A novel TiO2 nanotube arrays/MgTixOy

multiphase-heterojunction film with

high efficiency for
photoelectrochemical cathodic
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 Corrosion Science 166 (2020) 108441

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

A novel TiO2 nanotube arrays/MgTixOy multiphase-heterojunction film with T

high efficiency for photoelectrochemical cathodic protection
Chang Fenga,b,c,d,e, Zhuoyuan Chena,c,d,e,*, Jiangping Jinga,d,e, Mengmeng Suna,d,e,
Guiying Lua,b,d,e, Jing Tiana,b,d,e, Jian Houc
a
Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, 7 Nanhai Road, Qingdao 266071, China
b
University of Chinese Academy of Sciences, 19 (Jia) Yuquan Road, Beijing 100049, China
c
State Key Laboratory for Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Wenhai Road, Qingdao 266237, China
d
Center for Ocean Mega-Science, Chinese Academy of Sciences, 7 Nanhai Road, Qingdao 266071, China
e
Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology (Qingdao), No. 1 Wenhai Road, Qingdao, 266237, China

ARTICLE INFO ABSTRACT

Keywords: Heterojunction engineering, as a rising star in the photoelectrochemical cathodic protection (PECCP) field,
A. TiO2/MgTixOy contributes to promote the separation of the photoinduced electrons and holes. In this paper, the TiO2/MgTixOy
A. Multiphase-heterojunction film multiphase-heterojunction film was prepared and its PECCP performance was studied. Due to a good energy
B. SKP band alignment gradient formed between the multiphases, the separation efficiency of the photoinduced elec-
C. Photoelectrochemical cathodic protection
trons and holes generated by TiO2/MgTixOy are dramatically enhanced, leading to its good PECCP performance
C. Stability
and high stability. SKP is, for the first time, used to study the surface work function of the TiO2/MgTixOy
multiphase-heterojunction film for characterizing its PECCP performance.

1. Introduction excited photogenerated electrons for PECCP.

As a promising green technology, photocatalysis and photoelec-
trochemistry are extensively studied and used in the fields of environ-
ment and energy [1–6]. As an important branch of photocatalysis and
photoelectrochemistry, the photoelectrochemical cathodic protection
(PECCP) technology uses the separated photoinduced electrons gener-
ated by semiconductor materials and transfers them to the coupled
metal to provide cathodic protection. This is an effective way to protect
metallic materials using solar energy. During the PECCP process, the
photoelectric conversion semiconductor material will not be consumed
and thus this technology will not pollute the environment. Meanwhile,
the control synthesis of the photoelectrode is relatively simple and the
cost is low [7,8]. Therefore, the PECCP technology is a promising, green
and environmentally friendly corrosion protection technology with a
great application potential [9,10]. TiO2 [11,12], ZnO [13,14], g-C3N4
[15], SrTiO3 [16,17] etc. are common semiconductor materials with
good PECCP performance. However, a single photoelectric conversion
semiconductor material tends to have a fast recombination rate of the
photogenerated electrons and holes, enabling less photoinduced elec-
trons to be effectively utilized for PECCP. Therefore, further modifica-
tions of the photoelectric conversion semiconductor material is of great
significance to realize the sustainable and effective utilization of the
As an effective way to significantly inhibit the recombination of the
photogenerated electrons and holes, heterojunction engineering has
been reported to achieve effective separation of the photogenerated
electrons and holes [18–20], and to efficiently transfer the photo-
generated electrons to the coupled metals, thereby enhancing the
PECCP performance of semiconductor materials. The reported hetero-
junction systems, such as SrTiO3/TiO2 [21,22], Bi2X3/TiO2 (X is S or O)
[23,24], In2O3/TiO2 [25], SnO2/TiO2 [26], WO3/TiO2 [27,28], Ag2S/
TiO2 [29], Ni2S3/TiO2 [30], N-doped TiO2/TiO2 [31], BiVO4/TiO2
[32], ZnInS/TiO2 [33], Co3O4/ZnO [34], ZnxMg1-xO/ZnO [35], g-C3N4/
ZnO [36], TiO2/ZnO [37], g-C3N4/In2O3 [38], etc., show significant
improvements in the PECCP performance. Although the establishment
of heterojunctions can significantly improve the PECCP performance of
composite heterojunction materials, its long-term stability is still a big
challenge. Bu et al. have systematically reported the PECCP mechanism
for steel using the SrTiO3/TiO2 composite photoelectrodes [21]. How-
ever, the stability of the photoelectrodes applied for the PECCP showed
obvious shortcomings [21]. Sun et al. have investigated the enhanced
PECCP performance of the In2O3/TiO2 composite [25]. The stability
testing was still an important part to be further verified. Kuang et al.
have designed a dual-functional ZnxMg1-xO solid solution nanolayer
modified ZnO tussock-like nanorods to apply for the PECCP [35]. The

⁎
Corresponding author.
E-mail address: zychen@qdio.ac.cn (Z. Chen).

https://doi.org/10.1016/j.corsci.2020.108441
Received 18 October 2019; Received in revised form 31 December 2019; Accepted 4 January 2020
Available online 08 January 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
C. Feng, et al.
stability of the performance was an important factor that bothers them
in choosing the best photoelectrode. Accordingly, how to design a
photoelectrode with high PECCP activity and stability is still an urgent
issue to be solved. As can be well known, the establishment of multi-
phase heterojunctions can effectively accelerate the separation of the
photogenerated charge carriers [39–43]. A well band alignment formed
among the multi-heterojunctions can provide a larger charge carrier
transfer gradient [39], which can significantly inhibit the secondary
recombination of the photogenerated electrons and holes. And, this
provides an idea to design an efficient and stable photoelectrode ap-
plied for PECCP.
In addition, the scanning kelvin probe (SKP) testing system is con-
sidered to be a novel micro-electrochemical technology which can
measure the surface work function (WF) of a material. It has been
widely used in the fields of metallic corrosion, coatings, solar cells and
photocatalysis [44–51]. On one hand, SKP technology can be used to
record the surface potential of the material and observe the potential
distribution of different components in the micro-region. On the other
hand, the surface potential distribution measured by SKP technology
can be transformed into surface WF, which can be used to analyze the
capability of the surface electrons escaping from the material and study
the application in electrochemistry and photoelectrochemistry. Hua
et al. have used the SKP technology to prove that the diffusion rate of
hydrogen in (001) and (101) grains of 304 SS is faster than that in (111)
grains, and hydrogen is proved to be trapped at the phase boundary
between austenite and martensite [52,53]. Li et al. explored the reasons
for the improvement of the photocatalytic performance of Ag-modified
TiO2 through SKP technology [44]. Their results showed that low WF
made the Ag-modified TiO2 be easier to escape electrons, and thus
accelerated the separation of photogenerated charge carriers, leading to
the enhancement of the photocatalytic performance of the Ag-modified
TiO2. Although SKP technology has been applied in various research
fields, there is no report concerning about the SKP analysis in the field
of the PECCP. In view of this, the introduction of the SKP technology
into the area of the PECCP will play a positive role for comprehensively
and profoundly understanding the effect of the photoelectrodes on the
PECCP process.
MgTixOy is considered to be a wide band gap semiconductor ma-
terial with good photocatalytic performance [40,54]. The wide band
gap can make the photoinduced electrons and holes generated by
MgTixOy be difficult to recombine, therefore, the photogenerated
charge carriers can efficiently transfer in the process of the photo-
catalytic reactions. Furthermore, MgTixOy has a more negative con-
duction band potential than TiO2, which is beneficial to PECCP.
Meanwhile, a well band alignment can be formed between TiO2 and
MgTixOy, therefore, the TiO2/MgTixOy multiphase heterojunctions en-
able the photogenerated charge carriers to migrate directionally. In this
way, more photogenerated electrons can be separated and participate
in the PECCP reactions, thereby greatly improving the PECCP perfor-
mance and stability of the TiO2/MgTixOy multiphase heterojunction
system.
In the present paper, a novel TiO2/MgTixOy multiphase-hetero-
junction film was prepared and reported for the first time, and its
PECCP performance and stability for 304 SS were studied. SKP tech-
nique was used for the first time to study the significantly enhanced
PECCP performance of the prepared TiO2/MgTixOy multiphase-het-
erojunction film. The lowest surface WF of the TiO2/MgTixOy multi-
phase-heterojunction film makes it be easier to escape the electrons,
and higher amount of photogenerated electrons can be produced for
protecting 304 SS under simulated solar light illumination. In addition,
the establishment of multiphase heterojunctions makes the TiO2/
MgTixOy films have durable stability for the PECCP. This study further
enriches the means of characterizing the photoelectrodes, and provides
an important theoretical basis for understanding the promotion of the
PECCP performance and the stability of the photoelectrodes.
2
Corrosion Science 166 (2020) 108441
2. Experimental section
2.1. Preparation of the photoelectrodes
The reagents used in the experiments were all purchased from
Sinopharm Chemical Reagent Co., Ltd without further purification. The
anatase TiO2 nanotube arrays (NTAs) (TiO2(A)) photoelectrode was
prepared by a two-step anodization method according to the previous
reports [55,56]. A cleaned titanium (Ti) sheet was used as the anode
and a Pt electrode was used as the cathode, which was placed in parallel
in the electrolyte of ethylene glycol (0.35 wt% NH4F, 10 wt% H2O). A
constant potential (60 V) was applied for anodic oxidation for 1 h at
room temperature. After 10 min of ultrasonic cleaning in 10 wt% HCl
solution, the obtained Ti sheet was rinsed with deionized water for
several times. The above-mentioned process of anodic oxidation was
repeated one more time. After that, the sample was put into deionized
water and ultrasonically cleaned for 30 S. The sample was dried, and
then was annealed at 450 °C for 3.5 h to prepare the TiO2(A) photo-
electrode.
The TiO2/MgTixOy photoelectrode was prepared as follows. The
magnesium hydroxide was firstly deposited onto the surface of the
TiO2(A) photoelectrode by a multi-potential step method using a
CHI660D electrochemical workstation (Shanghai Chenhua Instrument
Co., Ltd., Shanghai, China). A three-electrode configuration was applied
in the deposition process, in which the prepared TiO2(A) was used as
the working electrode, the Pt electrode worked as the counter electrode,
and the saturated calomel electrode (SCE) acted as the reference elec-
trode, respectively. 0.1 M Mg(NO3)2 solution was used as the electro-
lyte. During the deposition process, the step potentials were −1.5 and
−1.2 V, respectively, and the corresponding time was 5 s and 0.5 s.
After 8 cycles of deposition, the obtained sample was washed with
deionized water and alcohol. Subsequently, the prepared sample was
thermally treated in a muffle furnace at 700 °C for 2 h to obtain the
TiO2/MgTixOy photoelectrode. As can be well known, the phase
transformation of TiO2 occurs during high temperature treatment (≥
550 °C), resulting in the coexistence of anatase and rutile TiO2
(TiO2(R)) [57–59]. Therefore, as a comparison, the prepared TiO2(A)
photoelectrode was also thermally treated in a muffle furnace at 700 °C
for 2 h to obtain the TiO2(A)/TiO2(R) photoelectrode.
2.2. Characterization of the prepared photoelectrodes
X-ray diffractometer (XRD, D/max-500, Rigaku Co., Tokyo, Japan)
was used to characterize the crystal structures of the prepared photo-
electrode. Fourier transform infrared (FT-IR) spectra were tested using
a Fourier transform infrared spectroscopy (FT-IR, Thermo-Nicolet 8700,
Thermo Electron Scientific Inc., USA) at room temperature. UV–vis
diffuse reflectance spectrophotometer (U-41000; HITACHI, Tokyo,
Japan) was used to analyze the optical absorption properties of the
prepared TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelec-
trodes. Photoluminescence (PL) spectra of the prepared photoelectrodes
were measured with a fluorescence spectrometer (PL, Microconfocal
Raman Spectrometer, Horiba Jobin Yvon LabRAM HR800, 325 nm,
France). Field emission scanning electron microscopy (FE-SEM, ZEISS,
ULTRA 55, Germany) was used to analyze the micromorphologies of
the prepared TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelec-
trodes. The elemental composition and mapping of the prepared pho-
toelectrode were analyzed by an X-ray energy dispersive spectrometer
(EDS, Oxford, UK). The microstructures of the prepared TiO2/MgTixOy
photoelectrode and interfacial information of different phase compo-
nents were observed by field emission transmission electron microscope
(FE-TEM, Tecnai G2 F20, FEI Company, USA).
C. Feng, et al.
2.3. Photoelectrochemical (PEC) performance, PECCP performance and
SKP measurements
The light source used for the PEC and PECCP performance mea-
surements is 150-W Xe lamp (PLSSXE300, Changtuo Co. Ltd., Beijing,
China). A simulated solar illumination is obtained by adding an AM1.5
G filter and adjusting the light intensity of this light source to 100 mW⋅
cm−2. The PEC performance was tested in a three-electrode cell system
using the CHI660D electrochemical workstation. The variations of the
current densities of the TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy
photoelectrodes were measured using the prepared photoelectrode as
the working electrode, the platinum electrode as the counter electrode,
and Ag/AgCl (saturated KCl) as the reference electrode. The bias vol-
tage was set as 0 V (vs Ag/AgCl) and the electrolyte was 0.1 M Na2SO4
solution. The variations in the current densities and the mixed poten-
tials, and the polarization curves of the galvanic couple of the 304 SS
electrode and the prepared photoelectrodes were measured to char-
acterize the PECCP performance. The galvanic couple of the 304 SS
electrode and the prepared photoelectrodes was used as the working
electrode. The Ag/AgCl (saturated KCl) electrode and the platinum
electrode served as the reference and counter electrode, respectively.
Both the 304 SS electrode and the prepared photoelectrodes are placed
in 3.5 wt% NaCl solution and the bias voltage was set as 0 V (vs Ag/
AgCl) during the testing process. Intermittent simulated solar light (100
mW, AM 1.5 G) was illuminated on the surface of the photoelectrodes.
Electrochemical impedance spectroscopy (EIS) tests were performed at
open circuit potential over the frequency range between 105 and 10-1
Hz, with an AC voltage magnitude of 5 mV. The polarization curves
were measured using the CHI660D electrochemical workstation with a
scan rate of 1 mV⋅s-1 from -400 to 400 mV (vs open circuit potential).
The surface WFs of the prepared photoelectrodes were analyzed
using SKP (VersaSCAN, Ametek). The tungsten probe with the diameter
of 250 μm was acted as the reference and detection probe. The testing
area on the surface of the prepared photoelectrodes was 1 × 1 mm2 and
the scanning rate was set as 50 μm⋅s−1 with sensitivity of 500 μV. The
surface WFs of the photoelectrodes can be calculated based on the
following formula [60–62]: WF (Sample) = WF (Tungsten) + ΔW
(photoelectrode)/1000. Among them, WF (Tungsten) is the WF of the
reference electrode with standard value of 4.55 eV for tungsten; WF
(Sample) is the surface WF for the prepared photoelectrode, ΔW
(photoelectrode) is the surface potential of the photoelectrode obtained
from the SKP measurement.
3. Results and discussion
Fig. 1A shows the XRD patterns of the prepared TiO2(A), TiO2(A)/
TiO2(R) and TiO2/MgTixOy. For the XRD pattern of TiO2(A), the dif-
fraction peaks at 25.5°, 37.9°, 48.4°, 54.2°and 55.3° are observed, cor-
responding to the (101), (004), (200), (105) and (211) crystal planes of
standard anatase TiO2 (JCPDS No. 21-1272), respectively. The other
Fig. 1. XRD patterns and FT-IR spectra of the prepared TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy.
3
Corrosion Science 166 (2020) 108441
diffraction peaks in the XRD pattern of TiO2(A) are attributed to the
characteristic ones of the Ti substrate [55,56]. For the XRD pattern of
TiO2(A)/TiO2(R), the coexistence of anatase and rutile phases of TiO2
can be clearly observed after high temperature treatment at 700 °C. In
addition to the diffraction peaks of Ti substrate and anatase TiO2, the
corresponding rutile phases of TiO2 (JCPDS No. 21-1276) are observed
at 27.6°, 36.1°, 41.2°, 44.1, 54.3°, 56.7°, 64.1°and 68.9°, which are as-
signed to the (110), (101), (111), (210), (211), (220), (310) and (301)
crystal planes, respectively. For the XRD pattern of TiO2/MgTixOy, the
weak characteristic peaks of MgTiO3 and MgTi2O5 can be observed. It
may be due to the relatively small amount of MgTixOy deposited on the
surface of TiO2 tube orifice. Although the intensities of the diffraction
peaks are weak, it can be clearly seen that the diffraction peaks are
located at 19.1°, 21.2°, 23.9°, 35.5°, 40.6° and 63.8°, respectively. These
diffraction peaks correspond well to the (003), (101), (012), (104),
(110) and (214) crystal planes of rhombohedral MgTiO3 (JCPDS no. 06-
0494). In addition, the diffraction peaks at 32.7° and 48.6° are ob-
served, which are assigned to the (230) and (331) crystal planes of
orthorhombic structure of MgTi2O5 (JCPDS no. 35-0792). The XRD
results suggest that MgTixOy was successfully modified on the surface of
TiO2. Fig. 1B displays the FT-IR spectra of the prepared TiO2(A),
TiO2(A)/TiO2(R) and TiO2/MgTixOy. The FT-IR spectra of TiO2(A) and
TiO2(A)/TiO2(R) show a high degree of consistency and the broad band
below 750 cm−1 is mainly from the stretching vibration mode of Ti-O-
Ti in TiO2 [63,64]. No other characteristic peaks were observed, in-
dicating the high purity of TiO2(A) and TiO2(A)/TiO2(R). For the FT-IR
spectrum of TiO2/MgTixOy, another broad region at approximately
1400−1550 cm−1 can be observed, which comes from the Ti–-
carboxylic complexes and hydroxyl group [65–67]. The FT-IR results
indicate that the carboxyl and hydroxyl groups can be easily adsorbed
on the surface of TiO2(A)/TiO2(R), which facilitates the contact be-
tween the photoelectrode and the electrolyte solution.
Fig. 2 shows the SEM images of TiO2(A), TiO2(A)/TiO2(R) and
TiO2/MgTixOy, respectively. As shown in Fig. 2A, TiO2(A) exhibits a
good NTA structure. The orifices are closely arranged with a diameter
of approximately 80 nm. Fig. 2B shows the SEM image of the TiO2(A)/
TiO2(R) photoelectrode. The surface of TiO2(A)/TiO2(R) is much
smoother than that of TiO2(A), which may be due to the formation of
anatase and rutile TiO2 after the high temperature treatment. For the
SEM image of TiO2/MgTixOy displayed in Fig. 2C, some nanoparticles
obviously appear at the orifices and are well coated on the surface of
the orifice of TiO2 NTAs. This may be the surface-modified MgTixOy
nanoparticles. Fig. 2D shows the SEM image of the cross section of
TiO2/MgTixOy. The height of the nanotubes can be measured as ap-
proximately 4 μm. The basic structure of the nanotubes has not been
destroyed after high temperature treatment at 700 °C, and the tubular
structure remains intact.
Fig. 3A shows the SEM image and the corresponding EDS spectrum
of TiO2(A). In addition to Ti and O elements, no other impurity ele-
ments are observed. The atomic mass percentages of Ti and O were
C. Feng, et al. Corrosion Science 166 (2020) 108441

Fig. 2. SEM images of (A) TiO2(A), (B) TiO2(A)/TiO2(R) and (C) TiO2/MgTixOy, and (D) SEM image of the cross section of TiO2/MgTixOy.

33.19 % and 66.81 %, which fits well with the element composition of
TiO2. Fig. 3B shows the SEM image and the corresponding EDS results
of TiO2/MgTixOy. Ti, O and Mg elements are clearly observed with the
atomic percentages of 24.13 %, 67.91 % and 7.96 %, respectively. As
shown in the corresponding EDS mapping results, Ti element covers the
whole scanning area due to the Ti substrate. While, O and Mg elements
correspond well to the SEM image shown in Fig. 3B. The tube orifice is
clearly observed in the EDS Mg and O mappings, indicating that Mg and
O elements are well dispersed on the surface of the TiO2 nanotube or-
ifices. The difference between the SEM images in Fig. 3 and those in
Fig. 2 is mainly due to the fact that EDS is tested under high excitation
voltages, which will break down the surface components and make the
surface morphology be difficult to be observed.
The composition and interfacial information of the TiO2/MgTixOy
multiphase heterojunctions are further studied by HRTEM. Fig. 4A
presents the TEM image observed at low magnification. The structure of
nanotubes can be clearly observed, which corresponds well to the SEM
image of TiO2/MgTixOy shown in Fig. 2. The edge of the nanotubes was
further enlarged, as shown in Fig. 4B. The nanostructures with different
lattice fringes are found and form the heterojunctions on the surface of
the nanotube. The observation results are further magnified at the se-
lected two rectangular areas. Fig. 4C corresponds to the rectangular

Fig. 3. SEM images and the corresponding EDS results of (A) TiO2(A) and (B) TiO2/MgTixOy.

4
C. Feng, et al.
Fig. 4. TEM (A) and HRTEM (B, C, D) images of TiO2/MgTixOy multiphase heterojunctions.
area I. The lattice fringes of TiO2(R), MgTiO3 and MgTi2O5 can be
observed with the values of 0.29, 0.27 and 0.33 nm, respectively.
Furthermore, the lattice fringes of TiO2(A), TiO2(R), MgTiO3 and
MgTi2O5 can be clearly observed corresponding to the rectangular area
II, as shown in Fig. 4D. Combining with the physical characterization
results shown in Figs. 1–4, it can be proved that MgTixOy is successfully
coated on the surface of TiO2 NTAs, and the multiphase heterojunctions
are formed.
Fig. 5 shows the UV–vis absorption spectra of the TiO2(A), TiO2(A)/
TiO2(R) and TiO2/MgTixOy photoelectrodes. As can be found, the light
absorption threshold of TiO2(A) is observed at 382 nm. For the
TiO2(A)/TiO2(R) photoelectrode, the light absorption threshold has a
slight red shift compared with that of TiO2(A), which may be caused by
the formation of TiO2(R) with a narrower band gap. In addition to
having the same absorption threshold as TiO2(A)/TiO2(R), the TiO2/
MgTixOy photoelectrode has an additional absorption threshold at ap-
proximately 330 nm, indicating the successful synthesis of MgTixOy on
the surface of TiO2 NTAs.
Fig. 5. UV–vis absorption spectra of the TiO2(A), TiO2(A)/TiO2(R) and TiO2/
MgTixOy photoelectrodes.
5
Corrosion Science 166 (2020) 108441
The PECCP performance of the prepared photoelectrodes are char-
acterized by measuring the photoinduced current densities and the
photoinduced potential drops, and the results are shown in Fig. 6.
Fig. 6A shows the variations in the galvanic current densities between
the 304 SS electrode and the prepared photoelectrodes in 3.5 wt% NaCl
solution under intermittent simulated solar light illumination. Positive
excitation current densities are obtained under light illumination, in-
dicating that the photoinduced electrons generated by the photoelec-
trodes transfer to the coupled 304 SS electrode and provide the PECCP
for it. The photoinduced current density of a prepared photoelectrode,
which is provided for protecting the coupled metallic electrode, is ob-
tained by subtracting the stable galvanic current density between the
protected metal electrode and the photoelectrode in the dark from that
under light illumination. As shown in Fig. 6A, the photoinduced current
density of TiO2(A) is 9 μA·cm−2 and that of TiO2(A)/TiO2(R) is 23
μA·cm−2. While, that of TiO2/MgTixOy is 49 μA·cm−2, which is 5.4 and
2.1 times of that of TiO2(A) and TiO2(A)/TiO2(R). The results shown in
Fig. 6A indicate that TiO2/MgTixOy can produce the most photo-
generated electrons and can provide the most electrons needed for the
cathodic protection of the coupled 304 SS. Fig. 6B shows the variations
of the mixed potential of the 304 SS electrode coupled with the pre-
pared photoelectrodes in 3.5 wt% NaCl solution under intermittent si-
mulated solar light illumination. The mixed potentials of the 304 SS
electrode coupled with the prepared photoelectrodes immediately shift
to negative direction once the light is switched on, demonstrating that
the prepared photoelectrodes can provide the PECCP for the coupled
304 SS electrode. The photoinduced mixed potential drop is the mixed
potential of the 304 SS electrode coupled with the prepared photo-
electrode under light illumination minus that in the dark. As shown in
Fig. 6B, the photoinduced mixed potential drops of TiO2(A), TiO2(A)/
TiO2(R) and TiO2/MgTixOy are -230, -250 and −320 mV, respectively.
The TiO2/MgTixOy exhibits the maximum photoinduced mixed poten-
tial drop, indicating its excellent PECCP performance. The photo-
induced mixed potential drop results shown in Fig. 6B are similar to the
photoinduced current density results shown in Fig. 6A, and both of
them prove that TiO2/MgTixOy has the best PECCP performance.
Meanwhile, in Fig. 6B, the stability of the prepared photoelectrodes is
evaluated by measuring the potential variations during the long dura-
tion of light illumination. As shown in Fig. 6B, the mixed potential of
the 304 SS electrode coupled with the prepared photoelectrodes is
C. Feng, et al.
Fig. 6. (A) The variations in the galvanic current densities between the 304 SS electrode and the prepared photoelectrodes and (B) the variation of the mixed
potentials of the galvanic couple of the 304 SS electrode and the prepared photoelectrodes in 3.5 wt% NaCl solution under intermittent simulated solar illumination.
stabilized for 900 s in the dark. Subsequently, the light is switched on
and illuminated for 2 h on the photoelectrodes. The mixed potentials of
the 304 SS electrode coupled with the TiO2(A) and TiO2(A)/TiO2(R)
photoelectrodes change from -0.37 and -0.42 V to -0.33 and -0.39 V,
showing a slight decrease in their PECCP performance during the light
illumination. However, for TiO2/MgTixOy, the mixed potential of the
304 SS electrode coupled with the TiO2/MgTixOy photoelectrode does
not have significant change during the 2-h light illumination. The re-
sults shown in Fig. 6B indicate that there is no obvious attenuation of
the PECCP performance of the TiO2/MgTixOy photoelectrode during the
long duration of light illumination, demonstrating that the TiO2/
MgTixOy photoelectrode possesses high stability and has good appli-
cation prospects in the field of PECCP.
The polarization curves of 304 SS electrode and 304 SS electrode
coupled with the TiO2, TiO2(A)/TiO2 and TiO2/MgTixOy photoelec-
trodes in the absence and presence of simulated solar light illumination
are shown in Fig. 7. The corrosion potential of the 304 SS was about
−154 mV (vs. Ag/AgCl) before coupling with the prepared photo-
electrodes in 3.5 wt% NaCl solution, however, those of 304 SS posi-
tively shift to -102, -101 and −113 mV after coupling with TiO2,
TiO2(A)/TiO2 and TiO2/MgTixOy photoelectrodes in the dark, respec-
tively. Under simulated solar light illumination, significant negative
potential shifts are obtained for 304 SS coupling with different photo-
electrodes, indicating the good PECCP performance of the prepared
photoelectrodes. Under the simulated solar light illumination, the cor-
rosion potentials of 304 SS coupling with TiO2, TiO2(A)/TiO2 and TiO2/
MgTixOy are -353, -426 and −486 mV, respectively. These results are in
Fig. 7. The polarization curves of the 304 SS electrode and the 304 SS electrode
coupled with the TiO2, TiO2(A)/TiO2 and TiO2/MgTixOy photoelectrodes in the
absence and presence of simulated solar light illumination.
6
Corrosion Science 166 (2020) 108441
good agreement with the previous PECCP tests shown in Fig. 6, which
further indicates the excellent PECCP performance of the TiO2/MgTixOy
photoelectrode.
SKP technology is used to further characterize the capability of the
electrons escaping from the surface of the prepared photoelectrodes.
The surface WF, which refers to the minimum energy required to escape
an electron from the surface of the photoelectrode, can be easily cal-
culated from the surface potential of the photoelectrodes measured by
SKP [68,69]. The smaller the WF is, the easier it is for electron to es-
cape, i.e. for electrons to flow out of the photoelectrode and participate
in the reactions [70]. Fig. 8A displays the surface potential distributions
of different photoelectrodes measured by SKP. As can be found in
Fig. 8A, the potential fluctuation of the prepared individual photo-
electrode is smaller than ± 50 mV around the median value, suggesting
that the surface of which is fairly flat and uniform. By comparing the
surface potentials of TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy
photoelectrodes, TiO2(A) has the most positive surface potential dis-
tribution with an average value of approximately 990 mV. TiO2(A)/
TiO2(R) has a surface potential of approximately 830 mV. While, TiO2/
MgTixOy has the most negative potential of approximately 690 mV,
which is 300 and 140 mV lower than those of TiO2(A) and TiO2(A)/
TiO2(R), respectively. Fig. 8B shows the surface WFs of the prepared
photoelectrodes obtained from the results shown in Fig. 8A. The surface
WFs of TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelectrodes
are 5.54, 5.38 and 5.24 eV, respectively. The lowest surface potential
distribution and surface WF of TiO2/MgTixOy indicate that the multi-
phase heterojunctions can easily excite the electrons and transfer them
to the surface of 304 SS to provide effective protection for it.
Fig. 9A shows the variations in the current densities of the TiO2(A),
TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelectrodes in 0.1 M Na2SO4
solution under intermittent simulated solar illumination. As shown in
Fig. 9A, all of the prepared photoelectrodes shows positive excitation
current densities under light illumination. The photoinduced current
density of the TiO2(A) photoelectrode is 0.12 mA⋅ cm−2, and that of the
TiO2(A)/TiO2(R) is 0.16 mA⋅ cm−2. However, the photoinduced current
density of the TiO2/MgTixOy photoelectrode is 0.29 mA⋅ cm−2, which is
approximately 2.4 times and 1.8 times of the TiO2(A) and TiO2(A)/
TiO2(R) photoelectrodes, respectively. The generation of photoinduced
current is a key factor that affects the PECCP performance of the pho-
toelectrode. The TiO2/MgTixOy photoelectrode has the highest photo-
induced current density, indicating that it has the best PECCP perfor-
mance.
The electrochemical impedance spectroscopy and the photo-
luminescence spectroscopy of the prepared photoelectrodes were
measured to evaluate the photogenerated charge carrier migration
ability and the recombination ability of the photogenerated electrons
and holes. The relevant results are shown in Figs. 9B and 9C. As shown
in Fig. 9B, the TiO2/MgTixOy photoelectrode has the smallest surface
resistance than TiO2(A) and TiO2(A)/TiO2(R), indicating that the TiO2/
MgTixOy has the fastest electron mobility. In addition, as shown in
C. Feng, et al. Corrosion Science 166 (2020) 108441

Fig. 8. (A) The surface potential distributions of TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelectrodes measured by SKP technique; and (B) the surface WFs
of the prepared photoelectrodes transformed from the SKP results in Fig. 8A.

Fig. 9. (A) The variations in the current densities of the TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelectrodes under intermittent light illumination, (B)
Electrochemical impedance spectra (EIS) and (C) photoluminescence spectra of the TiO2(A), TiO2(A)/TiO2(R) and TiO2/MgTixOy photoelectrodes.

Fig. 10. SEM image of the TiO2/MgTixOy photoelectrode after the PECCP test and the XRD and FT-IR spectra of the TiO2/MgTixOy photoelectrode before and after
the PECCP tests.

Fig. 11. The proposed transfer mechanism of the photogenerated charge carriers and the schematic diagram of the PECCP of the TiO2/MgTixOy multiphase het-
erojunctions.

7
C. Feng, et al.
Fig. 9C, the photoluminescence intensity of TiO2/MgTixOy has a sig-
nificant decrease compared with that of TiO2(A) and TiO2(A)/TiO2(R),
indicating that the secondary recombination of the photogenerated
electrons and hole is significantly inhibited for the TiO2/MgTixOy
photoelectrode. These results display that the TiO2/MgTixOy photo-
electrode can realize the fast transmission of the photogenerated charge
carriers, can effectively inhibit the secondary recombination of the
photogenerated electrons and holes, and can generate the highest
photoinduced current compared with the TiO2(A) and TiO2(A)/TiO2(R)
photoelectrodes, therefore, achieve the excellent PECCP performance of
the TiO2/MgTixOy photoelectrode.
The SEM image of TiO2/MgTixOy after the PECCP tests and the XRD
and FT-IR analyses of the TiO2/MgTixOy photoelectrode before and
after the PECCP tests are shown in Fig. 10. As shown in Fig. 10A, the
micromorphology of TiO2/MgTixOy does not have significant changes
after the PECCP tests. Furthermore, the XRD and FT-IR curves of the
TiO2/MgTixOy photoelectrode after PECCP tests are highly consistent
with those before PECCP tests, as shown in Fig. 10B and C. These results
demonstrate that TiO2/MgTixOy photoelectrode has a high stability in
the process of PECCP.
Fig. 11 shows the proposed transfer processes of the photogenerated
charge carriers in the TiO2/MgTixOy multiphase heterojunctions and its
PECCP mechanism. The TiO2/MgTixOy photoelectrode has significantly
enhanced photogenerated current density and photoinduced mixed po-
tential drop, indicating that the energy band structures of TiO2 and
MgTixOy match well and the TiO2/MgTixOy multiphase heterojunctions
with a good energy band alignment gradient are formed. The photo-
generated charge carriers can migrate directionally under the action of the
multiphase heterojunctions, making the photogenerated charge carriers be
well transferred. It was reported that the band gaps of MgTiO3, MgTi2O5,
TiO2(R) and TiO2(A) are 3.7 eV, 3.4 eV, 3.0 eV and 3.2 eV, respectively,
and the conduction band potentials of them are arranged in the following
order: MgTiO3 < MgTi2O5 < TiO2(R) < TiO2(A) [40,54,71,72]. The pho-
togenerated electrons can be transferred to TiO2(A) through the conduc-
tion band gradient formed by the TiO2/MgTixOy multiphase heterojunc-
tions, and eventually be transferred to 304 SS through the Ti substrate to
provide effective protection for it. Meanwhile, the photogenerated holes
will be further transferred to the TiO2/MgTixOy multiphase heterojunc-
tions under the action of the heterojunction electric field, and the corre-
sponding oxidation reactions will occur with the electrolyte. Furthermore,
the fabrication of the TiO2/MgTixOy multiphase heterojunctions greatly
increases the separation efficiency of the photogenerated charge carriers
and effectively suppresses the recombination of the photogenerated elec-
trons and holes. In this way, a large number of photogenerated electrons
will continuously flow from the TiO2/MgTixOy photoelectrode to the
coupled 304 SS electrode under light illumination, thus significantly en-
hancing the long-term PECCP performance.
4. Conclusions
In the present paper, a highly efficient and stable TiO2/MgTixOy
multiphase-heterojunction film was prepared and its PECCP perfor-
mance for 304 SS was studied. MgTixOy are uniformly dispersed on the
surface of TiO2 NTAs. MgTiO3, MgTi2O5, TiO2(R) and TiO2(A) contact
well and form a multiphase-heterojunction system. The photoinduced
current density of the TiO2/MgTixOy multiphase-heterojunction film is
49 μA·cm−2 under the simulated solar light illumination, which is 5.4
and 2.1 times of that of TiO2(A) and TiO2(A)/TiO2(R). The photo-
induced mixed potential drops of the TiO2/MgTixOy multiphase-het-
erojunction film is −320 mV, while, those of TiO2(A) and TiO2(A)/
TiO2(R) are -230 and -250 mV, respectively. Meanwhile, the TiO2/
MgTixOy multiphase-heterojunction film exhibits extremely high
PECCP stability. During the 2 h of light illumination, the PECCP of the
TiO2/MgTixOy multiphase-heterojunction film shows no weakening
trend. The lower surface WF makes the TiO2/MgTixOy multiphase-
heterojunction film be much easier to escape electrons, which is of great
8
Corrosion Science 166 (2020) 108441
benefit to the improvement of the PECCP performance of the TiO2/
MgTixOy multiphase heterojunctions. Furthermore, the good PECCP
performance of the TiO2/MgTixOy multiphase heterojunctions is at-
tributed to the establishment of multiphase heterojunction system,
which effectively inhibits the secondary recombination of the photo-
generated electrons and holes, and accelerates the migration of the
photogenerated charge carriers. SKP technology has been used for the
first time to study the PECCP performance of the TiO2/MgTixOy mul-
tiphase-heterojunction film. The introduction of SKP technology into
the PECCP research has greatly enriched the test methods in the field of
PECCP. At the same time, the establishment of multiphase hetero-
junctions provides a new idea for the design of the PECCP film.
Data availability
All data included in this study are available upon request by contact
with the corresponding authors.
Declaration of Competing Interest
None.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (Grant Nos. 41576114, 41676069), Key Research
and Development Program of Shandong Province (Grant Nos.
2019GHY112066, 2019GHY112085), State Key Laboratory for Marine
Corrosion and Protection, Luoyang Ship Material Research Institute,
China (Project No. 614290101011703), and Qingdao Innovative
Leading Talent Foundation (Grant No. 15-10-3-15-(39)-zch).
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Another random document with
no related content on Scribd:
The Project Gutenberg eBook of Het hol van
Kaan
 This ebook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
almost no restrictions whatsoever. You may copy it, give it away
or re-use it under the terms of the Project Gutenberg License
included with this ebook or online at www.gutenberg.org. If you
are not located in the United States, you will have to check the
laws of the country where you are located before using this
eBook.

Title: Het hol van Kaan

Author: Emmy J. Belinfante

Illustrator: Wam Heskes

Release date: November 13, 2023 [eBook #72117]

Language: Dutch

Original publication: Amsterdam: E.M. Querido, 1919

Credits: Jeroen Hellingman and the Online Distributed

Proofreading Team at https://www.pgdp.net/ for Project
Gutenberg

*** START OF THE PROJECT GUTENBERG EBOOK HET HOL VAN

KAAN ***
[Inhoud]

[Inhoud]

HET HOL VAN KAAN

[Inhoud]
 HET HOL VAN KAAN

DOOR
E. BELINFANTE
MET 25 ILLUSTRATIES DOOR W.
HESKES

EM. QUERIDO—1919—AMSTERDAM
[Inhoud]

BOEK-, COURANT- EN STEENDRUKKERIJ G. J. THIEME, NIJMEGEN.

[Inhoud]

AAN ERNST EN LYDIA

[Inhoud]
 INHOUD

Bladz.
De Bende uit het Hol van Kaan 1
„Van m’n eigen verdiende Centen” 6
„Tusschen Hemel en Aarde” 11
’n Kwartje ’n Rat! 18
Een droeve Dag 26
Het „Monster” 32
De geheimzinnige Macht 38
Nette Manieren.… en onnette Jongens 46
Wie een Kuil graaft voor een ander 58
Een „dikke” Vriend 69
De Kunstveiling 89
De mislukte Nacht-wandeling 96
Het geheimzinnige Apparaat 109
Van een Vlieger en een Meiske 117
Karel’s eerste optreden 127
Ratten, Kogelfleschjes en Ladders! 141
Ambro en Paul op Reis 160
Ambro redt een sectie Soldaten 170
Verraderlijke Rook! 182
Van een Diefstal op School en een Vuilnisbak als Koekepan 196
De Kermis 213
De Kermis 220
Besluit 244

[1]
[Inhoud]
 DE BENDE UIT HET HOL VAN KAAN

Ge zijt allen wel eens in een bioscoop geweest, niet waar? Hebt ge
dan wel eens gezien, hoe de film-helden en -heldinnen vóór het begin
van de film één voor één levensgroot op het doek kwamen?

Zoo zou ik u zoo gaarne de helden uit dit boek voorstellen.

Dan zou Ambro, de held van dit verhaal met z’n ondeugende, open
gelaat U guitig toelachen.

Chris zou zeker een half norsch, half spottend gezicht getrokken
hebben.

Puckie zou een scheef-getrokken mond hebben van ingehouden

lach.

Paul, met even schuin-gebogen hoofd, zou met lieven blik de zaal in
kijken.

Piet, in de houding van een Indianen-Opperhoofd, zou met

onverschilligen blik naar u kijken. [2]

Karel en Wim allebei met iets guitigs-verwonderds.

En Bob?… Ik denk, dat er weemoed in zijn blik zou zijn geweest.

Nu ik mijn helden dus aan het publiek heb voorgesteld, wil ik er nog
even bij vertellen, dat ze hun ondeugende rollen gespeeld hebben in
Rotterdam en ze den leeftijd hadden van tien tot twaalf.

Het stel was vanaf de bewaarschool trouwe kameraden en daar ze

allen, zonder uitzondering pientere, vlugge jongens waren, bleven ze
ook op de groote school steeds in dezelfde klas en zoo bleef het
oolijke jongensclubje steeds bijeen.

Wat al streken door die bengels werden uitgehaald, wordt in dit

verhaal beschreven.

De verschillende ouders van de jongens waren allen lid van den

Dierentuin en die tuin was, in de oogen der ouders een veilige
bewaarplaats voor hun jongens. Af en toe ging er eens ’n pa, moe of
groote zus kijken, wat ze wel uitvoerden, en dan kwamen ze altijd
een der clubgenooten tegen, die vol ijver zei: „Ik weet waar ze zijn, ik
zal ze wel even roepen.”

En al heel gauw kwamen ze dan als zoete joggie’s aangewandeld,

een boek of cahier in de handen en vol verhalen over de apen die
weer zoo leuk waren, of de leeuwen die net gevoerd werden.

„Het groote mensch” ging dan volkomen gerustgesteld heen.

Daarna dingen de jongens weer kalm verder, net [3]zoolang, tot ze bij
een stil plekje waren. Hier vormden ze een kring om den oudsten
jongen, een zekeren Ambrosius Verbrugge, die de hoofdleider van
het clubje was.

„Dat liep weer netjes af,” verklaarde deze op plechtigen toon. En dan
tot den jongen die ze was komen roepen toen het groote mensch
kwam opdagen:

„Bob, je hebt je best gedaan, je krijgt daar straks je belooning. Wie

moet er nu op post?”

„Ik,” zei een kleine, dikke snuiter en meteen haastte hij zich langs
denzelfden weg waarvan ze zooeven gekomen waren en posteerde
zich op een bank, vlak bij den ingang van den dierentuin.

Oogenschijnlijk zat hij ijverig te lezen in het boek dat hij in de handen
hield, maar in werkelijkheid hield hij den ingang in het oog en
monsterde iederen persoon die binnenkwam.

Na een half uur zou hij weer afgelost worden. Zoo luidde het
reglement van de club.

Maar nu gaan we eens zien wat die andere jongens uitvoerden.

Daar hebben we het troepje. Ze loopen lachend en babbelend voort,

maken een praatje met de oppassers, kijken eens naar de
verschillende beesten, maar loopen hoe langer hoe verder den tuin in
tot ze stilhouden bij een rhododendron-boschje. Het is een groot en
heel dicht begroeid boschje en ’t ligt er rustig en afgelegen.

Piet Kaan, een der club-genooten had op een mooien dag het plan
geopperd om op handen en [4]voeten in het boschje te kruipen en
daar plannen te beramen voor een nieuw spel.

Terwijl een der jongens als post uitgezet werd om te kijken of er geen
tuinman of suppoost in den omtrek was, kropen de anderen op
handen en voeten het boschje in.

En dáár werd dien dag het groote plan beraamd, het plan, waardoor
ze vele maanden een reeks van prettige dagen hadden.

Kaan inspecteerde nauwkeurig het boschje en kwam tot de

ontdekking, dat met hier en daar wat wegsnijden van takken en
stammen het boschje een prachtig roovershol zou zijn.

Dit plan had de volle instemming van de overige Club-genooten en

men besloot hun schuilplaats dan voortaan het hol van Kaan te
noemen, want Piet Kaan had ’t toch maar ontdekt.
’t Klonk zoo echt roover-achtig, het hol van Kaan en ze zagen in
gedachten al vreeselijke meesterlijke dingen gebeuren in hun
spelonk.

Er werd verder besloten, met de grootst mogelijke omzichtigheid te

werk te gaan, want ze wilden lang plezier hebben van hun hol. Het
was dus zaak, het heele suppoostenleger te slim af te zijn, en dit kon
alleen bereikt worden door steeds posten uit te zetten, terwijl de
anderen dan bij ’t geringste sein van dien post zorgden het hol juist
aan den tegenovergestelden kant te verlaten, als waarvan de
suppoost kwam. Verder moest er een post uitgezet bij den ingang
van den dierentuin om te kunnen waarschuwen als er familieleden
kwamen [5]controleeren wat hun jongens uitvoerden.

Ook dit voorstel werd met algemeene stemmen aangenomen.

Toen ze den daaropvolgende keer bijeen kwamen in het hol van

Kaan, had een der roovers een vel perkament meegebracht en
hierop werden alle notulen van het reglement neergeschreven en
omdat ’t echter en griezeliger was, prikte Ambrosius Verbrugge zich
in den arm, drukte eenige bloeddruppels uit en de bewoners van het
hol van Kaan zetten allen hun namen onder het gewichtig document,
„met bloed geschreven”.

Dit had hij gelezen in het aardige jongensboek van Mark Twain, „Tom
Sawyer”.

En dit is nu eigenlijk de inleiding van mijn verhaal. Jullie kunt je nu

wel zoo’n beetje voorstellen, hoe de bengels daar zaten, en ik ga je
nu alle booze streken vertellen, die in het hol van Kaan beraamd
werden.

Ze waren dan weer eens op een mooien dag bijeengekomen, toen

een der jongens voorstelde een paar stoelen uit de nabij gelegen
sociëteit te halen en die naar hun hol te sleepen.

De posten werden verdubbeld en tot bizondere waakzaamheid

aangezet.

Toen slopen zes jongens uit het hol, en gingen langzaam en telkens
omkijkend, naar de sociëteit, die op dit oogenblik geheel verlaten
was, en na eenige oogenblikken kwamen de zes roovers terug, ieder
een stoel met zich dragend.

Voetje voor voetje ging het terug naar ’t hol, [6]waar ze de witte vlag
(een zakdoek aan een stokje gebonden) zagen wapperen, ten
teeken, dat alles veilig was.

Die zes stoelen waren een genot voor ze, want het op den grond
zitten beviel ze toch niet op den duur, ’t lag er zoo vol takjes en … er
was thuis al eens geïnformeerd waardoor de broeken toch zoo vuil
waren aan den achterkant!

Ambrosius vond, dat ’t nu in hun hol de veiligste plaats was om alles

te doen wat ze thuis niet durfden, uit angst van betrapt te worden.

„Laten we beginnen,” zei hij en z’n ondeugende oogen glinsterden

van pret. „Met al onze centen bij elkaar te leggen en daarvoor telkens
een Wilson of Nick Carter te koopen.”

„Jô, fijn!” vonden de heeren eenparig. Zoo kochten ze iederen week

een spannend detective-verhaal en dat werd dan in hun hol door een
der jongens voorgelezen. En altijd zorgden ze er voor dat de posten
afgewisseld werden en die het verhaal dan op hun gemak konden
lezen.
[Inhoud]
 „VAN M’N EIGEN VERDIENDE CENTEN.”

Terwijl ze daar zoo gezellig zaten en genoten van het detective-

verhaal, kwam Ambrosius, de hoofdman op een nieuw idee.

„Zeg jongens,” zei hij en z’n stem daalde tot een zacht gefluister.
„Zeg, wat zouden jullie er van zeggen, als we in ons hol eens … ’n
pijpje zouden rooken?” [7]

„Heb jij ’t al eens gedaan?” vroeg Piet Kaan.

„Ikke niet,” antwoordde Ambrosius.

„Maar eens moet de eerste keer zijn en … ik durf best hoor!”

„Je wordt er zoo misselijk van,” zei Bob van Eest.

„Neen, je krijgt er buikpijn van,” meende Karel Boekers.

Ambrosius dacht eens na, ’t was wèl een moeilijk geval. ’t Zou zoo
echt zijn, een pijp te rooken in hun hol.

„Weet je wat,” zei hij. „Ik zal mijn Vader vragen of ik rooken mag, en
heeft hij er niets op tegen, dan doe ik ’t.”

„Flauwerd,” riep Wim Bolk. „Moet je dat aan je vader vragen!”

Maar de vuist van den hoofdman deed hem zwijgen.

Toen Ambrosius ’s avonds met vader een eindje omfietste, deed hij
z’n niets kwaads vermoedende vader plotseling de vraag of hij
rooken mocht.
Vader scheen niets gesticht over die vraag, vond hem nog véél te
jong.

„Maar wanneer mag ik dàn rooken, Vader?” hield zoonlief vol.

„Weet je wat, baas, laten we afspreken dat je mag rooken als je zelf
geld verdient.”

„Dat duurt nog zoo akelig lang,” klaagde Ambrosius.

„Net lang genoeg om te maken dat je geen al te hinderlijke gevolgen

van het rooken hebt. Geloof me, jongen, rooken is over ’t algemeen
genomen, [8]niet gezond, maar zeker niet als je nog zoo jong bent.”

Ambrosius was ’t verdere van den avond wat stil, vader dacht dat het
kwam door de teleurstelling, maar daar was nu eenmaal niets aan te
doen.

Had zijn vader kunnen zien wat er in het brein van zijn vindingrijke
spruit omging, dan zou hij zeker niet zoo gerust zijn geweest.

Toen de roovers weer bij elkaar kwamen in hun hol ging Ambrosius
plechtig in hun midden staan en verzocht de jongens zich om hem
heen te scharen.

„Jullie weet, dat mijn vader mij toestond te rooken, wanneer ik zelf
geld verdiende. Nu—ik heb een middel gevonden om centjes te
verdienen en daarvan zullen we, als de buit binnen is, pijpjes en
tabak koopen.”

„Wat is ’t?” vroegen de jongens nieuwsgierig.

Ambrosius haalde met een gewichtig gebaar iets uit zijn broekzak.
Allen verdrongen zich om hem heen om toch goed te kunnen zien
wàt daar te voorschijn kwam.
Het was een tamelijk breed wit lint, waarop met keurige, groote
letters het woord „Gids” geschreven stond. ’t Leek wel, of ’t er op
gedrukt was.

„Waar dient dat nou voor?” vroeg Piet Kaan.

„Dat zal ik je zeggen, jôh. Over eenige dagen krijgen we de

Septemberplaag, oftewel, de buitenmenschen die den dierentuin
komen bezichtigen. Nou heb ik al zoo vaak gezien dat die boertjes
van buuten steeds naar de verschillende beesten [9]loopen te zoeken
en dan telkens aan een suppoost moeten vragen waar dit of dat is.
Zie ik nu zoo’n stel loopen, dan zet ik gauw dit lint om m’n pet en
maak ze wijs, dat ik een vaste gids ben en leid ze netjes voor een
duppie of zoo den tuin rond.”

De roovers waren stil van bewondering. Die Ambro toch, hoe kòn ie
’t zoo bedenken!

„Wat zeggen jullie ervan?” vroeg de hoofdman, die wel gevleid was
door die stille bewondering, maar toch graag eens hoorde hoe ze het
plan vonden.

Toen klonken er allerlei geestdriftige uitroepen als echt jôh! fijn!

gepiept! enz.

Maar ze vonden het niet rechtvaardig, dat Ambro alle pijpjes zou
betalen; als ze heel zuinig waren, kon er nog best een pijp van 2
centen af en dan gaven ze nog wat bij aan de tabak.

Zoo gezegd, zoo gedaan. Eenige dagen daarna liep Ambro trouw
achter de goede buitenlui aan en als geen suppoost hem kon
betrappen werd de pet opgezet en bood hij zijn diensten als gids
aan, die door de goedmoedige boertjes graag aanvaard werden.
Hij kreeg ’t dan steeds erg warm, klaagde over zoo’n warme pet op
je hoofd, en liep al gauw met de pet in de hand naast ze. Zoo
hadden de suppoosten heelemaal geen verdenking op hem.

Hij leidde de menschen werkelijk bizonder goed rond, want hij kende
overal den weg en wist leuke dingen van de verschillende beesten te
vertellen.

’t Gebeurde dan ook menigmaal, dat de boertjes vol bewondering

zeiden: „Wa’n meroakel voorlijk [10]jong!” En daar de buitenlui als ze
zoo’n dagje uitgaan niet op de centjes zien, kreeg hij meestal een
fooitje dat zijn verwachting ver te boven ging.

En toen kocht de rakker van zijn zelf-verdiende geldje een pak tabak
en voor ieder een pijp.

En er gingen vreugdekreten op in het hol van Kaan toen de buit

binnen was, en ze allen in een kring om hun hoofdman gezeten, hun
eerste pijpje rookten.

De posten buiten snakten naar het oogenblik waarop ze ook hun

aandeel in de rookpartij zouden krijgen en het half uur duurde deze
keer wel bizonder lang.

„Willen we er nog een opsteken,” vroeg na een tijdje Ambro dapper,

maar hij voelde zich toch niet zoo prettig als anders.

„Dank je,” zei Bob van Eest lusteloos. „Een is genoeg voor de eerste
keer.”

Dit vonden de anderen ook en hoe ’t kwam begrepen ze zelf niet,

maar er was dien middag niet zoo’n pret in het hol als op de anderen
dagen.