Journal of Catalysis 352 (2017) 102–112

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Activation of amorphous bismuth oxide via plasmonic Bi metal for

efficient visible-light photocatalysis
Xinwei Li a, Yanjuan Sun a, Ting Xiong a, Guangming Jiang a, Yuxin Zhang b, Zhongbiao Wu c, Fan Dong a,⇑
a
Chongqing Key Laboratory of Catalysis and New Environmental Materials, Engineering Research Center for Waste Oil Recovery Technology and Equipment of Ministry of
Education, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China
b
State Key Laboratory of Mechanical Transmissions, College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
c
Department of Environmental Engineering, Key Laboratory of Environment Remediation and Ecological Health of Ministry of Education, Zhejiang University, Hangzhou 310058,
China

a r t i c l e i n f o a b s t r a c t

Article history: Amorphous semiconductors are seldom exploited as effective photocatalysts, as they are restricted by
Received 11 February 2017 abundant bulk defects as carrier recombination centers. To activate amorphous bismuth oxide for effi-
Revised 22 April 2017 cient visible-light photocatalytic performance, a novel and facile strategy was developed. Plasmonic
Accepted 22 April 2017
Bimetal-decorated amorphous bismuth oxide (Bi–BiO) was prepared by partial reduction with NaBH4.
The content of Bi metal and the photocatalytic activity of the catalysts can be modulated by controlling
the concentration of NaBH4 solution. Various techniques were employed to explore the structural fea-
Keywords:
tures, optical properties, and active species during photocatalysis. The as-synthesized Bi–BiO catalysts
Visible light photocatalysis
Mechanism
were applied in photocatalytic removal of NO in air under and exhibited highly enhanced visible light
Activation photocatalytic activity. The significantly increased photocatalytic capability can be attributed to the com-
Amorphous semiconductor bined effects of the enhanced visible light absorption and the improved separation efficiency of the
In situ DRIFT charge carriers attributed to the surface plasmon resonance conferred by Bi metal. The advanced Bi–
BiO catalysts also exhibited high photochemical and structural stability under repeated irradiation.
Moreover, in situ DRIFT was carried out to reveal the time-dependent evolution of reaction intermediates
during photocatalytic NO oxidation. A molecular-level photocatalysis mechanism was first proposed for
Bi–BiO based on ESR and in situ DRIFT. This work could provide a new perspective in utilizing non-noble-
metal Bi as a key activation factor to trigger the photocatalytic ability of amorphous semiconductors.
Ó 2017 Elsevier Inc. All rights reserved.

1. Introduction Recently, amorphous semiconductors have been developed by

relatively simple and facile methods [12–17]. However, these
Photocatalysis is a green technology for environmental remedi- amorphous materials are originally disordered, and the short-
ation and solar energy conversion. The development of efficient range order is in general so well defined that abundant bulk defects
visible light photocatalysts that could effectively utilize solar can occur at the charge recombination centers [18]. Thus, the
energy is the key to practical application of photocatalytic technol- amorphous semiconductors exhibit limited photocatalytic activity
ogy [1–3]. It is well known that the performance of photocatalysts due to a high charge carrier recombination rate. To overcome the
is predominantly determined by the light utilization efficiency and drawbacks of amorphous semiconductors, it is essential to enhance
charge separation efficiency [4–8]. Under light irradiation of semi- the crystallinity and reduce the number of bulk defects. For
conductors, the photogenerated electrons and holes may recom- instance, Amano et al. found that amorphous Bi2WO6 showed little
bine by certain routes before they can be involved in the photocatalytic activity [19]. Subsequently, they applied hydrother-
subsequent reactions. To promote charge separation, various mal treatment to improve the crystallinity of amorphous Bi2WO6,
strategies have been adopted, such as doping with heteroatoms, and enhanced photocatalytic activity was achieved due to pro-
formation of heterostructures, and enhancement of crystallinity moted charge separation [19]. Xiao and co-workers employed ther-
[9–11]. mal calcination for amorphous bismuth oxide with low
photocatalytic performance to obtain a-Bi2O3 and b-Bi2O3 with
⇑ Corresponding author.
excellent photocatalytic activity under visible light irradiation
E-mail address: [email protected] (F. Dong).
[20]. However, the approaches to enhancing the crystallinity of

http://dx.doi.org/10.1016/j.jcat.2017.04.025
0021-9517/Ó 2017 Elsevier Inc. All rights reserved.
 X. Li et al. / Journal of Catalysis 352 (2017) 102–112 103

semiconductors usually involve high-temperature or high-

pressure treatment.
Bismuth as a semimetal has attracted great interest, as it has
unique properties, such as a very small effective mass, a large mean
free path, a long Fermi wavelength, high carrier motilities, and
small band overlap energy [21–25]. Recently, low-cost Bi metal
has been found to exhibit surface plasmon resonance (SPR), allow-
ing it to achieve the function of noble metals (Au, Ag, etc.) in a sim-
ilar way [25,26]. With the significant advantages of Bi metal, it has
been widely applied to enhance the photocatalysis of other semi-
conductors as a plasmonic co-catalyst. For example, Bi/(BiO)2CO3
[27], Bi/g-C3N4 [28], Bi/TiO2 [29], and Bi/BiOCl [30] have been
developed and have exhibited upgraded photocatalytic perfor-
mance in comparison with their individual components by virtue
of the metal Bi, which can promote charge separation through
SPR. On the other hand, bismuth oxide has five polymorphic forms:
a-Bi2O3 (monoclinic), b-Bi2O3 (tetragonal), c-Bi2O3 (body-centered
cubic), d-Bi2O3 (cubic), and e-Bi2O3 (triclinic) [31]. Among these
polymorphic forms, b-Bi2O3 has a suitable band gap (
2.4 eV), Fig. 2. XRD patterns of all samples.
and demonstrates decent photocatalytic performance in
comparison with the other phases [31–33]. However, the 2. Experimental
amorphous bismuth oxide normally exhibits poor photocatalytic
performance. The photocatalytic activity would be promoted if 2.1. Catalyst preparation
the crystallinity of amorphous bismuth oxide could be enhanced
to form b-phase Bi2O3 [34]. To the best of our knowledge, the 2.1.1. Synthesis of amorphous bismuth oxide (A-BiO)
utilization of the SPR effects of Bi metal to activate amorphous bis- In a typical procedure, Bi(NO3)35H2O (2.91 g, 6 mmol) was dis-
muth oxide has never been reported. Also, there have been few solved in a mixed solution that contained glycerol (30 mL) and
studies on facile ways to activate the amorphous structure with absolute ethanol (30 mL). Then the mixture was treated with vig-
limited activity. orous stirring and ultrasonic dispersion to form a homogeneous
In the present work, amorphous bismuth oxide (A-BiO) was solution. The obtained solution was transferred into a Teflon-
prepared by a facile method. The A-BiO sample showed almost lined stainless steel autoclave (100 mL), sealed, and heated at
no activity, due to the high charge carrier recombination rate. To 160 °C for 3 h. After cooling to room temperature, the as-formed
activate the amorphous bismuth oxide, a facile partial reduction precipitate was collected and washed several times with deionized
method is developed to generate Bi metal in situ on amorphous water and absolute ethanol, followed by drying at 60 °C.
bismuth oxide with sodium borohydride as the reductant. The
as-prepared Bi–BiO nanohybrids were applied for photocatalytic 2.1.2. Synthesis of Bi-metal-decorated amorphous bismuth oxide
removal of low-concentration NO in air under visible light illumi- (Bi-BiO)
nation and showed dramatically enhanced activity because of A quantity of 1.0 mmol of the A-BiO was added into 100 mL of
SPR, enhanced visible light absorption, and accelerated deionized water containing 1.0 g PVP. A certain concentration of
electron–hole pair separation induced by the Bi nanoparticles. NaBH4 (30 mL) was added dropwise into the suspension, stirred
The relationship between amount of coupled Bi metal and photo- for 1 h, and then aged for 1 h. The resulting precipitates were gath-
catalytic performance was also revealed. The function of Bi ered, rinsed four times with ethanol and deionized water, and
nanoparticles as a co-catalyst is similar to that of noble metals. Sig- dried at 60 °C in air. The concentration of NaBH4 is controlled at
nificantly, the Bi–BiO samples also exhibited excellent photochem- 10, 30, and 50 mmol/L, and the obtained samples were denoted
ical stability, which will pave the way to a new approach for as Bi-BiO-10, Bi-BiO-30, and Bi-BiO-50, respectively.
substituting the inexpensive base metal for the precious noble
metals to activate the amorphous semiconductor photocatalyst 2.2. Characterization
for practical applications. Moreover, the photocatalytic NO oxida-
tion process over Bi–BiO catalysts was monitored for the first time The crystal phases of the sample were analyzed by X-ray
using in situ DRIFT, offering a powerful new method to investigate diffraction (XRD) with Cu Ka radiation (Model D/max RA, Rigaku
the gas-phase photocatalytic reaction mechanism. Co., Japan). Scanning electron microscopy (SEM, Model JSM-6490,

Fig. 1. Schematic diagram the of in situ DRIFT reactor system.

104 X. Li et al. / Journal of Catalysis 352 (2017) 102–112

Fig. 3. O1s XPS spectra for all samples (a) and Bi4f spectra for A-BiO (b), Bi-BiO-10 (c), Bi-BiO-30 (d), and Bi-BiO-50 (e).

Fig. 4. SEM images for A-BiO (a), Bi-BiO-10 (b), Bi-BiO-30 (c), and Bi-BiO-50 (d).

JEOL, Japan) and transmission electron microscopy (TEM, Model ated at 150 W (Thermo ESCALAB 250, USA) was used to
JEM-2010, Japan) were used to characterize the morphology and investigate the surface properties. UV–vis diffuse reflectance spec-
structure of the obtained products. X-ray photoelectron spec- trometry (DRS) spectra were obtained for the dry-pressed disk
troscopy (XPS) with Al Ka X-rays (hm = 1486.6 eV) radiation oper- samples using a Scan UV–vis spectrophotometer (UV–vis DRS:
 X. Li et al. / Journal of Catalysis 352 (2017) 102–112 105

(a) (b)

(c) (d)
Bismuth oxide layer

Bi (012) = 0.328 nm

Bismuth oxide layer

Bi (012) = 0.328 nm

Fig. 5. TEM images for A-BiO (a and b) and HRTEM images for Bi-BiO-10 (b), Bi-BiO-30 (c), and Bi-BiO-50 (d).

Fig. 6. Formation process for Bi–BiO sample.

Model UV-2450, Japan) equipped with an integrating sphere rated calomel electrodes were used as the reference electrodes.
assembly, using 100% BaSO4 as the reflectance sample. Nitrogen Bi-BiO-10, Bi-BiO-30, and Bi-BiO-50 film electrodes on ITO served
adsorption–desorption isotherms were obtained on a nitrogen as the working electrode, separately. The photoelectrochemical
adsorption apparatus (ASAP 2020, USA). All the samples were experiment results were recorded using an electrochemical system
degassed at 100 °C prior to measurements. A sample for electron (Model CHI-660B, China). All photoelectrochemical measurements
spin resonance (ESR) measurement was prepared by mixing A- were performed under visible light from a 500 W Xe lamp with
BiO and Bi-BiO-30 in a 50 mM DMPO solution tank (aqueous dis- 420 nm cutoff filters; the average light power was 45 mW/cm2.
persion for DMPO-OH and methanol dispersion for DMPO-O 2 ). Photoluminescence (PL, F-7000, HITACHI) was employed to probe
The photocurrent response measurements were performed in the charge separation properties. Time-resolved fluorescence
three-electrode quartz cells with a 0.1 M Na2SO4 electrolyte solu- decay spectra were taken with a fluorescence spectrophotometer
tion. Platinum wire was used as the counter electrode, and satu- (Edinburgh Instruments, Model FLSP-920). Time-resolved
106 X. Li et al. / Journal of Catalysis 352 (2017) 102–112

Table 1
SBET, pore volume, peak diameter, and NO removal ratio of as-prepared catalysts.

Samples SBET (m2/g) Total pore volume (cm3/g) Peak pore size (nm) NO (%)
A-BiO 1.4 0.004 0 0.0
Bi-BiO-10 15.6 0.081 3.6 45.4
Bi-BiO-30 20.2 0.109 3.6/25.6 53.0
Bi-BiO-50 35.4 0.196 3.6/43.7 52.1

Fig. 7. N2 adsorption–desorption isotherms (a) and the corresponding pore-size distribution curves (b) for all samples.

fluorescence decay spectra were taken with a fluorescence spec- dish was pretreated at 40 °C to remove water in the suspension
trophotometer (Edinburgh Instruments, Model FLSP-920). and placed in the center of the reactor after cooling to room tem-
perature. NO gas was acquired from a compressed gas cylinder at a
2.3. Visible light photocatalytic NO removal concentration of 100 ppm of NO (balance N2). The initial concen-
tration of NO was diluted to about 550 ppb by the air stream.
The photocatalytic activity of the as-prepared samples was The flow rates of the mixed stream of air and NO were controlled
evaluated by removal of NO at ppb level in a continuous-flow reac- at 2.4 and 15 mL min1, respectively. Then the two gas streams
tor. The volume of the reactor was 4.5 L (30  15  10 cm), made of were premixed by a three-way valve. After adsorption–desorption
stainless steel, and covered with Saint-Glass. A commercial tung- equilibrium was achieved, the lamp was turned on. The concentra-
sten halogen lamp (150 W) was vertically placed outside the reac- tion of NO was measured every 1 min by an NOx analyzer (Thermo
tor. A UV cutoff filter (420 nm) was applied to remove UV light for Scientific, Model 42i-TL), which monitors NO and NOx (NOx repre-
the test of visible light photocatalytic activity. An as-prepared sam- sents NO + NO2). The removal ratio (g) of NO was calculated as g
ple (0.20 g) was added to ethyl alcohol (20 ml) in a beaker and then (%) = (1  C/C0)  100%, where C is the outlet concentration of NO
coated onto a glass dish with a diameter of 12.0 cm. The coated after reaction for time t, and C0 represents the inlet concentration.

Fig. 8. UV–vis spectra of all samples (a) and plot of (a h m)1/2 versus photon energy of A-BiO and Bi-BiO-10 (b).
 X. Li et al. / Journal of Catalysis 352 (2017) 102–112 107

added at different concentrations (10–50 mmol/L) as a reduction

agent during the preparation, some diffraction peaks of the crystal-
lized structure can be observed for Bi-BiO-30 and Bi-BiO-50. These
diffraction peaks can be indexed as rhombohedral bismuth
(JCPDSICDD Card 85-1329) with peaks located at 27.1°, 37.9°, and
39.6° that refer to the (0 1 2), (1 0 4), and (1 1 0) crystal planes,
respectively. This result implies that a portion of Bi3+ in amorphous
bismuth oxide is reduced to Bi metal, forming B–BiO nanohybrids.
The chemical composition of the as-prepared samples was
investigated via XPS before and after the sputtering treatment of
the sample with depth 15 nm (Fig. 3). In Fig. 3a, the peak at
531.30 eV can be ascribed to the Bi–O bond in A-BiO [35]. Note that
the peak downshifts to a lower binding energy of 530.14 eV when
Bi metal is introduced on A-BiO. The negative chemical shift of Bi–
O binding energy can be attributed to the interaction between Bi
metal and A-BiO. Fig. 3b–e shows the XPS spectra for Bi4f before
and after sputtering of all samples. The binding energies of
Bi4f7/2 and Bi4f5/2 peaks are located at 158.65 and 163.98 eV,
Fig. 9. Solid state EPR spectra of A-BiO and Bi-BiO-30 under visible light.
respectively, which suggests the existence of Bi3+ in bismuth oxide.
2.4. In situ DRIFTS investigation of photocatalytic NO oxidation Another two peaks located at 156.7 and 162.0 eV, assigned to Bi
metal, can be observed for the Bi-BiO-30 and Bi-BiO-50 samples
In situ DRIFTS measurements were conducted using a Tensor II [36–39]. For the Bi-BiO-10 sample, the peak of Bi metal cannot
FTIR spectrometer (Bruker) equipped with an in situ diffuse reflec- be detected, as the content of Bi is low and the surface metal Bi
tance cell (Harrick), which contained three windows, including two can easily be oxidized [40]. However, after sputtering, the peaks
ZnSe windows for IR measurements and a quartz window for light for Bi metal can be clearly detected, as the Bi metal in the bulk
irradiation using a point- light source (Model MVL-210, Japan). The can be partially exposed on the surface. Similar results have also
catalyst bed was 3 mm deep and contained a 2.4 mm layer of inert been observed for Bi-BiO-30 and Bi-BiO-50 samples
sieved SiO2 particles with a 0.6 mm photocatalyst layer on top of (Fig. 2e and f). It is obvious that the peak intensity for Bi metal is
the SiO2. The total gas flow rate was 50 ml/min. The catalyst sam- increased with increased content of NaBH4.
ples were pretreated inside the cell at 80 °C under He for 30 min to
remove the residual hydrocarbons, H2O, and CO2. Then the reaction 3.2. Morphological structure
mixture (50 ppm NO, 50% O2) was introduced into the cell. The
adsorption of NO onto the catalysts was carried out both under The morphology of the as-prepared catalysts was characterized
NO flow and after additional He purging for 20 min. The IR scan- via SEM (Fig. 4) TEM, and HRTEM (Fig. 5). Fig. 4a clearly reveals
ning range was 4000–600 cm1 with averaging over 100 scans. A that the A-BiO is composed of many microspheres with a size
schematic diagram of the in situ DRIFTS reactor system is shown around 1–2 m. While reduction agent was added into the system,
in Fig. 1. those microspheres were gradually collapsed (Fig. 4b), and irregu-
lar nanostructures were finally produced with a large amount of
reduction agent added (Fig. 4c and d).
3. Results and discussion The pure A-BiO microspheres have a solid structure, as shown
by the TEM image in Fig. 5a. The Bi-BiO-10 sample (Fig. 5b) has a
3.1. Phase structure and chemical composition structure similar to that of pure A-BiO. Closer TEM and HRTEM
observation of Bi-BiO-30 and Bi-BiO-50 (Fig. 5c and d) indicates
The powder X-ray diffraction (XRD) patterns of the samples are that all the irregular nanostructures consist of numerous small
illustrated in Fig. 2. The A-BiO sample exhibited a broad peak with nanoparticles, around 10 nm, piled up together. The observed lat-
no characteristic peaks of crystallized bismuth oxide, indicating tice fringe of 0.328 nm corresponds to the (012) lattice plane of
that it has a typical amorphous structure [18]. When NaBH4 was Bi metal (Fig. 5e and f) [26], which indicates that the Bi metal is
generated on A-BiO. The change of morphology with the reduction
of NaBH4 indicates that the metal Bi is first reduced from the sur-
face of bismuth oxide. With increasing amounts of reduction agent,
the as-generated Bi metal disintegrates the structure of A-BiO
microspheres, producing plenty of randomly assembled Bi metal
nanoparticles. Note that an amorphous layer exists on the surface
of Bi metal (Fig. 5c and d), which suggests that newly formed Bi
metal is oxidized on its surface. Thus, according to the SEM, TEM,
and HRTEM images of as-prepared samples, the reduction process
for generation of Bi–BiO nanohybrids is presented in Fig. 6.
The BET surface areas of A-BiO, Bi-BiO-10, Bi-BiO-30, and Bi-
BiO-50 are 1.4, 15.6, 20.23, and 35.4 m2/g, respectively (Table 1).
Remarkably, the BET surface areas are significantly increased with
the addition of NaBH4, which can be ascribed to the fact that the
regular bismuth oxide spheres are ruptured during the reduction
process. Fig. 7a shows the nitrogen adsorption–desorption
isotherms and the corresponding pore size distribution curves of
Fig. 10. Transient photocurrent responses of all samples under visible light as-prepared samples. According to the BDDT classification, the
irradiation. majority of physisorption isotherms can be classified into six types.
108 X. Li et al. / Journal of Catalysis 352 (2017) 102–112

Fig. 11. The ns-level time-resolved fluorescence spectra (a) and PL spectra (b) of A-BiO and Bi-BiO-30 at room temperature.

Table 2 Bi metal is decorated on A-BiO. All Bi–BiO samples present signif-

The kinetics of emission decay parameters of A-BiO and Bi-BiO-30.
icantly enhanced visible light absorption, which can be attributed
Sample Component Lifetime (ns) Relative percentage (%) to the surface plasmon resonance and light scattering of Bi metal.
A-BiO s1 0.6492 100 The band gap energy (Eg) of Bi–BiO and Bi-BiO-10 is calculated
Bi-BiO-30 s1 0.5310 100 using a(hm) = A(hm  Eg)n/2, where a, h, m, Eg and A are absorption
coefficient, Planck’s constant, light frequency, band gap energy,
and a constant, respectively [42]. According to the literature, the
value of n is 1 for bismuth oxide [43]. By extrapolating the straight
A-BiO has a low N2 adsorption amount. Typically, Bi-BiO-30 and Bi- line to the x-axis in this plot, the energy gaps of Bi-BiO-10 and A-
BiO-50 have an isotherm of type IV, indicating the presence of BiO can be fitted to 2.16 and 2.90 eV, respectively (Fig. 8b).
mesopores. The corresponding pore size distribution curves of Considering that Bi metal nanoparticles are introduced in situ,
the samples are presented in Fig. 7b. The A-BiO sample displays the interfacial contact between bismuth oxide and Bi is intimate.
a horizontal isotherm, implying that it has no pores [41]. As for To investigate the existence of vacancies, room-temperature elec-
all Bi–BiO samples, the PSD curve possesses small mesopores (from tron paramagnetic resonance (EPR) spectra were recorded in
3.2 to 4.6 nm) and large mesopores (from 13.1 to 129.1 nm). Gen- Fig. 9. The Bi-BiO-30 sample gives a stronger EPR signal at
erally, larger surface areas and porous structures are beneficial to g = 2.004 than A-BiO, indicating the increased number of oxygen
promote photocatalytic activity, as more active sites can be vacancies generated at the interface due to the reduction treat-
exposed for absorption and reaction. ment during catalyst preparation [44,45]. The oxygen vacancies
that commonly form at metal/metal oxide interfaces may give rise
3.3. Optical absorption and charge separation properties to the bandgap narrowing of Bi-metal-decorated A-BiO [46,47]. A
similar phenomenon was also observed in the system of TiO2 and
The UV–vis DRS spectra demonstrate the optical properties of ZnO [44–47]. The valence band (VB) and conduction band (CB)
all samples. As shown in Fig. 8a, A-BiO could absorb visible light positions of Bi-BiO-10 and A-BiO could be calculated using the
at 400–600 nm. The light absorption is remarkably increased as empirical formulae

Fig. 12. Comparison of the visible light photocatalytic performance over all samples (a) and the cycling test of Bi-BiO-30 (b).
 X. Li et al. / Journal of Catalysis 352 (2017) 102–112 109

Fig. 13. The XRD (a), TEM (b), and XPS of O1s (c) and Bi4f (d) for Bi-BiO-30 before and after stability test.

Fig. 14. DMPO spin-trapping ESR spectra of Bi-BiO-30 in aqueous dispersion for DMPO- OH and in methanol dispersion for DMPO- O
2 (a) and in situ IR spectra of
photocatalytic reaction of NO on Bi-BiO-30 under visible light irradiation (b).

EVB ¼ X  Ee þ Eg =2 ð1Þ electrons on the hydrogen scale (approximately 4.5 eV); Eg is the
band gap energy of the semiconductor [55]. The calculated VB
and CB levels are 2.50 and 0.34 eV for Bi-BiO-10. For pure Bi-BiO,
ECB ¼ EVB  Eg : ð2Þ
the VB and CB levels are 2.87 eV and 0.03 eV, respectively.
X is the absolute electronegativity of the constituent atoms in a The transient photocurrent response was measured to investi-
semiconductor; X for bismuth oxide is 5.92. Ee is the energy of free gate the separation of photogenerated carriers. Generally, an
110 X. Li et al. / Journal of Catalysis 352 (2017) 102–112

Table 3 3.4. Visible light photocatalytic NO removal, photochemical stability,

Assignments of the IR bands observed during NO adsorption over Bi-BiO-30 followed and mechanism insight
by visible light irradiation.

Surface species Band positions (cm1) Ref. The as-prepared catalysts are applied in photocatalytic removal
Monodentate nitrite 1500–1440 48 of NO in the gas phase under visible light irradiation. As previously
Nitro compounds 1355, 1342, 1333 49, 50 reported, NO is very stable and cannot be photolyzed under light
Bi–NO2 1306 50, 51, 52, 53 irradiation in the absence of photocatalyst [49,50]. Fig. 12a shows
Monodentate nitrate 1274 54, 55
Bidentate nitrates 1058 49, 59
the variation of NO concentration (C/C0%) with irradiation time
Bridged nitrates 1030 49 over A-BiO, Bi-BiO-10, Bi-BiO-30, and Bi-BiO-50 under visible light
irradiation. Evidently, the A-BiO sample exhibits negligible visible
light activity due to the existence of abundant oxygen defects as
charge recombination centers (Fig. 9). Bi-BiO-10 exhibits enhanced
visible light photocatalytic activity, with a NO removal ratio of
increased photocurrent implies a higher efficiency of charge sepa- 45.4%. More strikingly, Bi-BiO-30 and Bi-BiO-50 present unprece-
ration [48]. Since A-BiO has abundant bulk defects as charge dentedly high NO removal ratios of 53.0 and 52.1%, respectively.
recombination centers, the photoinduced electron–hole pairs Considering that pure A-BiO has nearly no visible photocatalytic
could not be effectively separated, thus failing to produce relatively activity of NO removal, the increase in the specific surface area of
high photocurrent density (Fig. 10). Rapidly growing enhanced this inactive sample would not promote photocatalytic activity of
photocurrent can be observed for Bi-BiO-10, Bi-BiO-30 and Bi- the pristine A-BiO. Although Bi-BiO-30 has even more oxygen
BiO-50. The plasmonic Bi metal plays a key role as an electron trap defects than A-BiO, the plasmonic Bi metal exerts a great influence
in facilitated separation of photogenerated electrons and holes via on the promotion of charge carrier separation. The highly
the SPR-induced electromagnetic field [27–30]. enhanced visible light photocatalysis efficiency of Bi–BiO can thus
The ns-level time-resolved fluorescence decay spectra were fur- be ascribed directly to the plasmonic Bi metal as electron trap and
ther utilized to investigate the charge-transfer dynamics of A-BiO the SPR-induced electromagnetic field, which could promote the
and Bi-BiO-30 (Fig. 11a). The curves can be fitted well using a biex- separation of photogenerated electrons and holes.
ponential decay function (Table 2). The lifetime (s1) is 0.6492 ns for To examine the photocatalytic stability of the Bi-BiO-30 sample,
A-BiO and is decreased to 0.5310 ns after introduction of Bi metal. circulating runs in the photocatalytic removal of NO were carried
This result demonstrates that the metal Bi could store and shuttle out. As shown in Fig. 12b, the Bi-BiO-30 sample maintains rela-
the electrons from photoexcited A-BiO to Bi rapidly. In addition, tively durable photocatalytic activity, with no obvious deactivation
the apparent electron-transfer (ET) rate (kET) in Bi-BiO-30 can be after five repetitive cycles. The structure, morphology, and chemi-
obtained according to the following equation [39]: cal states of Bi-BiO-30 before and after the stability test were also
monitored, as presented in Fig. 13. There is no obvious change in
1 1
kET ¼  : ð3Þ the diffraction peaks in XRD patterns, morphology, and chemical
s1ðBi  BiO  30Þ s1ðA  BiOÞ
composition, confirming that Bi-BiO-30 is photochemically stable
The calculated value is 3.43  108 s1, revealing that the inter- under repeated light irradiation.
face formed between Bi and A-BiO is favorable for the effective DMPO spin-trapping ESR spectra were implemented to detect
electron-transfer quenching of the excited state of A-BiO. the reactive species under visible light (Fig. 14a). After irradiation
Photoluminescence (PL) is another valid way to survey the sep- under visible light for 10 min, there is nearly no signal of
aration efficiency of electrons and holes. Bi-BiO-30 displays lower DMPO-OH detected. However, four characteristic peaks of
emission intensity than that of A-BiO (Fig. 11b), indicating that DMPO-O 2 adducts with an intensity ratio of 1:2:2:1 can be dis-
the charge recombination rate of A-BiO is decreased by the activa- tinctively detected in methanol dispersion under visible light.
tion of Bi metal. Both the photoluminescence and the transient PL The results demonstrate that O 2 radicals are the major active spe-
lifetime could support the improved charge carrier separation cies for photocatalytic NO oxidation.
efficiency after in situ incorporation with metallic Bi as plasmonic The photoinduced electrons in the bottom conduction band of
co-catalyst. amorphous bismuth oxide (0.34 eV) cannot reduce O2 to generate

Fig. 15. Schematic diagram of charge separation and the possible photocatalysis mechanism under visible light irradiation.
 X. Li et al. / Journal of Catalysis 352 (2017) 102–112 111


O  
2 , as the E(O2/ O2 ) is
0.33 eV (vs. NHE) [51] normally. Never- The SPR-induced charge separation process and the visible light
theless, considering that the cutoff filter is 420 nm for visible light photocatalytic NO oxidation mechanism with Bi–BiO are illus-
with corresponding energy
2.9 eV, the photoinduced electrons trated in Fig. 15.
could jump to a reformed higher CB potential,
0.45 eV, which
is sufficient to reduce O2 to generate abundant O 2 on the surface
of the Bi-BiO-30 sample (Fig. 14a). Parallel results have also been 4. Conclusions
observed in BiOI [52,53]. The Bi Fermi level (vs. NHE) of Bi metal
is
0.17 eV [22]. By working as electron trap centers, Bi metal In summary, to activate amorphous bismuth oxide, a facile
could receive electrons from the conduction band of A-BiO method was developed to decorate Bi metal on amorphous bis-
thermodynamically. muth oxide. The increased absorption ability of Bi–BiO in the visi-
Fig. 14b shows the time-dependent in situ DRIFT spectra for ble light region was achieved by the SPR absorption of Bi metal.
photocatalytic NO oxidation. NO adsorption equilibrium is reached The SPR-induced electric field could enhance the charge separation
when NO and O2 are introduced in the absence of visible light for efficiency of Bi–BiO. The Bi metal could act as electron traps to
20 min. The IR spectra have also been recorded when photocat- inhibit charge recombination on bulk defects of amorphous bis-
alytic reaction is finished after 10 min. Assignments of bands muth oxide, thus favoring the production of abundant O 2 radicals.

observed in the region 1530–1000 cm1 are summarized in Table 3. The as-synthesized Bi–BiO catalysts exhibited highly enhanced and
The broad band at 1500–1440 cm1 belongs to monodentate stable photocatalytic NO removal under visible light irradiation.
nitrite [54,55]. The peaks observed in the region 1380–1330 cm1 The photocatalytic NO oxidation process over Bi–BiO was moni-
(peaks at 1355 and 1333 cm1) may be attributed to nitro com- tored using in situ DRIFT for the first time. A molecular mechanism
pounds [56,57]. The peaks for both monodentate nitrite and nitro for photocatalytic NO oxidation was proposed based on time-
compounds appear when a photocatalytic reaction takes place. dependent evolution of reaction intermediates and ESR trapping
The peak intensity is increased as the irradiation time is prolonged. of radicals. This present work could not only pave a new way to
The band at 1306 cm1 can be assigned to nitroso Bi–NO2 species utilizing the non-noble-metal element Bi to activate the photocat-
[57–60]. Notably, this band appears during absorption and the alytic ability of amorphous semiconductors with nonactivity, but
intensity is enhanced as the reaction goes by. The new band at also offer new insights into the photocatalytic NO oxidation
1274 cm1 observed after light on could be assigned to monoden- reaction.
tate nitrate [61,62], whose band intensity is decreased obviously
when the light is off. The band at 1058 cm1 observed after the
Acknowledgments
light is on could be assigned to bidentate nitrate [57,63], and the
band intensity decreases slightly with the light turned off. At the
This research was financially supported by the National Natural
same time, there is a band at 1030 cm1 assigned to bridged
Science Foundation of China (21501016, 51478070, 51108487, and
nitrates, whose intensity gradually increases as reaction time
21676037), the National Key R&D project (2016YFC0204702), the
passes [56].
Innovative Research Team of Chongqing (CXTDG201602014), the
Based on the information on intermediates obtained from
Natural Science Foundation of Chongqing (cstc2016jcyjA0481),
in situ IR spectra, we could reveal the mechanism of photocatalytic
and a project from the Chongqing Education Commission
NO oxidation. In adsorption time, NO and O2 together with reduced
(KJ1600625).
metal Bi seem to form a nitroso species in the mode of Bi–NO2 [60]:

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