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Decorated TiO2 Nanotube Arrays for
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 Corrosion Science 176 (2020) 108920

Contents lists available at ScienceDirect

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

Covalent Organic Framework Decorated TiO2 Nanotube Arrays for T

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

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

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

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

⁎
Corresponding authors.
E-mail addresses: [email protected] (N. Liu), [email protected] (X. Chen).
1
Authors contributed equally to this work.

https://doi.org/10.1016/j.corsci.2020.108920
Received 2 January 2020; Received in revised form 14 July 2020; Accepted 31 July 2020
Available online 06 August 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
C. Wang, et al. Corrosion Science 176 (2020) 108920

applied between the two electrodes for 1.5 h in an electrolyte comprised

of 80.0 mL ethylene glycol, 8.0 mL DI water, and 0.45 g NH4F. After
anodization, the samples were cleaned using DI water and ethanol
several times to remove any residual electrolyte. The as-prepared
samples were annealed at 450 °C for 2 h in air at a heating rate of
5 °C min−1 and naturally cooled afterward to obtain the TiO2 NTAs in
the anatase phase.

2.3. Fabrication of the TpBD/TiO2 NTA composite

1,3,5-triformylphloroglucinol (Tp 6.3 mg, 0.03 mmol) and benzi-

dine (BD 8.3 mg, 0.045 mmol) were dissolved in a mixture of mesity-
lene/1,4-dioxane (30 mL, 1:1). Subsequently, aqueous acetic acid (6 M,
0.5 mL) was added dropwise to the above mixture in a Teflon liner. The
resulting solution was sonicated for 10 min to obtain a homogeneous
Scheme 1. Condensation reaction and chemical structure of TpBD. dispersion; then, a piece of TiO2 foil was placed aslant into the solution
in the Teflon liner, which was loaded into a stainless steel autoclave and
decrease in the electron transfer resistance; (2) the absorption of visible heated at 120 °C for 72 h. After cooling to room temperature, a dark red
light is enhanced due to the low band gap of TpBD; (3) the reserved precipitate (TpBD) and a TpBD/TiO2 NTA composite on a Ti matrix
pore structure of a TpBD/TiO2 NTA composite hinders the recombina- were obtained after extraction with acetone for 24 h (Soxhlet extrac-
tion of carriers by offering a complete reaction between the holes and tion), the samples were then dried at 60 °C for 6 h under vacuum. The
the trapping agent (Na2S in this case); and (4) the formation of a het- fabrication process of the TpBD/TiO2 NTA composite is shown in
erojunction between TpBD and TiO2 would improve the separation of Scheme 2. The 10-TpBD/TiO2 NTA composite was synthesized using
the photoelectrons from the holes. the same procedure with increased amounts of Tp (63 mg, 0.3 mmol)
and BD (83 mg, 0.45 mmol).

2. Experimental
2.4. Characterization

2.1. Materials
The X-ray diffraction (XRD) patterns were recorded on a Bruker D8
Advance (Bruker, Germany) diffractometer using Cu Kα radiation (λ
Ti foils (> 99% purity) were purchased from Baoji Group Co., Ltd. =1.5406 Å). The attenuated total reflection infrared spectroscopy
(Baoji, China). Ammonium fluoride (NH4F), hydrogen peroxide (H2O2), (ATR-IR) was performed on a Nicolet 5700 Spectrometer (Thermo
nitric acid (HNO3), sodium sulfide (Na2S·9H2O), glycol, ethanol, acetic Nicolet, USA). The field emission scanning electron microscope (FE-
acid, 1,4-dioxane, acetone, and 1,3,5-trimethylbenzene were purchased SEM) images were recorded with a Hitachi SU8220 (Hitachi, Japan).
from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). The transmission electron microscopy (TEM) and high resolution
Benzidine (BD) was provided by Aladdin Bio-Chem Technology Co., transmission electron microscopy (HRTEM) analyses were carried out
Ltd. (Shanghai, China). 1,3,5-Triformylphloroglucinol (Tp) was pur- on a JEOL JEM-2100 (Tokyo, Japan) with an accelerating voltage of
chased from Tongchuangyuan Pharmaceutical Technology Co., Ltd. 200 kV. The X-ray photoelectron spectroscopy (XPS) was recorded on a
(Chengdu, China). Nafion solution was purchased from Sigma-Aldrich Thermo Escalab 250Xi (Thermo Fisher Scientific, USA) with an Al Kα X-
Co., (St. Louis, MO, USA). All the aqueous solutions were prepared ray source. The UV-vis diffuse reflectance spectra (DRS) were recorded
using deionized (DI) water (18.2 MΩ cm) purified using a SMART ultra- on a U-3900H spectrophotometer (Hitachi, Japan). The Electron Spin
pure water system. All of the reagents used were analytical grade Resonance (ESR) spectra were measured by the JES-FA200 (JEOL,
without further purification. Japan).

2.2. Preparation of TiO2 NTAs 2.5. Electrochemical measurements

Among the three crystalline phases, the anatase TiO2, which is The electrochemical measurements were made using a CHI760E
generally obtained by potentiostatic anodization, is more favorable in electrochemical workstation (Shanghai Chenhua Instrument Co. Ltd.,
the field of photocatalysis [34]. Ti foils (40 mm × 10 mm × 1 mm) China). The open circuit potential (OCP-t) and photoinduced current
were ultrasonically degreased in deionized water and ethanol for density (i-t) curves were recorded in an electrochemical cell, as shown
15 min each. Then, the Ti sheets were polished in a solution containing in Scheme 3. In the corrosion cell containing 3.5 wt% NaCl, a saturated
NH4F (4.5 g), H2O (25 mL), H2O2 (30 wt%, 60 mL), and HNO3 (68 wt%, calomel electrode (SCE) served as the reference electrode (RE) and a
60 mL) to remove surface oxides. The electrochemical cell composed of steel sample served as the working electrode (WE). The fabricated
a two-electrode system with Pt foil and a Ti sheet as the counter elec- photoanode was placed in the photoanode cell containing 0.1 M Na2S
trode and working electrode, respectively. A DC voltage of 20 V was and 0.2 M NaOH, which were used as sacrificial agents for promoting

Scheme 2. Schematic illustration of the TpBD/TiO2 NTA composite’s fabrication.

2
C. Wang, et al. Corrosion Science 176 (2020) 108920

Scheme 3. Schematic diagram of the electrochemical test for measuring (a) photoinduced open circuit potential and (b) photoinduced current density.

Fig. 1. SEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs, (c) 10-TpBD/TiO2 NTAs, and (d) TpBD, respectively. Insets are the cross-sectional image of (a) and (b).

the separation of the photoelectrons and holes. The photoanode cell and The results were analyzed using Princeton ZSimpWin version 3.60
the corrosion cell were separated by a Nafion membrane. The OCP-t software.
and i-t curves were measured under intermittent illumination. A 300 W The Mott-Schottky (MS) curve was measured in the potential range
Xenon lamp (PLS-SXE 300 C, Beijing Perfect light Company, China) of −0.6 V to 1.0 V with an AC potential frequency of 1000 Hz under
with a 420 nm cut-off filter was used to generate visible light with an dark conditions. The working electrode was prepared as follows: 5.0 mg
energy density of 100 mW cm−2. During the OCP-t measurement, the of TpBD, 1.0 mL of ethanol and 10 μL of Nafion solution (5 wt%) were
steel sample and the fabricated photoanode were electrically coupled mixed under sonication, and 200 μL of the above suspension was spread
and connected to the working electrode. For the i-t test, the photoanode onto the surface of an FTO (fluorine-doped tin oxide) glass substrate
and the steel sample were connected to the working electrode and with an area of 10 mm × 10 mm and then dried at room temperature.
ground wire, so that the photogenerated electrons could flow from the
photoanode to the steel. In addition, the counter electrode (CE) and RE 3. Results and discussion
interfaces were linked by a short circuit to remove the influence of
polarization. 3.1. Characterization of the fabricated material
The photoinduced i-V test was conducted in a three-electrode cell
containing 0.1 M Na2SO4, where the prepared photoanode served as the The surface morphologies of the TiO2 NTAs, TpBD, and TpBD/TiO2
WE, and the SCE and Pt foil served as the RE and CE, respectively. The i- NTAs are shown in Fig. 1. The well-ordered and compact TiO2 NTAs
V curve was recorded from −1.0 to 1.0 V at a scan rate of 0.02 V s−1, grown on the Ti foil had inner diameters in the range of 30 - 60 nm and
where the light was switched on and off every 5 s. an average length of ∼1000 nm (Fig. 1a). The top view of the TpBD/
The electrochemical impedance spectroscopy (EIS) was conducted TiO2 NTAs showed nanotubes with inner diameters in the range of 20 -
in a three-electrode cell containing 0.1 M Na2S and 0.2 M NaOH, using a 40 nm, which was due to the deposition of TpBD (Fig. 1b). Fig. 1d
GAMRY Interface 1000. The prepared photoanode was served as the showed that the synthesized free TpBD particles were spherical, with an
WE, and the SCE and Pt foil served as the RE and CE, respectively. The average diameter of ∼1 μm; however, the TpBD grown in situ on the
EIS test was carried out at OCP and spectra were recorded over a fre- TiO2 NTAs was quite different (Fig. 1b and 1c); the significant change of
quency range of 105 to 10−2 Hz with an AC voltage magnitude of 5 mV. the TpBD morphology on the TiO2 NTAs was caused by the preferred

3
C. Wang, et al. Corrosion Science 176 (2020) 108920

plane of the TpBD (0.325 nm) can be observed from the HRTEM image
(Fig. 2c) [35]. The results suggest that TpBD was successfully grown on
the TiO2 NTAs.
The XRD experiments were performed to determine the crystalline
structures of the synthesized materials (Fig. 3). The obtained TpBD
particles displayed moderate crystallinity, likely due to the fact that
rapid growth of the COFs via precipitation limited the formation of
highly crystalline structures [36]. The reflection peaks at 2θ = 3.6º,
6.0º, 7.1º, 9.3º and 26.7º were consistent with the simulated diffraction
data. While the diffraction peaks of Ti and TiO2 could be observed in
the TpBD/TiO2 NTAs sample, the characteristic peaks of TpBD were not
observed. Possible reasons for this are the fact that: a very small
quantity of TpBD was loaded on the TiO2 NTAs and the lack of crys-
tallinity of the TpBD grown in situ on the TiO2 NTAs. In Fig. 1, the
morphologies of the free TpBD particles (Fig. 1d) and the TpBD grown
in situ on the TiO2 NTAs (Fig. 1b and 1c) were quite different, thus
suggesting the morphology of the TpBD varied with the growth con-
ditions, which may influence the crystallinity of the TpBD. The HRTEM
and XRD results indicated contradictory information regarding the
crystallinity of the TpBD grown on the TiO2 NTAs. This may be due to
the different sample preparation methods for the XRD and TEM ana-
lyses. In the TEM analysis, the sample was super thin, thus enabling
local crystallinity of the TpBD to be detected.
The chemical composition of the TpBD/TiO2 NTA composite was
further studied by XPS analysis (Fig. 4). The result showed no obvious
Ti peaks in the full scan spectrum (Fig. 4a), because the detection limit
for the XPS analysis was only a few nanometers and the TiO2 NTAs was
covered with an appreciable amount of TpBD (Fig. 1) [37–39]. The full
scan spectrum of the TpBD/TiO2 NTA composite confirmed the pre-
sence of C 1s (285 eV), N 1s (400 eV), and O 1s (531 eV). Deconvolution
of the C 1s high resolution XPS spectrum (Fig. 4b) into four distinct
peaks allowed for the assignment of the C = C (284.8 eV), C-N
(286.2 eV), C-C (287.0 eV) and C = O (288.4 eV) bonds [22,32]. In the
N 1s spectrum (Fig. 4c), the peaks with binding energies of 398.8 and
399.9 eV were assigned to the C-N-C and N-H bonds, respectively
[27,40]. In the O 1s spectrum (Fig. 4d), two peaks located at 531.7 and
535.0 eV were assigned to the lattice oxygen in the TpBD structure
through C = O bonding [40] and chemically adsorbed water molecules
[41]. The XPS results indicated that TpBD was successfully loaded on
the TiO2 NTAs.
ATR-FTIR spectra of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs
are shown in Fig. 5. In the case of the TiO2 NTAs, a wide absorption
peak at 530 cm−1 corresponded to the stretching and bending vibra-
tions of the Ti-O-Ti bond [42]. For TpBD, absorption peaks at
Fig. 2. TEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs and (c) HRTEM 1618 cm−1 (carbonyl C = O stretching), 1571 cm−1 (C = C stretching),
image of the TpBD/TiO2 NTAs. 1450 cm−1 (aromatic C = C ring stretching) and 1282 cm−1 (C-N
stretching) were observed [43,44]. The peaks above could also be ob-
growth of TpBD along the edges of the pore opening on TiO2 NTAs [18]. served in the spectrum of the TpBD/TiO2 NTAs, thus demonstrating the
The retained channel structure of the TpBD/TiO2 NTA composite with a successful loading of TpBD.
large specific surface area, had the potential to provide sufficient con- The optical property of the fabricated materials was investigated by
tact between the fabricated material and the surrounding solution, UV-vis DRS spectra. In Fig. 6, the pure TiO2 NTAs exhibited a narrow
which could hinder the recombination of carriers by offering a com- absorption of light in the UV light region (200 - 380 nm), while the
plete reaction between the holes and its trapping agent (Na2S, in this TpBD showed a wider and stronger absorbance. After loading the TpBD,
case). Meanwhile, it is worth mentioning that although the pore the TpBD/TiO2 NTAs exhibited an enhanced absorption in the visible
structure was retained in the 10-TpBD/TiO2 NTA composite, the PEC light range. The band gap energy (Eg) of the semiconductor photo-
cathodic protection performance between the TpBD/TiO2 NTAs and 10- catalysts can be calculated by the Kubelka-Munk equation [11,45],
TpBD/TiO2 NTA composites showed minor differences (not shown). αhv = A (hv − Eg )n (1)
The microstructures of the TiO2 NTAs and TpBD/TiO2 NTAs were
further investigated by TEM and HRTEM (Fig. 2). Fig. 2a showed a where α is the absorption coefficient, h is Plank constant, ν is the light
batch of TiO2 nanotubes with inner diameters of ∼50 nm and the for- frequency, and A is a constant. Among them, n, depends on the char-
mation of ordered NTAs. Fig. 2b showed the microstructure of the acteristics of the transition of the semiconductor, e.g., direct transition
TpBD/TiO2 NTA composite. Compared with the TiO2 NTAs, the basic (n = 1/2) or indirect transition (n = 2). Both TiO2 and TpBD belong to
outlines of the nanotubes in the TpBD/TiO2 NTA composite were vague indirect transitions (n = 2) [11,30]. Hence, the Eg values of TiO2,
and unclear, likely due to the deposition of the TpBD. The interplanar TpBD/TiO2, and TpBD were calculated to be 3.37, 2.40, and 2.20 eV,
spacing of the (101) plane of the anatase TiO2 (0.351 nm) and the (100) respectively. The decrease of the band gap energy indicates an im-
proved absorption of visible light by the fabricated photoanode.

4
C. Wang, et al. Corrosion Science 176 (2020) 108920

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

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

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

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

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

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

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

6
C. Wang, et al. Corrosion Science 176 (2020) 108920

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

7
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 8. The photoinduced i-V curves of TiO2 NTAs and TpBD/TiO2 NTAs photoanodes under intermittent visible light illumination.

Fig. 9. (a) Nyquist plots, (b) Bode plots of log

|Z| vs. frequency, (c) phase angle vs. frequency
of the TpBD/TiO2 NTA composite under dark
and illuminated conditions, and the equivalent
circuits established to fit the EIS results of the
TpBD/TiO2 NTA composite under (d) dark and
(e) illuminated conditions.

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

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

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

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

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

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

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

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

Fig. 12. The valence band spectrum of XPS for TpBD.

Q=
1 intercept [45] and was −1.23 V by extrapolation [13]. It is known that
Y0 (j ω) n (2) the conduction band potential (ECB) for an n-type semiconductor is
0.2 V more negative than the Efb value [51,52]. Thus, the ECB for the
where Y0 represents the admittance modulus (Ω−1 sn cm−2), ω is the
TpBD was calculated to be −1.43 V, which was −1.19 V (vs. NHE)
angular frequency, and n is a constant with a value between 0 and 1.
[30]. The calculated valance band potential (EVB) for the TpBD was
CPE is converted to a pure resistor (n = 0) or a pure capacitor (n = 1).
1.01 V (vs. NHE) according to the formula of EVB = ECB + Eg [53]. This
For a CPE with n ≠ 1, its capacitance, C, can be calculated by,
is consistent with the calculated valance band potential based on the VB
1
1 −n n XPS spectrum of the TpBD in Fig. 12, which was 0.87 eV by extra-
C= R n Y0 (3) polating the leading edge of the spectra to the baseline [54].
where R is the resistance of the resistor paralleled with the CPE [49]. The ESR result (Fig. 13a) further verified the band structure of the
The electrochemical parameters obtained from the fitting results are TpBD, in which the photoelectrons can reduce the adsorbed O2 mole-
summarized in Table 1. According to equation (3), the double layer cules to produce •O2− radicals (O2/•O2− = −0.3 V vs. NHE), and the
capacitance under dark is calculated to be 6.98 × 10−5 F cm−2, which holes cannot oxidize the OH− to produce •OH (OH−/•OH = +2.68 V
is one magnitude lower than that under illuminated condition vs. NHE).
(6.35 × 10−4 F cm−2), this is likely due to the production and storage According to previous reports [54,55], the ECB and EVB values of the
of photo-generated electrons under illumination. The Rct value is an TiO2 were −0.29 and +2.91 V, respectively. Possible band structure
important parameter to evaluate the photocathodic protection perfor- alignments for the TiO2 and TpBD were shown in Fig. 14. Fig. 14a
mance of the prepared photoanode [49,50]. In Table 1, the Rct values of showed a conventional type-II heterojunction electron transfer path, in
the TpBD/TiO2 NTAs were 1.30 × 105 Ω cm2 under dark, and which the photoelectrons in the CB of the TpBD transfer to that of the
2.23 × 103 Ω cm2 under illumination, suggesting a rapid transfer of TiO2, while the holes localized at the VB of the TiO2 transfer to that of
photogenerated electrons under illuminated condition. Therefore, the the TpBD. However, the above mechanism could not explain the fol-
above results were consistent with the good photocathodic protection lowing results: (1) according to the ESR results, the accumulated holes
performance of the TpBD/TiO2 NTAs composite. in the VB of the TpBD cannot oxidize the OH− to produce •OH
Another requirement for successful PEC cathodic protection is the (Fig. 13a), indicating the accumulation of holes at the VB of the TiO2;
stability of the photoanode, which cannot be corroded by the sur- (2) the Q235 CS can be protected from corrosion by the photogenerated
rounding medium during the protection process. Fig. 10 showed the electrons in the TpBD/TiO2 (Fig. 7b,c), indicating the accumulation of
long-term variation of potential of 304 SS coupled with the TpBD/TiO2 photoelectrons at the CB of the TpBD (more negative than the corrosion
NTAs photoanode under intermittent visible light illumination. The potential of the Q235 CS, which is −0.51 V (vs. NHE)). Thus, a direct Z-
coupled potential of the 304 SS was stabilized at −0.9 V after a con- scheme mechanism [56–58] was proposed for the TpBD/TiO2 NTA
tinuous light illumination of 3 h. When the light was turned off, the composite system (Fig. 14b) in which the electrons in the TiO2 and
potential switched back immediately and stabilized at −0.34 V holes in the TpBD could recombine directly, thus leading to an efficient
(slightly lower than the corrosion potential of the 304 SS). After several separation of photoelectrons at the CB of the TpBD and holes at the VB
cycles, the TpBD/TiO2 NTA composite still exhibited good performance of the TiO2. The remarkable improvement of the PEC cathodic protec-
during the protection process. tion performance of the TpBD/TiO2 NTA composite was also attributed
to the enhanced reducing capacity of the photoelectrons.

3.3. Proposed mechanism

4. Conclusions
The Mott-Schottky plot was measured to study the band structure of
the TpBD (Fig. 11). The positive slope revealed that the TpBD was an n- In summary, COF-TpBD modified TiO2 NTAs (TpBD/TiO2 NTAs)
type semiconductor, and its Efb could be obtained from the horizontal were successfully fabricated. The TpBD/TiO2 NTA composite showed

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

Fig. 13. ESR spectra of radical adducts trapped by DMPO for (a) TpBD and (b) TpBD/TiO2 NTAs under visible light for 5 min.

significantly enhanced PEC cathodic protection performance for 304 SS CRediT authorship contribution statement
and Q235 CS under visible light irradiation. Additionally, the ESR and
PEC analyses indicated that a direct Z-scheme heterojunction was Chunli Wang: Investigation, Writing - original draft. Wei Gao:
formed between the TpBD and TiO2, by which an enhanced reduction Validation, Resources. Nazhen Liu: Conceptualization, Writing - re-
capacity of photoelectrons was reserved and an efficient separation of view & editing, Supervision, Project administration. Yu Xin: Resources.
charge carriers was achieved. This work demonstrates that COF mate- Xinyu Liu: Resources. Xiutong Wang: Writing - review & editing.
rials, as semiconductors which are capable of structure control and Yong Tian: Writing - review & editing. Xuwei Chen: Project admin-
functional design, show promise for applications in the field of PEC istration. Baorong Hou: Funding acquisition.
cathodic protection.
Declaration of Competing Interest

Data availability The authors report no declarations of interest.

The raw/processed data required to reproduce these findings cannot

Acknowledgements
be shared at this time as the data also forms part of an ongoing study.
This research work was financially supported by the National
Natural Science Foundation of China (No. 51901222, 41827805) and

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

Fig. 14. Proposed mechanism for the enhanced PEC cathodic protection performance of the TpBD/TiO2 NTAs on steel under illumination.

the CAS Pioneer Hundred Talents Program. I would like to express my Z.H. Chen, M.Z. Yuan, X. Wang, K. Kempa, G.F. Zhou, Modified nanopillar arrays
gratitude to Dr. Taylor Martino (CanmetMATERIALS, Canada) for lan- for highly stable and efficient photoelectrochemical water splitting, Global
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[45] Q.Q. Zhang, J.X. Wang, X.J. Ye, Z.Z. Hui, L.Q. Ye, X.C. Wang, S.F. Chen, Self-as- using visible light, Angew. Chem. Int. Ed. 57 (2018), https://doi.org/10.1002/anie.
sembly of CdS/CdIn2S4 heterostructure with enhanced photocascade synthesis of 201800579 2008-2008.

13
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The Project Gutenberg eBook of La montée aux enfers
 This ebook is for the use of anyone anywhere in the United
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Title: La montée aux enfers

Author: Maurice Magre

Release date: May 7, 2022 [eBook #68010]

Language: French

Original publication: France: Eugène Fasquelle, 1918

Credits: Laurent Vogel, Chuck Greif and the Online Distributed

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*** START OF THE PROJECT GUTENBERG EBOOK LA MONTÉE

AUX ENFERS ***
 LA

MONTÉE AUX ENFERS

EUGÈNE FASQUELLE, Éditeur, 11, rue de grenelle
OUVRAGES DU MÊME AUTEUR
Publiés dans la BIBLIOTHÈQUE-CHARPENTIER
à 3 fr. 50 le volume

POÉSIES
La Chanson des Hommes.
Le Poème de la Jeunesse.
Les Lèvres et le Secret.
Les Belles de Nuit.
CONTES
Histoire Merveilleuse de Claire d’Amour.
PSYCHOLOGIE
La Conquête des Femmes.

ROMAN
Les Colombes poignardées. L’Édition.
THÉATRE
Le Vieil Ami, pièce en un acte (Théatre Antoine). Fasquelle, éditeur.
Le Dernier Rêve, pièce en un acte en vers (Odéon). Fasquelle, éditeur.
Velléda, tragédie en quatre actes en vers (Odéon). Privat, éditeur.
Le Marchand de passions, comédie en trois actes en vers (Théatre des
Arts). La Belle Édition.
La Fille du Soleil, tragédie en trois actes en vers, musique d’André
Gailhard (Arènes de Béziers et Opéra). Fasquelle, éditeur.
L’An mille, tragédie en quatre actes en vers (Théatres de plein air).
Mauriès, éditeur.
Comediante, pièce en deux actes en vers (Comédie-Française).
Fasquelle, éditeur.

IL A ÉTÉ TIRÉ DE CET OUVRAGE

5 exemplaires numérotés sur papier de Hollande.

 MAURICE MAGRE

LA

MONTÉE AUX ENFERS

—POÉSIES—

QUATRIÈME MILLE

PARIS
BIBLIOTHÈQUE-CHARPENTIER
EUGENE FASQUELLE, ÉDITEUR
11, RUE DE GRENELLE, 11

1918
Tous droits réservés
TABLE
LE JARDIN MAUDIT
 LE JARDIN MAUDIT

Dans le jardin maudit je suis venu, moi, l’homme,

Ayant pour conducteur l’être aux yeux de serpent.
Là, la terre est pourrie et les poisons embaument,
Là, les oiseaux du ciel ne vivent qu’en rampant...

Or, les pierres saignaient, la rose était vivante,

J’ai pris la fleur aromatique du sureau,
Elle m’a fait aux doigts une tache sanglante,
Ses pétales gluants se collaient à ma peau.

D’un vivier croupissant sortait une odeur fade.

Des miasmes de typhus par le vent soulevés...
Vers ma face penchaient d’étranges lis malades.
Dans leur calice mort dormait un œil crevé.

Des arbres mous avaient des blessures ouvertes,

Des humeurs ressemblant à celles de la chair,
Et les pousses du bois au lieu de jaillir vertes
Étaient blanchâtres et vivaient comme des nerfs.

Le lait de chaque tige était la sève humaine.

La pivoine semblait un grand cœur arraché.
Dans la fleur du sorbier d’où soufflait une haleine
S’ouvrait un sexe affreusement martyrisé...

Un amandier était fleuri de mains coupées;

Un tronc, comme une femme, avait des cheveux d’or.
J’arrivai près d’un champ de grotesques poupées,
Des enfants dans le sol poussaient là, drus et morts.

Un printemps écœurant d’une chaleur mouillée

Baignait l’arbre de chair et la plante de sang.
La nature par la souffrance travaillée
Créait avec ardeur mille êtres repoussants.
Alors, je vis venir vers moi les créatures.
Impudiques et laids, enfantins et chenus
Et pareils à des échappés de la torture,
Vous trébuchiez et titubiez, hommes tout nus!

Ils étaient boursouflés, extravagants, exsangues.

Celui-ci dans l’œil droit avait un clou de fer,
L’un portait un carcan, l’autre avait une cangue,
Celui-là rayonnait et montrait un cancer.

Et tous, l’être sans dents, l’être aux orbites vides,

L’être dont des grosseurs faisaient le crâne lourd,
Tous étaient satisfaits, tous se trouvaient splendides,
Ils portaient avec eux leur mal avec amour.

Ils ne s’étonnaient pas de la forme des choses,

De la feuille trop pâle et du bois trop laiteux.
Ils pressaient sur leur peau le sang vivant des roses,
Aux tiges tièdes ils buvaient les sucs douteux.

Les saponaires savonneuses des pelouses

Étaient des lits mouillés pour leurs corps maladifs
Et la tulipe obscène et le chardon ventouse
Faisaient vibrer de spasmes fous leurs nerfs à vif.

Ils ont en me voyant poussé des cris de joie

Et l’un m’a fait toucher du doigt le trou sans œil.
Un autre m’a tendu le fer perçant son foie,
Tous m’ont montré leur plaie ouverte avec orgueil.

Ils ont cueilli des fleurs dans le parterre étrange

Et sur ma bouche ils sont venus les écraser
Et j’ai senti le goût humide du mélange
Des végétaux, du suc humain et du baiser.

Un soleil déformé, jaunâtre, bas, énorme

Se reflétait sur des marais de désespoir...
Et les plantes sans nom et les humains difformes
Se mêlaient dans l’éclat du fantastique soir
Se mêlaient dans l éclat du fantastique soir...

Et moi, je n’ai pas fui parmi les crucifères,

J’ai regardé jaunir le jardin sans regrets.
Je me suis rappelé que c’étaient là mes frères,
Que j’allais devenir leur pareil. J’ai pleuré...

—Ayant pris l’être aux yeux de serpent comme guide,

En mars, dans le mois de la guerre, un vendredi,
Moi, l’homme, avec mon cœur qui fut jadis candide,
Voilà ce que j’ai vu dans le jardin maudit.
ÉPIGRAPHE
 ÉPIGRAPHE

Sans robe, sur le lit, tu t’étais allongée.

Je regardais ton corps et la chambre orangée
Dans la phosphorescence et la chaleur du soir
Se refléter au fond des pâleurs du miroir.
Et tout à coup, je vis les choses familières,
Sous un verdissement bizarre de lumière,
Qui se décomposaient, prolongeaient leurs contours,
Se muaient en êtres humains aux torses courts,
Aux cous trop longs. Je vis les meubles de la chambre
Qui se prenaient entre eux et qui tordaient leurs membres,
Revêtaient une forme à l’aspect animal.
Un palais fantastique et caricatural,
Avec des lacs de chair, de vivantes tentures
Et des contorsions d’obscènes créatures
Et des sexes géants figurant des piliers,
Remplaçait l’endroit cher où, sur ton bras plié,
Reposait en rêvant ta tête éblouissante.
Mais hors du lit, coulant comme une eau jaillissante,
Tu tordis tes cheveux qu’électrisait le soir
Et tu vins écraser tes seins sur le miroir,
Et ton buste d’enfant, souple comme une lame.
Et moi, voyant cela, j’avais peur dans mon âme
Que les bouches et que les bras que tu frôlais
Ne te fissent tomber dans l’étrange palais.
Mais tu ne voyais pas l’architecture folle,
Ni les accouplements, ni les affreux symboles,
Et tu riais devant le miroir argenté
De ta peau de fruit clair et de ta nudité.
L’ANE A CORNES
 COMBAT DE FEMMES

Elles devaient se battre au couteau, toutes nues...

L’odeur du vin sortait d’un tonneau débouché...
Le bouge rayonnait sous la lumière crue...
Un patron monstrueux lavait le zinc taché...

Les filles attendaient avec des yeux qui flambent,

Couchant leurs corps contre les hommes attablés.
Par la porte du fond on voyait une chambre,
Les housses, la pendule et les draps maculés.

C’est pour ce paradis qu’elles allaient se battre,

Pour s’y vautrer avec l’enfant ensorceleur
Dont les yeux d’assassin et le teint olivâtre
Les changeaient toutes deux en louves en chaleur.

Il fumait et jetait au plafond la fumée.

Les voix se turent. L’on fit cercle avidement.
Les rivales étaient par le rut animées,
Impudiques, elles riaient sauvagement.

Et la blonde semblait une grande génisse

Avec des bas de soie et de puissantes mains.
La brune charriait dans son sang tous les vices
De la rue. Elle avait une odeur de jasmin.

C’était un serpent noir qui portait sur le crâne

Une rose et ses seins étaient fermes et droits.
Pour égayer encor le public qui ricane
Elle fit devant lui danser son ventre étroit.

Et puis les deux couteaux luirent dans l’air opaque,

La sueur ruissela sur les corps furieux,
On entendit les coups sur les membres qui craquent,
Une main empoigna la toison des cheveux.
Les yeux des spectateurs s’exorbitaient de joie,
Ils appelaient le sang par des mots orduriers.
La blonde par la nuque avait saisi sa proie
Et s’efforçait de l’écraser sur le plancher.

Alors, le serpent noir dans le sang qui l’inonde

Roula ses reins presque brisés sous l’étouffoir
Du corps et de son arme ouvrit en deux la blonde
Qui fit: Ahan! comme une bête à l’abattoir.

Les témoins prirent peur et vidèrent la salle.

Le jeune homme toujours fumait paisiblement,
Et la brune, les mains sanglantes, triomphale,
Sur la morte gesticulait obscènement.

Un gramophone au loin berçait la nuit des bouges...

Le pas de la police errait sur les pavés...
Et la chair qui sentait le jasmin, la chair rouge,
Put enfin s’enfoncer au fond du lit rêvé.

Celle qui demeurait vainqueur de la rafale

Des poings épais et du couteau la tailladant,
Geignit d’amour sous le baiser des lèvres mâles
Qui buvaient sa salive et qui mordaient ses dents.

L’autre, selon la loi du faible, n’eut pour couche

Que le plancher pourri maculé de son sang
Et n’eut pour seul baiser que celui d’une mouche
Bleue et verte, qui vint sur elle en bourdonnant...
 LE JEUNE HOMME AUX CITRONS

La porte était de bronze, étroite, ornementée...

Elle s’ouvrait au fond d’une rue écartée.
Tout de suite une odeur de rose et de jasmin
M’enivra, je suivis une petite main
Qui dans l’ombre sortait d’une manche vert pâle.
Un portique, une salle, un jet d’eau sur des dalles,
Des coussins noirs et des lanternes au plafond
Et de lourds citronniers tout chargés de citrons...
Avec trois fruits d’or clair un jeune homme nu jongle
Il vient de se baigner; l’eau fait briller ses ongles.
Il lance les citrons dans l’air et quelquefois
Une goutte d’argent vole aussi de ses doigts.
Derrière, à pas de loup, marche une jeune fille.
On comprend à ses bras levés, ses yeux qui brillent
Qu’elle va pour jouer le surprendre, baisant
Ses lèvres, étouffant son rire entre ses dents.
Mais je passe... Et c’est une chambre cramoisie
Avec une statue aux hanches amincies
D’une vierge peut-être ou d’un adolescent
Et du marbre du cœur coule un filet de sang,
Car un stylet d’acier traverse son sein gauche.
Et dans l’ombre, une forme à genoux, toute proche.
Fait le geste des mains pour recueillir le sang.
Mais je passe... Le bruit des gonds, le seuil glissant,
Les quartiers morts dormant au bleu des lunes mortes...
—Depuis, j’erre le soir pour retrouver la porte
De bronze et le parfum de rose et de jasmin.
Je gravis des perrons, je touche avec la main
Des heurtoirs et je cherche en les serrures vides
Le jongleur de citrons au visage splendide,
Les gouttes d’eau, la femme et son rire muet,
L’être au sexe inconnu dont le marbre saignait...
 LA PREMIÈRE NUIT AU COUVENT

Dans sa cellule s’éveilla la carmélite.

Elle tâta d’abord sa tête aux cheveux courts,
Se souvint du froid des ciseaux, de l’eau bénite
Et du bruit du portail fermant ses battants lourds.

Sa chemise grossière abîmait de brûlures

Son corps pur. Toute moite elle avait des frissons.
L’ombre du Christ faisait une caricature...
Elle entendit des voix derrière la cloison...

Et c’étaient les voix de désir, les cris, les plaintes,

Le doux frémissement de la chair sur les draps
Et les gémissements de deux femmes étreintes
Qui ne font plus qu’un corps par la chaîne des bras.

Des pas furtifs glissaient dans le couloir immense.

Elle entr’ouvrit la porte et vit courir ses sœurs
Et toutes relevaient leur robe avec aisance
Et découvraient leurs jambes longues sans pudeur.

Quelque chose d’étrange était dans leur allure

Un rire fou les secouait, faisant saillir
Des seins inattendus et des croupes impures
Sur ces corps qui semblaient de rêve seul fleurir.

Viens avec nous! lui dirent-elles. Leurs mains chaudes

L’entraînèrent. Dehors l’escalier solennel
Et le cloître d’argent sous la lune émeraude
Avaient l’air d’un décor fantastique et cruel...

Avec des ventres gros et des faces lubriques

Des moines à travers les piliers ont surgi,
Saisissant par les reins les nonnes impudiques,
Les renversant, les culbutant avec des cris.
Et les cloches soudain dans les tours retentirent,
Sonnant une danse burlesque, un galop fou,
Et parmi les appels hystériques, les rires,
Les poitrines cognaient et claquaient les genoux.

La novice fuyait avec sa robe ouverte,

Mais de partout, des mains sortaient, la pétrissant,
La roulant sur les dalles froides, l’herbe verte,
Meurtrissant son corps nu d’étreintes jusqu’au sang.

Les grands saints alignés sous les arceaux gothiques

Soulevaient leur robe de pierre en ricanant,
Ou, gardant sur leur socle une pose extatique,
Étaient à son passage horriblement vivants.

Elle courut à la chapelle. Là des vierges

Étalaient sur les croix leur corps crucifié.
Elles riaient dans le clignotement des cierges...
Un prêtre officiait en dansant sur un pied...

A cheval sur un grand balai, la supérieure

Conduisait une farandole dans le chœur,
Et des soupirs, des bruits d’amour, des voix qui pleurent
Venaient des coins obscurs dans des parfums de fleurs.

Et brisée, elle vit, par la porte des cryptes,

Un adolescent nu, mince et brun émerger,
Portant un croissant d’or et des bijoux d’Égypte,
Ayant le torse creux et le buste léger.

Sa chair était de bronze, un triple cercle en jade

Faisait sur son front mat comme un glauque bandeau.
Il marchait lentement parmi les colonnades
Et la fixait de loin avec des yeux vert d’eau.

«Satan, je suis à toi, cria-t-elle, je râle

De plaisir à te voir et tords pour toi mes reins.
Voici toute ma chair offerte sur ces dalles.
Prends moi sous cette châsse à l’ombre du lutrin »