Materials Letters 142 (2015) 201–203

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Photocatalytic hydrogenation of nitrobenzene to aniline over tungsten

oxide-silver nanowires
Li Fu a,b, Wen Cai c, Aiwu Wang c, Yuhong Zheng a,n
a
Institute of Botany, Jiangsu Province and Chinese Academy of Sciences, Nanjing Botanical Garden, Mem. Sun Yat-Sen, Nanjing 210014 P. R. China
b
Golden Yuanta Construction Engineering Co., Ltd, Zhejiang 311200, P. R. China
c
Department of Physics and Materials Science, City University of Hong Kong, 88 Tat Chee Avenue, Kowloon, Hong Kong P. R. China

art ic l e i nf o a b s t r a c t

Article history: We have developed a new synthesis method to prepare WO3-Ag hybrid nanowires (WO3-Ag NWs) for
Received 5 November 2014 photocatalytic hydrogenation of nitrobenzene (NB) to aniline. The catalyst was characterized by SEM,
Accepted 3 December 2014 XRD, N2 adsorption/desorption and Raman spectroscopy. Results showed that the WO3-Ag hybrid
Available online 12 December 2014
nanowires displays a porous network structure with high specific surface area. The synergy of Ag NWs
Keywords: and WO3 NWs plays the most vital role in this enhanced photocatalytic performance. Moreover, the
Composite materials synthesized WO3-Ag NWs also exhibited excellent reusability.
Crystal growth & 2014 Elsevier B.V. All rights reserved.
Semiconductors
Photocatalysis
Ag
WO3

1. Introduction showed enhancement of photocatalytic performance by suppres-

Aniline is an important chemical and intermediate in the produc-
tion of many industrial product including synthetic dyes, rubber,
amino resins and polyurethane [1,2]. Hydrogenation of nitrobenzene
(NB) using Cu, Ni, Pt, Pd and Au as catalyst is a common method used
for producing aniline [3–10]. However, this catalytic synthesis process
usually requires high temperature and H2 pressure. Recently, photo-
catalytic reduction of NB into aniline has been attracted considerable
attentions due to its low cost and can be conducted in the room
temperature. More importantly, the entire process only solar energy
as energy source. Therefore, designing a suitable photocatalyst for
photocatalytic hydrogenation of NB to aniline is very important to
enhance the production rate and yield.
Tungsten oxide (WO3), as an important n-type semiconductor
with a band gap of 2.8 eV, has attracted considerable interests due
to its promising physical and chemical properties. Taking into
account its strong adsorption within the solar spectrum and high
thermal and physicochemical stability, WO3 is considered as a
suitable candidate for visible light photocatalyst [11–14]. On the
other hand, noble metal nanostructures such as silver and gold
display unique catalytic properties. Silver nanoparticles have espe-
cially been of interests due to their high performance in various
catalytic reactions [15]. In addition, coupling Ag with WO3 also
n
Corresponding author.
E-mail address: yuhongzhengcas@gmail.com (Y. Zheng).
sing electron-hole pair recombination [16].
Herein, the WO3-Ag NWs have been the first time successfully
prepared through a facial chemical method using acetic acid as a
stabilizer. In order to inspect the properties of WO3-Ag NWs, SEM,
XRD, N2 adsorption/desorption and Raman spectroscopy charac-
terizations were carried out. In the meantime, the photocatalytic
activity of the WO3-Ag NWs towards hydrogenation of NB to
aniline under visible light irradiation was also investigated.
2. Experiments
Materials: Na2WO42H2O and AgNO3 were purchased from
Sigma-Aldrich. All other chemicals used were analytical grade
reagents without further purification.
Preparation of WO3 NWs: Firstly, 0.3 g Na2WO42H2O and 0.05 g
NaCl were dissolved into 20 mL acetic acid with half hour stirring. The
pH values of the dispersion were adjusted to about 2 using HCl
solution. After half hour stirring, the suspension was transferred to
50 mL Teflon-lined stainless steel autoclave. The autoclave was heated
to 180 1C and maintained for 24 h in an oven and naturally cooled
down to the room temperature. The product was centrifuged, washed
with water, and dried at 70 1C.
Preparation of WO3-Ag NWs: 5 mL of AgNO3 solution (10 mM)
and 0.01 g NaCl was added into 5 mL WO3 NWs (5 mg/mL)
dispersion with 1 h stirring. Then 0.02 g glucose was dissolved in
the above dispersion. After 30 min stirring, the suspension was

http://dx.doi.org/10.1016/j.matlet.2014.12.021
0167-577X/& 2014 Elsevier B.V. All rights reserved.
202 L. Fu et al. / Materials Letters 142 (2015) 201–203
transferred to 50 mL Teflon-lined stainless steel autoclave. The
autoclave was heated to 180 1C and maintained for 5 h in an oven
and naturally cooled down to the room temperature. The final
product was centrifuged, washed with water, and dried at 70 1C.
Photocatalytic hydrogenation of NB: 50 mg of photocatalyst was
dispersed into 50 mL of NB-methanol solution (20 mg/L) in a Pyrex
reactor. Prior to the photocatalytic test, the suspension was purged
with N2 to elimination of oxygen. After light illumination, 2 mL of
suspension was then taken out for a certain period and the
photocatalyst was separated by centrifugation. The absorption of
NB and aniline was then measured by a UV–vis spectroscopy. The
absorbance of NB and aniline at 268 nm and 229 nm was used for
measuring the concentration change, respectively.
3. Results and discussion
SEM was used to investigate the morphology of synthesized
samples. Fig. 1 shows the SEM images of WO3 NWs and WO3-Ag
NWs. As shown in Fig. 1A, the WO3 NWs are composed of a large
quantity of uniform nanowires with an average length and diameter
of 2 μm and 80 nm, respectively. On the other hand, the WO3-Ag
NWs are composed of WO3 NWs with many thin Ag NWs. Under
hydrothermal condition, the AgCl was reduced by glucose to form
silver nanowires. Moreover, the connection of thick WO3 NWs and
thin Ag NWs displays a porous network structure.
The crystalline phase of WO3 NWs and WO3-Ag NWs samples
was characterized by XRD. As shown in Fig. 2A, the XRD pattern of
the WO3 NWs is well crystallized in a single phase and all of the
diffraction peaks can be assigned to monoclinic WO3 (JCPDS
72–0677). Expect the peaks of WO3, the XRD pattern of the
WO3-Ag NWs also exhibits peaks at 2θ values of 38.21, 63.41,
and 76.91, and are indexed to the diffractions of the (1 1 1), (2 2 0)
Fig. 1. SEM image of (A) WO3 NWs and (B) WO3-Ag NWs.
Fig. 2. (A) XRD patterns and (B) Nitrogen adsorption/desorption isotherms of WO3 NWs and WO3-Ag NWs.
and (3 1 1) crystal planes of metallic Ag (JCPDS no. 04-0783),
respectively. Therefore, XRD characterization confirmed the suc-
cessful formation of WO3-Ag NWs.
Fig. 2B shows nitrogen adsorption-desorption isotherms of the
WO3 NWs and WO3-Ag NWs. It can be observed that the both
samples show a similar isotherm curve with H3-type hysteresis
loop. The specific surface area of WO3 and WO3-Ag nanocomposite
was determined as 29.85 and 77.07 m2/g, respectively. Therefore,
the incorporation of Ag NWs into the WO3 NWs shows an increase
of the specific surface area of photocatalyst, which is beneficial for
many photochemical and photocatalytic applications.
Fig. 3A displays the UV–vis spectra of NB solution during the
photocatalytic reaction over the WO3-Ag NWs. It can be seen that
the absorption of NB at 268 nm decreases rapidly. At the same time,
a new peak at 229 nm appears, which corresponds to the absorption
of aniline. This phenomenon indicates the photocatalytic hydroge-
nation of NB to aniline could be occurred using WO3-Ag NWs as
photocatalyst under visible light illumination. Fig. 3B shows the
conversion profiles of using different photocatalysts for hydrogena-
tion of NB. As can be observed in the figure, there is no conversion
process happening without light illumination. On the other hand,
the conversion rate is very slow with the absence of photocatalyst.
With the presence of WO3 NWs, about 50% of NB can be converted
to aniline. While the presence of Ag NWs, only about 26% of NB can
be converted. In contrast, this value is increased to 94% when using
WO3-Ag NWs as photocatalyst. Therefore, our proposed WO3-Ag
NWs is a promising candidate of visible-light photocatalyst for
hydrogenation of NB to aniline.
The stability of photocatalyst is a crucial factor in the practical
applications. Thus, the reusability test of the synthesized WO3-Ag
NWs was tested for four photocatalysis cycles. As shown in Fig. 3C,
the WO3-Ag NWs remains more than 90% of photocatalytic
performance in the 5th cycle, implying that the proposed hybrid
nanowires have excellent stability. Fig. 3D shows the Raman
 L. Fu et al. / Materials Letters 142 (2015) 201–203
Fig. 3. (A) UV–vis spectra of NB solution monitored during the photocatalytic reaction. (B) Conversion profiles of NB to aniline with no catalyst, no light, WO3 NWs, Ag NWs
and WO3-Ag NWs. (C) Recycle tests of the WO3-Ag NWs. (D) Raman spectra of the WO3-Ag NWs before and after photocatalysis.
spectra of the WO3-Ag NWs before and after five cycles of
photocatalysis. The intense band at 806 cm 1 can be assigned to
the symmetric stretching vibration and the band at 706 cm 1 is
corresponded to the asymmetric stretching vibration of O–W–O
bond. The bands at 270 and 326 are corresponded to the bending
vibrations of the O–W–O bond [17]. It can be seen from the figure,
the spectrum of photocatalyst remained unchanged after photo-
catalysis, further confirmed the structural stability of the proposed
photocatalyst.
4. Conclusion
In this work, we reported a facile wet chemical method for
fabricating WO3-Ag NWs. The hybrid nanowires were character-
ized by a series techniques. The hybrid nanowires are constructed
by thick WO3 NWs and thin Ag NWs. The synthesized WO3-Ag
NWs exhibited a significant enhancement of photocatalytic activ-
ity towards hydrogenation of NB to aniline under visible light
irradiation.
References
[1] Gelder EA, Jackson SD, Lok CM. The hydrogenation of nitrobenzene to aniline:
a new mechanism. Chem Commun 2005;4:522–4.
[2] Diao S, Qian W, Luo G, Wei F, Wang Y. Gaseous catalytic hydrogenation of
nitrobenzene to aniline in a two-stage fluidized bed reactor. Appl Catal A: Gen
2005;286:30–5.
[3] Kohler MA, Lee JC, Trimm DL, Cant NW, Wainwright MS. Preparation of
Cu/SiO2 catalysts by the ion-exchange technique. Appl Catal 1987;31:309–21.
[4] Man J. Simulating design of a fluidized bed reactor for aniline production by
the hydrogenation of nitrobenzene. Huaxue Fanying Gongcheng Yu Gongyi/
Chem React Eng Technol 1988;4:64–74.
203
[5] Petrov L, Kumbilieva K, Kirkov N. Kinetic model of nitrobenzene hydrogena-
tion to aniline over industrial copper catalyst considering the effects of mass
transfer and deactivation. Appl Catal 1990;59:31–43.
[6] Corma A, Concepción P, Serna P. A different reaction pathway for the
reduction of aromatic nitro compounds on gold catalysts. Angew Chem Int
Edit 2007;46:7266–9.
[7] Qusti AH, Mohamed RM, Abdel Salam M. Photocatalytic synthesis of aniline
from nitrobenzene using Ag-reduced graphene oxide nanocomposite. Ceram
Int 2014;40:5539–46.
[8] Turáková M, Králik M, Lehocký P, Pikna Ľ, Smrčová M, Remeteiová D, et al.
Influence of preparation method and palladium content on Pd/C catalysts
activity in the liquid phase hydrogenation of nitrobenzene to aniline. Appl
Catal A: Gen 2014;476:103–12.
[9] Islam SM, Ghosh K, Roy AS, Molla RA, Salam N, Chatterjee T, et al. Polystyrene
anchored ruthenium(II) complex catalyzed carbonylation of nitrobenzene and
amines for the synthesis of disubstituted ureas. J Organometal Chem
2014;772–773:152–60.
[10] Mohamed RM, Aazam ES. Effect of Sn loading on the photocatalytic aniline
synthesis activity of TiO2 nanospheres. J Alloy Compd 2014;595:8–13.
[11] Wang X, Zhang H, Liu L, Li W, Cao P. Controlled morphologies and growth
direction of WO3 nanostructures hydrothermally synthesized with citric acid.
Mater Lett 2014;130:248–51.
[12] Chen G-S, Chen J-H, Kuo J, Chen YW, Niu H. Synergy of sodium and WO3 for
the formation of anatase-based TiO2 nanoporous films with enhanced photo-
activity. Mater Lett 2013;109:217–20.
[13] Ohashi T, Sugimoto T, Sako K, Hayakawa S, Katagiri K, Inumaru K. Enhanced
photocatalytic activity of Pt/WO3 photocatalyst combined with TiO2 nano-
particles by polyelectrolyte-mediated electrostatic adsorption. Catal Sci Tech-
nol 2014.
[14] Yu CL, Chen JC, Zhou WQ, Wei LF, Fan QZ. Grinding calcination preparation of
WO3/BiOCl heterostructures with enhanced visible light photocatalytic activ-
ity. Mater Res Innovat0:1433075  14Y.0000000210, 2015.
[15] Lei Y, Mehmood F, Lee S, Greeley J, Lee B, Seifert S, et al. Increased silver
activity for direct propylene epoxidation via subnanometer size effects.
Science 2010;328:224–8.
[16] Zhang Q, Li F, Chang X, He D. Comparison of nickel foam/Ag-supported ZnO,
TiO2, and WO3 for toluene photodegradation. Mater Manuf Process
2014;29:789–94.
[17] Ghosh S, Acharyya SS, Adak S, Konathala LNS, Sasaki T, Bal R. Selective
oxidation of cyclohexene to adipic acid over silver supported tungsten oxide
nanostructured catalysts. Green Chem 2014;16:2826–34.