Covalent Organic Framework

Decorated TiO2 Nanotube Arrays for

Photoelectrochemical Cathodic
Protection of Steel - eBook PDF
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 Corrosion Science 176 (2020) 108920

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

Covalent Organic Framework Decorated TiO2 Nanotube Arrays for T

Photoelectrochemical Cathodic Protection of Steel
Chunli Wanga,b,c,1, Wei Gaob,1, Nazhen Liua,c,*, Yu Xina,c, Xinyu Liua,b,c, Xiutong Wanga,c,
Yong Tiand, Xuwei Chenb,*, Baorong Houa,c
a
Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao, 266071, China
b
Research Center for Analytical Sciences, Department of Chemistry, College of Sciences, Northeastern University, Box 332, Shenyang, 110819, China
c
Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology (Qingdao), 1 Wenhai Road, Qingdao 266237, China
d
School of Environmental and Municipal Engineering, Qingdao University of Technology, 11 Fushun Road, Qingdao 266033, China

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

Keywords: For the first time, a covalent organic framework TpBD was grown in situ on TiO2 nanotube arrays (NTAs), and
A. Steel the performance of the composite was investigated for the application of photoelectrochemical (PEC) cathodic
A. Polymer protection. The synthesized TpBD/TiO2 NTA composite exhibited enhanced PEC cathodic protection perfor-
B. SEM mance under visible light. Coupled with the TpBD/TiO2 NTA photoanode, the photoinduced potential drop
B. XPS
values for 304 stainless steel and Q235 carbon steel in 3.5 wt% NaCl solution were 910 and 370 mV, respec-
C. Cathodic protection
tively. It was proposed that the enhanced PEC performance was due to the formation of a Z-scheme hetero-
junction between TpBD and TiO2.

1. Introduction
Structural steel materials, e.g., stainless steel (SS) and carbon steel
(CS), are widely used in various industries due to their low costs and
excellent mechanical properties. However, these properties can be
compromised upon the corrosion of steel; a process that results in en-
vironmental pollution, energy waste, and serious engineering safety
incidents [1–5]. Thus, it is advantageous to protect steel against cor-
rosion. Compared with the traditional corrosion protection methods
(e.g., coating, impressed current, and sacrificial cathodic protection
[6–8]), photoelectrochemical (PEC) cathodic protection is an energy-
saving and economical anticorrosion technology [9]. The key feature of
this technology is the semiconductor photoanode, which produces
electrons under light irradiation. The photoelectrons produced then
transfer to the metal, with the potential difference as the driving force.
As a result, the potential of the metal shifts negatively, achieving
thermodynamic stability. In 1995, Yuan and Tsujikawa successfully
applied a TiO2 electrode as a suitable photoanode to protect copper
from corrosion under UV light [10]. Since then, the application of TiO2
for photocathodic protection has provoked widespread interest due to
its long-term chemical stability, low cost, relative nontoxicity, and fa-
cile synthesis [11–16]. However, the wide band gap (3.2 eV) of TiO2
limits its application to the UV light region, which accounts for only 5%
of the total solar spectrum [17]. Additionally, its high defect density
leads to an unfavorable combination of photoexcited carriers [18].
However, in recent years developments have been made that address
such limitations, including metal and nonmetal element doping [19,20]
and co-sensitization with some narrow band gap organic and inorganic
semiconductors [21,22].
Covalent organic frameworks (COFs), an emerging category of
porous materials, are constructed via self-assembly of pure organic
molecules [23]. With their chemical stability, tunable band gaps, long-
range order structures, and high surface area, COFs have been applied
extensively in gas storage, biosensing, degradation, catalysis, and bat-
tery applications [24–29]. Recent studies have demonstrated the ex-
cellent photocatalytic properties of COFs [30–33]. Thus the use of COFs
as semiconductors, which are capable of structure control and function
design, show great promise in the application of PEC cathodic protec-
tion.
Herein, for the first time, a highly stable COF (TpBD, Scheme 1) was
grown in situ on TiO2 NTAs via a simple hydrothermal step, and its
application in PEC cathodic protection was investigated. Since PEC
cathodic protection requires the absorption of light and the production
of photoelectrons, the TpBD/TiO2 NTA composite was expected to
improve protection performance compared to pure TiO2 NTAs, possibly
due to the following reasons: (1) the π-conjugated structure causes a

⁎
Corresponding authors.
E-mail addresses: liunazhen@qdio.ac.cn (N. Liu), chenxuwei@mail.neu.edu.cn (X. Chen).
1
Authors contributed equally to this work.

https://doi.org/10.1016/j.corsci.2020.108920
Received 2 January 2020; Received in revised form 14 July 2020; Accepted 31 July 2020
Available online 06 August 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
C. Wang, et al.
Scheme 1. Condensation reaction and chemical structure of TpBD.
decrease in the electron transfer resistance; (2) the absorption of visible
light is enhanced due to the low band gap of TpBD; (3) the reserved
pore structure of a TpBD/TiO2 NTA composite hinders the recombina-
tion of carriers by offering a complete reaction between the holes and
the trapping agent (Na2S in this case); and (4) the formation of a het-
erojunction between TpBD and TiO2 would improve the separation of
the photoelectrons from the holes.
2. Experimental
2.1. Materials
Ti foils (> 99% purity) were purchased from Baoji Group Co., Ltd.
(Baoji, China). Ammonium fluoride (NH4F), hydrogen peroxide (H2O2),
nitric acid (HNO3), sodium sulfide (Na2S·9H2O), glycol, ethanol, acetic
acid, 1,4-dioxane, acetone, and 1,3,5-trimethylbenzene were purchased
from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).
Benzidine (BD) was provided by Aladdin Bio-Chem Technology Co.,
Ltd. (Shanghai, China). 1,3,5-Triformylphloroglucinol (Tp) was pur-
chased from Tongchuangyuan Pharmaceutical Technology Co., Ltd.
(Chengdu, China). Nafion solution was purchased from Sigma-Aldrich
Co., (St. Louis, MO, USA). All the aqueous solutions were prepared
using deionized (DI) water (18.2 MΩ cm) purified using a SMART ultra-
pure water system. All of the reagents used were analytical grade
without further purification.
2.2. Preparation of TiO2 NTAs
Among the three crystalline phases, the anatase TiO2, which is
generally obtained by potentiostatic anodization, is more favorable in
the field of photocatalysis [34]. Ti foils (40 mm × 10 mm × 1 mm)
were ultrasonically degreased in deionized water and ethanol for
15 min each. Then, the Ti sheets were polished in a solution containing
NH4F (4.5 g), H2O (25 mL), H2O2 (30 wt%, 60 mL), and HNO3 (68 wt%,
60 mL) to remove surface oxides. The electrochemical cell composed of
a two-electrode system with Pt foil and a Ti sheet as the counter elec-
trode and working electrode, respectively. A DC voltage of 20 V was
Scheme 2. Schematic illustration of the TpBD/TiO2 NTA composite’s fabrication.
2
Corrosion Science 176 (2020) 108920
applied between the two electrodes for 1.5 h in an electrolyte comprised
of 80.0 mL ethylene glycol, 8.0 mL DI water, and 0.45 g NH4F. After
anodization, the samples were cleaned using DI water and ethanol
several times to remove any residual electrolyte. The as-prepared
samples were annealed at 450 °C for 2 h in air at a heating rate of
5 °C min−1 and naturally cooled afterward to obtain the TiO2 NTAs in
the anatase phase.
2.3. Fabrication of the TpBD/TiO2 NTA composite
1,3,5-triformylphloroglucinol (Tp 6.3 mg, 0.03 mmol) and benzi-
dine (BD 8.3 mg, 0.045 mmol) were dissolved in a mixture of mesity-
lene/1,4-dioxane (30 mL, 1:1). Subsequently, aqueous acetic acid (6 M,
0.5 mL) was added dropwise to the above mixture in a Teflon liner. The
resulting solution was sonicated for 10 min to obtain a homogeneous
dispersion; then, a piece of TiO2 foil was placed aslant into the solution
in the Teflon liner, which was loaded into a stainless steel autoclave and
heated at 120 °C for 72 h. After cooling to room temperature, a dark red
precipitate (TpBD) and a TpBD/TiO2 NTA composite on a Ti matrix
were obtained after extraction with acetone for 24 h (Soxhlet extrac-
tion), the samples were then dried at 60 °C for 6 h under vacuum. The
fabrication process of the TpBD/TiO2 NTA composite is shown in
Scheme 2. The 10-TpBD/TiO2 NTA composite was synthesized using
the same procedure with increased amounts of Tp (63 mg, 0.3 mmol)
and BD (83 mg, 0.45 mmol).
2.4. Characterization
The X-ray diffraction (XRD) patterns were recorded on a Bruker D8
Advance (Bruker, Germany) diffractometer using Cu Kα radiation (λ
=1.5406 Å). The attenuated total reflection infrared spectroscopy
(ATR-IR) was performed on a Nicolet 5700 Spectrometer (Thermo
Nicolet, USA). The field emission scanning electron microscope (FE-
SEM) images were recorded with a Hitachi SU8220 (Hitachi, Japan).
The transmission electron microscopy (TEM) and high resolution
transmission electron microscopy (HRTEM) analyses were carried out
on a JEOL JEM-2100 (Tokyo, Japan) with an accelerating voltage of
200 kV. The X-ray photoelectron spectroscopy (XPS) was recorded on a
Thermo Escalab 250Xi (Thermo Fisher Scientific, USA) with an Al Kα X-
ray source. The UV-vis diffuse reflectance spectra (DRS) were recorded
on a U-3900H spectrophotometer (Hitachi, Japan). The Electron Spin
Resonance (ESR) spectra were measured by the JES-FA200 (JEOL,
Japan).
2.5. Electrochemical measurements
The electrochemical measurements were made using a CHI760E
electrochemical workstation (Shanghai Chenhua Instrument Co. Ltd.,
China). The open circuit potential (OCP-t) and photoinduced current
density (i-t) curves were recorded in an electrochemical cell, as shown
in Scheme 3. In the corrosion cell containing 3.5 wt% NaCl, a saturated
calomel electrode (SCE) served as the reference electrode (RE) and a
steel sample served as the working electrode (WE). The fabricated
photoanode was placed in the photoanode cell containing 0.1 M Na2S
and 0.2 M NaOH, which were used as sacrificial agents for promoting
C. Wang, et al.
Scheme 3. Schematic diagram of the electrochemical test for measuring (a) photoinduced open circuit potential and (b) photoinduced current density.
Fig. 1. SEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs, (c) 10-TpBD/TiO2 NTAs, and (d) TpBD, respectively. Insets are the cross-sectional image of (a) and (b).
the separation of the photoelectrons and holes. The photoanode cell and
the corrosion cell were separated by a Nafion membrane. The OCP-t
and i-t curves were measured under intermittent illumination. A 300 W
Xenon lamp (PLS-SXE 300 C, Beijing Perfect light Company, China)
with a 420 nm cut-off filter was used to generate visible light with an
energy density of 100 mW cm−2. During the OCP-t measurement, the
steel sample and the fabricated photoanode were electrically coupled
and connected to the working electrode. For the i-t test, the photoanode
and the steel sample were connected to the working electrode and
ground wire, so that the photogenerated electrons could flow from the
photoanode to the steel. In addition, the counter electrode (CE) and RE
interfaces were linked by a short circuit to remove the influence of
polarization.
The photoinduced i-V test was conducted in a three-electrode cell
containing 0.1 M Na2SO4, where the prepared photoanode served as the
WE, and the SCE and Pt foil served as the RE and CE, respectively. The i-
V curve was recorded from −1.0 to 1.0 V at a scan rate of 0.02 V s−1,
where the light was switched on and off every 5 s.
The electrochemical impedance spectroscopy (EIS) was conducted
in a three-electrode cell containing 0.1 M Na2S and 0.2 M NaOH, using a
GAMRY Interface 1000. The prepared photoanode was served as the
WE, and the SCE and Pt foil served as the RE and CE, respectively. The
EIS test was carried out at OCP and spectra were recorded over a fre-
quency range of 105 to 10−2 Hz with an AC voltage magnitude of 5 mV.
3
Corrosion Science 176 (2020) 108920
The results were analyzed using Princeton ZSimpWin version 3.60
software.
The Mott-Schottky (MS) curve was measured in the potential range
of −0.6 V to 1.0 V with an AC potential frequency of 1000 Hz under
dark conditions. The working electrode was prepared as follows: 5.0 mg
of TpBD, 1.0 mL of ethanol and 10 μL of Nafion solution (5 wt%) were
mixed under sonication, and 200 μL of the above suspension was spread
onto the surface of an FTO (fluorine-doped tin oxide) glass substrate
with an area of 10 mm × 10 mm and then dried at room temperature.
3. Results and discussion
3.1. Characterization of the fabricated material
The surface morphologies of the TiO2 NTAs, TpBD, and TpBD/TiO2
NTAs are shown in Fig. 1. The well-ordered and compact TiO2 NTAs
grown on the Ti foil had inner diameters in the range of 30 - 60 nm and
an average length of ∼1000 nm (Fig. 1a). The top view of the TpBD/
TiO2 NTAs showed nanotubes with inner diameters in the range of 20 -
40 nm, which was due to the deposition of TpBD (Fig. 1b). Fig. 1d
showed that the synthesized free TpBD particles were spherical, with an
average diameter of ∼1 μm; however, the TpBD grown in situ on the
TiO2 NTAs was quite different (Fig. 1b and 1c); the significant change of
the TpBD morphology on the TiO2 NTAs was caused by the preferred
C. Wang, et al.
Fig. 2. TEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs and (c) HRTEM
image of the TpBD/TiO2 NTAs.
growth of TpBD along the edges of the pore opening on TiO2 NTAs [18].
The retained channel structure of the TpBD/TiO2 NTA composite with a
large specific surface area, had the potential to provide sufficient con-
tact between the fabricated material and the surrounding solution,
which could hinder the recombination of carriers by offering a com-
plete reaction between the holes and its trapping agent (Na2S, in this
case). Meanwhile, it is worth mentioning that although the pore
structure was retained in the 10-TpBD/TiO2 NTA composite, the PEC
cathodic protection performance between the TpBD/TiO2 NTAs and 10-
TpBD/TiO2 NTA composites showed minor differences (not shown).
The microstructures of the TiO2 NTAs and TpBD/TiO2 NTAs were
further investigated by TEM and HRTEM (Fig. 2). Fig. 2a showed a
batch of TiO2 nanotubes with inner diameters of ∼50 nm and the for-
mation of ordered NTAs. Fig. 2b showed the microstructure of the
TpBD/TiO2 NTA composite. Compared with the TiO2 NTAs, the basic
outlines of the nanotubes in the TpBD/TiO2 NTA composite were vague
and unclear, likely due to the deposition of the TpBD. The interplanar
spacing of the (101) plane of the anatase TiO2 (0.351 nm) and the (100)
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Corrosion Science 176 (2020) 108920
plane of the TpBD (0.325 nm) can be observed from the HRTEM image
(Fig. 2c) [35]. The results suggest that TpBD was successfully grown on
the TiO2 NTAs.
The XRD experiments were performed to determine the crystalline
structures of the synthesized materials (Fig. 3). The obtained TpBD
particles displayed moderate crystallinity, likely due to the fact that
rapid growth of the COFs via precipitation limited the formation of
highly crystalline structures [36]. The reflection peaks at 2θ = 3.6º,
6.0º, 7.1º, 9.3º and 26.7º were consistent with the simulated diffraction
data. While the diffraction peaks of Ti and TiO2 could be observed in
the TpBD/TiO2 NTAs sample, the characteristic peaks of TpBD were not
observed. Possible reasons for this are the fact that: a very small
quantity of TpBD was loaded on the TiO2 NTAs and the lack of crys-
tallinity of the TpBD grown in situ on the TiO2 NTAs. In Fig. 1, the
morphologies of the free TpBD particles (Fig. 1d) and the TpBD grown
in situ on the TiO2 NTAs (Fig. 1b and 1c) were quite different, thus
suggesting the morphology of the TpBD varied with the growth con-
ditions, which may influence the crystallinity of the TpBD. The HRTEM
and XRD results indicated contradictory information regarding the
crystallinity of the TpBD grown on the TiO2 NTAs. This may be due to
the different sample preparation methods for the XRD and TEM ana-
lyses. In the TEM analysis, the sample was super thin, thus enabling
local crystallinity of the TpBD to be detected.
The chemical composition of the TpBD/TiO2 NTA composite was
further studied by XPS analysis (Fig. 4). The result showed no obvious
Ti peaks in the full scan spectrum (Fig. 4a), because the detection limit
for the XPS analysis was only a few nanometers and the TiO2 NTAs was
covered with an appreciable amount of TpBD (Fig. 1) [37–39]. The full
scan spectrum of the TpBD/TiO2 NTA composite confirmed the pre-
sence of C 1s (285 eV), N 1s (400 eV), and O 1s (531 eV). Deconvolution
of the C 1s high resolution XPS spectrum (Fig. 4b) into four distinct
peaks allowed for the assignment of the C = C (284.8 eV), C-N
(286.2 eV), C-C (287.0 eV) and C = O (288.4 eV) bonds [22,32]. In the
N 1s spectrum (Fig. 4c), the peaks with binding energies of 398.8 and
399.9 eV were assigned to the C-N-C and N-H bonds, respectively
[27,40]. In the O 1s spectrum (Fig. 4d), two peaks located at 531.7 and
535.0 eV were assigned to the lattice oxygen in the TpBD structure
through C = O bonding [40] and chemically adsorbed water molecules
[41]. The XPS results indicated that TpBD was successfully loaded on
the TiO2 NTAs.
ATR-FTIR spectra of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs
are shown in Fig. 5. In the case of the TiO2 NTAs, a wide absorption
peak at 530 cm−1 corresponded to the stretching and bending vibra-
tions of the Ti-O-Ti bond [42]. For TpBD, absorption peaks at
1618 cm−1 (carbonyl C = O stretching), 1571 cm−1 (C = C stretching),
1450 cm−1 (aromatic C = C ring stretching) and 1282 cm−1 (C-N
stretching) were observed [43,44]. The peaks above could also be ob-
served in the spectrum of the TpBD/TiO2 NTAs, thus demonstrating the
successful loading of TpBD.
The optical property of the fabricated materials was investigated by
UV-vis DRS spectra. In Fig. 6, the pure TiO2 NTAs exhibited a narrow
absorption of light in the UV light region (200 - 380 nm), while the
TpBD showed a wider and stronger absorbance. After loading the TpBD,
the TpBD/TiO2 NTAs exhibited an enhanced absorption in the visible
light range. The band gap energy (Eg) of the semiconductor photo-
catalysts can be calculated by the Kubelka-Munk equation [11,45],
αhv = A (hv − Eg )n (1)
where α is the absorption coefficient, h is Plank constant, ν is the light
frequency, and A is a constant. Among them, n, depends on the char-
acteristics of the transition of the semiconductor, e.g., direct transition
(n = 1/2) or indirect transition (n = 2). Both TiO2 and TpBD belong to
indirect transitions (n = 2) [11,30]. Hence, the Eg values of TiO2,
TpBD/TiO2, and TpBD were calculated to be 3.37, 2.40, and 2.20 eV,
respectively. The decrease of the band gap energy indicates an im-
proved absorption of visible light by the fabricated photoanode.
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 3. XRD patterns for the TiO2 NTAs, TpBD, and TpBD/TiO2 NTA composite.

Fig. 4. (a) Survey, (b) C 1s, (c) N 1s, and (d) O 1s XPS spectrums for the TpBD/TiO2 NTA composite.

3.2. PEC cathodic performance of the fabricated material
Corrosion is the oxidation of metals; forming protective oxides or
dissolving cations depending on the condition of the environment (e.g.,
redox condition, acidity, temperature, etc.). Thermodynamically
speaking, a metal is stable and immune to corrosion below its equili-
brium potential, while metal oxidation/corrosion is favored above the
equilibrium potential. In Fig. 7, the photoinduced potential drop of 304
SS coupled with TiO2 NTAs was 290 mV, and a corresponding photo-
induced current density of 0.015 mA cm−2 was measured (Fig. 7a, c).
The PEC cathodic protection performance of the TpBD/TiO2 NTAs
showed significant improvement with a photoinduced potential drop of
910 mV and a photoinduced current density of 0.12 mA cm−2 (Fig. 7a,
c). In Fig. 7a, the onset potential of the 304SS after being coupled with
TiO2 was slightly higher than the corrosion potential of the 304SS
(black curve vs. blue curve). This observed phenomenon was incon-
sistent with previously reported studies [11,39,46,47] and was caused
by inevitable errors in the OCP measurements. In Fig. 7a, after the light
was turned off, the potential of the 304 SS coupled with TpBD/TiO2 did
not reach the original value in 300 s. The stability study (discussed later

5
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 5. FTIR-ATR spectrums of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs.

Fig. 6. UV-vis DRS spectra of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs.

in Fig. 10) showed that after the light was turned off, the coupled po-
tential stabilized at a value that was slightly lower than the corrosion
potential of 304 SS in ∼1000s, indicating that time was a key factor for
the recovery of the potential. When the light was off, no photoelectrons
were transferred from the photoanode to the 304 SS; the potential of the
304 SS was governed by the kinetics of its surface anodic and cathodic
reactions, which was influenced by its surface state. In Fig. 7a, the
photoinduced potential drop of the 304 SS coupled with TpBD/TiO2
was 910 mV, indicating a highly reduced surface state of 304 SS com-
pared to that of its original surface; thus, the recovery of the surface
state was more time consuming. In comparison, the photoinduced po-
tential drop of the 304 SS coupled with TiO2 was 290 mV; thus, it took
less time for the recovery of the surface state.
Compared to the 304SS, the cathodic protection of the Q235 CS is
more challenging, because the Q235 CS has a more negative corrosion
potential of −0.72 V (Fig. 7b), and one of the requirements for a suc-
cessful PEC cathodic protection is that the conduction band potential of
the semiconductor must be more negative than the corrosion potential
of the protected metal [9]. The potential of the Q235 CS did not shift
negatively by coupling to the TiO2 photoanode under light irradiation
(Fig. 7b). In fact, the photoinduced current of the TiO2-CS was negative
(Fig. 7c), indicating the flow of electrons from CS to TiO2. The corrosion
of the CS was accelerated slightly, and a small positive potential shift of
the CS was observed. Compared with the TiO2 NTAs, the TpBD/TiO2
NTA composite showed favorable PEC cathodic protection for the Q235
CS. Under illumination, the photoinduced potential drop was 370 mV
and the photoinduced current density was 0.16 mA cm−2 (Fig. 7b and
7c). After three cycles, the coupled potential of the Q235 CS and 304 SS

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C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 7. OCP-t curves of (a) 304 SS and (b) Q235 CS, and (c) i-t curves of 304 SS and Q235 CS connected with the TiO2 NTAs and TpBD/TiO2 NTAs photoanodes under
intermittent visible light irradiation.

7
C. Wang, et al.
Fig. 8. The photoinduced i-V curves of TiO2 NTAs and TpBD/TiO2 NTAs photoanodes under intermittent visible light illumination.
maintained a relatively steady value, demonstrating the fast and stable
response of the TpBD/TiO2 NTA composite to light.
The enhanced PEC performance of the TpBD/TiO2 NTA composite
was also confirmed by the i-V curves of the photoanodes under inter-
mittent visible light illumination (Fig. 8). The onset potential for
semiconductors to produce photoinduced current density under light
irradiation is approximately equal to the Fermi level of the corre-
sponding semiconductor, which was −0.62 V for the TiO2 and −0.92 V
for the TpBD/TiO2 NTA composite [48]. The 0.3 V negative shift of the
threshold potential indicated the enhanced reducing capacity of elec-
trons in the TpBD/TiO2 NTA composite. Additionally, the enhanced
8
Corrosion Science 176 (2020) 108920
Fig. 9. (a) Nyquist plots, (b) Bode plots of log
|Z| vs. frequency, (c) phase angle vs. frequency
of the TpBD/TiO2 NTA composite under dark
and illuminated conditions, and the equivalent
circuits established to fit the EIS results of the
TpBD/TiO2 NTA composite under (d) dark and
(e) illuminated conditions.
PEC cathodic performance of the TpBD/TiO2 composite is further
confirmed by the larger photoinduced current density compared to that
of the TiO2.
To study the interfacial properties of the TpBD/TiO2 NTA compo-
site, electrochemical impedance spectroscopy (EIS) tests were carried
out under dark and illuminated conditions, as shown in Fig. 9. In
Fig. 9a, under dark, the Nyquist plot of the TpBD/TiO2 NTA composite
was composed of a big and incomplete semicircle; under illumination,
the Nyquist diagram was featured of a much smaller and incomplete
semicircle. In Fig. 9b, the impedance modulus value of the TpBD/TiO2
NTAs under illumination was two orders of magnitude lower than that
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 10. The long-term potential variation of the 304 SS electrode coupled with the TpBD/TiO2 NTAs photoanode under intermittent visible light illumination.

Table 1
The electrochemical impedance parameters for the TpBD/TiO2 NTA composite under dark and illuminated conditions.
Conditions Rs Qf Rp Qdl Rct
(Ω cm2) (Ω cm2) (Ω cm2)
Y0 n Y0 n
(Ω−1 cm−2 sn) (Ω−1 cm−2 sn)

Under dark 4.24 4.65 × 10−4 0.61 17.54 5.98 × 10−5 0.93 1.30 × 105
Under illumination 3.45 1.45 × 10−3 0.59 9.46 6.35 × 10−4 1 2.23 × 103

Fig. 11. The Mott-Schottky plot of TpBD.

under the dark condition. According to the Bode plots (Fig. 9c), two
time constants corresponding to the double layer capacitance at the
electrode/electrolyte interface and a film capacitance were observed.
The impedance data was modeled by the equivalent circuits shown in
Fig. 9d (under dark) and 9e (under illumination), where Rs is the so-
lution resistance, Qf is the capacitance of the surface film; due to the
porous surface of the TpBD/TiO2 NTAs shown in Fig. 2b, Rp represents
the electrolyte resistance in the pore. In addition, Rct and Qdl represent
the charge transfer resistance and double layer capacitance, respec-
tively. The constant phase element (CPE) is used to replace the capa-
citance with a non-ideal capacitive response, and is calculated by,

9
C. Wang, et al.
Fig. 12. The valence band spectrum of XPS for TpBD.
Q=
1 intercept [45] and was −1.23 V by extrapolation [13]. It is known that
Y0 (j ω) n (2)
where Y0 represents the admittance modulus (Ω−1 sn cm−2), ω is the
angular frequency, and n is a constant with a value between 0 and 1.
CPE is converted to a pure resistor (n = 0) or a pure capacitor (n = 1).
For a CPE with n ≠ 1, its capacitance, C, can be calculated by,
1
1 −n n
C= R n Y0 (3)
where R is the resistance of the resistor paralleled with the CPE [49].
The electrochemical parameters obtained from the fitting results are
summarized in Table 1. According to equation (3), the double layer
capacitance under dark is calculated to be 6.98 × 10−5 F cm−2, which
is one magnitude lower than that under illuminated condition
(6.35 × 10−4 F cm−2), this is likely due to the production and storage
of photo-generated electrons under illumination. The Rct value is an
important parameter to evaluate the photocathodic protection perfor-
mance of the prepared photoanode [49,50]. In Table 1, the Rct values of
the TpBD/TiO2 NTAs were 1.30 × 105 Ω cm2 under dark, and
2.23 × 103 Ω cm2 under illumination, suggesting a rapid transfer of
photogenerated electrons under illuminated condition. Therefore, the
above results were consistent with the good photocathodic protection
performance of the TpBD/TiO2 NTAs composite.
Another requirement for successful PEC cathodic protection is the
stability of the photoanode, which cannot be corroded by the sur-
rounding medium during the protection process. Fig. 10 showed the
long-term variation of potential of 304 SS coupled with the TpBD/TiO2
NTAs photoanode under intermittent visible light illumination. The
coupled potential of the 304 SS was stabilized at −0.9 V after a con-
tinuous light illumination of 3 h. When the light was turned off, the
potential switched back immediately and stabilized at −0.34 V
(slightly lower than the corrosion potential of the 304 SS). After several
cycles, the TpBD/TiO2 NTA composite still exhibited good performance
during the protection process.
3.3. Proposed mechanism
The Mott-Schottky plot was measured to study the band structure of
the TpBD (Fig. 11). The positive slope revealed that the TpBD was an n-
type semiconductor, and its Efb could be obtained from the horizontal
10
Corrosion Science 176 (2020) 108920
the conduction band potential (ECB) for an n-type semiconductor is
0.2 V more negative than the Efb value [51,52]. Thus, the ECB for the
TpBD was calculated to be −1.43 V, which was −1.19 V (vs. NHE)
[30]. The calculated valance band potential (EVB) for the TpBD was
1.01 V (vs. NHE) according to the formula of EVB = ECB + Eg [53]. This
is consistent with the calculated valance band potential based on the VB
XPS spectrum of the TpBD in Fig. 12, which was 0.87 eV by extra-
polating the leading edge of the spectra to the baseline [54].
The ESR result (Fig. 13a) further verified the band structure of the
TpBD, in which the photoelectrons can reduce the adsorbed O2 mole-
cules to produce •O2− radicals (O2/•O2− = −0.3 V vs. NHE), and the
holes cannot oxidize the OH− to produce •OH (OH−/•OH = +2.68 V
vs. NHE).
According to previous reports [54,55], the ECB and EVB values of the
TiO2 were −0.29 and +2.91 V, respectively. Possible band structure
alignments for the TiO2 and TpBD were shown in Fig. 14. Fig. 14a
showed a conventional type-II heterojunction electron transfer path, in
which the photoelectrons in the CB of the TpBD transfer to that of the
TiO2, while the holes localized at the VB of the TiO2 transfer to that of
the TpBD. However, the above mechanism could not explain the fol-
lowing results: (1) according to the ESR results, the accumulated holes
in the VB of the TpBD cannot oxidize the OH− to produce •OH
(Fig. 13a), indicating the accumulation of holes at the VB of the TiO2;
(2) the Q235 CS can be protected from corrosion by the photogenerated
electrons in the TpBD/TiO2 (Fig. 7b,c), indicating the accumulation of
photoelectrons at the CB of the TpBD (more negative than the corrosion
potential of the Q235 CS, which is −0.51 V (vs. NHE)). Thus, a direct Z-
scheme mechanism [56–58] was proposed for the TpBD/TiO2 NTA
composite system (Fig. 14b) in which the electrons in the TiO2 and
holes in the TpBD could recombine directly, thus leading to an efficient
separation of photoelectrons at the CB of the TpBD and holes at the VB
of the TiO2. The remarkable improvement of the PEC cathodic protec-
tion performance of the TpBD/TiO2 NTA composite was also attributed
to the enhanced reducing capacity of the photoelectrons.
4. Conclusions
In summary, COF-TpBD modified TiO2 NTAs (TpBD/TiO2 NTAs)
were successfully fabricated. The TpBD/TiO2 NTA composite showed
C. Wang, et al.
Fig. 13. ESR spectra of radical adducts trapped by DMPO for (a) TpBD and (b) TpBD/TiO2 NTAs under visible light for 5 min.
significantly enhanced PEC cathodic protection performance for 304 SS
and Q235 CS under visible light irradiation. Additionally, the ESR and
PEC analyses indicated that a direct Z-scheme heterojunction was
formed between the TpBD and TiO2, by which an enhanced reduction
capacity of photoelectrons was reserved and an efficient separation of
charge carriers was achieved. This work demonstrates that COF mate-
rials, as semiconductors which are capable of structure control and
functional design, show promise for applications in the field of PEC
cathodic protection.
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.
11
Corrosion Science 176 (2020) 108920
CRediT authorship contribution statement
Chunli Wang: Investigation, Writing - original draft. Wei Gao:
Validation, Resources. Nazhen Liu: Conceptualization, Writing - re-
view & editing, Supervision, Project administration. Yu Xin: Resources.
Xinyu Liu: Resources. Xiutong Wang: Writing - review & editing.
Yong Tian: Writing - review & editing. Xuwei Chen: Project admin-
istration. Baorong Hou: Funding acquisition.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This research work was financially supported by the National
Natural Science Foundation of China (No. 51901222, 41827805) and
C. Wang, et al.
Fig. 14. Proposed mechanism for the enhanced PEC cathodic protection performance of the TpBD/TiO2 NTAs on steel under illumination.
the CAS Pioneer Hundred Talents Program. I would like to express my
gratitude to Dr. Taylor Martino (CanmetMATERIALS, Canada) for lan-
guage editing, and Dr. Zack Qin for EIS discussion.
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kettle boiling on the stove, the air is moistened and feels warmer.
 A Carbon Electric Water Heater
The water heater illustrated is for use on a 110-volt circuit without
added resistance. It consists of two electrodes which are immersed
directly in the water; and while it is not as artistic as the usual
nickelplated heater, it is usually more economical and has the
distinct advantage that it cannot be burnt out. It may be made as
rapid in action as desired, is inexpensive and very convenient where
water is required for experimental or industrial purposes.
 For the electrodes, procure two ¹⁄₂-in. uncoppered carbons, and
drill a hole in the top of each of these so that feed wires can be
attached. The handle is shaped from a piece of hard wood. The
lower end is hollowed out half round at either side, so that the
carbons will fit in snugly. Four small holes are then drilled through
from side to side for binding wires, and a large hole is made in the
center for the feed wires. Two smaller branch holes are then drilled
to join the center hole, so that the double feed cord may be branched
out to reach both electrodes. The outer edge of the handle is neatly
rounded off and boiled in paraffin so as to render it impervious to
moisture.
 Remove sufficient insulation from the feed cord to make a good
connection with the carbons. Fish the wire through the handle from
the upper end. Pull each of the two ends pretty well through, so that
they can be securely threaded into the holes previously made in the
carbons. Have the latter quite hot and run in as much solder as
possible, forcing it in with the end of a match as it becomes plastic.
Remove all traces of the flux, and paint the connection with some
melted pitch, taken from the top of a discarded dry cell. The feed
cord may then be pulled up tightly, which will draw the carbons in
place. They are then bound by threading through several strands of
copper wire. If the holes in the wood are slightly countersunk, and
two small grooves filed around each carbon at the right places to let
the holding wires in, the binding feature may be disposed of very
neatly.
In some localities the water is so free from all mineral salts that it
will not carry the current freely, which means that the electrodes
must be placed closer together, or else a small pinch of common salt
may be added to the water. Although, in sterilizing instruments,
boiling eggs, or something of that sort, this would be of no
advantage, the salt greatly hastens the boiling.
 Preventing Looseness of Drawer Handles

Drawer handles frequently become loosened and sometimes

cause further annoyance by falling to the floor or becoming lost,
because the bolt fastening, as shown in the sketch, is not secure.
This may be avoided by inserting a rubber band between the head of
the bolt and the drawer front. When the knob is drawn up tightly the
pressure of the rubber band prevents it from becoming loosened.—
Contributed by O. F. Germaine, Akron, Ohio.
 An Electrical Dancer
The modification of the well-known mechanical dancer shown in
the illustration is based on the principle of the electric bell. While the
amusing antics of the mechanical dancer are controlled by the hand,
the manikin shown is actuated by the electromagnet.

When the Contact is Made the Figure Dances

 The mechanism is contained in a box. It consists of an
electromagnet with a soft-iron armature carried by a spring. A wire
from the battery goes to the magnet. The other terminal of the
magnet connects with the armature spring at L1. The spring is bent
at a right angle at its other end, L2, and carries a platform, L3,
strengthened by a smaller disk underneath. The dancer performs
upon this platform.
A contact spring, S, is carried by the armature spring. A contact
screw, C, is adjustable in its contact with the spring S. A wire runs
from the contact screw to the binding post B, to which the other
battery wire is connected.
The current keeps the platform in constant vibration, causing the
dancer to “dance.” By means of the screw C, the action of the
current may be varied, and the “dancing” will vary correspondingly.
The figure is made of wood with very loose joints and is
suspended so that the feet barely touch the platform.—Contributed
by Edward C. Connelly, Wilkesbarre, Pa.
 Child’s Swing Built of Pipes in Narrow Space

This Substantial Swing Guards the Youngsters from Injury by Brushing

against the Brick Walls

A narrow space between two city houses was used to erect a

swing, as detailed in the illustration. A piece of 2-in. iron pipe, A, was
cut 1 ft. longer than the space between the walls. Two pieces of 2¹⁄₂-
in. pipe and a 2¹⁄₂ by 2¹⁄₂ by 1¹⁄₄-in. tee, as shown in the detail, was
slipped over the 2-in. pipe, which was built into the walls. A 1¹⁄₄-in.
pipe, B, 20 ft. long, bent as shown, was joined to the tee, and a seat,
C, was attached. The construction of the seat is shown in detail,
being fixed to the wooden part with washers, nuts, and a threaded
nipple, D. A cushion and a removable safety bar, E, were also
features. This swing is safer than one of rope, and will stand much
greater wear.—James N. Reed, San Francisco, Calif.
 Door Bumpers Raise Height of Chair
Four wooden door bumpers, of the rubber-tipped knob type,
fastened to the lower ends of the legs of one of the kitchen chairs,
make an almost indispensable high chair, which will bring the table
work to a more comfortable height than the ordinary chair does. The
young child also will appreciate such a chair at the dining table.
When it is no longer needed, the knobs can be unscrewed quickly.—
J. E. McCoy, Philadelphia, Pa.
 A Homemade Hawaiian Ukulele
By S. H. SAMUELS

T he one-string banjo, the cigar-box guitar, and similar vaudeville

favorites are giving way to the tantalizing ukulele, and the home
mechanic, to be up to date in his musical craftsmanship, must fall in
line. The size of this instrument makes it especially suited to the
cigar-box type of body construction, as detailed in the several
sketches and shown in the photograph reproduced. This neat
ukulele was made at a cost of 30 cents, by careful selection of
materials from the shop scrap stock.

This Cigar-Box Ukulele Cost the Maker 80 Cents, and Affords Him the
Pleasures of a More Expensive One

A cigar box of good-quality Spanish cedar, about 2¹⁄₂ by 6 by 9 in.,

as shown in Fig. 1, is used for the body. Remove the paper carefully,
so as not to mar the surface, soaking it if necessary. Take it apart,
and if the nail holes are too numerous, or broken out, trim off the
edges. Fit the parts of the body together, as shown in Fig. 2, the top
and bottom pieces resting against the side and end pieces, and the
latter between the sides. Cut the 2¹⁄₂-in. hole in the top piece, as
shown, 3³⁄₄ in. from the neck end. To reinforce the body make strips
A, ¹⁄₄ in. square, and fit them to be glued into the corners at the top
and bottom. Make strips B, ¹⁄₄ by ⁵⁄₈ by 4¹⁄₂ in., and glue them under
the top and on the bottom as indicated in Fig. 2. The final
assembling and gluing of these parts, using animal glue, should be
done after the bridge C is in place, and the other parts are made.
The bridge is of hard wood hollowed underneath the notched edge,
as detailed, and is fitted with a metal string contact.

Fig. 1 Fig. 3
Fig. 2

To Keep in the Fashion in His Musical Craftsmanship, the Home Mechanic

may Make a Cigar-Box Ukulele as Detailed

Spanish cedar or mahogany is suitable for the neck, detailed in

Fig. 3. A single piece is best, but the extension for the pegs and the
wider end at the body may be joined and glued to the main portion of
the neck. Dowels should then be used to reinforce the joints. The
outline of the parts of the neck are shown in detail in Fig. 3. In the
sectional view at the right, the shape of the neck at the thinnest and
thickest parts is shown by the two upper curved, dotted lines. The
nut D is made of mahogany, walnut, or other hard wood, the grain
extending lengthwise, and the notches for the strings spaced as
shown.
The making and spacing of the frets must be done very carefully.
They are of aluminum, brass and other metals being suitable also.
Make the frets ¹⁄₁₆ by ³⁄₁₆ in. and cut grooves ¹⁄₈ in. deep for them.
The spacing of the frets is determined as follows, a standard
practice: The distance from the metal string-contact on the bridge to
the nut should be measured carefully. The first fret, near the head, is
¹⁄₁₈ of this distance from the nut, the total length being in this
instance, 13 in. The second fret is set ¹⁄₁₈ the distance from the first
fret to the bridge; the third, ¹⁄₁₈ from the second fret to the bridge, etc.
The frets must fit tightly in the grooves, requiring no special
fastening. The tuning pegs may be bought or made.
In assembling the parts, fasten the end of the body to the neck,
with glue, reinforced by screws. Set its upper edge parallel with the
fingerboard, and so that the latter is flush with the top of the body,
when fitted to it. Assemble the body, without the top, gluing it to the
end, fixed to the neck. When this portion is thoroughly dried, fit the
top into place finally, and glue it. The whole construction is then
cleaned, sandpapered, stained, and shellacked or varnished. The
stringing of the instrument is simple, and the strings may be
purchased in sets.
 Homemade Suitcase Extension

A handy addition to the traveler’s equipment is a suitcase

extension that may be removed when not in use, and folded
compactly, inside of the suitcase if desired. This latter feature is
provided for by arranging the extension to be folded vertically at the
middle. Heavy leather, cloth board covered with strong linen, or
canvas of a suitable color may be used. If cloth board is used it
should be cut the size of the side of the suitcase, and smaller
sections hinged to it at the folds. The leather need not be reinforced
if it is fairly strong. Cut the leather at A, B, C, and D, and arrange it to
be folded on the dotted lines. Rivet guides for the straps, as at E. Fit
the corners with buttons or snaps F, which are locked in position
when the extension is in use. The device slides over the suitcase
and may be drawn tightly against it when empty.—R. S. Matzen, Fort
Collins, Colo.
 Putty Deadens Glossy Surfaces in Photography
Attempts to make “close-up” photographs of machinery, or highly
polished objects, often fail because the reflection of light upon the
bright surfaces causes a blur in the photograph. Some
photographers use putty to deaden the gloss. A lump of putty is
rubbed over the surface gently where a brilliant reflection is visible,
or the entire surface is rubbed so that it presents an even, dead
finish on the ground glass of the camera, when focusing.—Ralph W.
Tillotson, Erie, Pennsylvania.