Carbon quantum dots (CQDs) modified

TiO2 nanorods photoelectrode for

enhanced photocathodic protection of
Q235 carbon steel Min Feng & Ying Liu
& Sainan Zhang & Yupeng Liu & Ning
Luo & Daoai Wang
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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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 From insinuations he proceeded to open accusations. After
having kept himself secluded for a fortnight, he one day appeared in
the public fold and proclaimed that he had at last discovered the
cause of the drought. After keeping the audience in suspense for a
short time, he suddenly broke forth: “Do you not see,” he asked,
“when the clouds cover us, that Hamilton and Moffat look at them?
Their white faces scare them away, and you cannot expect rain so
long as they are in the country.” This was a home stroke. The people
became impatient, and poured forth their curses against the poor
missionaries as the cause of all their sorrows. The bell which was
rung for public worship, they said, frightened the vapours; the
prayers even came in for a share of the blame. “Don’t you,” said the
chief one day rather fiercely to Mr. Moffat, “bow down in your houses
and pray, and talk to something bad in the ground?”
But to shorten a long story, after exposing the missionaries to
much risk and danger by his insinuations and accusations, the tables
were turned in their favour. The rain-maker now was suspected, his
gross impositions were unveiled, and he was about to pay the
penalty of death,—the well-merited reward for his scandalous
conduct, when Mr. Moffat generously interfered, and through his
presence of mind and humanity succeeded in saving the life of one
who had so often threatened his own, and who would not have
scrupled to take it could he thereby have served his purpose. Death,
however, soon overtook him, for he was eventually murdered
amongst the Bauangketsi nation.
There is scarcely a savage country on the face of the earth but
has its professional rain-makers; Figi has; and these, like other
players of a game of chance, occasionally win in a manner that
seems surprising even to an educated European.
During Mr. Seeman’s stay in Figi, one of the days was rainy,
preventing him from making an excursion. On expressing his regret
to that effect, a man was brought who may be called the clerk of the
weather. He professed to exercise a direct meteorological influence,
and said that, by burning certain leaves and offering prayers only
known to himself, he could make the sun shine or rain come down;
and that he was willing to exercise his influence on Mr. Seeman’s
behalf if paid handsomely. He was told that there was no objection to
giving him a butcher’s knife if he could make fine weather until the
travellers returned to the coast; but if he failed to do so, he must give
something for the disappointment. He was perfectly willing to risk the
chance of getting the knife, but would not hear of a forfeit in case of
failure; however, he left to catch eels. “When returning,” says Mr.
Seeman, “the clouds had dispersed, and the sun was shining
brilliantly, and he did not fail to inform me that he had ‘been and
done it.’ I must farther do him the justice to say, that I did not
experience any bad weather until I fairly reached the coast; and that
no sooner had I set my foot in Navua than rain came down in regular
torrents. This man has probably been a close observer of the
weather, and discovered those delicate local indications of a coming
change with which people in all countries living much in the open air
are familiar; and he very likely does not commence operations until
he is pretty sure of success.”
This was not the only singular ceremony witnessed by the
gentleman just quoted, and who is the most recent of Figian
travellers. While out one day he and his friends met a company of
natives, and were struck with the fact that all the young lads were in
a state of absolute nudity; and, on inquiry, learned that preparations
were being made to celebrate the introduction of Kurudwadua’s
eldest son into manhood; and that until then neither the young
chieftain nor his playmates could assume the scanty clothing
peculiar to the Figians. Suvana, a rebellious town, consisting of
about five hundred people, was destined to be sacrificed on the
occasion. When the preparations for the feast were concluded, the
day for the ceremony appointed, Kurudwadua and his warriors were
to make a rush upon the town and club the inhabitants
indiscriminately. The bodies were to be piled into one heap, and on
the top of all a living slave would lie on his back. The young chief
would then mount the horrid scaffold, and standing upright on the
chest of the slave, and holding in his uplifted hands an immense club
or gun, the priests would invoke their gods, and commit the future
warrior to their especial protection, praying he may kill all the
enemies of the tribe, and never be beaten in battle; a cheer and a
shout from the assembled multitude concluding the prayer. Two
uncles of the boy were then to ascend the human pile, and to invest
him with the malo or girdle of snow white tapa; the multitude again
calling on the deities to make him a great conqueror, and a terror to
all who breathe enmity to Navua. The malo for the occasion would
be, perhaps, two hundred yards long, and six or eight inches wide.
When wound round the body the lad would hardly be perceivable,
and no one but an uncle can divest him of it.
“We proposed,” says Mr. Seeman, “to the chief that we should be
allowed to invest his son with the malo, which he at first refused, but
to which he consented after deliberation with his people. At the
appointed hour the multitude collected in the great strangers’ house
or bure ni sa. The lad stood upright in the midst of the assembly
guiltless of clothing, and holding a gun over his head. The consul
and I approached, and in due form wrapped him up in thirty yards of
Manchester print, the priest and people chanting songs and invoking
the protection of their gods. A short address from the consul
succeeded, stirring the lad to nobler efforts for his tribe than his
ancestors had known, and pointing to the path of fame that
civilization opened to him. The ceremony concluded by drinking
kara, and chanting historical reminiscences of the lad’s ancestors;
and thus we saved the lives of five hundred men. During the whole
of this ceremony the old chief was much affected, and a few tears
might be seen stealing down his cheeks; soon, however, cheering
up, he gave us a full account of the time when he came of age, and
the number of people that were slain to celebrate the occasion.”
To return, however, to the rain-making business. Lucky is it for the
dim-minded heathen that these false priests of his have not the
advantage of studying for their profession either in England or
America; if it were so, heaven only knows the awful extent to which
they would be bamboozled. Rain-makers especially would have a
fine time of it, at least, if they were all as clever as Mr. Petherick,
who, in his “Egypt and the Soudan,” unblushingly narrates how he
“Barnumized” the Africans as a rain-maker.
“The rainy season was now approaching, and still no tidings of my
men, and the natives daily continued to surround my encampment,
and attempted, sometimes by the report of the murder of my men,
and at others by night attacks upon ourselves when in the darkness
we could not see them, to induce us to return to our boats and
abandon our property. This they more strenuously insisted on, as
they were convinced that as long as we remained in the country the
rain would not fall, and both themselves and their cattle would be
reduced to starvation. This idea being seriously entertained, I one
day plainly stated to the chief and several of the principal men the
absurdity of their assertions, and endeavoured to explain that God
alone,—who had created heaven and earth,—could exercise any
power over the elements. The attention with which my discourse was
received induced me to prolong it, but to my discomfiture, at its
close, it was treated as a capital joke, and only convinced them the
more that I endeavoured to conceal from them my own powers.
Finding no relief from their increasing persecutions, I at length was
reduced to a ruse; and after a reference to an antiquated Weekly
Times, I told them that the Supreme Being whose it was to afford
them the so much-required rains, withheld them in consequence of
their inhospitality towards myself; this, although it had the effect of
procuring increased temporary supplies, could not induce them to
furnish me with porters. Endless were the straits and absurdities to
which I had recourse in order to obtain a respite, but the one creating
the greatest amusement to myself and my followers was the
following. A deputation of several hundred men, headed by a
subchief, from their kraals some miles distant, in the most
peremptory manner demanded rain or my immediate departure; the
latter they were determined at whatever sacrifice to enforce. Placing
my men under arms in an enclosure, and with a pair of revolver
pistols at my waist, and a first-rate Dean and Adams’ revolver rifle in
my hand, I went into the midst of them, and seated myself in the
centre of them, opposite to the subchief, a man fully six feet six
inches high, and proportionably well made. I stated that no
intimidation could produce rain, and as to compelling me to withdraw,
I defied them; that if I liked, with one single discharge of my gun, I
could destroy the whole tribe and their cattle in an instant; but that
with regard to rain, I would consult my oracle, and invited them to
appear before me to-morrow, upon which, with as much dignity as I
could command, I withdrew. Various were the feelings of the
savages. Some expressed a wish to comply with my desire, whilst
others showed an inclination to fall upon me. Although I was
convinced that the chief, Tschol, secretly encouraged his men, he in
the present instance made a demonstration in my favour; he
threatened them with a curse unless they dispersed. Some device
now became necessary to obtain a further respite for the desired
rains; and setting my wits to work, I hit upon an expedient which I at
once put in execution. Despatching some men to catch half-a-dozen
large flies, bearing some resemblance to a horse-fly, but much
larger, which infested a temporary shed where my donkey had been
kept; the men, confident in the success of anything I undertook, set
about the task with a will. In the course of the afternoon they were
fortunately obtained, and were consigned to an empty bottle. At the
appointed time my persecutors did not fail to appear, and shaking a
little flower over my flies, I sallied out amongst them, bottle in hand.
Referring to their wants, I treated them to a long harangue, touching
the depredations which I had learnt in conversation with the chief
they had committed upon the cattle of neighbouring tribes, and
assassinations of unoffending men who had fallen into their power;
also to several abstractions of girls from poor unprotected families of
their own tribe, without the payment of the customary dowry in cattle,
and dwelt upon the impossibility of their obtaining rain until restitution
and satisfaction were made. They unanimously denied the charges;
when I told them that it was nothing less than I had expected, but
that I was furnished with the means of satisfying myself of the
veracity of their assertions. The proof would consist in their restoring
to me the flies, which I intended to liberate from the bottle I held. In
the event of their succeeding, they should be rewarded with
abundant rain; but if one fly escaped, it was a sign of their guilt, and
they would be punished with a continuation of drought until
restitution was made; therefore it was in their own power to procure
rain or otherwise. Hundreds of clubs and lances were poised high in
the air, amidst loud shouts of ‘Let them go! let them go! let them go!’
With a prayer for the safety of my flies, I held up the bottle, and
smashing it against the barrel of my rifle, I had the satisfaction of
seeing the flies in the enjoyment of their liberty. Man, woman, and
child gave chase in hot pursuit, and the delight of my men at the
success of the stratagem may be imagined. It was not until after the
sun had set that the crest-fallen stragglers returned, their success
having been limited to the capture of two of the flies, though several
spurious ones, easily detected by the absence of the distinctive flour
badge, were produced. A long consultation ensued, and in the firm
belief of my oracle they determined to adopt measures for the
carrying out of its requirements, but with a threat that if the promised
rain did not follow, I should incur their vengeance. Aware of the
difficulties in store for them from their unwillingness to part with cattle
under any circumstances, I promised myself a long cessation from
their molestations. I was not disappointed.”
Further still into the country, and still no sign of amendment; not
that it should be expected, as in this region—Equatorial Africa—the
Christian crusader never yet penetrated, unless indeed we so regard
Mr. Du Chaillu, who certainly appears to have done his best by
example, at least, to convince the barbarous people among whom
he found himself of the advantages of Christianity. Here is a sample
of one of many Sabbaths spent by the renowned gorilla hunter
amongst the savages here abiding.
“The next day was Sunday, and I remained quietly in my house
reading the Scriptures, and thankful to have a day of rest and
reflection. My hunters could scarcely be prevailed upon not to hunt;
they declared that Sunday might do for white people, but the blacks
had nothing to do with it. Indeed, when customs thus come in
contact, the only answer the negro has to make—and it applies to
everything—is, that the God who made the whites is not the God
who made the blacks.
“Then the king and a good many of his people gathered about me,
and we astonished each other with our talk. I told them that their
fetishes and greegrees were of no use and had no power, and that it
was absurd to expect anything of a mere wooden idol that a man
had made, and could burn up. Also that there was no such a thing as
witchcraft, and that it was very wrong to kill people who were
accused of it; that there was only one God, whom the whites and
blacks must alike love and depend on. All this elicited only grunts of
surprise and incredulity.
 “Then the king took up the conversation, and remarked that we
white men were much favoured by our God, who was so kind as to
send guns and powder from heaven.
“Whereupon the king’s brother remarked that it must be very fine
to have rivers of alougou (rum) flowing through our country all the
year round, and that he would like to live on the banks of such a
river.
“Hereupon I said that we made our own guns, which no one
present seemed to believe; and that there were no rivers of rum,
which seemed a disappointment to several.”
It would appear that our traveller betrayed at least as much
curiosity respecting the singular rites and superstitions of these
Equatorial African heathens as they evinced in the matter of
Christianity.
“One day the women began their peculiar worship of Njambai,
which it seems is their good spirit: and it is remarkable that all the
Bakalai clans and all the females of tribes I have met during my
journeys, worship or venerate a spirit with this same name. Near the
seashore it is pronounced Njembai, but it is evidently the same.
“This worship of the women is a kind of mystery, no men being
admitted to the ceremonies, which are carried on in a house very
carefully closed. This house was covered with dry palm and banana
leaves, and had not even a door open to the street. To make all
close, it was set against two other houses, and the entrance was
through one of these. Quengueza and Mbango warned me not to go
near this place, as not even they were permitted so much as to take
a look. All the women of the village painted their faces and bodies,
beat drums, marched about the town, and from time to time entered
the idol house, where they danced all one night, and made a more
outrageous noise than even the men had made before. They also
presented several antelopes to the goddess, and on the 4th, all but a
few went off into the woods to sing to Njambai.
“I noticed that half-a-dozen remained, and in the course of the
morning entered the Njambai house, where they stayed in great
silence. Now my curiosity, which had been greatly excited to know
what took place in this secret worship, finally overcame me. I
determined to see. Walking several times up and down the street
past the house to allay suspicion, I at last suddenly pushed aside
some of the leaves, and stuck my head through the wall. For a
moment I could distinguish nothing in the darkness. Then I beheld
three perfectly naked old hags sitting on the clay floor, with an
immense bundle of greegrees before them, which they seemed to be
silently adoring.

Du Chaillu’s Peep into a Heathen Temple.

“When they saw me they at once set up a hideous howl of rage,
and rushed out to call their companions from the bush; in a few
minutes these came hurrying in, crying and lamenting, rushing
towards me with gestures of anger, and threatening me for my
offence. I quickly reached my house, and seizing my gun in one
hand and a revolver in the other, told them I would shoot the first one
that came inside my door. The house was surrounded by above
three hundred infuriated women, every one shouting out curses at
me, but the sight of my revolver kept them back. They adjourned
presently for the Njambai house, and from there sent a deputation of
the men, who were to inform me that I must pay for the palaver I had
made.
“This I peremptorily refused to do, telling Quengueza and Mbango
that I was there a stranger, and must be allowed to do as I pleased,
as their rules were nothing to me, who was a white man and did not
believe in their idols. In truth, if I had once paid for such a
trangression as this, there would have been an end of all travelling
for me, as I often broke through their absurd rules without knowing it,
and my only course was to declare myself irresponsible.
“However, the women would not give up, but threatened
vengeance, not only on me, but on all the men of the town; and as I
positively refused to pay anything, it was at last, to my great surprise,
determined by Mbango and his male subjects, that they would make
up from their own possessions such a sacrifice as the women
demanded of me. Accordingly Mbango contributed ten fathoms of
native cloth, and the men came one by one and put their offerings on
the ground; some plates, some knives, some mugs, some beads,
some mats, and various other articles. Mbango came again, and
asked if I too would not contribute something, but I refused. In fact, I
dared not set such a precedent. So when all had given what they
could, the whole amount was taken to the ireful women, to whom
Mbango said that I was his and his men’s guest, and that they could
not ask me to pay in such a matter, therefore they paid the demand
themselves. With this the women were satisfied, and there the
quarrel ended. Of course I could not make any further investigations
into their mysteries. The Njambai feast lasts about two weeks. I
could learn very little about the spirit which they call by this name.
Their own ideas are quite vague. They know only that it protects the
women against their male enemies, avenges their wrongs, and
serves them in various ways, if they please it.”
Before Chaillu left Goumbi a grand effort was made by the people
to ascertain the cause of their king’s sufferings. Quengueza had sent
word to his people to consult Ilogo, a spirit said to live in the moon.
The rites were very curious. To consult Ilogo, the time must be near
full moon. Early in the evening the women of the town assembled in
front of Quengueza’s house and sang songs to and in praise of the
moon. Meantime a woman was seated in the centre of the circle of
singers, who sung with them and looked constantly towards the
moon. She was to be inspired by the spirit and to utter prophecies.
Two women made trial of this post without success. At last came
a third, a little woman, wiry and nervous. When she seated herself,
the singing was redoubled in fury—the excitement of the people had
had time to become intense; the drums beat, the outsiders shouted
madly. Presently the woman who, singing violently, had looked
constantly towards the moon, began to tremble. Her nerves twitched,
her face was contorted, her muscles swelled, and at last her limbs
straightened out, and she lay extended on the ground insensible.
The excitement was now intense and the noise horrible. The
songs to Ilogo were not for a moment discontinued. The words were
little varied, and were to this purport:

“Ilogo, we ask thee,

Tell who has bewitched the king!
Ilogo, we ask thee,
What shall we do to cure the king?
The forests are thine, Ilogo!
The rivers are thine, Ilogo!
The moon is thine.
O moon! O moon! O moon!
Thou art the house of Ilogo.
Shall the king die, O Ilogo?
O Ilogo! O moon! O moon!”

These words were repeated again and again with little variation.
The woman who lay for some time as she had fallen was then
supposed to be able to see things in the world of Ilogo, and was
brought to after half an hour’s insensibility; she looked very much
prostrated. She averred that she had seen Ilogo, that he had told her
Quengueza was not bewitched.
Chaillu heard one day by accident that a man had been
apprehended on a charge of causing the death of one of the chief
men of the village, and went to Dayoko, the king, and asked about it.
He said yes, the man was to be killed; that he was a notorious
wizard, and had done much harm.
Chaillu begged to see this terrible being, and was taken to a
rough hut, within which sat an old, old man, with wool white as snow,
wrinkled face, bowed form, and shrunken limbs. His hands were tied
behind him, and his feet were placed in a rude kind of stocks. This
was the great wizard. Several lazy negroes stood guard over him,
and from time to time insulted him with opprobrious epithets and
blows, to which the poor old wretch submitted in silence. He was
evidently in his dotage.
When asked if he had no friends, no relatives, no son or daughter
or wife to take care of him, he said sadly, “No one.”
Now here was the secret of this persecution. They were tired of
taking care of the helpless old man, who had lived too long, and a
charge of witchcraft by the greegree man was a convenient pretext
for putting him out of the way.
 The Wizard in the Stocks.
Chaillu went, however, to Dayoko, and argued the case with him,
and tried to explain the absurdity of charging a harmless old man
with supernatural powers; told him that God did not permit witches to
exist, and dually made an offer to buy the old wretch, offering to give
some pounds of tobacco, one or two coats, and some looking-
glasses for him, goods which would have bought an able-bodied
slave.
 Dayoko replied that for his part he would be glad to save him, but
that the people must decide; that they were much excited against
him, but that he would, to please Chaillu, try to save his life.
During the night following our travellers heard singing all over the
town all night, and a great uproar. Evidently they were preparing
themselves for the murder. Even these savages cannot kill in cold
blood, but work themselves into a frenzy of excitement first, and then
rush off to do the bloody deed.
Early in the morning the people gathered together with the fetish
man, the rascal who was at the bottom of the murder, in their midst.
His bloodshot eyes glared in savage excitement as he went round
from man to man getting the votes to decide whether the old man
should die.
In his hands he held a bundle of herbs, with which he sprinkled
three times those to whom he spoke. Meantime a man was stationed
on the top of a high tree, whence he shouted from time to time in a
loud voice, “Jocoo! Jocoo!” at the same time shaking the tree
strongly.
Jocoo is devil among the Mbousha, and the business of this man
was to keep away the evil spirit, and to give notice to the fetish-man
of his approach.
At last the sad vote was taken. It was declared that the old man
was a most malignant wizard, that he had already killed a number of
people, that he was minded to kill many more, and that he must die.
No one would tell Chaillu how he was to be killed, and they proposed
to defer the execution till his departure. The whole scene had
considerably agitated Chaillu, and he was willing to be spared the
end. Tired and sick at heart, Chaillu lay down on his bed about noon
to rest and compose his spirits a little. After a while he saw a man
pass his window, almost like a flash, and after him a horde of silent
but infuriated men. They ran towards the river. Then in a little while
was heard a couple of sharp piercing cries, as of a man in great
agony, and then all was still as death. Chaillu got up, guessing the
rascals had killed the poor old man, and turning his steps toward the
river, was met by the crowd returning, every man armed with axe,
knife, cutlass, or spear, and these weapons and their own hands and
arms and bodies all sprinkled with the blood of their victim. In their
frenzy they had tied the poor wizard to a log near the river bank, and
then deliberately hacked him into many pieces. They finished by
splitting open his skull and scattering the brains in the water. Then
they returned; and to see their behaviour, it would have seemed as
though the country had just been delivered from a great curse.
By night the men, whose faces for two days had filled Chaillu with
loathing and horror, so bloodthirsty and malignant were they, were
again as mild as lambs, and as cheerful as though they had never
heard of a witch tragedy.
The following is a fair sample of “witch-test,” as practised in this
region. A Gaboon black trader in the employment of a white
supercargo, died suddenly. His family thinking that the death had
resulted from witchcraft, two of his sisters were authorised to go to
his grave and bring his head away in order that they might test the
fact. This testing is effected in the following manner: An iron pot with
fresh water is placed on the floor; at one side of it is the head of the
dead man, at the other side is seated a fetish doctor. The latter
functionary then puts in his mouth a piece of herb, supposed to
impart divining powers, chews it, and forms a magic circle by spitting
round the pot, the head, and himself. The face of the murderer, after
a few incantations, is supposed to be reflected on the water
contained in the pot. The fetish man then states he sees the
murderer, and orders the head to be again put back to its proper
grave, some days being then given to him for deliberation. In the
mean time he may fix on a man who is rich enough to pay him a
sufficient bribe to be excused of the charge, and if so he confesses
that the fetish has failed.
In the central regions of Eastern Africa all that is sacerdotal is
embodied in individuals called Mganga or Mfumbo. They swarm
throughout the land; are of both sexes: the women, however,
generally confine themselves to the medical part of the profession.
The profession is hereditary; the eldest or the cleverest son begins
his education at an early age, and succeeds to his father’s functions.
There is little mystery, says Burton, in the craft, and the magicians of
Unyamwezi have not refused to initiate some of the Arabs. The
power of the Mganga is great; he is treated as a sultan, whose word
is law, and as a giver of life and death. He is addressed by a kingly
title, and is permitted to wear the chieftain’s badge, made of the base
of a conical shell. He is also known by a number of small greasy and
blackened gourds filled with physic and magic hanging round his
waist, and by a little more of the usual grime, sanctity and dirt being
closely connected in Africa. These men are sent for from village to
village, and receive as spiritual fees sheep and goats, cattle and
provisions. Their persons, however, are not sacred, and for criminal
acts they are punished like other malefactors. The greatest danger to
them is an excess of fame. A celebrated magician rarely, if ever, dies
a natural death; too much is expected from him, and a severe
disappointment leads to consequences more violent than usual.
The African phrase for a man possessed is ana’p’hepo, he has a
devil. The Mganga is expected to heal the patient by expelling the
possession. Like the evil spirit in the days of Saul, the unwelcome
visitant must be charmed away by sweet music; the drums cause
excitement, the violent exercise expels the ghost. The principal
remedies are drumming, dancing, and drinking till the auspicious
moment arrives. The ghost is then enticed from the body of the
possessed into some inanimate article which he will condescend to
inhabit. This, technically called a Keti or stool, may be a certain kind
of bead, two or more bits of wood bound together by a strip of
snake’s skin, a lion’s or a leopard’s claw, and other similar articles
worn round the head, the arm, the wrist, or the ankle. Paper is still
considered great medicine by the Wasukuma and other tribes, who
will barter valuable goods for a little bit: the great desideratum of the
charm in fact appears to be its rarity, or the difficulty of obtaining it.
Hence also the habit of driving nails into and hanging rags upon
trees. The vegetable itself is not worshipped, as some Europeans,
who call it the devil’s tree, have supposed; it is merely the place for
the laying of ghosts, where by appending the keti most acceptable to
the spirit, he will be bound over to keep the peace with man. Several
accidents in the town of Zanzibar have confirmed even the higher
orders in their lurking superstition. Mr. Peters, an English merchant,
annoyed by the slaves, who came in numbers to hammer nails and
to hang iron hoops and rags upon a devil’s tree in his court-yard,
ordered it to be cut down, to the horror of all the black beholders.
Within six months five persons died in that house—Mr. Peters, his
two clerks, his cooper, and his ship’s carpenter. Salim bin Raschid, a
half caste merchant, well known at Zanzibar, avers, and his
companions bear witness to his words, that on one occasion, when
travelling northwards from Unyamzembe, the possession occurred to
himself. During the night two female slaves, his companions, of
whom one was a child, fell without apparent cause into the fits which
denote the approach of a spirit. Simultaneously the master became
as one intoxicated; a dark mass—material, not spiritual—entered the
tent, threw it down, and presently vanished, and Salim bin Raschid
was found in a state of stupor, from which he did not recover till the
morning. The same merchant circumstantially related, and called
witnesses to prove, that a small slave boy, who was produced on the
occasion, had been frequently carried off by possession, even when
confined in a windowless room, with a heavy door carefully bolted
and padlocked. Next morning the victim was not found although the
chamber remained closed. A few days afterwards he was met in the
jungle, wandering absently, like an idiot, and with speech too
incoherent to explain what had happened to him. The Arabs of Iman
who subscribe readily to transformation, deride these tales; those of
African blood, believe them. The transformation belief, still so
common in many countries, and anciently an almost universal
superstition, is, curious to say, unknown amongst these East African
tribes.
The Mganga, Mr. Burton further informs us, is also a soothsayer.
He foretels the success, or failure of commercial undertakings, of
wars, and of kidnapping; he foresees famine and pestilence, and he
suggests the means of averting calamities. He fixes also before the
commencement of any serious affair fortunate conjunctions, without
which, a good issue cannot be expected. He directs, expedites, or
delays the march of a caravan; and in his quality of augur, he
considers the flight of birds, and the cries of beasts like his prototype
of the same class, in ancient Europe, and in modern Asia.
 The principal instrument of the Mganga’s craft is one of the dirty
little buyou, or gourds, which he wears in a bunch round his waist,
and the following is the usual programme when the oracle is to be
consulted. The magician brings his implements in a bag of matting;
his demeanour is serious as the occasion, he is carefully greased,
and his head is adorned with the diminutive antelope horns, fastened
by a thong of leather above the forehead. He sits like a sultan, upon
a dwarf stool in front of the querist, and begins by exhorting the
highest possible offertory. No pay no predict. The Mganga has many
implements of his craft. Some prophesy by the motion of berries
swimming in a cup full of water, which is placed upon a low stool,
surrounded by four tails of the zebra, or the buffalo, lashed to stakes
planted upright in the ground. The Kasanda is a system of folding
triangles, not unlike those upon which plaything soldiers are
mounted. Held in the right hand, it is thrown out, and the direction of
the end points to the safe and auspicious route; this is probably the
rudest appliance of prestidigitation. The shero is a bit of wood, about
the size of a man’s hand, and not unlike a pair of bellows, with a
dwarf handle, a projection like a muzzle, and in a circular centre a
little hollow. This is filled with water, and a grain, or fragment of wood
placed to float, gives an evil omen if it tends towards the sides, and
favourable if it veers towards the handle or the nozzle. The Mganga
generally carries about with him, to announce his approach, a kind of
rattle. This is a hollow gourd of pine-apple, pierced with various
holes prettily carved, and half filled with maize grains, and pebbles;
the handle is a stick passed through its length, and secured by
cross-pins.
The Mganga has many minor duties. In elephant hunts he must
throw the first spear, and endure the blame if the beast escapes. He
marks ivory with spots disposed in lines and other figures, and thus
enables it to reach the coast, without let or hindrance. He loads the
kirangoze, or guide, with charms to defend him from the malice
which is ever directed at a leading man, and sedulously forbids him
to allow precedence even to the Mtongi, the commander and
proprietor of the caravan. He aids his tribe by magical arts, in wars
by catching a bee, reciting over it certain incantations, and loosing it
in the direction of the foe, when the insect will instantly summon an
army of its fellows and disperse a host however numerous. This
belief well illustrates the easy passage of the natural into the
supernatural. The land being full of swarms, and man’s body being
wholly exposed, many a caravan has been dispersed like chaff
before the wind by a bevy of swarming bees. Similarly in South
Africa the magician kicks an ant-hill, and starts wasps which put the
enemy to flight.
Here is an account of a queer dance witnessed in this land of
Mgangas and Mfumbos and fetishes, furnished by the celebrated
explorer Bakie:—“A little before noon Captain Vidal took leave of
King Passol, in order to prosecute his observations. I remained, but
shortly afterwards prepared to leave also. Passol, however, as soon
as he perceived my intention, jumped up, and in a good-humoured
way detaining me by the arm, exclaimed, ‘No go, no go yet; ‘top a
little; bye-bye you look im fetish dance; me mak you too much laugh!’
It appeared that the old man had heard me some time before, on
listening to the distant tattoo of a native drum, express a
determination to the young midshipman who was with me to go
presently to see the dance, with which I had little doubt that it was
accompanied. The noise of the drum, almost drowned by the
singing, whooping, and clamour of a multitude of the natives, was
soon heard approaching. When close to us the procession stopped,
and the dancers, all of whom were men, ranged themselves in
parallel lines from the front of an adjoining house, and commenced
their exhibition. They were specially dressed for the purpose, having
suspended from their hips a complete kilt formed of threads of grass-
cloth, manufactured by the natives of the interior, and likewise an
appendage of the same kind to one or both arms, just above the
elbow. Some had their faces and others their breasts marked with
white balls, given to them by the fetish as a cure or safeguard
against some disease which they either had or dreaded. The
dancing, although not elegant, was free from that wriggling and
contortion of body so common on the east coast. It consisted
principally in alternately advancing and drawing back the feet and
arms, together with a corresponding inclination of the body, and, at
stated times, the simultaneous clapping of hands, and a loud sharp
ejaculation of ‘Heigh!’ Although I have remarked that it was not
elegant, yet it was pleasing, from the regularity with which it was
accompanied. There were two men who did not dance in the line
among the rest, but shuffled around, and at times threaded the
needle among them: one was termed the master fetish, and the
other appeared to be his attendant; neither wore the fancy dress, but
they were both encircled by the usual wrapper round the loins. The
former had on a French glazed hat, held in great request by the
natives, and the other, chewing some root of a red colour, carried a
small ornamented stick, surmounted at the end like a brush with a
bunch of long and handsome feathers. At times one of these men
would stop opposite a particular individual among the dancers, and
entice him by gestures to leave the line and accompany him in his
evolutions, which finally always ended where they began, the
pressed man returning to his former place. For some time I had
observed the master fetish dancing opposite to the house, and with
many gesticulations apparently addressing it in a half threatening
half beseeching tone. Old Passol, who was standing close by me,
suddenly exclaimed, ‘Now you laugh too much; fetish he come!’
“Sure enough, forthwith rushed from the house among the
dancers a most extraordinary figure. It was a man mounted on stilts
at least six feet above the ground, of which from practice he had
acquired so great a command that he certainly was as nimble in his
evolutions as the most active among the dancers. He was
sometimes so quick that one stilt could hardly be seen to touch the
earth before it was relieved by the other. Even when standing still he
often balanced himself so well as not to move either stilt for the
space of two or three minutes. He wore a white mask with a large
red ball on each cheek, the same on his chin, and his eyebrows and
the lower part of his nose were painted with the same colour. Over
his forehead was a sort of vizor of a yellow colour, having across it a
line of small brass bells; it was armed in front by long alligator’s
teeth, and terminated in a confused display of feathers, blades of
grass, and the stiff hairs of elephants and other large animals. From
the top of his head the skin of a monkey hung pendant behind,
having affixed to its tail a wire and a single elephant’s hair with a
large sheep’s bell attached to the end. The skin was of a beautiful
light green, with the head and neck of a rich vermilion. From his
shoulders a fathom of blue dungaree with a striped white border
hung down behind; and his body and legs and arms were completely
enshrouded in a number of folds of the native grass-cloth, through
which he grasped in each hand a quantity of alligator’s teeth, lizard’s
skins, fowl’s bones, feathers, and stiff hairs, reminding me strongly of
the well-known attributes of Obi, the dread of the slave-owners of
Jamaica.
“The fetish never spoke. When standing still he held his arms
erect, and shook and nodded his head with a quick repetition; but
when advancing he extended them to their full length before him. In
the former case he appeared as if pointing to heaven, and
demanding its vengeance on the dancers and the numerous
bystanders around; and in the latter as one who, finding his
exhortations of no avail, was resolved to exterminate, in the might of
his gigantic stature and superior strength, the refractory set. The
master fetish was his constant attendant, always following, doubling,
and facing him, with exhortations uttered at one minute in the most
beseeching tone, accompanied hat in hand by obsequious bows,
and in the next threatening gestures, and violent, passionate
exclamations. The attendant on the master fetish was likewise
constantly at hand, with his stick applied to his mouth, and in one or
two instances when the masquerader approached, he crouched
close under him, and squirted the red juice of the root he was
chewing into his face. For upwards of an hour I watched the dance,
yet the fetish appeared untired; and I afterwards heard that the same
ceremony was performed every day, and sometimes lasted three or
four hours. I at first thought that it was merely got up for our
amusement, but was soon undeceived; and when, under the first
impression, I inquired of a bystander what man it was who performed
the character, he answered, with a mixture of pique at the question
and astonishment of my ignorance, ‘He no man; no man do same as
him; he be de diable! he be de debil!’ Still I was a little sceptic as to
their really holding this belief themselves, though they insisted on the
fact as they represented it to me; and therefore, after I had received
the same answer from all, I used to add in a careless way to try their
sincerity, ‘In what house does he dwell?’ ‘What! fetish! I tell you he
de debil; he no catch house; he lib (live) in dat wood,’ pointing to a