ordered structure of TiO2 nanorods
array accelerates the separation and transmission of photogenerated
electron-hole pairs. The Al2O3 ultrathin film on C/TNRs can highly
stabilize the surface state of the nanocomposite to prevent the fall of
CQDs from TNRs, and it can also depress the recombination of photo-
induced charges owing to the low interface defect density of Al2O3 layer
by ALD method [30]. These composite photoanode materials exhibited
high and stable photoelectrochemical and photocathodic protection
performances, which provide a new way to prevent metals from cor-
rosion by photocathodic protection effects in marine environment.
2
Corrosion Science 176 (2020) 108919
2. Materials and methods
2.1. Materials
Hydrochloric acid (HCl, 37 %), Tetra-n-butyl titanate (TNBT) and
trimethyl-aluminum (TMA, 99.99 %) were purchased from Sinopharm
Chemical Reagent Co., Ltd. Formamide and acetone were obtained from
local suppliers with the highest purity. Citric acid was purchased from
Sigma. All of the chemicals were of analytical reagent grades and used
without further purification. Fluorine-doped tin oxide (FTO) con-
ducting glasses (10 mm × 50 mm × 1.1 mm) were purchased from
Qingdao Amy Commerce & Trading Co., Ltd. Q235 CS was obtained
from Beijing Hanlongda Technology Development Co., Ltd.
2.2. Preparation of TNRs and CQDs
The rutile TiO2 nanorods arrays were in situ grown on the surface of
FTO conducting glasses by a modified hydrothermal method [31].
Firstly, a piece of FTO conducting glass sequentially ultrasonic cleaned
by acetone, ethyl alcohol and deionized (DI) water was set obliquely
against the inner wall of Teflon-lined stainless steel autoclave (100 mL)
with the conductive side facing up. And then a mixed solution con-
sisting of 25 mL HCl, 25 mL DI water and 720 μL TNBT was transferred
into the above autoclave after magnetically stirring for 20 min, and
then reacted in an oven at 180 °C for 6 h. After the autoclave cooled
down to room temperature naturally in air, the TNRs were rinsed by DI
water and annealed in a muffle furnace (KSL-1200X) at 450 °C for 2 h in
air to get crystallized monocrystalline TNRs. CQDs were synthesized
through a modified method based on the established procedures
[32,33]. Typically, a solution of citric acid in formamide (0.3 g/mL)
was refluxed for 15 min and cooled down to room temperature natu-
rally, then the acetone with the volume of equivalent to 5 times of the
initial volume was added to the solution. Finally, the precipitates were
successively filtrated and dialysed with a 1000 Da dialysis tube, and the
obtained solution containing CQDs was lyophilized for further use.
2.3. Preparation of CQDs/TNRs photoelectrode
The as-prepared TNRs were impregnated in the aqueous solution of
CQDs with the concentration of 0.5 mg/mL at 60 ℃ for 20 h in an
electric thermostatic water chamber (H. SWX-600BS) under dark con-
dition. Then the samples were taken out and dried in the vacuum drying
chamber (DZ-1BC Ⅱ) at 80 ℃ overnight and annealed in a tube furnace
(OTF-1200X) under 50 sccm of N2 carrier (Airgas, Ultra High Purity) at
200 ℃ for 20 min.
2.4. Preparation of Al2O3 anchored CQDs/TNRs photoelectrode
Al2O3 film of 5 nm was grown on the as-prepared C/TNRs in a
commercial ALD reactor at 150 ℃ after deposition of 50 cycles by using
TMA and DI water as precursor compounds [34]. One complete de-
position cycle was proceeded with 1 s TMA pulse, 8 s TMA exposure,
20 s purge with N2 followed with 0.1 s DI water pulse, 8 s DI water
exposure and finally 25 s purge with N2. TMA and DI water respectively
reacted with eOH groups and eCH3 groups on the surface. Then TMA
was pumped away by pumping into N2 carrier gas stream when the
surface reaction finished. Based on the measurement on the Si substrate
by using ellipsometry, it had been proved that one intact cycle that
comprised of sequential exposure to TMA and DI water obtained a
growth rate of 1.1 Å Al2O3 layer per cycle under the optimal reaction
conditions. [35] Finally, Al/C/TNRs composites were fabricated com-
pletely.
2.5. Characterizations
The morphologies of TNRs, C/TNRs and Al/C/TNRs were observed
M. Feng, et al. Corrosion Science 176 (2020) 108919

Fig. 1. Schematic sketches of the experimental devices for photoelectrochemical (a) and photocathodic protection (b) characterizations. The CE, RE and WE re-
present the counter electrode, reference electrode and working electrode, respectively.

on a field emission scanning electron microscope (FE-SEM, S-4800,
Hitachi). High resolution transmission electron microscopy (HRTEM)
images were obtained from a FEI Tecnai G2 TF20 transmission electron
microscope operating at the acceleration voltage of 200 kV. The com-
positions of samples were measured through X-ray photoelectron
spectroscope (XPS) with an ESCALAB 250Xi system and binding en-
ergies were corrected based on containment carbon (C 1s 284.6 eV).
Raman spectra were collected on a DXR Raman Microscope with +12V
DC voltage. UV–vis absorption spectra were measured by U-4100
Spectrophotometer (Solid).
2.6. Electrochemical measurements
All the electrochemical measurements are conducted on an elec-
trochemical workstation (CHI 660E, Shanghai) by using a typical three-
electrode cell at room temperature. The experimental devices for
measuring PEC properties and photogenerated cathodic protection
performances are illustrated in Fig. 1a and b, respectively. As shown in
Fig. 1a, PEC properties of the samples were measured in a single elec-
trochemical cell with the electrolyte of 0.1 M NaOH solution (PH 13)
after purging with argon gas for 15 min to remove dissolved oxygen, in
which the Pt foil, saturated calomel electrode (SCE) and Al/C/TNRs
composite photoelectrode served as counter electrode (CE), reference
electrode (RE) and working electrode (WE), respectively. The active
illumination area of the samples was controlled to be 1 × 1 cm2, and
the photoanodes were illuminated by a 300 W Xe lamp (PLS-SXE 300
UV, Beijing) coupled with an AM 1.5 G filter to demarcate the light
intensity to 100 mW/cm2. Photocurrent density vs. time curves and
incident-photon-to-current efficiencies (IPCE) were measured at 0.23 V
vs. SCE under the illumination of simulated sunlight (100 mW/cm2).
The stability of photocurrent density measurements was conducted for
a certain time at 0.23 V vs. SCE. Photoinduced OCP data were collected
by using the above three-electrode cell under simulated sunlight illu-
mination (100 mW/cm2). To evaluate photocathodic protection per-
formances of the coupled metals, a double-cell system was introduced
shown as Fig. 1b. Q235 CS electrode was polished by metallographic
polishing machine (MP-2A), ultrasonically cleaned with acetone, ethyl
alcohol and DI water respectively, and then dried by N2. Finally, the
Q235 CS electrode was sealed up with setting one square centimeter
(1 cm × 1 cm) aside by epoxy resin for later measurements. The pho-
toanodes (TNRs, C/TNRs, Al/C/TNRs) and Q235 CS electrode coupled
by a conducting wire were isolatedly placed in the electrochemical cell
and the corrosion cell, respectively. The salt bridge (1 M KCl in agar, U-
type glass tube) provided connection and completed the circuit between
the two cells. The corrosion cell consisting of 3.5 wt% NaCl solution
possesses three-electrode structure with Q235 CS electrode, SCE and Pt
foil acting as WE, RE and CE, respectively. Before EIS measurement,
electrodes were immersed in 3.5 wt% NaCl solution for 30 min to
achieve OCP and environmental stabilization in this condition. EIS tests
were conducted at frequencies between 105 and 10−2 Hz with 10 mV
AC amplitude, and the constant OCP was used as initial potential.
DZsimDemo software was used to analyze the corresponding EIS re-
sults. Tafel curves were measured at the scan rate of 1 mV/s from
−300 mV to 300 mV vs. OCP. The calculated Ecorr, corrosion current
density (jcorr), cathodic Tafel slope (βc) and anodic Tafel slope (βa) va-
lues were analyzed by a CHI 660E software.

Fig. 2. Schematic diagram of the procedures of preparing TiO2 NRs (TNRs), CQDs-loaded TiO2 NRs (C/TNRs) and Al2O3 anchored CQDs-loaded TiO2 NRs by ALD
method (Al/C/TNRs).

3
M. Feng, et al.
Fig. 3. SEM images of TiO2 NRs (a), CQDs-loaded TiO2 NRs (b), CQDs-loaded TiO2 NRs covered with 5 nm Al2O3 layer (c) and HRTEM image of CQDs-loaded TiO2
NRs (d). The inset of (b) shows the TEM image of CQDs.
3. Results and discussion
Fig. 2 shows the preparation process of Al/C/TNRs electrode fab-
ricated through three steps. Firstly, ordered TiO2 nanorods arrays were
in situ grown on FTO conductive glasses by hydrothermal method, and
then immersed into CQDs solution for several hours under dark con-
dition. The unique one-dimensional structure of TNRs with a high as-
pect ratio and good oxidation resistance offers unidirectional channels
beneficial for the transportation of photogenerated charges and pos-
sesses higher PEC performances than that in bulk materials. This simple
in situ hydrothermal growth of TNRs on FTO conductive glasses im-
proves the interface bonding force between them [36]. Finally, to im-
prove the adhesion between CQDs and TNRs, the final Al/C/TNRs were
obtained by depositing thin Al2O3 film on CQDs/TNRs through thermal
ALD technique.
The morphologies of TNRs, C/TNRs and Al/C/TNRs arrays are
shown in Fig. 3a–c. In Fig. 3a, the diameters of densely-arranged TNRs
distribute within the range of 50−100 nm. Fig. 3b shows the mor-
phology of TiO2 NRs after loading CQDs. The inset of Fig. 3b shows the
TEM image of CQDs with the size of about 2−5 nm. After loading CQDs
and depositing 5 nm Al2O3 layer, the nanorods show slight changes on a
large scale as shown in Fig. 3b and c. While the HRTEM image shown in
Fig. 3d can provide more details on a smaller scale which ensures the
successful loading of CQDs, from which the amorphous carbon particles
with blurry lattice fringes and highly-crystalline rutile TiO2 with clear
lattice fringes can be clearly detected [37]. The lattice spacings of
0.32 nm and 0.35 nm correspond to the (002) and (101) lattice plane of
carbon and TiO2, respectively [38].
To further determine the composition of the samples, TNRs, C/TNRs
and Al/C/TNRs were characterized by XPS as shown in Fig. 4a and b.
The C 1s peak for TNRs may originate from the absorbed hydrocarbon
or contamination from XPS instruments [39], and the peak intensity
largely increases after loading CQDs. Fig. 4b exhibits XPS spectra of C
1s for TNRs before and after loading CQDs. As XPS spectrum of C ele-
ment of TNRs displays, the peaks at 284.4 eV, 286.4 eV and 288.5 eV
correspond to CeC, CeOH and C]O bond from the test system,
4
Corrosion Science 176 (2020) 108919
respectively [40]. For C/TNRs composite, because of the nitrogen
constituent of CQDs, the appearance of CeN peak located at 285.8 eV
and the newly-formed N 1s peak in full spectrum of Fig. 4a demonstrate
the successfully loading of CQDs on the surface of TNRs [41]. As Fig. 4c
of Raman spectra shows, characteristic Raman peaks at 236 cm−1,
448.4 cm−1 and 611.7 cm−1 belong to the compound vibration peak, Eg
and A1g mode of rutile TiO2 phase, respectively [42]. After loading
CQDs, there appears new peaks at 1359.2 cm−1 and 1626.5 cm−1
corresponding to Raman-active D-band and G-band of carbon [43],
indicating the presence of CQDs on C/TNRs and Al/C/TNRs. There is no
active group of Al2O3 for the sample of Al/C/TNRs because of the
amorphous state of alumina. UV–vis absorption spectra of CQDs, TNRs,
C/TNRs and Al/C/TNRs are shown in Fig. 4d. For TNRs, the intersec-
tion between X-axis and the tangent line of absorption band edge (λ) is
about 415 nm. According to the formula Eg = 1240/λ [44], the corre-
sponding band gap energy (Eg) is calculated to be 2.99 eV. This result is
in good agreement with the previously reported results of rutile TiO2
(Eg =3.0 eV, corresponding λ =413 nm) [45]. Compared with TNRs, a
slight red shift to around 447 nm (calculating Eg =2.77 eV) of the op-
tical absorption edge is observed for C/TNRs. The band gap does not
change much after modifying CQDs because TiO2 and CQDs are not
compounded and no new phase is formed. As shown in the inset of
Fig. 4d, the absorption band edge reaches 685 nm and an independent
absorption peak around 530 nm is observed for single CQDs. The en-
hanced absorption within UV and visible light region and the bulge
between 500 and 600 nm for C/TNRs and Al/C/TNRs are therefore
mainly caused by CQDs, since CQDs enable single photon to provide
multiple excitons and play essential roles in utilizing sunlight, which
imply the ameliorative photocatalytic performances compared with
TNRs. In addition, a blue shift of absorption band wavelength reaching
∼427 nm occurs after depositing Al2O3 because the Al2O3 layer nearly
has no effects on visible light absorption of photoanodes [14].
To test the PEC properties of samples and evaluate the separation
efficiency of photogenerated charge carriers, linear sweep voltammetry
(LSV) and transient photocurrent measurements with several on/off
cycles had been conducted. Fig. 5a exhibits LSV curves of TNRs, C/
M. Feng, et al.
Fig. 4. (a) XPS spectra, (c) Raman spectra and (d) UV–vis spectra of CQDs, TiO2 NRs (TNRs), CQDs-loaded TiO2 NRs (C/TNRs) and Al2O3 anchored C/TNRs (Al/C/
TNRs), (b) XPS spectra of C 1s in TNRs and C/TNRs.
TNRs and Al/C/TNRs measured under simulated sunlight (100 mW/
cm2). The photocurrent density of pure TNRs shows nearly 0.60 mA/
cm2 because of the poor visible light absorption and high recombina-
tion rate of photoinduced electron-hole pairs in bulk TiO2. Subsequent
processings including CQDs modification and Al2O3 deposition improve
PEC performances of the photoanodes respectively, and the final pho-
tocurrent density of Al/C/TNRs composite reaches 2.28 mA/cm2 owing
to the synergistic effects of CQDs and ALD Al2O3 layer on extending
visible light absorption, restraining carriers recombination and
lengthening the life span of electrons. As shown in Fig. 5b, the typical
photocurrent response curves display good reproducibility of photo-
anodes during the transient switching process from illumination to dark
conditions.
PEC performances of as-prepared photoanodes were further eval-
uated by IPCE measurements. IPCE values as a function of irradiation
wavelength of TNRs, C/TNRs and Al/C/TNRs electrodes are shown in
Fig. 5c. The maximal IPCE value of C/TNRs calculated from the fol-
lowing formula reaches approximately 30.36 % at 385 nm, which is
thrice higher than that of TNRs (9.58 %, 380 nm). The formula is:
IPCE = 1240 I/(λJlight)
where I, λ and Jlight mean photocurrent density, wavelength of incident
light and irradiation intensity, respectively [46]. It can be seen that
high IPCE values of pure TNRs only exist within UV light region
(λ < 415 nm), and decrease to about 0.15 % at wavelengths longer
than 415 nm. This cascade curve coincides closely with UV–vis ab-
sorption spectrum of pure TNRs shown in Fig. 4d. From the IPCE plots
of C/TNRs, we can see that the absorption edge shifts ∼15 nm to longer
wavelength region compared with TNRs. Moreover, the presence of
CQDs increases the IPCE values to 3.04 % in visible light region
(λ > 425 nm) owing to the excellent optical properties of CQDs. The
ALD Al2O3 shell not only gives rise to a remarkable enhancement of
IPCE in the whole UV region (375−400 nm) with a maximum of 55.33
% at 385 nm, but also has a broader light harvesting range to 435 nm,
and the IPCE value increased to 4.36 % when λ > 435 nm. This could
5
Corrosion Science 176 (2020) 108919
be the result of reduced charge recombination and efficient charge
collection. The relatively lower IPCE value at longer wavelengths
(λ > 435 nm) in comparation with that in near UV light region may be
caused by the existence of an activation energy threshold at the Al/C/
TNRs interface and poor light-to-electricity conversion in visible light
region [47].
However, the photocurrent density of C/TNRs is reduced by 32.40
% compared to the original value after immersing and measuring in the
electrolyte in the first 13 h (shown as Fig. 5d), further dropped by 30.10
% after 7 days (shown as Fig. 5e), which means poor photoresponse
stability of this photoelectrode due to the weak physical adsorption
force between CQDs and TNRs. In contrast, the photoanode of Al/C/
TNRs reveals excellent long-time stability with little decline of photo-
current density under the illumination of simulated sunlight (100 mW/
cm2) for 13 h. More importantly, this value maintains even for 7 days
with a small drop of only 4.23 % as shown in Fig. 5f, which proves the
stabilization function of depositing ALD Al2O3 on the surface of C/
TNRs, and further ensure photocathodic protection properties of Q235
CS. To further study the catalytic activity of the photoanodes, cyclic
voltammetry curves were analyzed as shown in Fig. S1. Theoretically,
overpotential (η) in oxygen evolution reaction means the portion of the
actual voltage (Ei) required to reach a certain current density (i, mA/
cm2) over the theoretical voltage (Et) during a catalytic reaction. Ac-
cording to the formula ηi = Ei - Et, we can see that Al/C/TNRs possesses
the lowest ηi, and is the most active photoanode [48].
In order to investigate photocathodic protection effects of TNRs, C/
TNRs and Al/C/TNRs on Q235 CS, OCP measurements and Tafel curves
of Q235 CS were conducted. Fig. 6a shows photo-induced OCP mea-
surement results of TNRs, C/TNRs and Al/C/TNRs nanocomposites
under intermittent simulated sunlight (100 mW/cm2). It can be seen
that the potential values exhibit obvious positive shifts when the light is
turned off, and come back to the original value under illumination. This
indicates that the obtained negative shifts of potential are entirely on
account of the PEC property of the photoanodes. Moreover, the po-
tential change of Al/C/TNRs electrode is much more evident than that
M. Feng, et al.
Fig. 5. (a) Linear sweep voltammetric curves, (b) photocurrent density vs. time plots, (c) IPCE spectra, (d) time-dependent photocurrent profiles at 0.23 V vs. SCE
obtained from CQDs-loaded TiO2 NRs (C/TNRs) and Al2O3 anchored C/TNRs (Al/C/TNRs). (e, f) Long-time stability curves with error bar at 0.23 V vs. SCE for C/
TNRs and Al/C/TNRs under simulated solar light (100 mW/cm2, AM 1.5 G) illumination.
of the pure TNRs and C/TNRs, suggesting a much better photo-
generated cathodic protection property for the Al/C/TNRs.
The Tafel curves of Q235 CS coupled with photoelectrodes in the
presence of simulated solar light (100 mW/cm2) in 3.5 wt% NaCl so-
lution are shown in Fig. 6b. The electrochemical parameters including
Ecorr, jcorr, βc and βa obtained from Tafel curves are exhibited in Table 1.
It’s clear that there are obvious negative shifts of Ecorr when coupling
Q235 CS with TNRs, C/TNRs and Al/C/TNRs, respectively. The Ecorr of
Q235 CS coupled with Al/C/TNRs exhibits the most negative value of
−0.92 V vs. SCE compared with Q235 CS coupled with TNRs (−0.69 V
vs. SCE) and Q235 CS coupled with C/TNRs (−0.76 V vs. SCE). As
shown in Fig. 6c, such a negative shift can still be maintained even for
about 9 h so that the Al/C/TNRs nanocomposite can provide long term
anticorrosion protection for Q235 CS. Moreover, jcorr exhibits in-
creasement compared with pure TNRs after modifying CQDs and Al2O3.
This finding is in accordance with the photocurrent spectrum shown in
Fig. 5a. The enhancement of jcorr can be ascribed to the increase of
superficial electrochemical reactions derived from the polarization of
photoinduced electrons [49]. It is worth highlighting that the photo-
anodes remain unchanged when generating electron-hole pairs under
illumination, so the increasements of anodic polarization current in-
formed from the polarization curves bring the enhancement of photo-
current transfusing into Q235 CS but not the aggravation of corrosion
rate. In a word, the composition of TNRs and CQDs which possess
6
Corrosion Science 176 (2020) 108919
different energy level from TNRs and wide absorption range provides
more excited electron injection to Q235 CS substrate, and the holes
react with dissolved oxygen under the isolation effect of Al2O3 layer in
the rust medium [50]. Thereby a more negative Ecorr and a bigger jcorr
value are matched to the coupling electrode of Q235 CS and Al/C/TNRs
owing to the higher electrons transportation rate and lower re-
combination rate of photogenerated charge carriers.
The stability and durability experiments of Al/C/TNRs were also
conducted to investigate photocathodic protection performance in
3.5 wt% NaCl solution under intermittent illumination of simulated
sunlight (100 mW/cm2). In each cycle, the photoelectrode was alter-
nately illuminated on and off at intervals of more than one hour for two
loops, and then it was subsequently placed in dark conditions for 7 h. As
shown in Fig. 6d, Ecorr of Q235 CS coupled with Al/C/TNRs im-
mediately negatively shifts by 620 mV under illumination, and the
potential value remains far below Ecorr of Q235 CS after the second use
of Al/C/TNRs photoanode under dark condition, which implies that Al/
C/TNRs composites are still highly active and have good durability for
photocathodic protection performances of Q235 CS.
Photocathodic protection performances of the samples, the charge
transfer properties and interfacial properties between electrodes and
electrolyte were analyzed by EIS. The charge transfer process is re-
flected from the archs displayed in typical Nyquist plots of Fig. 7a, and
the high-frequency arc diameters represent charge transfer resistance
M. Feng, et al. Corrosion Science 176 (2020) 108919

Fig. 6. (a) Photo-induced OCP variation of

TiO2 NRs (TNRs), CQDs-loaded TiO2 NRs (C/
TNRs) and Al2O3 anchored C/TNRs (Al/C/
TNRs) photoelectrodes, (b) Tafel curves of
Q235 carbon steel (CS) electrode connected
with TNRs, C/TNRs and Al/C/TNRs, (c) OCP of
Q235 CS electrode before and after connecting
with Al/C/TNRs and (d) OCP changes of Q235
CS electrode coupled with Al/C/TNRs in 3.5 wt
% NaCl solution under simulated sunlight il-
lumination (AM 1.5 G, 100 mW/cm2).

Table 1 the reduction of Rct and interface resistance. It can be explained that the
Electrochemical parameters obtained by the Tafel curves of TiO2 NRs (TNRs), visible-light-excited electrons transfer from C/TNRs to the surface of
CQDs-loaded TiO2 NRs (C/TNRs) and with 5 nm ALD Al2O3 (Al/C/TNRs) cou- Q235 CS, making electrochemical reaction rate largely enhanced, and
pled with Q235 carbon steel in 3.5 wt% NaCl solution under simulated solar the outer ALD Al2O3 layer significantly accelerate the separation of
light (AM 1.5 G, 100 mW/cm2). electron-hole pairs through hole-harvesting effect. The AC impedance
Samples Ecorr/V vs. SCE jcorr/μA cm−2 βc/mV dec−1 βa/mV dec−1 at low frequencies usually represents the Faraday reaction resistance
and double-layer capacitance. From the Bode plots in Fig. 7b, it can be
TNRs −0.69 3.116 −6.634 5.329
seen that pure TNRs has one peak while C/TNRs and Al/C/TNRs have
C/TNRs −0.76 28.43 −4.312 5.544
Al/C/TNRs −0.92 132.70 −7.277 6.006 two peaks, indicating that pure TNRs has one time constant, and both of
C/TNRs and Al/C/TNRs have two time constants. In addition, the
characteristic peak frequency (fmax) in the low frequency region ob-
(Rct) between photoelectrodes and electrolyte during the electro- tained from Bode plots was used to estimate the lifetime (τ) of photo-
chemical process [51]. Clearly, the semicircle diameters of impedance generated electrons from the empirical formula τ ≈ 1/2πfmax, here τ is
arcs decrease with the introduction of CQDs and Al2O3, which implies inversely proportional to fmax. For Al/C/TNRs composite film, the

Fig. 7. (a) Nyquist plots, (b) Bode plots and (c,d) schematic diagrams of the equivalent circuit by EIS result fitting for TiO2 NRs (TNRs), CQDs-loaded TiO2 NRs (C/
TNRs) and Al2O3 anchored C/TNRs (Al/C/TNRs) photoanodes under simulated sunlight (AM 1.5 G, 100 mW/cm2) irradiation at room temperature.

7
M. Feng, et al.
Table 2
Fitting values of equivalent circuit elements of TiO2 NRs (TNRs), CQDs-loaded
TiO2 NRs (C/TNRs) and with 5 nm ALD Al2O3 (Al/C/TNRs) coupled with Q235
carbon steel.
Samples Rs (Ω Q1 Rf (Ω Cd1 (μF Rct (kΩ
cm2) Y01 (S cm−2 s−n cm2) cm−2) cm2)
× 10−5) n1
TNRs 9.726 5.638 0.4362 – – 169.4
C/TNRs 6.938 7.744 0.7924 123.1 186.4 99.66
Al/C/TNRs 8.253 6.012 0.6125 58.85 1.772 0.2298
logarithm of fmax was smaller than TNRs and C/TNRs, thus the lifetime
of the photogenerated electrons in the Al/C/TNRs composite film
reached the longest, resulting from the inhibited charge carrier re-
combination and enhanced charge separation efficiency in the compo-
site film [52]. EIS results were also analyzed through equivalent circuit
models as shown in Fig. 7c and d, where Q1 represents constant phase
element (CPE) to replace capacitance owing to that pure capacitance is
hard to realize in real electrochemical process. CPE is defined by ad-
mittance Y and power index number n, given by Y = Y0 (jω)n. By this
formula, CPE would convert to resistance (n = 0) or capacitance
(n = 1). The equivalent circuit of TNRs can be described as Rs (Q1Rct),
which is a typical circuit for a passive oxide layer [6]. As exhibited in
Fig. 7c, Rs and Q1 represent electrolyte resistance and constant phase
element, respectively. The equivalent circuit of C/TNRs and Al/C/TNRs
is interpreted using a model with two time constants as Rs (Q1Rf)
(CdlRct). As shown in Fig. 7d, Rs stands for the electrolyte resistance, Rf
and Q1 at high frequencies represent the resistance and constant phase
element corresponding to the CQDs and Al2O3, while Cdl at low fre-
quencies stands for the double layer capacitance. Table 2 shows the
fitting values of equivalent circuit elements, we can see that the values
of Rf and Rct become smaller than that of TNRs after modifying CQDs
and Al2O3, which indicate the electrode resistivity and charge transfer
resistance decrease. CQDs may act as the transporter that makes charge
transfer easier between the interface of semiconductor and solution
when CQDs attached on the surface of TNRs [27], thereby improved
PEC properties and photopotential performances are realized combined
with the efficient charge separation and transportation through Al2O3
layer.
Fig. 8 illustrates the proposed mechanism for the enhanced photo-
cathodic protection performance of Al/C/TNRs composite for Q235 CS
under simulated solar light illumination. In photoanode, photoinduced
electrons transport through semiconductor film to the protected metal,
and photogenerated holes react with hole-trapping agents on semi-
conductor surface simultaneously. As shown in Fig. 8a, visible-light-
excited electrons from the Highest Occupied Molecular Orbital (HOMO)
Fig. 8. (a) Schematic representation of the energy band structure and electron transfer processes in CQDs/TiO2 NRs composite and (b) the role of atomic layer
deposited Al2O3 layer as filter membrane.
8
Corrosion Science 176 (2020) 108919
to LUMO of CQDs are transferred to CB of TiO2, and together with the
photogenerated electrons excited by UV light from TiO2, finally arrive
and accumulate at the surface of Q235 CS substrate through FTO con-
ducting glass. This electron migration leads to the increase of electron
density on metal surface, which shows the macroscopical reduction of
Q235 CS electrode potential that far below its natural corrosion po-
tential, to prevent Q235 CS from corrosion under simulated sunlight.
While the photoinduced holes will be left on the HOMO level of CQDs
and the VB of TiO2, to participate in oxidative decomposition of water
or organic active species [53]. Simultaneously, a portion of photo-
induced electrons may be stored in CQDs, and then released under dark
conditions to realize the delayed cathodic protection of metal substrate
[4,29,54]. In addition, unlike photocorrosive materials such as CdS,
CQDs are stable enough and do not decompose under light conditions
[55].
Furthermore, ALD Al2O3 ultrathin layer plays an active role in hole-
harvesting effect, which brings enhanced hole injection and blocks
electron injection from the gate. In Al2O3 shell, a high density of ne-
gative fixed charges and a low interface defect density cause the en-
hanced field-effect passivation and the depression of charge re-
combination, respectively, therefore the surface trap states of C/TNRs
after deposition of ALD Al2O3 show passivation effect [30]. As shown in
Fig. 8b, there are negatively fixed charges existing in Al2O3 shell, by
which only holes with positive charges can be traversed and migrated
to the interface between Al2O3 layer and solution. In this way, the se-
paration efficiency of photogenerated electron-hole pairs is largely
enhanced, and the lifetime of photoinduced electrons is prolonged, ei-
ther [32]. In addition, the ALD layer completely covers substrate ma-
terial (TiO2 and CQDs) and prevent CQDs from falling off with water
flow, thus greatly improves the interface bonding strength. Therefore,
CQDs and ALD Al2O3 take a synergistic effect on improving photo-
cathodic protection performances of Q235 CS and provide possibility
and a new way for practical application of photocathodic protection.
4. Conclusion
In summary, a new Al2O3 anchored carbon quantum dots modified
TiO2 nanorods (Al/C/TNRs) photoelectrode material were fabricated
for efficient photocathodic protection of Q235 carbon steel under solar
light. From UV–vis absorption spectra, the introduction of CQDs ex-
tended light absorption into visible light region successfully. The outer
Al2O3 layer prompted better photogenerated charge separation activ-
ities compared with pure rutile nanorod arrays, solved the photoetching
dissolution of CQDs and brought improved photocurrent density and
photocathodic protection performances in synergy. The electrochemical
measurements showed that photocurrent density of Al/C/TNRs reached
2.28 mA/cm2 at 0.23 V vs. SCE under simulated sunlight illumination
M. Feng, et al.
(100 mW/cm2) and this value maintained for 7 days with only a small
drop of 4.23 %. The potential of Q235 CS in 3.5 wt% NaCl solution
dropped by 620 mV when coupling to Al/C/TNRs photoanode. When
light was cut off, the potential of Q235 CS was 132 mV lower than its
corrosion potential for over 7 h, exhibiting protection effects on carbon
steel. The results demonstrated that the proposed Al/C/TNRs nano-
composite is promising for metal corrosion protection in practical ap-
plication.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
CRediT authorship contribution statement
Min Feng: Conceptualization, Methodology, Validation,
Investigation, Writing - original draft. Ying Liu: Conceptualization,
Writing - review & editing. Sainan Zhang: Methodology, Validation.
Yupeng Liu: Writing - review & editing. Ning Luo: Methodology.
Daoai Wang: Conceptualization, Resources, Writing - review & editing,
Supervision, Project administration, Funding acquisition.
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
Thanks for the financial support of the NSFC (No. 51722510), the
program for Taishan Scholars of Shandong province (No. ts20190965),
Innovation Leading Talents program of Qingdao (19-3-2-23-zhc) and
Open Fund of Key Laboratory for Intelligent Nano Materials and
Devices of the Ministry of Education (INMD-2019M01).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.corsci.2020.108919.
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Fall-fish, 600
Fierasfer, 549
Fighting-fish, 519
File-fishes, 684
Fins, 40
Fishing-Frog, 470
Fistularia, 507, 508
Fitzroyia, 615
Flat-fishes, 553
Flounder, 557
Flute-mouth, 507
Flying-fish, 621
Flying Gurnard, 482
Forskal, 13
Forster, 13
Freshwater-fishes, 208
Freshwater-Herring, 645
Fries and Ekström, 27
Frog-fish, 470
Frontal bone, 57, 89
Frost-fish, 436
Fuegian sub-region, 248
Fundulus, 615

Gadiculus, 541
Gadidæ, 539
Gadopsis, 537
Gadus, 539
Galapagoes district, 280
Galaxias, 624
Galeichthys, 569
Galeocerdo, 317
Galeoides, 425
Galeus, 318
Gallo, 451
Gambusia, 616
Ganodus, 349
Ganoidei, 350
Ganoid scales, 47
Gar-pike, 367, 620
Gaspereau, 659
Gastrochisma, 455
Gastrocnemus, 452
Gastromyzon, 604
Gastropelecus, 610
Gastrosteus, 505
Gastrotokeus, 682
Gazza, 450
Gegenbaur, 32
Gempylus, 437
Genidens, 569
Genyoroge, 384
Genypterus, 549
Geoffroy, 33
Geophagus, 537
Geotria, 693
Gerres, 388
Gillaroo, 645
Gill-cover, 38
Gill-opening, 38
Gill-rakers, 59, 139
Gills, 136
Gilthead, 409
Ginglymostoma, 326
Girardinus, 618
Girella, 406
Glanidium, 572
Glanis, 566
Glaucosoma, 384
Globe-fish, 687
Glossohyal, 58
Glottis, 149
Glut, 673
Glutinous hag, 694
Glyphidodon, 525
Glyptauchen, 415
Glyptolæmus, 365
Glyptolepis, 365
Glyptopomus, 365
Glyptosternum, 572
Gmelin, 13
Gobiesocidæ, 510
Gobiesox, 513
Gobio, 595
Gobiodon, 487
Gobiosoma, 487
Gobius, 486
Goby, 486
Gold-fish, 591
Gold-Sinny, 527
Gomphodus, 319
Gomphosus, 530
Gonatodus, 370
Goniognathus, 452
Gonorhynchus, 652
Gonostoma, 629
Gourami, 517
Grammistes, 382
Granular teeth, 126
Graphiurus, 365
Grayling, 649
Greenland Shark, 333
Grey Mullet, 501
Grig, 673
Gronow, 12
Growler, 393
Growth of Fishes, 170
Grystes, 392
Gudgeon, 596
Gular plates, 80
Güldenstedt, 13
Gunellichthys, 498
Gunnel-fish, 496
Günther, 27, 30
Gurnard, 479
Gwyniad, 649
Gymnachirus, 558
Gymnarchus, 626
Gymnelis, 538
Gymnocrotaphus, 406
Gymnocypris, 595
Gymnomuræna, 677
Gynmoscopelus, 585
Gymnotus, 667
Gyracanthus, 314
Gyrodus, 367
Gyropristis, 314
Gyroptychius, 365

Haddock, 540
Hadot, 540
Hæmal arches, 86
Hæmal spine, 52
Hæmapophyses, 51
Hæmulon, 386
Hag-fish, 694
Hair-tail, 436
Hake, 542
Halargyreus, 541
Halec, 656
Halecidæ, 656
Half-beak, 621
Halidesmus, 549
Halieutæa, 475
Halieutichthys, 475
Haliophis, 550
Haller, 16
Haloporphyrus, 543
Halosauridæ, 665
Hamilton, 17
Hammerhead, 318
Hapalogenys, 386
Haplochilus, 615
Haplochiton, 651
Haplodactylina, 406
Hapuku, 392
Harpagifer, 467
Harpodon, 583
Harttia, 580
Hasse, 32
Hasselquist, 13
Hausen, 361
Head, 36
Heart, 150
Heckel, 28
Hector, 32
Heliastes, 525
Helicophagus, 566
Heliodus, 359
Helmichthys, 180
Helogenes, 567
Helotes, 385
Hemerocœtes, 491
Hemichromis, 535
Hemiculter, 604
Hemigaleus, 319
Hemigymnus, 530
Hemilepidotus, 480
Hemiodus, 607
Hemipimelodus, 569
Hemipristis, 317
Hemirhamphus, 621
Hemirhombus, 556
Hemirhynchus, 437
Hemisaurida, 582
Hemisilurus, 566
Hemisorubim, 568
Hemithyrsites, 434
Hemitrichas, 656
Hemitripterus, 417
Heniochus, 399
Heptanchus, 325
Heptapterus, 581
Hermaphroditism, 157
Heros, 536
Herring, 658
Heteracanth, 41
Heterobranchus, 563
Heterocercy, 80
Heteroconger, 674
Heterognathodon, 389
Heterolepidotidæ, 491
Heteropygii, 618
Heterostichus, 498
Heterotis, 655
Hexanchus, 325
Hexapsephus, 588
Himantolophus, 472
Hippocampus, 683
Hippoglossoides, 555
Hippoglossus, 555
Histiophorus, 431
Histiopterus, 387
Holacanthus, 400
Holibut, 555
Hollardia, 684
Holocentrum, 423
Holocephala, 348
Holophagus, 365
Holoptychidæ, 365
Holosteus, 619
Homacanth, 41
Homaloptera, 604
Hombron et Jacquinot, 27
Homelyn Ray, 341
Homocanthus, 314
Homocercy, 83
Homoeolepis, 366
Homonotus, 421
Hopladelus, 568
Hoplichthys, 478
Hoplognathus, 410
Hoplopleuridæ, 665
Hoplopteryx, 421
Hoplopygus, 365
Hoplostethus, 421
Hoplunnis, 674
Horse-mackerel, 442
Hounds, 319
Huchen, 645
Humeral arch, 59
Hunds-fish, 619
Hunter, 16
Huro, 393
Hutton, 32
Huxley, 33
Hybernation, 188
Hybodontidæ, 328
Hybognathus, 596
Hyborhynchus, 596
Hybridism, 178
Hydrocyon, 611
Hygrogonus, 536
Hyodon, 653
Hyoid arch, 58
Hyomandibular, 55, 89
Hyoprorus, 674
Hyoptopoma, 578
Hyostylic skull, 74
Hypamia, 372
Hyperoglyphe, 387
Hyperopisus, 625
Hypnos, 340
Hypobranchial, 58
Hypomessus, 647
Hypophthalmichthys, 602
Hypophthalmus, 566
Hypophysis, 98
Hypotympanic, 55
Hypsinotus, 402
Hypsodon, 500
Hypural, 53, 84
Hyrtl, 32
Hysterocarpus, 534
Hystricodon, 611

Icelus, 477
Ichthyborus, 612
Ichthyocampus, 681
Ichthyodorulites, 194
Ichthyomyzon, 693
Id, 599
Ikan sumpit, 403
Impregnation, artificial, 186
Indian region, 220
Indo-Pacific ocean, 278
Infraorbital, 54
Infundibulum, 98
Interhæmals, 53
Intermaxillary, 53
Interneurals, 53
Interoperculum, 38, 55, 91
Intestine, 127
Ipnops, 585
Ischyodus, 349
Ischyrocephalus, 666
Isistius, 334
Isthmus, 39, 58
Isurus, 457
Japanese District, 270
Jenyns, 27
Jenynsia, 616
John Dory, 451
Jugular fins, 42
Julis, 529

Kabeljau, 540
Kalm, 13
Kamtschatkan district, 269
Karausche, 591
Karpfen, 589
Kathetostoma, 463
Kaup, 33
Kelb el bahr, 611
Kelb el moyeh, 611
Kelp-fish, 533
Keris, 440
Ketengus, 569
Kidney, 155
King of the herrings, 522
Klein, 12
Klipvisch, 549
Klunzinger, 30
Kner, 27, 28
Kneria, 606
Kokopu, 625
Kölliker, 32
Kovalevsky, 33
Kröyer, 27
Kurtus, 425

Labberdan, 540
Labeo, 593
Labials, 64, 69
Labrax, 376
Labrichthys, 530
Labridæ, 525
Labroides, 530
Labrus, 526
Labyrinthici, 514
Lachnolæmus, 528
Lachs, 644
Lacépède, 15
Lactarius, 450
Ladislavia, 596
Læmargus, 333
Læmonema, 543
Læops, 557
Lais, 566
Laminæ branchiales, 136
Lamna, 320
Lamnidæ, 319
Lampern, 692
Lampris, 454
Lamprey, 692
Lancelet, 696
Lanioperca, 397
Larimus, 431
Lateral line, 48
Lates, 377
Latilus, 466
Latris, 412
Latrunculus, 486
Launce, 550
Leather-carp, 591
Lebiasina, 607
Lemon-sole, 558
Lentipes, 487
Lepadogaster, 513
Lepidoblennius, 498
Lepidocephalichthys, 606
Lepidocephalus, 606
Lepidocottus, 476
Lepidopsetta, 556
Lepidopus, 435
Lepidosiren, 355
Lepidosteidæ, 367
Lepidotrigla, 479
Lepidotus, 368
Lepidozygus, 525
Leporinus, 608
Lepracanthus, 314
Leptacanthus, 314
Leptobarbus, 597
Leptocarcharias, 319
Leptocardii, 696
Leptocephali, 179
Leptoichthys, 681
Leptojulis, 529
Leptolepidæ, 371
Leptopterygius, 513
Leptoscopus, 463
Leptosomus, 656
Leptotrachelus, 666
Lesson, 26
Lethrinus, 407
Leucaspius, 604
Leuciscus, 598
Leucosomus, 600
Liacanthus, 314
Liachirus, 558
Liassic fishes, 198
Lichia, 446
Ligamentum longitudinale, 72
Limnurgus, 615
Ling, 544, 549
Linnæus, 10
Liocassis, 567
Liopsetta, 556
Lioscorpius, 415
Liparis, 485
Liposarcus, 576
Liver, 132
Loach, 604
Lobotes, 387
Lonchurus, 431
Lophiogobius, 487
Lophiosilurus, 569
Lophiostomus, 368
Lophius, 470
Lophobranchii, 678
Lophonectes, 556
Loricaria, 578
Lota, 544
Lotella, 543
Loxodon, 319
Lucania, 615
Lucifuga, 547
Luciocephalidæ, 519
Luciogobius, 489
Lucioperca, 378
Luciosoma, 598
Luciotrutta, 646
Lump-sucker, 484
Lütken, 32
Lycodes, 537

Mackerel, 456, 457

Mackerel Midge, 544
Macrodon, 607
Macrolepis, 421
Macrones, 567
Macropoma, 365
Macropus, 517
Macrosemius, 368
Macruridæ, 557
Macruronus, 552
Macrurus, 552
Mæna, 390
Mahaseer, 594
Malacanthus, 467
Malacocephalus, 552
Malacopterus, 528
Malacopterygian, 41
Malacosteus, 629
Malapterurus, 574
Mallotus, 647
Malpighi, 7
Malpighian corpuscle, 155
Malthe, 475
Mandible, 54
Margrav, 7
Marine fishes, 254
Mary sole, 555
Maskinonge, 624
Mastacembelus, 498
Mastoid, 57, 88
Maurolicus, 628
Maynea, 538
Maxillary, 53, 90
Meagre, 427
Meckel’s cartilage, 54
Meda, 601
Mediterranean district, 264
Medulla oblongata, 98
Megalichthys, 365
Megalobrycon, 610
Megalops, 661
Meidinger, 13
Melamphaes, 423
Melanocetus, 473
Melanonus, 541
Membrane-bones, 75, 84
Mendosoma, 412
Mene, 455
Menhaden, 659
Merluccius, 542
Mesencephalon, 97
Mesoarium, 158
Mesodon, 367
Mesogaster, 500
Mesolepis, 370
Mesonauta, 536
Mesoprion, 384
Mesops, 537
Mesopterygium, 70
Mesotympanic, 55
Mesturus, 367
Metacarpals, 59
Metamorphosis, 170
Metapterygium, 70
Metapterygoid, 55, 90
Metencephalon, 97
Micracanthus, 519
Microconodus, 370
Microdesmus, 538
Microdon, 367
Micropogon, 428
Micropteryx, 443
Micropus, 416
Microstoma, 650
Miller’s-thumb, 476
Minnow, 596, 599
Minous, 417
Misgurnus, 604
Mishcup, 408
Mitchell, 17
Mixogamous, 177
Mollienesia, 617
Molva, 544
Monacanthus, 684
Monk-fish, 334
Monocentris, 421
Monocirrhus, 418
Monopterus, 669
Moon-eye, 653
Mora, 541
Mordacia, 693
Moringua, 675
Mormyrops, 626
Mormyrus, 625
Mossbanker, 659
Motella, 544
Mouth, 37, 123
Moxostoma, 589
Mud-fish, 372, 619
Mugil, 501
Müller, H., 33
Müller, J., 22, 32, 33
Müller, O. F., 13
Müller, W., 33
Mullidæ, 403
Mulloides, 404
Mullus, 404
Munro, 16
Muræna, 675
Murænesox, 674
Murænichthys, 674
Murænolepis, 545
Murray-Cod, 392
Muscles, 93
Muskellunge, 624
Mustelus, 318
Mylesinus, 613
Myletes, 613
Myliobatis, 344
Mylocyprinus, 588
Myloleucus, 601
Mylopharodon, 601
Myology, 93
Myriacanthus, 314
Myriodon, 383
Myriolepis, 370
Myripristis, 423
Myroconger, 677
Myrophis, 674
Myrus, 674
Mystacoleucus, 598
Myxine, 695
Myxodes, 498
Myxus, 504

Nandus, 418
Nannœthiops, 610
Nannobrachium, 587
Nannocampus, 681
Nannocharax, 608
Nannostomus, 607
Narcine, 340
Naseus, 438, 440
Nauclerus, 446
Naucrates, 444
Nautichthys, 480
Nealotus, 434
Nearctic region, 246
Nebris, 431
Nebrius, 326
Neetroplus, 536
Nefasch, 612
Nemacanthus, 314
Nemachilus, 605
Nemadactylus, 412
Nematogenys, 581
Nematops, 557
Nematoptychius, 370
Nemichthys, 670
Nemophis, 498
Nemopteryx, 434, 539
Neochanna, 624
Neoclinus, 498
Neoconger, 674
Neophrynichthys, 469
Neotropical region, 233
Nerfling, 599
Nerophis, 681
Nerves, 103
Nesiarchus, 434
Nettastoma, 674
Neural arches, 85
Neural spine, 52
Neurapophyses, 51
Neurology, 96
Neuroskeleton, 85
New Zealand sub-region, 248
Nictitating membrane, 113
Nilsson, 27
Niphon, 397
Nomeidæ, 455
Nomeus, 456
Nonnat, 501
Nordmann, 28
North American district, 266
North American region, 246
North Atlantic, 262
Northern temperate zone, 262
Northern zone, 240
North Pacific, 268
Nostrils, 37, 109
Notacanthus, 523
Notidanus, 325
Notochord, 63
Notoglanis, 569
Notograptus, 498
Notopterus, 665
Notothenia, 466
Noturus, 568
Novacula, 529
Nummopalatus, 526
Nuria, 598
Nutrition, organs of, 121

Oar-Fish, 522
Oblata, 406
Occipital, 56
Ochetobius, 602
Odax, 532
Odontaspis, 321
Odonteus, 525
Odontostomus, 587
Oil-sardine, 660
Old Red Sandstone, 194
Old wife, 406
Olfactory lobes, 97
Olfactory organ, 109
Oligorus, 392
Oligosarcus, 611
Olistherops, 533
Ombre, 429
Ombre chevalier, 645
Omentum, 132
Onchus, 314
Oncorhynchus, 646
Oneirodes, 473
Oolithic fishes, 199
Opercular gill, 138
Operculum, 38, 54, 91
Ophichthys, 674
Ophidiidæ, 546
Ophidium, 549
Ophiocephalidæ, 513
Ophiodon, 491
Ophiopsis, 368
Opisthognathus, 466
Opisthopteryx, 656
Opisthoticum, 88
Opsariichthys, 602
Optic lobes, 97
Oracanthus, 314
Orbitosphenoid, 57, 88
Oreinus, 595
Oreonectes, 606
Orestias, 615
Orfe, 599
Orthacanthus, 334
Orthagoriscus, 690
Orthodon, 601
Orthostomus, 489
Osbeck, 13
Osmeroides, 582, 631
Osmerus, 646
Os operculare, 91
Osphromenus, 517
Osteobrama, 604
Osteochilus, 596
Osteogeniosus, 569
Osteoglossum, 654
Osteolepis, 365
Ostracion, 686
Os transversum, 56
Otolith, 116
Otolithus, 430
Oulachon, 647
Ovaries, 158, 166
Ovum, 158, 159, 167
Owen, 33
Oxuderces, 489