Bismuth terephthalate induced Bi(0) for enhanced RhB photodegradation and 4-nitrophenol reduction

Article abstract of DOI:10.1016/j.jpcs.2017.08.034

A facile reductive method was used to prepare the semimetal Bi⁽⁰⁾ through reacting Bi(NO₃)₃ with NaI. The Bi⁽⁰⁾ incorporated bismuth terephthalate hybrids were prepared from two different strategies with enhanced visible light photodegradation of RhB and reduction of 4-nitrophenol. The synergistic interaction between layered bismuth terephthalate and Bi⁽⁰⁾ with SPR effects could induce the effective separation of photogenerated electrons and holes that leading to the enhancement of their oxidation performance. In the reduction of 4-nitrophenol, bismuth terephthalate may act as an excellent supporter and as a precursor which in situ produces the semimetal Bi⁽⁰⁾. The Bi⁽⁰⁾ incorporated bismuth terephthalate reported in this work can be potentially applied in visible light photooxidation and reduction of organic compounds.

Full text of DOI:10.1016/j.jpcs.2017.08.034

Accepted Manuscript
(0)
Bismuth terephthalate induced Bi for enhanced RhB photodegradation and 4-
nitrophenol reduction
Xinyun Zhao, Jianping Zhong, Juncheng Hu, Lamei Wu, Xi Chen
PII:
S0022-3697(17)30897-1
10.1016/j.jpcs.2017.08.034
PCS 8188
DOI:
Reference:
To appear in: Journal of Physics and Chemistry of Solids
Received Date: 23 May 2017
Revised Date: 25 July 2017
Accepted Date: 23 August 2017
(0)
Please cite this article as: X. Zhao, J. Zhong, J. Hu, L. Wu, X. Chen, Bismuth terephthalate induced Bi
for enhanced RhB photodegradation and 4-nitrophenol reduction, Journal of Physics and Chemistry of
Solids (2017), doi: 10.1016/j.jpcs.2017.08.034.
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Bismuth Terephthalate Induced Bi(0) for Enhanced RhB Photodegradation
and 4-Nitrophenol Reduction
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Xinyun Zhao, Jianping Zhong, Juncheng Hu, Lamei Wu, Xi Chen*
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Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs
Commission & Ministry of Education, South-Central University for Nationalities,
Wuhan 430074, PR China
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Abstract
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A facile reductive method was used to prepare the semimetal Bi(0) through reacting
Bi(NO3)3 with NaI. The Bi(0) incorporated bismuth terephthalate hybrids were
prepared from two different strategies with enhanced visible light photodegradation of
RhB and reduction of 4-nitrophenol. The synergistic interaction between layered
bismuth terephthalate and Bi(0) with SPR effects could induce the effective separation
of photogenerated electrons and holes that leading to the enhancement of their
oxidation performance. In the reduction of 4-nitrophenol, bismuth terephthalate may
act as an excellent supporter and as a precursor which in situ produces the semimetal
Bi(0). The Bi(0) incorporated bismuth terephthalate reported in this work can be
potentially applied in visible light photooxidation and reduction of organic
compounds.
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Keywords Bi(0) incorporated bismuth terephthalate; Photodegradation; Reduction of
4-nitrophenol
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Corresponding author: Xi Chen: ccnuchen@yahoo.com
South-Central University for Nationalities, Wuhan 430074, PR China
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1. Introduction
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Bismuth-based materials have attracted considerable attention due to its nontoxicity,
low cost and high earth abundance[1]. Bismuth oxyhalides BiOX (X=Cl, Br, I) and
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their heterostructures [2-10], BiVO4[11], Bi2WO6[12, 13]
nitrogen-doped-
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(BiO)2CO3[14] and other bismuth based materials[15-17] were found to exhibit
promising photocatalytic activities for the degradation of organic pollutants in waste
water. Zero valence bismuth (Bi(0)), as a semimetal with a rhombohedral structure, has
been discovered to display appealing applications as it has a very small band gap, a
highly anisotropic Fermi surface, and a long carrier mean free path[18]. It can be
applied in thermoelectricity[19]. It also was involved in many chemical reactions such
as the allylation of aldimines [20], transformation of aldehydes to homoallylic
alcohols[21], the reduction of aromatic α–halo ketones[22] and nitro compounds[23].
The aerobic oxidation of benzyl alcohol on Pt-Bi/CNT has been reported[24]. In
addition, Bi(0) was reported as a photocatalyst which can enhance the photocatalytic
oxidation of NO in air[23, 25]. Bismuth also can act as an alternative electron trap in
Bi/BiOCl[26-28]. Bi-coupled Bi2O3[29], Bi/BiOI[30], Bi/(BiO)2CO3[31] and
Bi/BiPO4[32]catalytic systems to degrade organic pollutants and remove Cr(VI) in
wastewater[33, 34]. Their higher photocatalytic activities are ascribed to effective
separation of photogenerated electron-hole pairs. Bi(0) has also shown surface
plasmon resonance (SPR) effects for enhancing light harvesting[35, 36]. Several
methods have been used to prepare semimetal bismuth, including thermal
decomposition[37], and electrochemical methods[38]. Simple chemical reduction
using a bismuth precursor and different reducing agents such as NaBH4[39-41],
hydrazine[42], ethylene glycol [43] and zinc power[44] have also been developed. To
date, all these reported synthetic methods are related to high temperature, unavailable
precursors including organic bismuth salts, special apparatus or complicated
post-processing. Additionally, the capping agents were usually used to enhance its
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stability of elemental bismuth[45]. Therefore, an economically available and facile
strategy to prepare stable semimetal bismuth base materials is still urgently needed.
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In our early studies [46, 47] a layered bismuth terephthalate was found to act as an
excellent candidate for preparation of functional materials. But bismuth terephthalate
itself has weak photocatalytic activities[7]. In order to further explore the potential of
layered bismuth terephthalate as promising catalytic materials and enhance the
stability of elemental bismuth, Bi(0) particles with SPR effects were expected to load
into bismuth terephthlate. Herein, we report a simple solvothermal method to prepare
semimetal Bi(0) through reacting Bi(NO3)3 with NaI in N,N-dimethylformamide (DMF)
solution. Bi(0) incorporated bismuth terephthalate were prepared through two different
strategies. The incorporated amounts of Bi(0) into bismuth terephthalate were tuned by
reducing the same amounts of Bi(NO3)3 with different amounts of NaI. A one-pot
synthesis was performed through in situ reduction of Bi(NO3)3 with controlled
amounts of NaI (molar ratios of NaI/Bi(NO3)3 at 0.5, 0.75 and 1) in the presence of
terephthalic acid to give the hybrids BiBDC-I(n) (n = 0.5, 0.75 and 1). A two-step
solvothermal method was used by controlling the same molar ratios of NaI/Bi(NO3)3
based on the firstly prepared bismuth terephthalate. Their catalytic activities were
evaluated on rhodamine B (RhB) photodegradation under visible light and/or UV
light irradiation from 350W xenon lamp and reduction of 4-nitrophenol under visible
light irradiation from the same xenon lamp or without it at room temperature. Active
species involved into RhB photodegradation process under visible light irradiation has
been investigated.
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2. Experimental section
2.1 Preparation of catalysts
2.1.1 Preparation of bismuth terephthalate (BiBDC)
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The preparation of bismuth terephthalate (BiBDC) was given in our earlier
report[46]. In brief, Bi(NO3)3·5H2O and terephthalic acid (H2BDC) were dissolved
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into 35 mL of DMF. The resulting mixture was heated at 120ꢀ in a Teflon-lined
stainless steel autoclave for 24 h. The resulting precipitates were collected, washed
with ethanol, water and dried to give 0.38 g of the product which was denoted as
BiBDC.
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2.1.2 General procedures for the one-pot synthesis of Bi(0) incorporated BiBDC
This involved dissolving terephthalic acid (0.332 g, 2 mmol) into 15 mL of DMF
with stirring. A solution of Bi(NO3)3·5H2O (0.645 g, 1.33 mmol) in 20 mL of DMF
was prepared by ultrasonic dissolution. Different amounts of NaI with the molar ratios
(0.5, 0.75 and 1) of NaI/Bi(NO3)3 were added into the above solution of terephthalic
acid with stirring. Then the solution of Bi(NO3)3 was added slowly into the above
mixture with stirring. The final mixture was transferred into a 100 mL Teflon-lined
stainless steel autoclave. The subsequent procedure was the same as that used for the
preparation of BiBDC. These hybrids were denoted as BiBDC-I(0.5), BiBDC-I(0.75)
and BiBDC-I(1), respectively.
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2.1.3 A two-step method for the preparation of Bi(0) incorporated BiBDC
Bismuth terephthalate (BiBDC, 0.38 g) was prepared firstly, then was dispersed by
sonication into 20 mL of DMF with Bi(NO3)3·5H2O (0.645 g, 1.33 mmol) and
different amounts of NaI with the molar ratios of NaI/Bi(NO3)3 at 0.5, 0.75 and 1. The
resulting suspension was treated sequentially as done for the BiBDC, and the
complexes formed were denoted as BiBDC-I’’(0.5), BiBDC-I’’(0.75) and
BiBDC-I’’(1), respectively.
2.1.4 Preparation of semimetal bismuth (Bi(0))
Semimetal Bi(0) was prepared according to the one-pot synthesis procedure of Bi(0)
incorporated BiBDC (Experimental section 2.1.2) using Bi(NO3)3 (0.645 g, 1.33
mmol) and NaI with the molar ratio of NaI/Bi(NO3)3 at 0.75 without terephthalic acid.
Bi(0) was obtained as black powders.
2.2 Catalyst characterization
Powder X-ray diffraction (XRD) patterns were obtained on a Bruker D8 Advance
using Cu Kα radiation. Fourier transform infrared spectra were recorded on a Thermo
Scientific Nicolet NEXUS 4700 spectrometer. X-ray photoelectron spectroscopy
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(XPS) measurements were performed on a VG Multilab 2000 photoelectron
spectrometer using Al Kα radiation as the excitation source under vacuum at 2×10−6
Pa. All the binding energy values were calibrated using the C 1s peak at 284.6 eV of
the surface adventitious carbon. The morphologies of the samples were investigated
by an SU8000 field emission scanning electron microscope (SEM). Transmission
electron microscopy (TEM) and high resolution transmission electron microscopy
(HRTEM) images were obtained on a Tecnai G20 microscope operated at an
accelerating voltage of 200 kV. UV–Vis diffuse reflectance spectra (DRS) were
measured on a UH4150 spectrophotometer. Photoluminescence measurements were
carried out at room temperature on a Hitachi F-7000. Transient photocurrent tests
were carried out on CHI760E electrochemical station with a standard three electrode
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system. The visible light was from a 3W LED lamp. H NMR spectra were recorded
on a Varian NMR 400 MHz instrument and the chemical shifts are in ppm and
tetramethylsilane as internal standard.
2.3 Photodegradation of RhB
The photocatalytic degradation of RhB (20 mg/L) in aqueous solution (50 mL) was
performed under visible light and/or UV light irradiation over as-prepared samples.
The reaction temperature was maintained at room temperature by using a
double-walled reactor with the circulating water. The visible light was provided by a
350 W xenon lamp with a 420 nm cutoff filter and UV light was from the same light
source using a 365 nm cutoff filter. In each experiment, 50 mg of catalyst was
dispersed in RhB solution under sonicated condition for 10 min. The suspension was
magnetically stirred in the dark for 2 h for establishment of adsorption equilibrium.
Then the suspension was irradiated with visible light or UV light. During the given
irradiation time, 3 mL aliquots were collected, centrifuged, and filtered through a
Millipore filter (pore size 0.45 ꢀm) to remove the residual catalyst. The characteristic
absorption of RhB at 553 nm was used to monitor the photodegradation process.
2.4 Active species trapping experiments over BiBDC-I’’(0.75)
Isopropyl alcohol (IPA), benzoquinone (BQ) and ethylenediaminetetraacetic acid
disodium salt (EDTA) with final concentrations of 1 mmol/L were added into 50 mL
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RhB solution with the concentration of 20 mg/L as active species scavengers[48]. The
procedure of photodegradation over BiBDC-I’’(0.75) was similar to that of RhB
degradation under visible light irradiation.
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2.5 Catalytic reduction of 4-nitrophenol
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20 mg of the as-prepared catalyst was used to start the 50 mL of reduction system
including 1×10-4 mol/L of 4-nitrophenol and 1×10-2 mol/L of NaBH4 with visible light
irradiation from a 350W xenon lamp or without it at room temperature. The process
was the same as that used for RhB photodegradation. After NaBH4 was added into
reaction system for 5 min, the catalyst was sequentially added. at specific time
interval, 3ml suspensions were taken and filtered through 0.45 ꢀm Millipore filter and
the filtrate was analysized intermediately by monitoring the variation of intensity of
peak at 400 nm using UV-Vis spectroscopy[45]. The reduction product
4-aminophenol was obtained from the filtrate treated with HCl and extracted by ethyl
acetate then separated through column chromatography.
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3. Results and discussion
3.1 Composition analysis
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All hybrids and Bi(0) were prepared by a solvothermal method in DMF. BiBDC was
used for a comparison. All the XRD diffraction peaks of the prepared Bi(0) can be
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readily indexed to a rhombohedral phase of Bi(0) [space group: R3m(166), JCPDS No.
44-1246] and no other diffraction peaks of the impurity are observed (a in Fig. 1B). It
is highly crystalline and can be indexed by the representative peaks of (012), (104),
(110), (202), (024), (122) planes[49]. The result suggests that semimetal Bi(0), not
bismuth oxide, was obtained in the presence of Bi(NO3)3 and NaI. When the solution
of Bi(NO3)3 was added slowly into NaI solution at room temperature, an orange-red
color occurred. However, neither a color change on potassium iodide-starch test paper
nor a black precipitate was observed. This suggested that semimetal Bi(0) particles
were obtained through reduction of the Bi(NO3)3 using NaI at a temperature of 120ꢀ,
not at room temperature. This is ascribed to the stronger reductive ability of I-. The
reduction proceeds to the formation of semimetal Bi(0) according to the following
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stoichiometry.
2Bi3+
2 Bi(0)
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+
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(1)
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Powder XRD patterns of all the BiBDC-I(n) can be seen in Fig. 1A. They all
exhibit characteristic diffraction peaks of Bi(0). For those hybrids BiBDC-I’’(n) (n=
0.5, 0.75 and 1) prepared from the two-step method, when NaI with the molar ratio of
NaI/ Bi(NO3)3 at 0.5 was added, BiBDC-I’’(0.5) was formed. But its XRD patterns (b
in Fig. 1B) are similar to that of our prepared BiBDC (a in Fig. 1A), i.e. no semimetal
Bi(0) was detected. When the amounts of NaI increased in which the molar ratios of
NaI/ Bi(NO3)3 varied from 0.75 to 1, semimetal Bi(0) was formed. So semimetal Bi(0)
were formed from a two-step method by controlling the amounts of NaI with the
molar ratios of NaI/ Bi(NO3)3 at 0.75 and 1. Overall, Bi(0) particles were found in five
hybrids including BiBDC-I(n) (n= 0.5, 0.75,1), BiBDC-I’’(0.75) and BiBDC-I’’(1).
IR spectra of representative hybrids including semimetal Bi(0), terephthalic acid and
BiBDC can be seen in Fig. 2. It is noted that terephthalic acid has characteristic
absorption peaks at 1683.2, 1423.1 and 1286.4 cm-1 (Fig. 2a)[50]. The disappearance
of the peak at 1683.2 , 1286.4 cm-1 and the concomitant appearance of new peaks
located at about 1532.0 and 1382.0 cm-1 for those five hybrids indicate that the
–COOH groups of terephthalic acid were completely coordinated with the Bi3+ ions in
which bismuth terephthalate was formed[7]. Combining with the conclusion from the
XRD patterns in which Bi(0) particles exist in the above hybrids, we can safely
conclude that Bi(0) incorporated bismuth terephthalate hybrids were obtained. But for
BiBDC-I(0.75) from the one-pot synthesis, absorption peaks at 1562.6 cm-1 (νas
C=O) and 1384.7 cm-1 (νs C=O) were found. For BiBDC-I’’(0.75) which was formed
from the two-step method, its IR spectrum (Fig. 2b) indicates strong absorption peaks
locate at 1533.1 cm-1 and 1384.0 cm-1. The BiBDC-I’’(1) has characteristic peaks at
1528.9 cm-1 and 1383.7 cm-1. These characteristic absorption peaks of C=O are close
to those of BiBDC. However, the frequency of asymmetric stretching vibration of
C=O (1562.6 cm-1) for BiBDC-I(0.75) is larger than that for BiBDC-I’’(0.75) (1533.1
cm-1). The increase in absorption wavenumber for the carbonyl stretching vibration
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within BiBDC-I(0.75) was attributed that stretching force constant of carbonyl bond
increased. It seems that the interactions between Bi(0) and O atom within BiBDC are
weaker for BiBDC-I(0.75) which leads to decreased polarity of C=O bond. It could be
ascribed to the less amounts of Bi(NO3)3 was used to react with the same amounts of
NaI for the preparation of BiBDC-I(0.75). For the one-pot synthesis, Bi(NO3)3 plays
two different roles in being reduced by NaI and coordinating with terephthlic acid as a
nucleating agent. While for the two-step method, the same amounts of Bi(NO3)3 was
only reduced by the same amounts of NaI (NaI can’t reduce the BiBDC at the same
conditions). Theoretically, less amounts of Bi(0) was incorporated into BiBDC-I(0.75).
In fact, there is no easy way of quantifying the loading amounts of Bi(0) owing to the
presence of Bi3+.
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The surface chemical compositions and electronic states of BiBDC-I(0.75),
BiBDC-I’’(0.75) and BiBDC hybrids were further investigated by XPS patterns (Fig.
2). The high-resolution Bi 4f spectra show two individual and the same peaks at 159.3
eV, 164.5 eV for BiBDC and BiBDC-I(0.75) (Fig. 2c). The corresponding peaks could
be attributed to Bi 4f7/2 and Bi 4f5/2, respectively [51-53]. The data show oxidation
states for Bi is +3. While the Bi 4f spectra of BiBDC-I’’(0.75) show two individual
peaks at 159.4 eV, 164.7 eV (Fig. 2d). Binding energies of Bi3+ within BiBDC-I’’(0.75)
from the two-step method slightly increase with respect to those of BiBDC-I(0.75).
This can be attributed to stronger synergistic interactions between incorporated Bi(0)
and O atom within BiBDC for BiBDC-I’’(0.75). This result is consistent with the
conclusion from IR data. However, The characteristic peaks of zero valence Bi(0) at
156.8 and 162.1 eV were not observed in the XPS patterns of BiBDC-I’’(0.75) as well
as those of BiBDC-I(0.75)[54]. The information from the XRD patterns of
BiBDC-I(0.75) and BiBDC-I’’(0.75) shows that Bi(0) exists in the hybrids. So it is
estimated that most of the Bi(0) entered into the internal surface of the metal-organic
framework BiBDC which can not be detected owing to the limitation of XPS surface
technology[55]. This also can be confirmed from SEM and TEM images of those
hybrids as shown in Fig. 3. Semimetal Bi(0) has a granular morphology and BiBDC
has a rod like morphology (Fig. S1 in Supporting Information), Bi(0) incorporated
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BiBDC hybrids have a similar morphology to that of BiBDC(Fig. 3a-3e). Other
information from the TEM images of BiBDC-I’’(0.75) demonstrates more details
about the interior structure of this hybrid. As can be seen from Fig. 3f-3g, the prepared
sample is highly sensitive to electron beam irradiation during the TEM examination
due to the relatively low melting point of Bi(0) (273.1ꢀ), which makes it much more
difficult to get clear HRTEM images[44]. The fast Fourier transform (FFT) pattern
(Fig. 3h) of high magnification TEM image of Fig. 3g shows lattice fringes with a
lattice spacing of about 0.32 nm, which is close to the interplanar spacing of the (012)
lattice planes of the rhombohedral bismuth (Bi(0)). Semimetal Bi(0) really exists in
BiBDC-I’’(0.75). So BiBDC-I(0.5), BiBDC-I(0.75), BiBDC-I(1), BiBDC-I’’(0.75)
and BiBDC-I’’(1) are regarded as Bi(0) incorporated BiBDC hybrids.
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Fig. 1 XRD patterns of as-prepared samples (A): (a) BiBDC; (b) BiBDC-I(0.5);
(c)BiBDC-I(0.75); (d)BiBDC-I(1) and (B): (a) prepared Bi(0); (b) BiBDC-I’’(0.5);
(c)BiBDC-I’’(0.75); (d)BiBDC-I’’(1).
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Fig.2 IR spectra of representative samples. BiBDC-I(0.75) and terephthalic acid(a);
BiBDC-I’’(0.75), BiBDC-I’’(1), prepared Bi(0) and BiBDC (b); XPS patterns of BiBDC-I(0.75),
BiBDC-I’’(0.75) and BiBDC(c), (d).
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Fig. 3 SEM images of Bi(0) incorporated BiBDC hybrids. BiBDC-I(0.5) (a); BiBDC-I(0.75)
(b); BiBDC-I(1) (c); BiBDC-I’’(0.75) (d); BiBDC-I’’(1) (e); TEM image of BiBDC-I’’(0.75) (f);
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TEM image of the region indicated by the box in f (g); The selected area FFT pattern of Fig.3g(h).
3.2 Optical absorption and charge separation
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UV-Vis diffuse reflectance spectra (DRS) were used to investigate the light
absorption properties of the as-prepared samples. UV−Vis DRS of BiBDC, Bi(0),
BiBDC-I(n) (n=0.75), and BiBDC-I’’(0.75) are shown in Fig. 4. The results from
DRS demonstrate that BiBDC has absorption edges at about 350 nm in the UV light
region (Fig. 4a). When the semimetal bismuth particles were incorporated into
bismuth terephthalate, BiBDC-I(n) and BiBDC-I’’(n) (n=0.75,1) hybrids exhibit a
promising extended absorption edge in the visible light region. Compared with
BiBDC-I(0.75), BiBDC-I’’(0.75) shows a conspicuously enhanced optical absorption
edge which ranges from the UV (350 nm) to the visible light region (650 nm) (Fig.
4a). This could be ascribed to a surface plasmon resonance (SPR) effect of Bi(0) which
leading to more visible light harvesting[36]. This enhanced light absorption is crucial
for photoexciting more electrons and holes to improve the photodegradation
efficiency.
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Fig. 4 UV-Vis diffuse reflectance spectra of representative hybrids BiBDC-I(0.75),
BiBDC-I’’(0.75) and BiBDC, Bi(0) (a) their photoluminescene emission spectra (b) and transient
photocurrent of representative hybrids (c).
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Photoluminescence (PL) spectra were further used to investigate the separation
efficiency of photoexcited electron−hole pairs for the semiconductor. PL spectra of
the representative hybrids BiBDC-I(0.75), BiBDC-I’’(0.75), and BiBDC, Bi(0)
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excited at 245 nm were recorded (Fig. 4b). Hybrid BiBDC-I’’(0.75) shows the lowest
PL intensity among all the tested hybrids except the Bi(0). This implies that the
recombination of photoelectrons and holes could be effectively prohibited. In order to
further confirm the separation of photocarriers, transient photocurrent test was
performed under visible light irradiation from a 3W LED lamp (Fig. 4c). The results
show that BiBDC-I’’(0.75) has better separation effect than BiBDC. This is attributed
to the promotion effect of incorporated Bi(0) which has a similar Mott−Schottky
effect[56]. Bi(0) was incorporated to build a Schottky barrier at the interface which is
beneficial for charge transfer during the separation of photogenerated electrons and
holes.
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3.3 Visible light degradation of RhB
Photodegradation activities of as-prepared samples were evaluated under visible
light irradiation using 20 mg/L of RhB in aqueous solution. The variation of RhB
concentration (C/C0) versus irradiation time t (min) over different samples during the
degradation process are shown in Fig. 5, where C and C0 are the concentration values
of RhB at a given time t and 0 min. A blank control assay (without catalysts) was
performed for comparison. The direct RhB degradation is negligible under visible
light irradiation. When BiBDC was used to degrade 20 mg/L of RhB, the result shows
that BiBDC itself has only a weak degradation activity under visible light
irradiation[46]. In order to quantitatively evaluate the degradation activities of Bi(0)
incorporated BiBDC and prepared Bi(0), the corresponding reaction rate constants k
are determined using a pseudo first-order kinetic model. The results are summarized
in Table 1. Compared to BiBDC and Bi(0), the BiBDC-I(0.75) shows significantly
higher RhB photodegradation activities. Thus, the semimetal Bi(0) was incorporated
into BiBDC which can effectively accelerate RhB degradation and enhance the
photocatalytic performance of Bi(0). In order to further improve the catalytic activities
of hybrids, a two-step method was used to prepare BiBDC-I’’(0.75) and BiBDC-I’’(1).
Their RhB Degradation results under visible light irradiation are also shown in Fig. 5
and Table 1. Surprisingly, BiBDC-I’’(0.75) and BiBDC-I’’(1) both have better
degradation activity than that of BiBDC-I(0.75). When the content of incorporated
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Bi(0) into BiBDC increased, the photocatalytic process was little hampered. The
degradation activity of RhB over BiBDC-I’’(1) is lower than that of BiBDC-I’’(0.75).
This could be ascribed to substantial Bi(0) covering the interface of BiBDC that
prevented the incident photons from impinging on the surface of catalyst, thereby
decreasing its photocatalytic performance[57]. This can be confirmed from the results
of the lower degradation activity of BiBDC-I(1) compared with that of BiBDC-I(0.75)
(Table 1). The reaction rate constants for BiBDC-I’’(0.75) and BiBDC-I’’(1) are
larger relative to those of BiBDC-I(n) (n=0.5, 0.75 and 1) and Bi(0). Reaction rate
constant for BiBDC-I’’(0.75) is 6 times than that of Bi(0) and 4 times than that of
BiBDC. A two-step method occurs prior to the one–pot synthesis for the preparation
of Bi(0) incorporated BiBDC. The higher RhB degradation activity of BiBDC-I’’(0.75)
was attributed to a synergistic interaction between Bi(0) and the metal-organic
framework BiBDC.
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Fig. 5 Degradation of RhB under visible light irradiation over Bi(0) incorporated bismuth
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Table 1 Degradation rate constants of RhB over Bi(0) and Bi(0) incorporated bismuth
terephthalate
Catalysts
Rate constant k
(min-1)
Bi(0)
0.008
BiBDC
0.011
0.011
0.019
0.014
0.048
0.033
BiBDC-I(0.5)
BiBDC-I(0.75)
BiBDC-I(1)
BiBDC-I’’(0.75)
BiBDC-I’’(1)
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3.4 Plausible process for RhB degradation
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To further understand the visible light photodegradation process of RhB over the
BiBDC-I’’(0.75), active species trapping experiments were performed. Isopropanol
(IPA), benzoquinone (BQ) and ethylenediaminetetraacetic acid disodium salt (EDTA)
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were used to trap the active hydroxyl radical (·OH), superoxide radical (·O2 ) and
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active holes (h+) involved in the photocatalytic process, respectively[58]. Fig. 6a
shows the photodegradation of RhB over BiBDC-I’’(0.75) in the absence or presence
of scavengers under visible light irradiation. The RhB degradation is markedly
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suppressed by BQ and EDTA, suggesting that ·O2 and h+ are primarily responsible for
RhB degradation. RhB degradation was little inhibited by IPA which suggesting ·OH
-
was only involved in the catalytic process to a small degree. The crucial species ·O2
are produced by reacting O2 with the separated electrons. It implies that photoexcited
electrons and holes play important roles for RhB degradation. Those results from PL
and transient photocurrent tests further also confirm this hybrid has the excellent
separation efficiency of the photogenerated electrons and holes. Thus, the
incorporation of the semimetal Bi(0) into bismuth terephthalate will lead to the
formation of a Schottky barrier at the BiBDC–Bi(0) interface, which is beneficial for
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the charge transferring during the separation of electron-hole pairs.
A possible degradation process of the dye under visible light irradiation can
proceed through three possible pathway, i.e. a photolysis process, a dye
photosensitization process, or a photocatalytic process[59]. As for RhB, its photolysis
process is negligible under visible light irradiation as illustrated in Fig.5[46]. To
determine whether a dye photosensitization or photocatalytic process plays a role in
RhB degradation over BiBDC-I’’(0.75), the same degradation procedure was carried
out under UV light irradiation. The results are shown in Fig. 6b. Comparing with the
results from the visible light irradiation, RhB was degraded completely in 60 minutes
under visible light irradiation, while only 75% of RhB was degraded under UV light
irradiation with the same irradiation time. Degradation efficiency is higher under
visible light irradiation than that under UV light irradiation. This is consistent with the
results from DRS of this catalyst which has an extended absorption edge into the
visible light region (Fig. 4a). RhB degradation over BiBDC-I’’(0.75) under visible
light irradiation is a photocatalytic and photosensitization process[60]. Overall,
semimetal Bi(0) with SPR effects was incorporated layered bismuth terephthalate
which can effectively enhance the photooxidation efficiency of RhB under visible
light irradiation.
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Fig. 6 Photodegradation of RhB over BiBDC-I’’(0.75) in the absence or presence of
scavengers (BQ, EDTA and IPA) under visible light irradiation (a) and RhB degradation over
BiBDC-I’’(0.75) under visible light and UV light irradiation (b).
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3.5 Reduction of 4-nitrophenol
It was reported that the 4-NP could not be reduced solely by NaBH4 , but in the
presence of certain catalyst the reduction reaction can occur [61]. In order to test the
catalytic activity of the catalysts in this work on the reduction of 4-NP, a series of
reactions were performed. These experiments were carried out in the following
conditions: 1) excessive NaBH4; 2) using Bi(0) or Bi(0) incorporated BiBDC and 3)
visible light irradiation from 350 W xenon lamp or without it. In these reactions, the
4-nitrophenol in aqueous solution (with the weak UV absorption peak at 317 nm) was
converted by NaBH4 to the deep yellow 4-nitrophenolate (with main strong
absorption peak at 400 nm), which will be eventually reduced to the final the
4-aminophenolate (with absorption peak at 231 nm)[62]. When the as-prepared
catalysts were added to the 4-nitrophenolate solution, a fading process of the
deep-yellow color of 4-nitrophenolate solution was also observed. Similar
characteristic phenomena appeared when the pure phase Bi(0) was added (Fig. S2 and
S3 in Supporting Information). Thus, the reduction process was monitored through
the gradually disappearance of this absorbance peak (400 nm). In order to confirm the
final product of this reaction, the reduction product 4-aminophenol was obtained by a
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sequential acidification process and was characterized by H NMR (Fig. S4). Its
melting point and 1H NMR data were consistent with a standard sample.
The influence of visible light on the reduction of 4-NP over Bi(0) incorporated
bismuth terephthalate hybrids was also investigated (Fig. S5 and S6 in Supporting
Information). Depicted in the Fig. 7 are plots of C/C0 versus time (t) for the reduction
of 4-NP in the presence of different catalysts, where C and C mean the concentration
’
0
of 4-nitrophenolate at t and 5 min after adding of NaBH4. Since a hundred-fold molar
excess of NaBH4 with respect to the concentration of 4-nitrophenolate was used, the
reaction could be considered to follow pseudo-first order kinetics. The reaction rate
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constant k can be derived from the dataset in Fig. 7 by using the following equation.
(2)
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The obtained rate constants k are collected in Table 2. At a glance of Fig.7, it can
be seen that the reductive capability of all Bi(0) incorporated BiBDC hybrids were
more potent than that of Bi(0). Obviously, the BiBDC composite within these hybrids
was responsible for enhanced reduction activities. As can be seen from Table 2, the
corresponding rate constants k are ~1.1-2.0 times that of pure Bi(0). The relative low
efficiency of pure Bi(0) may be due to its instability under reduction reaction system.
In addition, when white color bismuth terephthalate (BiBDC) was used, some black
powder was observed, which was confirmed to be semimetal Bi(0). Obviously, the
black Bi(0) was in situ generated by the reaction of BiBDC with NaBH4, and the
freshly formed Bi(0) would sequentially reduce the 4-NP with higher efficiency. We
speculated that BiBDC could be a good supporter that was beneficial to the generation
of Bi(0) and the enhancement of reductive capability. Additionally, it can also be seen
from Table 2 that under visible light irradiation the catalytic ability of the hybrids
from one-pot synthesis such as BiBDC-I(0.5), BiBDC-I(0.75), BiBDC-I(1) successively
decreases with the increasing of the incorporated Bi(0) amount. Similar trends were
also observed for those hybrids from two-step method. The present experimental
results suggests that visible light irradiation is not beneficial for the enhancing the
reduction efficiency of 4-nitrophenol over catalyst in this work.
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Fig. 7 Reduction of 4-NP over Bi(0) and Bi(0) incorporated BiBDC with visible light
irradiation or without light irradiation from xenon lamp (C, concentration of 4-nitrophenolate at t
min; C , concentration of 4-nitrophenolate after adding of NaBH for 5 min ).
ꢁ
0
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Table 2. The rate constants of reduction of 4-NP with visible light irradiation or without light
irradiation from 350 W xenon lamp
samples
Rate constants
without visible light
0.139
k
(min-1) Rate constants k (min-1) under
visible light irradiation
BiBDC-I(0.5)
BiBDC-I(0.75)
BiBDC-I(1)
BiBDC-I’’(0.75)
BiBDC-I’’(1)
Bi(0)
0.150
0.115
0.101
0.151
0.107
0.089
0.153
0.129
0.166
0.133
0.145
0.081
BiBDC
0.144
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4. Conclusion
In this study, we have introduced a new facile reductive method to prepare
semimetal Bi(0) in DMF solution by reacting of Bi(NO3)3 with NaI at 120ꢀ.
Semimetal Bi(0) incorporated bismuth terephthalate hybrids were prepared from two
different methods. A one-pot synthesis was carried out by varying the amounts of NaI
with the molar ratios of NaI/Bi(NO3)3 at 0.5, 0.75 and 1. A two-step method was used
by reacting Bi(NO3)3 with controlled amounts of NaI with the molar ratios of
NaI/Bi(NO3)3 at 0.75 and 1 in the presence of firstly prepared BiBDC. The hybrid
BiBDC-I’’(0.75) from a two-step method exhibits excellent photodegradation
performance towards RhB. Its reaction rate constant is 6 times larger than that of Bi(0)
and 5 times larger than that of BiBDC. The higher visible light degradation activity
was attributed to synergistic interaction between Bi(0) with a surface plasmon
resonance and BiBDC which induced more light harvesting and effective separation
of electron-hole pairs. The results from active species trapping experiments show
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that ·O2 and h+ are the most important active species.
These Bi(0) incorporated bismuth terephthalate hybrids also exhibit better reduction
capability of 4-nitrophenol than Bi(0). Visible light and incorporated amount of Bi(0)
significantly affect the catalytic efficiency of 4-NP reduction.
Put all thing together, BiBDC not only acts as an excellent supporter but also as a
precursor to in situ produce the semimetal Bi(0) which will sequentially reduce the
4-NP. Thus, Bi(0) incorporated bismuth terephthalate hybrids were found to be
promising visible light catalysts for the removal of organic pollutants and reduction of
4-NP. They can be potentially applied in visible light photooxidation and reduction of
organic compounds.
Acknowledgement
The research was supported by the National Natural Science Foundation of China
(grants number: 21273089) and the Special Fund for Basic Scientific Research of
Central Colleges, South-Central University for Nationalities (CZP17004).
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ACCEPTED MANUSCRIPT
Highlights
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Bi(0) incorporated bismuth terephthalate were prepared.
The prepared hybrid exhibits higher visible light photodegradation activity.
This hybrid also shows better reduction capability of 4-nitrophenol with visible
light.
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Visible light inhibited the reduction process of 4-nitrophenol and enhance
photooxidation of RhB.