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 Corrosion Science 136 (2018) 60–69

Contents lists available at ScienceDirect

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

Fabrication of heterostructured β-Bi2O3-TiO2 nanotube array composite film T

for photoelectrochemical cathodic protection applications
⁎
Zi-Chao Guan, Hai-Peng Wang, Xia Wang, Juan Hu, Rong-Gui Du
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: An ordered TiO2 nanotube array (NTA) film was first fabricated on a Ti substrate by anodization, β-Bi2O3
A. Titanium nanoparticles were then electrodeposited on the film for obtaining a heterostructured β-Bi2O3-TiO2 NTA com-
A. Stainless steel posite film with enhanced photocathodic protection performances. Compared to the bare TiO2 NTA film, the
B. EIS composite film showed a wider light absorption region and higher charge carrier separation efficiency. Under
B. XPS
white light illumination, the composite film as a photoanode made the potential of 403 stainless steel in a 0.5 M
C. Cathodic protection
C. Oxide coatings
NaCl solution decrease by 450 mV relative to its corrosion potential, showing an effective photoelectrochemical
cathodic protection effect.

1. Introduction remarkable dielectric permittivity and photoluminescence property.

Titanium dioxide (TiO2), an n-type semiconductor, has been at-
tracting much attention since it was found to have the ability to de-
compose H2O under illumination by Fujishima and Honda in 1972 [1].
TiO2 shows many special properties, such as low toxicity, easy fabri-
cation, low cost, high stability and excellent photosensitivity [2]. As a
result, it has been widely applied in photodegradation of organics [3,4],
photocatalytic water splitting [5], dye-sensitized solar cells [6], gas
sensors [7], photoelectrochemical cathodic protection (namely photo-
cathodic protection) [8,9], biomedical materials [10], etc. Compared to
a TiO2 nanoparticle or nanowire film, a vertically oriented anatase TiO2
nanotube array (NTA) film prepared by a simple electrochemical ano-
dization method possesses higher photoelectrochemical activity owing
to its large interfacial area and excellent electron transport property
[11]. However, TiO2 has a wide band gap of 3.2 eV and can absorb only
UV light which makes up a small portion of sunlight. Moreover, the
photogenerated charge carriers in TiO2 easily recombine, which ad-
versely affects the photoelectrochemical performance of TiO2.
In recent years, various methods have been developed to modify
TiO2 NTA films for enlarging the spectral response and suppressing the
fast recombination of photogenerated carriers, such as metal doping (Fe
[12], Mo [13], Co [14] and Cr [15]), non-metal doping (N [16,17], S
[18], B [19] and C [20]) and semiconductor heterostructure fabrication
(CdS-TiO2 [21], WO3-TiO2 [22], SnO2-TiO2 [23], Bi2S3-TiO2 [24] and
NiO-TiO2 [25]). Bi2O3 (a p-type semiconductor) is the simplest Bi-based
oxide, and is used in extensive photoelectrochemical applications due
to its excellent properties [26–29], such as the high refractive index,
There are six polymorphic forms for Bi2O3: α-Bi2O3 (monoclinic), β-
Bi2O3 (tetragonal), γ-Bi2O3 (body-centered cubic), δ-Bi2O3 (face-cen-
tered cubic), ε-Bi2O3 (orthorhombic), and ω-Bi2O3 (triclinic)
[27,30,31]. Among these polymorphs, β-Bi2O3 has a distinctive crystal
structure, which gives it a narrower band gap [32] and further provides
the transfer channels for the photogenerated electrons and holes [33].
Consequently, β-Bi2O3 is usually recommended as a promising visible-
light-driven photocatalyst, thanks to its relatively narrow band gap
(2.3–2.8 eV) [34], strong light absorption over the UV–vis region and
high separation efficiency of photogenerated carriers [35]. So β-Bi2O3
should be a suitable candidate for TiO2 nanotube modification for their
matching energy levels. More importantly, a p-n heterojunction will be
formed at the interface between the p-type Bi2O3 and the n-type TiO2 if
they are combined into a composite, which can significantly improve
the separation efficiency of photogenerated electrons and holes.
There have been some reports about Bi2O3-TiO2 nanotube compo-
sites for their photocatalytic or photoelectrocatalytic applications
[36–41]. For example, Ge et al. [36] developed an ultrasonication-as-
sisted successive ionic layer adsorption and reaction (SILAR) method to
synthesize a uniform p-Bi2O3-TiO2 nanotube p-n heterojunction that
showed commendable photocatalytic degradation performance for
methyl orange. Other methods such as chemical bath deposition [38],
dip-coating [39,40] and vacuum-assisted impregnation [41] were also
reported to prepared Bi2O3-TiO2 NTA composites for the purpose of
photocatalytic and other applications. However, there have been no
reports on Bi2O3-TiO2 NTA composite films applied for photocathodic
protection (a photoelectrochemical approach for preventing metal

⁎
Corresponding author.
E-mail address: rgdu@xmu.edu.cn (R.-G. Du).

https://doi.org/10.1016/j.corsci.2018.02.048
Received 25 August 2017; Received in revised form 10 February 2018; Accepted 20 February 2018
Available online 21 February 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.
Z.-C. Guan et al.
corrosion damage [42]).
In this work, a β-Bi2O3-TiO2 NTA composite film was fabricated by
electrochemical anodization combined with ultrasonic-assisted elec-
trodeposition for its application in photoelectrochemical cathodic pro-
tection. The protection effects and mechanisms of the composite film on
403 stainless steel (403SS) were especially investigated.
2. Experimental
2.1. Preparation of β-Bi2O3-TiO2 NTA films
Ti foils (99.8% purity) were processed into the specimens with di-
mensions of 15 mm × 10 mm × 0.1 mm and used as the substrates to
fabricate β-Bi2O3-TiO2 NTA composite films. Before use, the specimens
were ultrasonically cleaned in acetone, ethanol, and deionized water
for 20 min successively and then dried.
A TiO2 NTA film was directly prepared on the Ti substrate through
anodization in a classical two-electrode system with a Ti foil specimen
as the working electrode, and a platinum sheet as the counter electrode.
The anodization was conducted at a constant voltage of 20 V for 30 min
in a 0.5 wt% HF solution at room temperature. After the anodization,
the sample was rinsed with deionized water, and then heated from
room temperature to 450 °C (heating rate of 5 °C min−1) in air and
annealed at 450 °C for 2 h to obtain a crystalline anatase TiO2 NTA film.
A desired β-Bi2O3-TiO2 NTA composite film was prepared via an
ultrasonic-assisted pulse current electrodeposition technique. The as-
prepared TiO2 NTA film was first soaked in a 3 M HCl solution con-
taining 0.1 M Bi(NO3)3 and 0.04 M EDTA (ethylenediaminetetraacetic
acid) for 20 min under ultrasonication (frequency of 40 kHz) to remove
air in the nanotubes and let the electrolyte enter into the nanotubes.
Then the TiO2 NTA film was transferred to the electrolytic cell with the
same HCl solution and acted as the working electrode in the electro-
deposition procedure, while a saturated calomel electrode (SCE) and a
platinum sheet served as the reference and counter electrodes, respec-
tively. The electrodeposition was carried out by applying a
−80 mA cm−2 cathodic current for 20 ms and an 80 mA cm−2 anodic
current for 2 ms alternately for 100 cycles, and the break time (no
applied current) was 1 s between each cycle. Finally, the sample was
heated from room temperature to 550 °C in air with a heating rate of
5 °C min−1 and annealed at 550 °C for 2 h.
2.2. Characterization
A field emission scanning electron microscope (FE-SEM, Hitachi
S4800) was employed to observe the morphologies of the prepared
films. The energy dispersive X-ray spectroscopy (EDS) instrument at-
tached to the FE-SEM was used for the film surface elemental analyses.
The crystalline structures of the films were characterized by X-ray dif-
fraction (XRD, Rigaku Ultima IV) and the surface chemical composi-
tions were determined by X-ray photo-electron spectroscopy (XPS, PHI
Quantum 2000).
Light absorption efficiencies were detected by a UV–vis-NIR spec-
trophotometer (Varian, Cary 5000). The photoluminescence (PL)
measurements were performed with a fluorescence spectrometer
(Hitachi F-7000) with the excitation at 370 nm.
2.3. Photoelectrochemical and electrochemical measurements
The time-dependent photocurrent density (in open-circuit situa-
tions) and photopotential (photo-induced open circuit potential) for the
TiO2 NTA and β-Bi2O3-TiO2 NTA films were measured separately in a
three-electrode cell with the prepared film as the working electrode, an
SCE as the reference electrode and a platinum coil as the counter
electrode. The electrolyte in the cell was a 0.5 M Na2SO4 solution. A Xe
lamp was used as the light source to provide white light from 190 nm to
1100 nm, and the prepared film was illuminated with the white light
61
Corrosion Science 136 (2018) 60–69
which had passed through a quartz window. The time evolution of the
photocurrent and photopotential were recorded under dark and illu-
mination conditions for several cycles. Under dark conditions, the
current density-potential (i-E) curves of the prepared films in the 0.5 M
Na2SO4 solution were measured in the above three-electrode cell with
the film working electrode, SCE reference electrode and platinum
counter electrode at a scan rate of 10 mV s−1 from −1.2 V to 1.2 V (vs.
SCE). All the measurements were performed by a model 263A po-
tentiostat/galvanostat (Princeton Applied Research, USA).
403SS specimens with dimensions of 15 mm × 10 mm × 1 mm
were prepared and used as the metal to be protected by the prepared
films. The composition of 403SS was (wt%): 0.95 C, 0.08 P, 0.94 Si,
0.53 Mn, 0.96 Ni, 13.03 Cr and balance Fe. Before use, the specimen
was mechanically abraded by SiC paper from 600 to 1200 grit gradually
and polished with 1.0 μm Al2O3 powder, and ultrasonically cleaned
sequentially in ethanol and deionized water. Then, each specimen was
clamped to a Cu core wire and covered with nail polish leaving a single
working surface with an area of 1 cm2 to act as an electrode.
The potential measurements and electrochemical impedance spec-
troscopy (EIS) tests were conducted for the 403SS specimen coupled
with the different films (as photoanodes) to investigate the photoelec-
trochemical cathodic protection performances of the prepared films.
The schematic diagram of the experimental setup is shown in Scheme 1,
which is similar to the measurement system reported previously by our
group [43]. In this setup, there were two electrolytic cells connected by
a salt bridge (saturated KCl in agar in a flexible glass tube). One was a
corrosion cell with the 403SS plate working electrode, the SCE re-
ference electrode and the platinum sheet counter electrode in a 0.5 M
NaCl solution for electrochemical measurements. The other was a
photoelectrochemical cell with a photoanode (namely the prepared film
sample) in a 0.5 M Na2SO4 solution, and a quartz window as an optical
channel. The photoanode was coupled to the 403SS plate by a copper
wire. The light source was a 150 W Xe lamp. A computer-controlled
potentiostat/galvanostat (model 263A, Princeton Applied Research,
USA) was employed for photoelectrochemical and electrochemical
measurements. The corrosion potential (open circuit potential) change
of the uncoupled 403SS was measured in the corrosion cell with a 0.5 M
NaCl solution. The photopotential (photo-induced open circuit poten-
tial) change of the 403SS in the same NaCl solution coupled with the
TiO2 NTA or β-Bi2O3-TiO2 NTA film photoanode under intermittent
white light illumination was measured in open-circuit situations (no
Scheme 1. Schematic diagram of the experimental setup for photoelectrochemical
cathodic protection measurements in open-circuit situations. Potential variations and EIS
spectra of 403SS uncoupled and coupled to different films as photoanodes with time were
measured under illumination and dark conditions. The electrolytes in the corrosion cell
and photoelectrochemical cell were a 0.5 M NaCl solution and a 0.5 M Na2SO4 solution,
respectively. 403SS was coupled with the photoanode by a Cu wire. A 150 W Xe lamp was
used to provide white light.
Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69

Fig. 1. SEM images of (a) top-view, (b) cross-sectional view of the TiO2 NTA film, (c) top-view and (d) cross-sectional view of the β-Bi2O3-TiO2 NTA composite film. The inset in (c) shows
the magnified view of the nanotube of the β-Bi2O3-TiO2 NTA film.

externally supplied currents or potentials). EIS spectra of the 403SS

electrode were recorded at its corrosion potential over a frequency
range from 100 kHz to 0.01 Hz with an applied AC voltage of 10 mV for
the stainless steel uncoupled or coupled with the prepared film pho-
toanode under white light illumination. The EIS data were analyzed by
using ZView−Impedance Software.
All the chemicals used in this work were analytical grade. All
measurements were carried out at room temperature (typically
25 ± 2 °C) and repeated at least three times to check the reproduci-
bility.

3. Results and discussion

3.1. Materials characterization

Fig. 1 shows the SEM images of different film samples with good
reproducibility. It can be seen that an ordered NTA film was formed on
the Ti foil surface by the electrochemical anodization (Fig. 1a). The film
was composed of single-wall TiO2 nanotubes with average internal
diameter of about 100 nm. Fig. 1b provides a lateral view image of the Fig. 2. EDS spectrum of the β-Bi2O3-TiO2 NTA composite film, the inset shows the
TiO2 NTA film, in which the TiO2 nanotubes were arranged perpendi- magnified view of the spectrum between 2.0 keV and 3.2 keV.

cularly to the Ti substrate surface, and the tube length ranged from
300 nm to 400 nm. After the deposition of Bi2O3 (which would be
confirmed below) on the TiO2 NTA film, the SEM images of the top-
view and cross-sectional views of the Bi2O3-TiO2 composite film are
shown in Figs. 1c and d, respectively. The ultrasonic treatment and
electrodeposition procedures did not destroyed the intrinsic structure of
the TiO2 NTA film. Some nanoparticles were evenly distributed on the
NTA surface without blocking the nanotube orifices, and the tube wall
thickness increased. During the SEM observation, the EDS measurement
was accomplished to confirm the elemental composition of the com-
posite film. Fig. 2 shows the corresponding EDS result, which indicated
the presence of Ti, O and Bi elements in the composite film. The pre-
sence of Bi provided an important evidence for the formation of the
desired Bi2O3-TiO2 composite through the ultrasonic-assisted electro-
deposition method. The ultrasonication process could efficaciously re-
move air from the TiO2 nanotube surfaces, and simultaneously force the
electrolyte to diffuse quickly into the pores of the nanotubes. The
subsequent electrodeposition procedure was intended to make the
electropositive Bi3+ ions be adsorbed onto both the exterior and in-
terior surfaces of the nanotubes, and finally they were transformed into
the Bi oxide.
The XPS measurements were performed to further confirm the
chemical compositions and oxidation states of the composite film,
especially for the Bi oxide deposited on the TiO2 NTA film. XPS wide
scan spectra for both the bare TiO2 and Bi2O3-TiO2 films are presented

62
Z.-C. Guan et al.
Fig. 3. XPS spectra of the TiO2 NTA and β-Bi2O3-TiO2 NTA films, (a) full spectra for both films, (b–d) high-resolution spectra of the β-Bi2O3-TiO2 NTA film for: (b) Ti 2p, (c) Bi 4f and (d) O
1s.
in Fig. 3a, and the high-resolution narrow scan spectra of the Bi2O3-
TiO2 composite film for Ti 2p, Bi 4f and O 1s are presented in
Figs. 3b–d, respectively. In the wide scan spectra, the peaks for C 1s
(284.2 eV), Ti 3s (60.7 eV), Ti 2p (458.2 eV), Ti 2s (580.0 eV) and O 1s
(529.5 eV) could be observed both for the bare TiO2 and composite
Bi2O3-TiO2 films, and the corresponding AES peaks of O KLL and Ti
LMM appeared at 975.6 eV and 1071.4 eV, respectively. While the
peaks at 160.6 eV and 442.1 eV corresponding to Bi 4f and Bi 4d could
be observed for the composite film, respectively. The C 1s peak was
thought to be caused by the adventitious hydrocarbon contamination
[36]. The high-resolution narrow scan spectrum of Ti 2p of the com-
posite film is displayed in Fig. 3b. The two peaks centered at 458.1 eV
and 463.8 eV were ascribed to Ti 2p3/2 and Ti 2p1/2, respectively, and
the doublet separation of Ti 2p was 5.7 eV, which had good agreement
with the reported value [44], indicating the existence of Ti4+ in the
composite film. As presented in Fig. 3c, the high resolution XPS spec-
trum of the Bi 4f region exhibited two peaks located at 158.7 eV and
164.1 eV, which belonged to Bi 4f7/2 and Bi 4f5/2, respectively. Fur-
thermore, the energy difference between the two peaks was exactly
5.4 eV in agreement with the data reported in the literature [36]. So,
the XPS data in Fig. 3c provided a convincing proof that the valence
state of Bi was +3 in the composite film, indicating the existence of
Bi2O3 [36,45,46]. In Fig. 3d, the narrow spectrum of O 1s contained
only one broad peak, which could be fitted into three peaks with
binding energies of 528.5 eV, 529.5 eV and 531.2 eV, respectively.
Apparently, there were some overlapping parts among these three
63
Corrosion Science 136 (2018) 60–69
peaks, suggesting that there were different chemical states of O element
in the composite film [47]. Specifically, the peak at 528.5 eV belonged
to the O of Bi-O, and the peak at 529.5 eV was attributed to the O from
Ti-O. These two chemical states of O were considered as lattice O, and
indicated the existence of Bi2O3 and TiO2, respectively. The peak at
531.2 eV could be ascribed to the adsorbed oxygen brought by irre-
versibly adsorbed H2O on the film surface [48,49].
XRD analyses were also performed to study the crystalline phase of
film samples. Fig. 4 presents the XRD patterns of the Ti foil, TiO2 NTA
and Bi2O3-TiO2 NTA films. The additional peaks were ascribed to TiO2
or Bi2O3 in the TiO2 NTA and/or Bi2O3-TiO2 composite films besides
the main diffraction peaks of Ti from the films. To be specific, the
diffraction peaks at 25.3° and 48.1° for the bare TiO2 NTA film (Fig. 4b)
could be indexed to the (101) and (200) planes of anatase TiO2 phase
(PDF #02-0387), respectively. At the same time, no peaks corre-
sponding to rutile TiO2 were detected, demonstrating that the TiO2
obtained by anodization and 450 °C calcination was anatase phased
TiO2. As shown in Fig. 4c, after the electrodeposition of Bi2O3, a dif-
fraction peak at 27.5° originated from the composite film was indexed
to the (121) plane of β-Bi2O3 (PDF #72-0398). So the Bi2O3 deposited
on TiO2 NTA film was confirmed as β-Bi2O3.
Based on the above analyses and discussions, we concluded that the
desired β-Bi2O3-TiO2 NTA composite film has been fabricated by an
anodization combined with ultrasonic-assisted electrodeposition
method. Additionally, the above characterization results showed the
good reproducibility of the preparation method of the composite film.
Z.-C. Guan et al.
Fig. 4. XRD patterns of (a) Ti foil, (b) the TiO2 NTA film and (c) the β-Bi2O3-TiO2 NTA
film.
3.2. Light absorption properties
In order to investigate the photoelectrochemical performances of
the prepared films, their UV–vis absorption spectra and photo-
luminescence (PL) emission spectra were measured. Fig. 5a presents the
UV–vis absorption spectra of the TiO2 and β-Bi2O3-TiO2 NTA films. The
bare TiO2 NTA film exhibited an absorption edge about 380 nm caused
by the electron transition from the valence band (VB) of O 2p to the
conduction band (CB) of Ti 3d in anatase TiO2 [50]. Compared with the
bare TiO2 NTA film, the absorption edge of the β-Bi2O3-TiO2 NTA
composite film showed a significant red shift to about 490 nm in the
visible light region. Furthermore, the absorption performance of the
composite film in both the UV and visible light regions was also en-
hanced. That is to say, the β-Bi2O3-TiO2 composite film exhibited a
broader and stronger light absorption, the main reason for which is the
synergistic absorption effect of the Bi2O3 photosensitizer and the for-
mation of p-n heterojunction [36,37,51,52]. Based on the absorption
data from the UV–vis spectroscopic measurements, the band gap of the
film can be estimated from the following equation [53]:
αhν = A(hν − Eg)η
where α, h, ν are the absorption coefficient, Planck's constant and light
frequency, respectively. A is a constant related to temperature, photon
energy and phonon energy. Eg is the band gap and η value is determined
by the transition type of electrons in the semiconductor, i.e., η = 1/2 is
for the direct transition and η = 2 is for the indirect transition. Here η is
Fig. 5. (a) UV–vis absorption spectra of the TiO2 NTA and β-Bi2O3-TiO2 NTA films, (b) the corresponding plots of (αhν)1/2 versus hν.
Corrosion Science 136 (2018) 60–69
taken as 2 because of the indirect transition in TiO2 semiconductor [9].
Based on the absorption data from the UV–vis measurements and Eq.
(1), the (αhν)1/2-hν curves of the prepared films could be obtained (as
shown in Fig. 5b) and their band gaps could be determined from ex-
trapolating the straight lines to α = 0 [54]. According to the UV–vis
spectroscopic results and the above estimation method, the band gap
energy of the bare TiO2 film was 3.21 eV, close to the theoretical band
gap of anatase TiO2 (3.2 eV), while the band gap energy of the β-Bi2O3-
TiO2 composite film was 2.55 eV, which was noticeably narrowed by
the deposition of β-Bi2O3 nanoparticles. The presence of Bi orbit might
efficiently decrease the energy gap between Ti and O orbitals of TiO2 in
the composite film [55]. The smaller band-gap energy could lead to the
broader light absorption region and induce the red shift of the ab-
sorption edge of the β-Bi2O3-TiO2 NTA film (Fig. 5a).
Fig. 6 presents the PL spectra of the bare TiO2 and β-Bi2O3-TiO2
NTA films. The two film samples showed the similar peak positions in
the PL spectra, but they differed in the peak intensity. The peak located
at 440–520 nm could be fitted into three peaks separately at 465 nm,
474 nm and 486 nm (inset of Fig. 6). The two peaks at 465 nm and
474 nm were mainly ascribed to the emission peaks caused by the
oxygen vacancies in TiO2 [56], while the peaks of 486 nm and 580 nm
came from the electron capture emission by surface states (Ti4+-OH)
[57]. The PL peaks result from the recombination of photogenerated
electron-hole pairs, the lower PL peak intensity implies the higher se-
paration and transfer efficiency of electron-hole pairs and the better
photoelectrochemical performance of a semiconductor material
[58,59]. The β-Bi2O3-TiO2 NTA composite film showed the lower PL
intensity than the bare TiO2 NTA film, indicating that the recombina-
tion of electron-hole pairs in the composite film was efficiently reduced
and the separation and transfer efficiency of electron-hole pairs was
enhanced, which is really essential for photoelectrochemical applica-
tions.
According to the foregoing discussion, the incorporation of β-Bi2O3
into the TiO2 NTA film could optimize the energy band structure of
TiO2, narrow the band-gap and extend the light absorption to the
visible region, which would be beneficial to generate more electron-
hole pairs in the β-Bi2O3-TiO2 NTA composite film under illumination.
These properties would be very important for photoelectrochemical
cathodic protection applications.
3.3. Photoelectrochemical cathodic protection effect
(1)
Compared to the traditional cathodic protection (sacrificial anode
and impressed current cathodic protection), the photoelectrochemical
cathodic protection has high research value and inviting application
prospects because it does not consume anode materials and external
electric energy. The basic mechanism of photoelectrochemical cathodic
protection is that a semiconductor photoanode is used as a replacement
64
Z.-C. Guan et al.
Fig. 6. Photoluminescence spectra of (a) the TiO2 NTA film and (b) the β-Bi2O3-TiO2 NTA
film with the excitation wavelength of 370 nm, the inset shows the fitting result of the
peak between 440 nm to 520 nm.
for the traditional sacrificial anode, and provides CB electrons gener-
ated from the VB under illumination for a metal to be protected. In a
photoelectrochemical cathodic protection system, the semiconductor
photoanode supplies the metal with a photocurrent resulting from
photoelectric conversion to protect the metal cathodically from corro-
sion [23,24,42].
In order to inhibit the metal corrosion by the photoelectrochemical
approach, the photoanode under illumination must have the ability to
provide enough cathodic current for the metal. Fig. 7a compares the
instantaneous photocurrent densities of the TiO2 and β-Bi2O3-TiO2 NTA
films in the 0.5 M Na2SO4 solution under white light illumination in
open-circuit situations for evaluating the sensitivity of the film to the
light. The currents as recorded were anodic on the Ti specimen. The β-
Bi2O3-TiO2 NTA composite film showed a photocurrent density of
80 μA cm−2, which was about 4 times as high as that of the bare TiO2
NTA film (about 20 μA cm−2). The enhancement of the photocurrent
density for the composite film presaged higher photoelectrochemical
conversion efficiency. And this enhancement could be attributed to the
deposition of β-Bi2O3, leading to the faster transfer and higher se-
paration efficiency of the photogenerated electron-hole pairs. In addi-
tion, the photocurrent densities of the two samples immediately
changed once the light was turned on or off, indicating the high sen-
sitivity of the films to the light. The two films also showed excellent
Fig. 7. (a) Transient photocurrent density and (b) photopotential (photo-induced open circuit potential) responses of the TiO2 NTA and β-Bi2O3-TiO2 NTA films served as anodes in the
0.5 M Na2SO4 solution in open-circuit situations under intermittent white light illumination.
65
Corrosion Science 136 (2018) 60–69
stability during the entire test period, which is also propitious to their
applications in photoelectrochemical cathodic protection. Fig. 7b dis-
plays the photopotential (photo-induced open circuit potential) varia-
tions of the TiO2 NTA and β-Bi2O3-TiO2 NTA films in the 0.5 M Na2SO4
solution under intermittent white light illumination and open-circuit
conditions. Before the white light illumination (dark conditions), the
potentials of TiO2 NTA and β-Bi2O3-TiO2 NTA films were about
−110 mV (vs. SCE) and −200 mV (vs. SCE), respectively. When the
films were separately illuminated, their potentials shifted in the nega-
tive direction because of the generation of photoelectrons in these two
semiconductor films. For the bare TiO2 NTA film, its photopotential was
about −280 mV (vs. SCE), which was 170 mV lower than its original
open-circuit potential (namely the potential before illumination).
Especially, the photopotential of the β-Bi2O3-TiO2 NTA film reached
about −460 mV (vs. SCE), which was 260 mV lower than its original
open-circuit potential. That is to say, the photopotential of the β-Bi2O3-
TiO2 NTA film was more negative than that of the bare TiO2 NTA film
under white light illumination, which indicated that the β-Bi2O3-TiO2
NTA film might provide a more effective photoelectrochemical cathodic
protection effect than the bare TiO2 NTA film. When the light was
turned off, the potentials of the two films immediately shifted positively
due to the electron-hole recombination, which was in accordance with
the results of photocurrent density measurements. Furthermore, the
potential response of both the bare TiO2 and β-Bi2O3-TiO2 films was
almost repeatable, showing good photosensitivity and high stability
during the entire test period, which is important for the application in
photoelectrochemical cathodic protection.
As is known to all, when a metal is under cathodic protection, its
actual potential is more negative than its open circuit potential (OCP).
In this work, the changes of the 403SS potential under different con-
ditions were measured to evaluate the photoelectrochemical cathodic
protection performance of the TiO2 and β-Bi2O3-TiO2 NTA films as
photoanodes. The potential changes of 403SS in the 0.5 M NaCl solution
are presented in Fig. 8. Before coupling, the corrosion potential of
403SS stabilized at about 50 mV vs. SCE (Fig. 8a). As seen in Fig. 8b and
c, when 403SS was coupled to the TiO2 and β-Bi2O3-TiO2 NTA films
under dark conditions, the potentials were negatively shifted to
−150 mV vs. SCE and −190 mV vs. SCE, respectively, because of the
galvanic effect. When the white light illumination was provided, po-
tentials showed further negative shifts to −250 mV vs. SCE and
−400 mV (vs. SCE) for the 403SS electrode coupled with the TiO2 and
β-Bi2O3-TiO2 films, respectively. Under these illumination conditions,
the 403SS were under cathodic protection. The potential of the 403SS
coupled with the β-Bi2O3-TiO2 composite film was 150 mV more ne-
gative than that coupled with the bare TiO2 NTA film, showing more
effective photoelectrochemical cathodic protection by the β-Bi2O3-TiO2
Z.-C. Guan et al.
Fig. 8. Potential changes of 403SS in the corrosion cell with a 0.5 M NaCl solution in
open-circuit situations, (a) corrosion potential of uncoupled 403SS, (b) 403SS coupled
with the TiO2 NTA film and (c) 403SS coupled with the β-Bi2O3-TiO2 NTA film under
intermittent white light illumination. The inset shows the potential change of 403SS
coupled with the β-Bi2O3-TiO2 film under 6 light on/off cycles. The films as photoanodes
were in the photoelectrochemical cell with a 0.5 M Na2SO4 solution.
composite film. When the illumination was turned off, the potential of
the 403SS coupled with the TiO2 film immediately shifted back to the
value (−150 mV vs. SCE) before illumination and remained stable,
while the potential of the 403SS coupled with the composite film
shifted positively to a potential level (−240 mV vs. SCE) lower than
that (−190 mV vs. SCE) before illumination, indicating that the com-
posite film remaining some cathodic protection effect. When the illu-
mination was provided again, the potential of the 403SS coupled with
TiO2 or β-Bi2O3-TiO2 film decreased to the same value as before and
was stable, showing good sensitivity to light. After cutting off the light,
the 403SS potential again rose sharply to the same value as before
(Figs. 8b and c). But the potential of the 403SS coupled with the β-
Bi2O3-TiO2 composite film increased gradually to the level as that be-
fore the first illumination, indicating that the composite film could
provide some degree of cathodic protection even after the light was cut
off during this period (about 15 h). To investigate the stability of the
composite film in the photoelectrochemical cathodic protection appli-
cation, the potential response of the 403SS coupled with the composite
film to 6 on/off cycles of illumination was recorded as shown in the
inset of Fig. 8. The results showed that the composite film was quite
stable and its protecting effect on the 403SS did not evidently attenuate
during the illumination for the 6 cycles.
EIS can provide valuable electrochemical information of the metal/
solution interface. So, EIS measurements were executed to evaluate the
photoelectrochemical cathodic protection effects of the prepared films
[23,24,60]. The Nyquist, Bode-phase and Bode-modulus plots of 403SS
in the 0.5 M NaCl solution uncoupled and coupled with different film
photoanodes are presented in Fig. 9A–C, respectively. The Nyquist plots
featured only one capacitive loop, and the Bode plots showed only one
time constant accordingly. The radius of the capacitive loop in the
Nyquist plot decreased when 403SS coupled with the film photoanode
under white light illumination, and showed the smallest radius when
403SS coupled with the β-Bi2O3-TiO2 composite film. The similar var-
iation trend was observed in Bode plots. Therefore, the EIS spectra
could be modeled by the equivalent circuit shown in the inset of
66
Corrosion Science 136 (2018) 60–69
Fig. 9A. In the presented equivalent circuit model, Rs, Rct and CPE re-
present the solution resistance, charge transfer resistance and constant
phase element, respectively. The main objective of the EIS measure-
ments is to obtain the Rct value of the coupled 403SS in the corrosion
cell for the comparison between illumination and dark conditions. For
simplicity, the EIS analysis focused on the effect of the film under white
light illumination on the coupled steel. The fitting results showed that
the Rct of the uncoupled 403SS was 287.70 ± 4.32 kΩ cm2, but de-
creased sharply to 19.53 ± 0.23 kΩ cm2 and 6.24 ± 0.25 kΩ cm2
when the 403SS was coupled with the bare TiO2 and β-Bi2O3-TiO2 NTA
composite films under white light illumination, respectively. When the
403SS was coupled with the film photoanode under illumination, the
photogenerated electrons were transferred from the photoanode to the
steel to participate in the electrochemical reactions, which accelerated
the cathodic reaction at the steel/solution interface and showed a lower
Rct value. Therefore, the 403SS was polarized cathodically and its
corrosion was reduced. Furthermore, the Rct value of the 403SS coupled
with the composite film was lower than that coupled with the bare TiO2
film, suggesting that the composite film under illumination could pro-
vide more electrons due to its superior photoelectrochemical perfor-
mance, which was in agreement with the foregoing analysis results.
Thus, it is conclusive that the prepared β-Bi2O3-TiO2 NTA composite
film could provide a higher cathodic current density under white light
illumination relative to the bare TiO2 NTA film, and more effectively
inhibit the corrosion of 403SS.
3.4. Mechanism
Based on the above results and discussions, the mechanism of the
enhanced photoelectrochemical cathodic protection provided by the β-
Bi2O3-TiO2 composite film for 403SS is illustrated in Scheme 2.
TiO2 is a recognized n-type semiconductor, while β-Bi2O3 belongs to
a p-type semiconductor. In the β-Bi2O3-TiO2 NTA film, a p-n hetero-
junction was built between the p-type Bi2O3 and the n-type TiO2, which
could be proved by the i-E curves shown in Fig. 9D. The dark current of
the bare TiO2 film was almost zero, showing the poor p-n heterojunction
effect. However, the current of the β-Bi2O3-TiO2 NTA film was asym-
metric in forward and reverse scans, showing an obvious diode beha-
vior. This result provided reliable evidence that the p-n heterojunction
was built and there was an internal electrostatic field at the interface
between TiO2 and Bi2O3 [61]. When the p-n heterojunction was formed,
electrons transferred from n-type TiO2 to p-type Bi2O3, while holes
transferred in the opposite direction until the system reached equili-
bration because of the diffusion effect of carriers. This carrier diffusion
results in the formation of internal electrostatic field in the p-n het-
erojunction (shown in Scheme 2), which made the n-type TiO2 be po-
sitively charged and the p-type Bi2O3 be negatively charged [62,63].
As shown in Scheme 2, when the β-Bi2O3-TiO2 NTA film was irra-
diated by white light (Xe lamp, 190–1100 nm), TiO2 could absorb the
UV light to excite its VB electrons to the CB, while the photogenerated
holes migrated from the TiO2 VB to the β-Bi2O3 VB due to the driving
force of the internal electrostatics in the p-n heterojunction. Meanwhile,
β-Bi2O3 could absorb UV light and part of visible light due to its narrow
band-gap, and more photoelectrons were generated in the CB of the
excited β-Bi2O3. Similarly, the photoelectrons were transferred from the
β-Bi2O3 CB to the TiO2 CB due to the driving force of the internal
electrostatics. Taken as a whole, the photogenerated electron-hole pairs
in the β-Bi2O3-TiO2 composite film were separated effectively, the
photogenerated electrons were transferred from the TiO2 CB to the
403SS to provide cathodic protection, and the photogenerated holes in
the β-Bi2O3 VB were consumed by hole scavengers in the solution. So,
the β-Bi2O3-TiO2 NTA film had a higher charge carrier separation and
transfer efficiency and superior photoelectrochemical performance
compared with the unmodified TiO2 film. Therefore, the deposition of
β-Bi2O3 nanoparticles on the TiO2 nanotubes could improve the
Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69

Fig. 9. (A) Nyquist, (B) Bode-phase and (C) Bode-modulus plots of 403SS in the 0.5 M NaCl solution uncoupled and coupled with different film photoanodes under white light
illumination at open-circuit potential conditions: (a) uncoupled, (b) coupled with TiO2 NTA film and (c) coupled with the β-Bi2O3-TiO2 NTA film. The scatter plots are experimental data
and solid lines are the fitting results. The two insets in (A) show the simulating equivalent circuit of 403SS with the above conditions and the magnified plots, respectively. (D) i-E curves
of the TiO2 NTA and β-Bi2O3-TiO2 NTA films in the 0.5 M Na2SO4 solution at a scan rate of 10 mV s−1 under dark conditions.

the bare TiO2 NTA film, the β-Bi2O3-TiO2 NTA composite film exhibited
a broader light absorption region and a higher photogenerated carrier
separation and transfer efficiency. The photocurrent density of the
composite film in the 0.5 M Na2SO4 solution under white light illumi-
nation was 4 times as high as that of the bare TiO2 film, indicating that
the photoelectrochemical performance of the composite film was lar-
gely enhanced. The potential of 403SS in the 0.5 M NaCl solution de-
creased by 300 mV and 450 mV compared to its corrosion potential
when it was coupled to the TiO2 and β-Bi2O3-TiO2 films in the 0.5 M
Na2SO4 solution under white light illumination, respectively, indicating
that the β-Bi2O3-TiO2 composite film could provide a more effective
photoelectrochemical cathodic protection for 403SS than that provided
by the bare TiO2 film.

Acknowledgement
Scheme 2. Schematic illustration of the energy band structure and the electron-hole pair
separation/transfer mechanism in the β-Bi2O3-TiO2 NTA composite film under white light
Financial support from NSFC (Nos. 21573182, 21173177, 21073151,
illumination for the photoelectrochemical cathodic protection application.
and 21621091) is gratefully acknowledged.

photoelectrochemical cathodic protection performance of the TiO2 References

composite film.
4. Conclusions
In this study, a method containing anodization and electrodeposi-
tion has been developed to fabricate a β-Bi2O3 nanoparticle modified
TiO2 NTA composite film with a p-n heterostructure. Compared with
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Another random document with
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 The American Sabbath Tract Society is the publishing agency of
the denomination. Its head-quarters are at Alfred Center, N. Y. It
publishes the Sabbath Recorder, the organ of the S. D. Baptists, and
it also publishes a series of valuable works relating to the Sabbath
and the law of God.
During the two hundred years which have elapsed since the
organization of the first Sabbatarian church in America, God has
raised up among this people men of eminent talent and moral worth.
He has also in providential ways called attention to the sacred trust
which he so long since confided to the S. D. Baptists, and which they
have been slow to realize in its immense importance.
Among those converted to the Sabbath through the agency of this
people, the name of J. W. Morton is particularly worthy of honorable
mention. He was sent in 1847 a missionary to the island of Hayti by
the Reformed Presbyterians. Here he came in contact with
Sabbatarian publications, and after a serious examination became
satisfied that the seventh day is the Sabbath of the Lord. As an
honest man, what he saw to be truth he immediately obeyed, and
returning home to be tried for his heresy, was summarily expelled
from the Reformed Presbyterian church without being suffered to
state the reasons which had governed his conduct. He has given to
the world a valuable work, entitled, “Vindication of the True Sabbath,”
in which his experience is related, and his reasons for observing the
seventh day set forth with great force and clearness.
The S. D. Baptists do not lack men of education and of talent, and
they have ample means in their possession with which to sustain the
cause of God. If in time past they have not fully realized that they
were debtors to all mankind because of the great truth which God
committed to their trust, there is reason to believe that they are now
to some extent awakening to this vast indebtedness.[1100]
There is also in the State of Pennsylvania a small body of German
S. D. Baptists found in the counties of Lancaster, York, Franklin, and
Bedford, and in the central and western parts of the State. They
originated in 1728 from the teaching of Conrad Beissel, a native of
Germany. They practice trine immersion, and the washing of feet,
and observe open communion. They encourage celibacy, but make it
obligatory upon none. Even those who have chosen this manner of
life are at liberty to marry if at any time they choose so to do. They
established and successfully maintained a Sabbath-school at
Ephrata, their head-quarters, forty years before Robert Raikes had
introduced the system of Sunday-schools. This people have suffered
much persecution because of their observance of the seventh day,
the laws of Pennsylvania being particularly oppressive toward
Sabbatarians.[1101] The German S. D. Baptists do not belong to the
S. D. Baptist General Conference.
We have already noticed the fact that Sabbath-keepers are
numerous in Russia, in Poland, and in Turkey. We find the following
statement respecting Sabbath-keepers in Hungary:—

“A congregation of seventh-day Christians in Hungary,

being refused tolerance by the laws, has embraced Judaism,
in order to be allowed to exist in connection with one of the
‘received religions.’”[1102]

The probability is that as the laws of the Austrian Empire bear very
heavily upon all religious bodies not belonging to some one of the
tolerated sects or orders, these “Seventh-day Christians” on “being
refused tolerance” in their own name, secured the privilege of
observing the seventh day by allowing their doctrine to be classed by
the civil authorities under the head of Judaism, and so bringing
themselves under the tolerance accorded to the “received religions.”
We do not say that this was right, even as a technicality, but it is
evidently the extent of what they did. There is no reason to believe
that they abjured Christ. We also learn that there are Sabbath-
keepers in the north of Asia:—

“There is a sect of Greek Christians in Siberia who keep the

Jewish Sabbath (Saturday). Such sects already exist in the
United States, in Germany, and we believe in England.”[1103]
 The Sabbath was first introduced to the attention of the Advent
people at Washington, N. H. A faithful Seventh-day Baptist sister,
Mrs. Rachel D. Preston, from the State of New York, having removed
to this place, brought with her the Sabbath of the Lord. Here she
became interested in the doctrine of the glorious advent of the
Saviour at hand. Being instructed in this subject by the Advent
people, she in turn instructed them in the commandments of God,
and as early as 1844, nearly the entire church in that place,
consisting of about forty persons, became observers of the Sabbath
of the Lord.[1104] The oldest body of Sabbath-keepers among the
Seventh-day Adventists is therefore at Washington, N. H. Its present
number is small, for it has been thinned by emigration and by the
ravages of death; but there still remains a small company to bear
witness to this ancient truth of the Bible.
From this place, several Advent ministers received the Sabbath
truth during the year 1844. One of these was Eld. T. M. Preble, who
has the honor of first bringing this great truth before the Adventists
through the medium of the press. His essay was dated Feb. 13,
1845. He presented briefly the claims of the Bible Sabbath, and
showed that it was not changed by the Saviour, but was changed by
the great apostasy. He then said:—

“Thus we see Dan. 7:25, fulfilled, the little horn changing

‘times and laws.’ Therefore it appears to me that all who keep
the first day for the Sabbath, are Pope’s Sunday-keepers, and
God’s Sabbath breakers.”[1105]

Within a few months many persons began to observe the Sabbath

as the result of the light thus shed on their pathway. Eld. J. B. Cook,
a man of decided talent as a preacher and a writer, was one of these
early converts to the Sabbath. Elders Preble and Cook were at this
time in the full vigor of their mental powers, and were possessed of
talent and a reputation for piety, which gave them great influence
among the Adventists in behalf of the Sabbath. These men were
called in the providence of God to fill an important place in the work
of Sabbath reform.
 But both of them, while preaching and writing in its behalf,
committed the fatal error of making it of no practical importance.
They had apparently the same fellowship for those who rejected the
Sabbath that they had for those who observed it. Such a course of
action produced its natural result. After two or three years of this kind
of Sabbath observance, each of these men apostatized from it, and
thenceforward used what influence they possessed in warring
against the fourth commandment. The larger part of those who
embraced the Sabbath from their labors were not sufficiently
impressed with its importance to become settled and grounded in its
weighty evidences, and, after a brief period, they turned back from
its observance. But enough had been done to excite bitter opposition
toward the Sabbath on the part of many Adventists, and to bring out
the ingenious and plausible arguments by which men attempt to
prove that God has abolished his own sacred law.
Such was the fruit of their course, and such the condition of things
at the time of their defection. But the result of their plan of action
taught the Advent Sabbath-keepers a lesson of value, which they
have never forgotten. They learned that the fourth commandment
must be treated as a part of the moral law, if men are ever to be led
to its sacred observance.
Eld. Preble’s first article in behalf of the Sabbath was the means of
calling the attention of our venerable brother, Joseph Bates, to this
divine institution. He soon became convinced of its obligation, and at
once began to observe it. He had acted quite a prominent part in the
Advent movement of 1843-4, and now, with self-sacrificing zeal, he
took hold of the despised Sabbath truth to set it before his fellow-
men. He did not do it in the half-way manner of Elders Preble and
Cook, but as a man thoroughly in earnest and fully alive to the
importance of his subject.
The subject of the heavenly Sanctuary began about this time to
interest many Adventists, and especially Eld. Bates. He was one of
the first to see that the central object of that Sanctuary is the ark of
God. He also called attention to the proclamation of the third angel
relative to God’s commandments. He girded on the armor to lay it
down only when his work should be accomplished. He has been
instrumental in leading many to the observance of the
commandments of God and the faith of Jesus, and few who have
received the Sabbath from his teaching have apostatized from it.
[1106]

It was but a few months after Eld. Bates, that our esteemed and
efficient brother, Eld. James White, also embraced the Sabbath. He
had labored with much success in the great Advent movement, and
he now entered heartily into the work of Sabbath reform. Uniting with
Eld. Bates in the proclamation of the doctrine of the advent and the
Sabbath as connected together in the Sanctuary and the message of
the third angel, he has, with the blessing of God, accomplished great
results in behalf of the Sabbath.
The publishing interests of the Seventh-day Adventists originated
through his instrumentality. He began the work of publishing in 1849,
without resources, and with very few friends, but with much toil, self-
sacrifice, and anxious care; and with the blessing of God upon his
efforts, he has been the means of establishing an efficient office of
publication, and of disseminating many important works throughout
our country, and, to some extent, to other nations also. The
publication of the Advent Review and Herald of the Sabbath, the
organ of the Seventh-day Adventists, was commenced by him in
1850. For most of the years of its existence, he has served as one of
its editors; and for all its earlier years, he was both publisher and
sole editor. During this time, he has also labored with energy as a
minister of the gospel of Christ.
The wants of the cause demanding an enlargement of capital and
more extensive operations, to this end an Association was
incorporated in the city of Battle Creek, Michigan, May 3, 1861,
under the name of the Seventh-day Adventist Publishing
Association. This Association owns three commodious publishing
houses, with engine, power presses, and all the fixtures necessary
for doing an extensive business. There are about fifty persons
constantly employed in this work of publication. The Association has
a capital of about $82,000. Under God, it owes its prosperity to the
prudent management and untiring energy of Eld. James White.
 The Advent Review has at the present time (Nov., 1873) a
circulation of about 5000 copies. The Youth’s Instructor, a monthly
paper designed for the children of Sabbath-keeping Adventists,
began to be issued in 1852, and has now attained a circulation of
nearly 5000 copies.
The Advent Tidende, a Danish monthly with a circulation of 800, is
published for the benefit of those who speak the Danish and
Norwegian tongues, of whom a considerable number have
embraced the Sabbath.
The S. D. Adventists have taken a strong interest in the subject of
hygiene and the laws of health, and have established a Health
Institute at Battle Creek, Mich., which publishes the Health Reformer,
a monthly journal, magazine form, having a circulation of nearly 5000
copies.
Numerous publications on Prophecy, the Signs of the Times, the
Coming of Christ, the Sabbath, the Law of God, the Sanctuary, &c.,
&c., have been issued within the past twenty years, and have had an
extensive circulation, amounting, in the aggregate, to many millions
of pages.
The ordinary financial wants of the cause are sustained by a
method of collecting means known as Systematic Benevolence. By
this system, it is designed that each friend of the cause shall pay a
certain sum weekly proportioned to the property which he
possesses. But there is no compulsion in this matter. In this manner
the burden is borne by all, so that it rests heavily upon none; and the
means needed for the work flows with a steady stream into the
treasury of the several churches, and finally into that of the State
Conferences. A settlement is instituted each year at the State
Conferences, in which the labors, receipts, and expenditures, of
each minister are carefully considered. Thus none are allowed to
waste means, and none who are recognized as called of God to the
ministry are allowed to suffer.
The churches sustain their meetings for the most part without the
aid of preaching. They raise means to sustain the servants of Christ,
but bid them mainly devote their time and strength to save those who
have not the light of these important truths shining upon their
pathway. So they go out everywhere preaching the word of God, as
his providence guides their feet. During the summer months, the
work in new fields is carried forward principally by means of large
tents, which enable the preacher to provide a suitable place of
worship, wherever he may think it desirable to labor.
The Seventh-day Adventists have thirteen State Conferences,
which assemble annually in their respective States. These bear the
names of Maine, Vermont, New England, New York and
Pennsylvania, Ohio, Michigan, Indiana, Illinois, Wisconsin,
Minnesota, Iowa, Missouri and Kansas, and California. These
Conferences are designed to meet the local wants of the cause.
There is also a General Conference, which assembles yearly,
composed of delegates from the State Conferences. This
Conference takes the general oversight of the work in all the State
Conferences, supplying the more destitute with laborers as far as
possible, and uniting the whole strength of the body for the
accomplishment of the work. It also takes the charge of missionary
labor in those States which have no organized Conferences.
There are about fifty ministers who devote their whole time to the
work of the gospel. There is also a considerable number who preach
a portion of the time and devote the remainder to secular labor.
There are about 6000 members in the several Conference
organizations. But such is the scattered condition of this people (for
they are found in all the northern States and in several of the
southern), that a very large portion have no connection with its
organization. They are to be found in single families scattered all the
way from Maine to California and Oregon. The Review and Instructor
constitute, in a great number of cases, the only preachers of their
faith.
Those subjects which more especially interest this people, are the
fulfillment of prophecy, the second personal advent of the Saviour as
an event now near at hand, immortality through Christ alone, a
change of heart through the operation of the Holy Spirit, the
observance of the Sabbath of the fourth commandment, the divinity
and mediatorial work of Christ, and the development of a holy
character by obedience to the perfect and holy law of God.[1107]
They are very strict with regard to the ordinance of baptism,
believing not only that it requires men to be buried in the watery
grave, but that even such baptism is faulty if administered to those
who are breaking one of the ten commandments. They also believe
that our Lord’s direction in John 13 should be observed in connection
with the supper.
They teach that the gifts of the Spirit set forth in 1 Cor. 12 and
Eph. 4, were designed to remain in the church till the end of time.
They believe that these were lost in consequence of the same
apostasy that changed the Sabbath. They also believe that in the
final restoration of the commandments by the work of the third angel,
the gifts of the Spirit of God are restored with them. So the remnant
of the church, or last generation of its members, is said to “keep the
commandments of God, and have the testimony of Jesus
Christ.”[1108] And the angel of God explains this by saying, “The
testimony of Jesus is the spirit of prophecy.”[1109] The spirit of
prophecy therefore has a distinct place assigned to it in the final
work of Sabbath reform. Such are their views of this portion of
Scripture; and their history from the beginning has been marked by
the influence of this sacred gift.
In the face of strong opposition, the people known as Seventh-day
Adventists have arisen to bear their testimony for the Sabbath of the
Lord. They have had perils from open foes, and from false brethren;
but they have thus far overcome the difficulties of the way, and from
each have gathered strength for the conflict before them. They have
a definite work which they hope to accomplish. It is to make ready a
people prepared for the advent of the Lord.
Honorable mention should be made of the Seventh-day Adventists
of Switzerland. They first learned these precious truths from Elder M.
B. Czechowski, who a few years since instructed them in the
commandments of God and the faith of Jesus. Since his labors with
them ceased, God has given them strength to stand with firmness for
his truth, and has added to their numbers. They have a heart to obey
the truth and to sacrifice for its advancement. They number about
sixty persons. There are a few individuals of this faith also in Italy,
Germany, and Denmark.
The observance of the Sabbath is sometimes advocated on the
ground that man needs a day of rest and will grow prematurely old if
he labor seven days in each week, which is doubtless true; and it
has also been advocated on the ground that God will bless in basket
and in store those who hallow his Sabbath, which may be true in
many cases; but the Bible does not urge motives of this kind in
respect to this sacred institution. Without doubt there are great
incidental advantages in the observance of the Sabbath. But these
are not what God sets before us as the reasons for its observance.
The true reason is infinitely higher than all considerations of this
kind, and should constrain men to obey, even were it certain that it
would cost them all that is dear in the present life.
The Sabbath has been advocated on the ground that it secures to
men a day for divine worship in which by common consent they may
appear before God. This is a very important consideration, and yet
the Bible says little concerning it. It is one of the incidental blessings
of the Sabbath, and not the chief reason for its observance. The
Sabbath was ordained to commemorate the creation of the heavens
and the earth.
The importance of the Sabbath as the memorial of creation is that
it keeps ever present the true reason why worship is due to God. For
the worship of God is based upon the fact that he is the Creator and
that all other beings were created by him. The Sabbath therefore lies
at the very foundation of divine worship, for it teaches this great truth
in the most impressive manner, and no other institution does this.
The true ground of divine worship, not of that on the seventh day
merely, but of all worship, is found in the distinction between the
Creator and his creatures. This great fact can never become
obsolete, and must never be forgotten. To keep it in man’s mind,
God gave to him the Sabbath. He received it in his innocency, and
notwithstanding the perversity of his professed people, God has
preserved this sacred institution through the entire period of man’s
fallen state.
 The four and twenty elders in the very act of worshiping Him who
sits upon the throne, state the reason why worship is due to God:—

“Thou art worthy, O Lord, to receive glory and honor and

power; for thou hast created all things, and for thy pleasure
they are and were created.”[1110]

This great truth is therefore worthy to be remembered even in the

glorified state. And we shall presently learn that what God gave to
man in Paradise, to keep this great truth before his mind, shall be
honored by him in Paradise restored.
The future is given to us in the prophetic Scriptures. From them we
learn that our earth is reserved unto fire, and that from its ashes shall
spring new heavens and earth, and ages of endless date.[1111] Over
this glorified inheritance, the second Adam, the Lord of the Sabbath,
shall bear rule, and under his gracious protection the nations of them
which are saved shall inherit the land forever.[1112] When the glory of
the Lord shall thus fill the earth as the waters cover the sea, the
Sabbath of the Most High is again and for the last time brought to
view:—

“For as the new heavens and the new earth, which I will
make shall remain before me, saith the Lord, so shall your
seed and your name remain. And it shall come to pass, that
from one new moon to another, and from one Sabbath to
another, shall all flesh come to worship before me, saith the
Lord.”[1113]

Does not Paul refer to these very facts set forth by Isaiah when he
says, “There remaineth therefore a rest [Greek, Sabbatismos,
literally “a keeping of the sabbath”] to the people of God”?[1114]
The reason for this monthly gathering to the New Jerusalem of all
the host of the redeemed from every part of the new earth may be
found in the language of the Apocalypse:—
 “And he showed me a pure river of water of life, clear as
crystal, proceeding out of the throne of God and of the Lamb.
In the midst of the street of it, and on either side of the river
was there the tree of life, which bare twelve manner of fruits
and yielded her fruit every month; and the leaves of the tree
were for the healing [literally, the service][1115] of the
nations.”[1116]

The gathering of the nations that are saved to the presence of the
Creator, from the whole face of the new earth on each successive
Sabbath, attests the sacredness of the Sabbath even in that holy
state, and sets the seal of the Most High to the perpetuity of this
ancient institution.
 FOOTNOTES
[1] For the scriptural and traditional evidence on this point, see
Shimeall’s Bible Chronology, part i. chap. vi; Taylor’s Voice of the
Church, pp. 25-30; and Bliss’ Sacred Chronology, pp. 199-203.
[2] Isa. 57:15; 1 Sam. 15:29, margin; Jer. 10:10, margin; Micah
5:2, margin; 1 Tim. 6:16; 1:17; Ps. 90:2.
[3] Dr. Adam Clarke, in his Commentary on Gen. 1:1, uses the
following language: “Created] Caused that to exist which
previously to this moment, had no being. The rabbins, who are
legitimate judges in a case of verbal criticism on their own
language, are unanimous in asserting that the word bara,
expresses the commencement of the existence of a thing: or its
egression from nonentity to entity.... These words should be
translated: ‘God in the beginning created the substance of the
heavens and the substance of the earth; i. e., the prima materia,
or first elements, out of which the heavens and the earth were
successively formed.’”
Purchase’s Pilgrimage, b. i. chap, ii., speaks thus of the
creation: “Nothing but nothing had the Lord Almighty, whereof,
wherewith, whereby, to build this city” [that is the world].
Dr. Gill says: “These are said to be created, that is, to be made
out of nothing; for what pre-existent matter to this chaos [of verse
2] could there be out of which they could be formed?”
“Creation must be the work of God, for none but an almighty
power could produce something out of nothing.” Commentary on
Gen. 1:1.
John Calvin, in his Commentary on this chapter, thus expounds
the creative act: “His meaning is, that the world was made out of
nothing. Hence the folly or those is refuted who imagine that
unformed matter existed from eternity.”
The work of creation is thus defined in 2 Maccabees 7:28:
“Look upon the heaven and the earth, and all that is therein, and
consider that God made them of things that were not; and so was
mankind made likewise.”
That this creative act marked the commencement of the first
day instead of preceding it by almost infinite ages is thus stated in
2 Esdras 6:38: “And I said, O Lord, thou spakest from the
beginning of the creation, even the first day, and saidst thus: Let
heaven and earth be made; and thy word was a perfect work.”
Wycliffe’s translation, the earliest of the English versions,
renders Gen. 1:1, thus: “In the first, made God of naught heaven
and earth.”
[4] Heb. 11:3; Gen. 1.
[5] Gen. 1:1-5; Heb. 1.
[6] Gen. 1:6-8; Job 37:18.
[7] Gen. 1:9-13; Ps. 136:6; 2 Pet. 3:5.
[8] Gen. 1:14-19; Ps. 119:91; Jer. 33:25.
[9] Gen 1:20-23.
[10] Gen. 1:24-31; 2:7-9, 18-22; 3:20; Job 38:7.
[11] “On the sixth day God ended his work which he had made;
and he rested on the seventh day,” &c., is the reading of the
Septuagint, the Syriac, and the Samaritan; “and this should be
considered the genuine reading,” says Dr. A. Clarke. See his
Commentary on Gen. 2.
[12] Gen. 2:2; Ex. 31:17.
[13] Isa. 40:28.
[14] Gen. 2:3; Ex. 20:11. In an anonymous work entitled
“Morality of the Fourth Commandment,” London, 1652, but not the
same with that of Dr. Twisse, of the same title, is the following
striking passage:
“The Hebrew root for seven signifies fullness, perfection, and
the Jews held many mysteries to be in the number seven: so
John in his Apocalypse useth much that number. As, seven
churches, seven stars, seven spirits, seven candlesticks, seven
angels, seven seals, seven trumpets; and we no sooner meet
with a seventh day, but it is blessed; no sooner with a seventh
man [Gen. 5:24; Jude 14], but he is translated.” Page 7.
 [15] Webster’s Unabridged Dictionary on the words sanctify and
hallow. Ed. 1859.
The revised edition of 1864 gives this definition: “To make
sacred or holy; to set apart to a holy or religious use; to
consecrate by appropriate rites; to hallow. God blessed the
seventh day, and sanctified it. Gen. 2:3. Moses ... sanctified
Aaron and his garments. Lev. 8:30.”
Worcester defines it thus: “To ordain or set apart to sacred
ends; to consecrate; to hallow. God blessed the seventh day and
sanctified it. Gen. 2:3.”
[16] Gen. 2:15; 1:28.
[17] Morality of the Fourth Commandment, pp. 56, 57, London,
1641.
[18] Hebrew Lexicon, p. 914, ed. 1854.
[19] Josh. 20:7; Joel 1:14; 2:15; 2 Kings 10:20, 21; Zeph. 1 7,
margin.
[20] Ex. 10:12, 23.
[21] Dr. Lange’s Commentary speaks on this point thus, in vol. i,
p. 197: “If we had no other passage than this of Gen. 2:3, there
would be no difficulty in deducing from it a precept for the
universal observance of a Sabbath, or seventh day, to be devoted
to God, as holy time, by all of that race for whom the earth and its
nature were specially prepared. The first men must have known it.
The words, ‘He hallowed it,’ can have no meaning otherwise.
They would be a blank unless in reference to some who were
required to keep it holy.”
Dr. Nicholas Bound, in his “True Doctrine of the Sabbath,”
London, 1606, page 7, thus states the antiquity of the Sabbath
precept:
“This first commandment of the Sabbath was no more then first
given when it was pronounced from Heaven by the Lord, than any
other one of the moral precepts, nay, that it hath so much
antiquity as the seventh day hath being; for, so soon as the day
was, so soon was it sanctified, that we might know that, as it
came in with the first man, so it must not go out but with the last
man; and as it was in the beginning of the world, so it must
continue to the end of the same; and, as the first seventh day was
sanctified, so must the last be. And this is that which one saith,
that the Sabbath was commanded by God, and the seventh day
was sanctified of him even from the beginning of the world; where
(the latter words expounding the former) he showeth that, when
God did sanctify it, then also he commanded it to be kept holy;
and therefore look how ancient the sanctification of the day is, the
same antiquity also as the commandment of keeping it holy; for
they two are all one.”
[22] Ex. 20:8-11.
[23] Buck’s Theological Dictionary, article, Sabbath; Calmet’s
Dictionary, article, Sabbath.
[24] Ex. 16:22, 23.
[25] John 1: 1-3; Gen. 1:1, 26; Col. 1:13-16.
[26] Mark 2:27.
[27] Barrett’s Principles of English Grammar, p. 29.
[28] Job 14:12; 1 Cor. 10:13; Heb. 9:27.
[29] Dr. Twisse illustrates the absurdity of that view which
makes the first observance of the Sabbath in memory of creation
to have begun some 2500 years after that event: “We read that
when the Ilienses, inhabitants of Ilium, called anciently by the
name of Troy, sent an embassage to Tiberius, to condole the
death of his father Augustus, he, considering the
unseasonableness thereof, it being a long time after his death,
requited them accordingly, saying that he was sorry for their
heaviness also, having lost so renowned a knight as Hector was,
to wit, above a thousand years before, in the wars of Troy.”—
Morality of the Fourth Commandment, p. 198.
[30] Ex. 16:23.
[31] Ex. 16.
[32] Ex. 20:8-11.
[33] Compare Gen. 2:1-3; Ex. 20:8-11.
[34] Heb. 3:4; Jer. 10:10-12; Rom. 1:20; Ps. 33:9; Heb. 11:3.
[35] Antiquities of the Jews, b. i. chap. i. sect. 1.
[36] Works, vol. i. The Creation of the World, sect. 30.
[37] Isa. 58:13, 14; Heb. 9:10.
[38] Gen. 3; Rom. 5:12.
[39] Gen. 9:5, 7.
 [40] Gen. 5:24; 6:9; 26:5.
[41] See the beginning of chap. viii. of this work.
[42] Ezra 3:1-6; Neh. 8:2, 9-12, 14-18; 1 Kings 8:2, 65; 2 Chron.
5:3; 7:8, 9; John 7:2-14, 37.
[43] “The week, another primeval measure, is not a natural
measure of time, as some astronomers and chronologers have
supposed, indicated by the phases or quarters of the moon. It
was originated by divine appointment at the creation—six days of
labor and one of rest being wisely appointed for man’s physical
and spiritual well-being.”—Bliss’ Sacred Chronology, p. 6; Hale’s
Chronology, vol. i. p. 19.
“Seven has been the ancient and honored number among the
nations of the earth. They have measured their time by weeks
from the beginning. The original of this was the Sabbath of God,
as Moses has given the reasons of it in his writings.”—Brief
Dissertation on the first three Chapters of Genesis, by Dr.
Coleman, p. 26.
[44] Gen. 29:27, 28; 8:10, 12; 7:4, 10; 50:10; Ex. 7:25; Job
2:13.
[45] Ex. 16:22, 23.
[46] The interest to see the first man is thus stated: “Sem and
Seth were in great honor among men, and so was Adam above
every living thing in the creation.” Ecclesiasticus 49:16.
[47] Gen. 26:5; 18:19.
[48] Gen. 2-6; Heb. 11:4-7; 1 Pet. 3:20; 2 Pet. 2:5.
[49] Gen. 7; Matt. 24:37-39; Luke 17:26, 27; 2 Pet. 3:5, 6.
[50] Deut. 32:7, 8; Acts 17:26.
[51] Gen. 11:1-9; Josephus’ Ant., b. i. chap. iv. This took place
in the days of Peleg, who was born about one hundred years after
the flood. Gen. 10:25, compared with 11:10-16; Ant., b. i. chap. vi.
sect. 4.
[52] Rom. 1:18-32; Acts 14:16, 17; 17:29, 30.
[53] Gen. 12:1-3; Josh. 24:2, 3, 14; Neh. 9:7, 8; Rom. 4:13-17;
2 Chron. 20:7; Isa. 41:8; James 2:23.
[54] Gen. 18:19.
 [55] Gen. 17:9-14; 34:14; Acts 10:28; 11:2, 3; Eph. 2:12-19;
Num. 23:9; Deut. 33:27, 28.
[56] Gen. 15; Ex. 1-5; Deut. 4:20.
[57] Ex. 12:29-42; Gal. 3:17.
[58] Ps. 105:43-45; Lev. 22:32, 33; Num. 15:41.
[59] Gen. 2:2, 3; 26:5; Ex. 16:4, 27, 28; 18:16.
[60] Ps. 90:2.
[61] Ex. 19:3-8, 24:3-8; Jer. 3:14, compared with last clause of
Jer. 31:32.
[62] Ex. 20:2; 24:10.
[63] Ex. 20:10; Deut. 5:14; Neh. 9:14.
[64] On this verse Dr. A. Clarke thus comments:—“On the sixth
day they gathered twice as much—This they did that they might
have a provision for the Sabbath.”
[65] The Douay Bible reads: “To-morrow is the rest of the
Sabbath sanctified unto the Lord.” Dr. Clarke comments as
follows upon this text: “To-morrow is the rest of the holy Sabbath.
There is nothing either in the text or context that seems to
intimate that the Sabbath was now first given to the Israelites, as
some have supposed; on the contrary, it is here spoken of as
being perfectly well known, from its having been generally
observed. The commandment, it is true, may be considered as
being now renewed; because they might have supposed, that in
their unsettled state in the wilderness, they might have been
exempted from the observance of it. Thus we find, 1. That when
God finished his creation he instituted the Sabbath; 2. When he
brought the people out of Egypt, he insisted on the strict
observance of it; 3. When he gave the law, he made it a tenth
part of the whole: such importance has this institution in the eyes
of the Supreme Being!”
Richard Baxter, a famous divine of the seventeenth century,
and a decided advocate of the abrogation of the fourth
commandment, in his “Divine Appointment of the Lord’s Day,”
thus clearly states the origin of the Sabbath: “Why should God
begin two thousand years after [the creation of the world] to give
men a Sabbath upon the reason of his rest from the creation of it,
if he had never called man to that commemoration before? And it
is certain that the Sabbath was observed at the falling of the
manna before the giving of the law; and let any considering
Christian judge..... 1. Whether the not falling of the manna, or the
rest of God after the creation, was like to be the original reason of
the Sabbath. 2. And whether if it had been the first, it would not
have been said, Remember to keep holy the Sabbath-day; for on
six days the manna fell, and not on the seventh; rather than ‘for in
six days God created heaven and earth, &c., and rested the
seventh day.’ And it is casually added, ‘Wherefore the Lord
blessed the Sabbath-day, and hallowed it.’ Nay, consider whether
this annexed reason intimates not that the day on this ground
being hallowed before, therefore it was that God sent not down
the manna on that day, and that he prohibited the people from
seeking it.”—Practical Works, Vol. iii. p. 784. ed. 1707.
[66] The Douay Bible reads: “Because it is the Sabbath of the
Lord.”
[67] Ex. 16.
[68] It has indeed been asserted that God by a miracle
equalized the portion of every one on five days, and doubled the
portion of each on the sixth, so that no act of the people had any
bearing on the Sabbath. But the equal portion of each on the five
days was not thus understood by Paul. He says: “But by an
equality, that now at this time your abundance may be a supply
for their want, that their abundance also may be a supply for your
want; that there may be equality; as it is written, He that had
gathered much had nothing over; and he that had gathered little
had no lack.” 2 Cor. 8:14, 15. And that the double portion on the
sixth day was the act of the people, is affirmed by Moses. He says
that “on the sixth day they gathered twice as much bread.” Verse
22.
[69] Gen. 7:4, 10; 8:10, 12; 29:27, 28; 50:10; Ex. 7:25; Job
2:13.
[70] By this three-fold miracle, occurring every week for forty
years, the great Law-giver distinguished his hallowed day. The
people were therefore admirably prepared to listen to the fourth
commandment enjoining the observance of the very day on which
he had rested. Ex. 16:35; Josh. 5:12; Ex. 20:8-11.
[71] The twelfth chapter of Exodus relates the origin of the
passover. It is in striking contrast with Ex. 16, which is supposed
to give the origin of the Sabbath. If the reader will compare the
two chapters he will see the difference between the origin of an
institution as given in Ex. 12, and a familiar reference to an
existing institution as in Ex. 16. If he will also compare Gen. 2 with
Ex. 12, he will see that the one gives the origin of the Sabbath in
the same manner that the other gives the origin of the passover.
[72] This implies, first, the fall of a larger quantity on that day,
and second, its preservation for the wants of the Sabbath.
[73] This must refer to going out for manna, as the connection
implies; for religious assemblies on the Sabbath were
commanded and observed. Lev. 23:3; Mark 1:21; Luke 4:16; Acts
1:12; 15:21.
[74] John 7:22.
[75] Gen. 17:34; Ex. 4. Moses is said to have given
circumcision to the Hebrews; yet it is a singular fact that his first
mention of that ordinance is purely incidental, and plainly implies
an existing knowledge of it on their part. Thus it is written: “This is
the ordinance of the passover: There shall no stranger eat
thereof; but every man’s servant that is bought for money, when
thou hast circumcised him, then shall he eat thereof.” Ex. 12:43,
44. And in like manner when the Sabbath was given to Israel, that
people were not ignorant of the sacred institution.
[76] Eze. 20:12; Ex. 31:17.
[77] Jer. 10:10-12.
[78] That the Lord was there in person with his angels, see
besides the narrative in Ex. 19; 20; 32-34, the following
testimonies: Deut. 33:2; Judges 5:5; Nehemiah 9:6-13; Ps. 68:17.
[79] Ex. 24:10; Lev. 22:32, 33; Num. 15:41; Isa. 41:17.
[80] Ps. 147:19, 20; Rom. 3:1, 2; 9:4, 5. The following from the
pen of Mr. Wm. Miller presents the subject in a clear light: “I say,
and believe I am supported by the Bible, that the moral law was
never given to the Jews as a people exclusively; but they were for
a season the keepers of it in charge. And through them the law,
oracles, and testimony, have been handed down to us. See Paul’s
clear reasoning in Rom. chapters 2, 3, and 4, on that point.”—
Miller’s Life and Views, p. 161.
[81] Ex. 19; Deut. 7:6; 14:2; 2 Sam. 7:23; 1 Kings 8:53; Amos
3:1, 2.
[82] Ex. 20:1-17; 34:28, margin; Deut. 5:4-22; 10:4, margin.
[83] Deut. 5:22.
 [84] He who created the world on the first day of the week, and
completed its organization in six days, rested on the seventh day,
and was refreshed. Gen. 1; 2; Ex. 31:17.
[85] To this, however, it is objected that in consequence of the
revolution of the earth on its axis, the day begins earlier in the
East than with us; and hence that there is no definite seventh day
to the world of mankind. To suit such objectors, the earth ought
not to revolve. But in that case, so far from removing the difficulty,
there would be no seventh day at all; for one side of the globe
would have perpetual day and the other side perpetual night. The
truth is, everything depends upon the revolution of the earth. God
made the Sabbath for man [Mark 2:27]; he made man to dwell on
all the face of the earth [Acts 17:26]; he caused the earth to
revolve on its axis that it might measure off the days of the week;
causing that the sun should shine on the earth, as it revolves from
west to east, thus causing the day to go round the world from east
to west. Seven of these revolutions constitute a week; the
seventh one brings the Sabbath to all the world.
[86] Luke 23:54-56; 24:1.
[87] See also Matt. 28:1; Mark 16:1, 2.
[88] Neh. 9:13, 14.
[89] This expression is strikingly illustrated in the statement of
Eze. 20:5, where God is said to have made himself known unto
Israel in Egypt. This language cannot mean that the people were
ignorant of the true God, however wicked some of them might be,
for they had been God’s peculiar people from the days of
Abraham. Ex. 2:23-25; 3:6, 7; 4:31. The language implies the
prior existence both of the Law-giver and of his Sabbath, when it
is said that they were “made known” to his people.
[90] It should never be forgotten that the term Sabbath day
signifies rest-day; that the Sabbath of the Lord is the rest-day of
the Lord; and hence that the expression, “Thy holy Sabbath,”
refers the mind to the Creator’s rest-day, and to his act of blessing
and hallowing it.
[91] Ex. 20-24.
[92] Ex. 23:12.
[93] See also Ex. 20:10; Deut. 5:14; Isa. 56.
[94] Ex. 12:43-48.