Photo catalytic properties of Zirconium oxide (zirconia)/graphene composite

Sumita Rani, Mukesh Kumar, Dinesh Kumar

Electronic Science Department, Kurukshetra University, Kurukshetra-136119, Haryana, India

Email (Corresponding author):
ABSTRACT

Fine powders of zirconia were prepared from Zirconium oxychloride (ZrOCl2.8H2O) by

combustion method with varying annealing temperature. Zirconia powders contained more
amount of monoclinic phase as the annealing temperature increased. Further graphene was
incorporated in zirconia using graphene oxide (GO) as precursor and reducing it with hydrazine
hydrate, this aspects were verify by XRD, FTIR, TGA, UV-Visible spectroscopy and raman
spectroscopy. The crystalline size for pure zirconia is in range of about 14-45 nm. The photo
catalytic properties of zirconia (ZrO2) and ZrO2/graphene (Zr-Gr) were also investigated by
studying the degradation of methyl orange (MO) dye in UV light. The rate of decolorization was
recorded with respect to the change in intensity of absorption peaks for methyl orange .The
absorption peaks, diminished and finally disappeared during reaction, indicating that the dye had
been degraded. The photocatalytic activity is strongly affected by the concentration of graphene
in the ZrO2. Finally, it has been concluded that graphene when employed as catalytic support for
ZrO2 boost the photo catalytic efficiency.

KEYWORDS: Combustion synthesis, ZrO2, Photo catalytic, Graphene oxide, XRD, UV-Visible
spectroscopy.
Introduction

Photo catalysis, has been recently used for water decontamination, As industries uses color for
dyeing their products and unused color is released in water, because the dyes which are mainly
used for coloring are non biodegradable and harmful for flora and fauna. There is variety of
materials used for photo catalytic degradation, Zirconium oxide (ZrO2) because of its
semiconducting properties [1], high density, low thermal conductivity, chemical inertness, water
insolubility and ionic electrical conduction, etc can be considered as strong candidate for photo
catalytic activity. It is inorganic oxide, whose band gap estimates from 5–7 eV [2] depending on
the phase (cubic, tetragonal, monoclinic, or amorphous) and preparation methods. Under the
irradiation of ultraviolet (UV) light with the wavelength lower than that corresponding to the
band-gap energy of ZrO2, photo induced electron–hole pairs can be produced by absorbing
photons. The photo generated electrons then drive the water-splitting reaction to produce
hydrogen [3]. The degradation reactions take place in the interphase region between the liquid
and photo excited solid [4].
A variety of strategies have been employed to improve the photo catalytic performance of
semiconductor photo catalysts [5-7], In particular , to enhance the photo catalytic properties of
ZrO2 include doping with metallic particles such Cu, Mn, etc [8].
After the discovery of graphene by Geim et al. in 2004, because of its excellent mobility of
charge carriers (200 000 cm2 V-1 s-1) [9], a large specific surface area (calculated value, 2630 m2
g-1) [10] and good mechanical stability [11], graphene are also expected to enhance the photo
catalytic activity of the photo catalytic materials. So, lots of work has been done on improving
the photo catalytic activity of semiconductor materials such as TiO 2 [12-14] by making Graphene
and TiO2 composites. It has been reported that ZrO2 as a better catalyst and catalyst support as
compared to Al2O3, SiO2 and TiO2 [15]. So, in this paper photo catalytic activity of ZrO2 and
ZrO2/graphene (Zr-Gr) was examined using the photo degradation of methyl orange aqueous
solution in UV light. ZrO2 is synthesized by convenient method from zirconium oxychloride
using combustion method. Further to enhance the photo catalytic activity of zirconia,
ZrO2/graphene (Zr-Gr) composites are synthesized by chemical reduction using hydrazine
hydrate. The catalysts show enhanced photo catalytic activity towards the degradation of the
methyl orange dye UV light irradiation.

MATERIALS AND METHODS

Methyl Orange is an azo dye with the molecular formula C 14H14N3NaO3S (sodium- 4- dimethyl
amino - azo benzene -4 sulfonate) and molecular mass is 327.34 (gram /mol). It is used in
textiles, food stuffs, pulp and paper and leather industry. It is most frequently employed acid –
base indicator (it changes color from red to yellow in the pH range 3.1- 4.4). Graphite powder
(purity 99.99%), sodium nitrate (99.0%) and sulphuric acid, and Potassium permanganate (99%)
was used. The hydrogen peroxide, sodium borohydride, Zirconium oxychloride and
Hydrochloric acid and hydrazine hydrate were used. All chemicals were used directly as received
and stock solutions were prepared by using doubly deionized water.
Experiment

Synthesis of GO
GO is a water-soluble nanomaterial prepared through chemical attack on graphite powder to
introduce oxygen containing impurities in graphite crystal. Modified Hummers’ method was
used to prepare GO by reacting the commercially obtained graphite powder in a mixture of
H2SO4, NaNO3, and KMnO4.[16]Subsequently, H2O2 was added to the reaction vessel to remove
excess of KMnO4. Solution was then filtered, washed with deionized water and dry in oven at
80oC for 12 h. The GO has the appearance of dry, brown color powder.

Preparation of Zr-Gr composites

To prepare Zr-Gr composite firstly, ZrO2 powder was prepared, for this Zirconium oxychloride
was dissolved in distilled water, from this solution of zirconium hydroxide was precipitated by
addition ammonium hydroxide (maintaining constant pH about 10.5) with stirring. The resulting
mixture was filtered and washed with hot distilled water several time. Finally, the filtered paste
was kept in oven at 100oC for 12 hour followed by calcination at different temperatures (400 oC,
600oC, 1000 oC) for 2h in furnace.
The obtained ZrO2 and GO were used as precursors to synthesize the Zr-Gr composite.
ZrO2 aqueous solution was prepared in distilled water, GO and hydrazine hydrate (10µl) was also
added in it, hydrazine hydrates act as a reducing agent to reduce GO in to graphene. The mixture
was reflux for 36h at 130 oC. After refluxing the solution was filtered and washed with deionized
water and kept in oven at 80oC for drying. The same procedure was repeated for different
concentration of GO (100mg, 130mg and 150mg) in ZrO2.
To study the photo catalytic properties of MO, 4mg MO have been taken in 500ml
deionized water and Zr-Gr and 0.2µl H2O2 was added to it. H2O2 provide oxygen during course
of reaction. In 100ml of prepared solution of MO 150mg of catalyst was added and kept under
UV irradiation and photo degradation was studied using UV-Visible spectroscopy.

Results and discussion

Thermal stability of the Natural Graphite Powder (NGP), GO, graphene, Zr-Gr composite was
study by TGA, as shown in Fig.1 Thermogravimetry traces of NGP and Zr-Gr composite
exhibited almost no weight loss during the whole heating process (in the range from room
temperature to 700oC, Fig. 1), whereas GO shows low thermal stability due to reduced Vander
Waal interaction because interlayer spacing is higher in GO as compare to graphite. TGA results
shows GO starts to lose mass upon heating even below 100 oC due to evaporation of water
molecules that were held in the material. Significant major weight loss of GO exhibits around
200oC and 500oC (Fig 1), presumably due to pyrolysis of the labile oxygen-containing functional
groups to yield CO, CO2, and steam. Above 500oC there is steady weight loss due to removal of
more stable oxygen groups. As compared to GO graphene shows higher thermal stability and
major weight loss occur near 400 oC.
 Fig 1 TGA of GO and Natural Graphite Powder, graphene, Zr-Gr composite

X-Ray diffraction

Powder X-ray diffraction (XRD) patterns were obtained from XPERT-PRO diffractometer (45
kV, 40 mA) equipped with a Giono-meter PW3050/60 working with Cu K α radiation of
wavelength 1.5406Å in the 2θ range from 5 to 80°. The XRD of GO shows diffraction peak at
11.26° which disappear in Zr-Gr composite (shown in fig 2b) indicating that the GO was
completely reduced to graphene . The XRD of ZrO2(anneal at 400 oC) shows prominent peaks at
30.18, 35.17, 50.07, 60.07, corresponding to diffraction patterns of (111), (200), (220), (311)
respectively to cubic phase,[17,18] After the formation of Zr-Gr the peaks slightly shifted and as
the concentration of Gr increase new peaks at 24.12°, 28.10° and 31.37° appears , which may be
due to Small deviations resulted from the interactions between graphene and ZrO2. The XRD of
ZrO2 (anneal at 600 oC) shows prominent peaks at 24.25, 28.20, 31.47, 34.33, 38.40, 44.66,
50.18, 60.21, 62.85 corresponding to diffraction patterns of monoclinic phase, peaks at 30.25,
35.28 corresponding to cubic phase of zirconia (shown in Fig 2b).[17-18] in this also it was
observed that in Zr-Gr samples the peaks slightly shifted . Also similar pattern (as for ZrO2
anneal at 600oC) was observed for zirconia anneal at 1000 oC but the peak corresponding to cubic
phase at 30.25 almost disappear and with some extra peaks at 49.26, 57.15, 58.13, 71.09 which
corresponds to monoclinic phase. XRD results show as the annealing temperature increased
monoclinic phase (m) is more compare to tetragonal (t) or cubic (c) and also monoclinic phase
increase with increase in concentration of reduced GO. The corresponding percentage of
monoclinic phase in ZrO2 and ZrO2/reduced GO (anneal at different temperatures) is summarized
in Table 3. The amount of monoclinic and cubic phase content in pure zirconia powder are
calculated by peak area of the monoclinic peak (11 1 ) and (111) vs. cubic peak (111) using
equation [20-22]

I(111)m + I(111)m
% M= I(111)m + I(111)m + I(111)c

The crystalline size of ZrO2 powder has been calculated using Debye-Scherrer formula:
 Kλ
D= βcosθ
Where D is the average crystallite size, K=correction factor (0.9), λ = 0.154nm wavelength of Cu
Kα, β the peak width and θ the peak angle.

The values of crystalline size of pure zirconia (anneal at 400 oC, 600 oC, 1000 oC) is 14.32, 26.5,
45.3 nm respectively. The crystalline size increases as reduced GO concentration increases for
400oC, but at 1000 oC it reversed the size goes on decreasing and for 600 oC it remain almost
constant (Table 2).

Table1. d-spacing, average crystalline size and phase of ZrO2(anneal at different temperatures)

Temp d11¯1Å d111Å d111Å d220Å d311Å d002Å d21ˉ1Å d220Å d311Å d300 d013 avg phase
(°C) Å Å D(nm)
               
400 2.95 1.82 1.53 14.32 c

600 3.16 2.95 2.84 1.81 1.53 2.61 2.21 1.81 1.53 26.5 m(45.5%)
c(54.5%)
1000 3.16 2.94 2.83 1.81 1.53 2.61 2.21 1.81 1.53 1.69 1.65 45.3 m(92.3%)
                          c(7.7%)

Table2. Average crystalline size ZrO2 and ZrO2/reduced GO (anneal at different temperatures)
Temp(° Avg D(nm)
C) ZrO ZrO2/ ZrO2/ ZrO2/
2 Gr Gr(130mg) Gr(150mg)
(100m
g)
400 14.3 24.4 34.3 25.7
2
         
600 26.5 30.53 27 29.6
         
1000 45.3 41.8 33.45 33.9

Table3. Phase of ZrO2 and ZrO2/reduced GO (anneal at different temperatures)

Temp(° Phase     
C) ZrO2 ZrO2/ ZrO2/ ZrO2/
Gr Gr(130mg) Gr(150mg)
(100mg
)
       
400 c c c c
         
600 45.5% 69.5% 73.3%(m) 73%(m)
( m) (m)
         
 1000 92.3% m m m
(m)

Fig 2 a) XRD of GO and Natural Graphite Powder (b) ZrO2 (anneal at 400oC, 600oC, 1000oC),
ZrO2/graphene of different concentration

Photo catalytic analysis

The photo catalytic activity of pure and graphene doped ZrO2 was compared by studying photo
catalytic degradation of methyl orange dye in UV light. Figure 3 shows the absorbance of methyl
orange with time under irradiation of UV light with using pure ZrO 2 anneal at 400oC as photo
catalyst. It was observed that the photo catalytic activity shows strong dependence on the UV
irradiation time and degradation increases with increase in irradiation time.

ZrO2 surface gain more energy from UV light at higher exposure time, and due to this
reason the degradation of methyl orange was increased with time. It was also observed that the
photo degradation of MO was more for ZrO 2 anneal at higher temperatures. This effect may be
observed due to decrease in band gap (Eg400>Eg600> Eg1000), reduction in recombination centers,
improved crystallinity and pore size at higher temperatures. Improved crystallinity is important
for OH group formation which acts as active sites for photo degradation. The analysis was
carried out using a LAMBDA™ 650 UV/Vis/NIR spectrometer (PerkinElmer, Inc., Shelton, CT
USA). The degradation of MO for ZrO2 (anneal at 400oC) occur in 1h 50 min but for Zr-Gr
composite it occurs in 1h 40min, 1h 10min and 1h (for 100mg, 130mg ,150mg graphene in
zirconia). For ZrO2 (anneal at 600oC) the degradation of MO occur in one and half hour but for
Zr-Gr composite it occurs in 80min, 1h and 51min (for 100mg, 130mg ,150mg graphene in
zirconia). Further for ZrO2 (anneal at 1000oC) the degradation of MO occur in 80min but for Zr-
Gr composite it occurs in 67min, 55min and 45min (for 100mg, 130mg ,150mg graphene in
zirconia) shown in Fig 5.

Fig 3) Photo catalytic properties of ZrO2 (anneal at 400°C) and ZrO2/Gr (100mg), ZrO2/Gr
(130mg), ZrO2/Gr (150mg)

Fig 4) Photo catalytic properties of ZrO2 (anneal at 600°C) and ZrO2/Gr(100mg), ZrO2/Gr
(130mg), ZrO2/Gr (150mg)
 Fig 5) Photo catalytic properties of ZrO2 (anneal at 1000°C) and ZrO2/Gr (100mg), ZrO2/Gr
(130mg), ZrO2/Gr (150mg)

Degradation(X) at any time can be calculated by equation

C o −C
X=
Co
Where Co, is the initial concentration and C is the concentration at any time t of methyl
orange respectively. The concentration profiles can be correlated with the following exponential
function.
C=C o (−kt )
The rate constant k in the above equation decreases with the increase in the initial
concentration of MO when the other parameters are kept constant. Hence the photo degradation
follows the kinetic first-order reaction:
C
ln =−kt
Co
Fig 6 shows the variation of degradation constant with time and it has been concluded that Zr-
Gr composite which have higher concentration of graphene degrade the MO more fastly
irrespective to the anneal temperature of ZrO2.

Fig6 Degradation vs time variation of a) ZrO2 (anneal at 400ºC) and ZrO2/Gr having different
conc. of Gr (100mg, 130mg, and 150mg) b) ZrO2 (anneal at 600ºC) and ZrO2/Gr c) ZrO2 (anneal
at 1000ºC) and ZrO2/Gr
 Fig7a Degradation vs time variation of a) ZrO 2 (anneal at 400ºC, 600ºC, 1000ºC) and b)
ZrO2/Gr (150mg) anneal at 400ºC, 600ºC, 1000ºC respectively.

Fig 7a shows that for ZrO2 (anneal at 400ºC, 600ºC, 1000ºC) the degradation are more quickly in
ZrO2 anneal at 1000ºC and Fig 7b shows degradation of MO for zirconia graphene composite
having same concentration of Gr and it can be concluded that higher the annealing temperature
of zirconia and more is the graphene faster degradation of MO occur.This is mainly due to the
fact that graphene enhance the light absorption range, promote charge separation and increase
adsorption of pollutants.

The reaction oocurs at the time of photocatalysis on the surface of ZrO2 /graphene are shown
below:

ZrO2+ hv e- + h+ (at the ZrO2 surface)

ZrO2 (e-) + Graphene ZrO2 + Graphene (e-)
Graphene (e-) + O2 Graphene + O2-
ZrO2 (h+) + OH_ ZrO2+ *OH
*OH+ Pollutants Degradation products

Conclusion

Graphene-based semiconductor photocatalysts have attracted extensive attention for their

potential in environmental and energy-related applications.

Acknowledgments

One of author Sumita Rani is thankful to Department of Science and Technology (DST), India
for funding support.
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