Next Materials 4 (2024) 100191

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Next Materials
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Research article

A facile synthesis of metal vanadate incorporated with metal oxide/rare

earth metal oxide composite for photocatalytic application
Tazeen Shahid a, Misbah Mirza a, *, Shazia Kosar a, Aqsa Ramzan a, Asma Ismail a,
Rukhsana Fareed a, Sanam Husain a, Sidra Mustafa a, Nazia Yasmeen a, Aqsa Ameer a,
Asma Nawaz a, Muhammad Safdar b, *
a
Department of Physics, The Women University Multan, Pakistan
b
Department of Basic Sciences & Humanities Khawaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, Pakistan

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

Keywords: In this work (Ag2O/BiVO4) binary and (Ag2O/BiVO4/Eu2O3) ternary heterojunction photo-catalysts have been
Dye degradation synthesized through a hydrothermal technique for the purpose of photocatalytic degradation of hazardous dyes.
Metal oxide The facile synthesized composites of (Ag2O/BiVO4) and (Ag2O/BiVO4/Eu2O3)have been prepared using a hy­
Photocatalysis
drothermal process. The synthesized composites used to degrade the Methylene blue and Congo-red dyes under
Rare earth
sunlight. The X-ray diffraction confirms the crystalline structure of synthesized composites. The calculated
Optical properties
crystalline sizes for (Ag2O/BiVO4) and (Ag2O/BiVO4/Eu2O3) are 9.9 nm and 2.84 nm respectively. The
morphology of samples has been analyzed by SEM while the absorption spectrum and bonding of molecules were
observed using FTIR in the range of 600–4000 cm− 1. The elemental percentage of synthesized material is
determined by using EDX spectroscopy and UV spectroscopy used to study optical properties. Using Tauc plot
calculated band gap of (Ag2O/BiVO4)is 1.84 eV and (Ag2O/BiVO4/Eu2O3) is 1.65 eV. The degradation efficiency
of composites(Ag2O/BiVO4) (Ag2O/BiVO4/Eu2O3) towards a dye MB is 38% and 41% respectively, while these
composites were found to degrade the dye CR 82% and 99%respectively in the exposure of sunlight. Both
synthesized composites showed excellent %age degradation toward acidic dye (CR). The outcomes of synthesized
composites indicates that suitable optical absorption, better segregation of charge carries and reduction of
electron-hole recombination these factor effectively contribute to enhance photocatalytic activity towards acidic
dye CR.

1. Introduction [3]. The normal penetration of sunlight in rivers is disturbed by such

synthetic dyes causing a reduction in photosynthetic activities which has
Metal oxide semiconductor photocatalyst have a high potential for a significant effect on aquatic organisms [4]. Hence for the dye degra­
the degradation of organic pollutants in wastewater using solar spec­ dation different biological and physicochemical processes have been
trum of visible light. A photocatalyst is defined as a material that absorbs applied and many processes have been explored like froth floatation,
light and generates an electron-hole pair by which the transformation of electrolysis, chemical coagulation, azo-reductase, biodegradation, ab­
chemicals occurs in reaction participants and chemical composition is sorption process, membrane separation [5–10]. A major problem is the
generated after each cycle of such interaction [1]. It also involves the cost-effective removal of these dyes from effluents [11].
conversion of solar energy into chemical energy. Bismuth vanadate BiVO4 was identified as a highly responsive pho­
To solve the promptly evolving problem of environmental pollution, tocatalyst because of its visible light-driven properties [12]. BiVO4 has
researchers pay significant attention to semiconductor-based photo­ three leading phases, scheelite and tetragonal zircon phases have a band
catalytic degradation of hazardous dyes [2]. Especially, in the textile gap of 3.1 eV and 2.4 eV is the band gap of the monoclinic phase. One of
industry these dyes are considered harmful pollutant because of their these monoclinic BiVO4 is a promising photocatalyst to enhance photo
oxygen-absorbing ability from water bodies and strong persistent color reactivity due to its narrow band gap [13–16].Although many

* Corresponding authors.
E-mail addresses: [email protected] (M. Mirza), [email protected] (M. Safdar).

https://doi.org/10.1016/j.nxmate.2024.100191
Received 12 January 2024; Received in revised form 19 March 2024; Accepted 27 March 2024
Available online 4 April 2024
2949-8228/© 2024 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
T. Shahid et al. Next Materials 4 (2024) 100191

approaches have been reported like rare earth metal doped WO3 [17], 2.4. Photocatalytic activity
(La, Nd, Dy Sm doped ZnO [18], SmNA, EuNA, GdNA [19], Er3+ doped
TiO2 [20], La3+, Nd3+ substituted Co-Sr [21], La doped TiO2 [22], TiO2 10 ppm CR and MB solution was made in 100 ml of distilled water in
doped (Ln3+, Sm3+, Gd3+, Yb3+) [23], La doped TiO2 [24],today’s desire separate beakers with continuous stirring on a magnetic stirrer for
is to exploit the broader range of the solar spectrum. For this new photo 10 minutes and its pH after 10 minutes was between 6 and 7. Add
catalysts are developing to enhance environmental therapeutic for catalyst 0.005 g (Ag2O/BiVO4) in dye solution and put this solution
continuous reactivity [25]. under continuous stirring for 45 minutes in the dark to attain
To create a different offset scenario the pairing of BiVO4 with metal adsorption-desorption equilibrium between dye and photocatalyst so­
oxide (Ag2O/BiVO4) and rare earth oxide (Ag2O/BiVO4/Eu2O3) is pre­ lution. Again check its pH and take a sample from this solution to check
sent in this study. Ag2O has been used as a composite with Bismuth absorption of the material. After this place the solution under contin­
vanadate that can optimally utilize the visible part of the solar spectrum, uous magnetic stirring for 60 minutes in the sunlight and collected the
for the requirement of medium and small bandgap which is necessary for samples after every 10 minutes. Sample of dye solution taken in falcon
fabricating photo catalysts. Ag2O is very effective in the separation of tube. Similarly all samples of composite were also collected for (Ag2O/
excited charge carriers [26]. Using a hydrothermal process, in this study BiVO4/Eu2O3) byrepeating the same process. UV-spectroscopy has been
we prepare this composite (Ag2O/BiVO4)in order to facile the segrega­ used to analyze the absorbance of MB and CR after a specific interval of
tion of charge carriers and the ability of high light absorption [27]. time.
To the best of our knowledge, there are no reports published on the
composite (Ag2O/BiVO4/Eu2O3).The advantage of doping metal oxide 3. Results and discussions
with rare earth metal oxide is 4 f vacant orbit that readily combine with
a functional group. In addition, by doping of rare earth metals in elec­ 3.1. Analysis of XRD spectrum
tromagnetic spectrum absorbance shifted to visible region as a result
photocatalysis enhanced in this region [28,29].This composite(Ag2O/­ To analyze the crystalline nature, XRD measurements were done of
BiVO4/Eu2O3) has been used for the degradation of both acidic dye (CR) composite (Ag2O/BiVO4) as shown in Fig. 1(a). The XRD pattern
and basic dye (MB). Its results show composite (Ag2O/BiVO4)is more showedAg2O/BiVO4diffraction pattern is monoclinic scheelite match
favorable for the acidic dye. To make the degradation rate better we with the (JCPDS card no 75–2840 and 14–0688). By splitting diffraction
have used these composite with new rare earth elements and observed peaks 2θ degree = 28.8◦ , 29.4◦ , 35.3◦ , 39.0◦ , 42.7◦ , 46.5◦ and 57.9◦
all the properties of this composite. This rare earth oxide with bismuth which are indexed to (112), (004), (220), (114), (105), (204), (107) m-
vanadate and silver dioxide tested on the degradation of dyes MB and BiVO4 is pure monoclinic structure [30]. The new peaks observed at 2θ
CR. These results are efficiently good in photocatalytic activity. The = 20.4◦ , 22.8◦ , 24.8◦ , 25.8◦ , 29.9◦ , 31.6◦ , 32.8◦ , 40.9◦ , 44.1◦ , 47.9◦ ,
synthesized samples are characterized by XRD, SEM, XPS and UV 48.8◦ , 49.2◦ , 50.8◦ , 52.1◦ , 54.4◦ , 59.8◦ and their hkl values are (410),
spectroscopy, under the same condition the activity of (Ag2O/Bi­ (402), (420), (004), (502), 9432), (040), (434), (615), (535), (353),
VO4/Eu2O3)analyzed for comparison. (345), (161), (553), (461) and (662) respectively. When sufficient
amount of Ag is loaded then the peaks of Ag2O are observed (PDF
2. Materials and methods 41–1104). It is difficult to distinguish between the Ag+ and Ag◦ due to
very close overlapping of diffraction peaks but their symmetric shape of
2.1. Chemicals diffraction pattern confirms the presence of both Ag/Ag+ [31–33]. Such
interference exhibited the presence of Ag based sample with BiVO4 as a
The chemicals used for the preparation of composites (Ag2O/BiVO4) composite.
and (Ag2O/BiVO4/Eu2O3) are AgNO3, tartaric acid, Eu2O3, HNO3, D = k λ/β cos θ (1)
yogurt, NaOH, EDA and hydrazine, Bismuth Nitrate,Ammonium Meta­
vanadate, acetic acid, NH4OH. All these are purchased from Merck and Eq. (1) shows Debye Scherrer formula in which k is the shape factor
used without any further purification. constant, λ is the wavelength, β is the full width half maximum in radian
and θ is Bragg’s diffraction angle. Using Eq. (1) calculate the crystalline
size and its value is 9.9 nm.Fig. 1(b) gives the XRD pattern of (Ag2O/
2.2. Synthesis of (Ag2O/BiVO4) BiVO4/Eu2O3). The results show some of the characteristics peaks match
with cubic structure of Eu2O3 at the diffraction peaks 2θ= 29.9◦ 33.2◦ ,
First of all, 0.33 g AgNO3was add to 20 ml H2O and 1.08 g of BiVO4 49.2◦ , 57.2◦ which can be indexed to (222), (400), (440), (444) with
was added to the AgNO3 solution and then added 2 g of tartaric acid in (JCPDS no 86–2476) [34]. XRD pattern also confirms the composition of
this solution under continuousstirring and then put the solution into the monoclinic (JCPDS 14–0688) BiVO4 at diffraction peaks 22.4◦ , 24.7◦ ,
autoclave.pH of the solutionwas in between 4 and 5. Then placed the 28.4◦ , 34.9◦ , 38.2◦ , 40.2◦ , 44.4◦ , 46.4◦ , 47.5◦ , 54.4◦ ,with indices (110),
autoclave in the oven for 14 h at a temperature of 130 ◦ C. Filter the (112), (200), (202), (051), (103), (321),(421), (411) [25]. The charac­
attained precipitates with the help of filter paper and place it in a petri teristic peaks match with (JCPDS 01–075–1532) of cubic Ag2O at po­
dish. Dry this sample in the oven for 24 h at 80 ◦ C. sition 2θ= 27.0◦ , 31.1◦ , 36.6◦ , 42.2◦ , 50.6◦ with indices (111), (101),
(211), (200) [35]. The calculated crystalline size of (Ag2O/Bi­
VO4/Eu2O3) is 2.84 nm.
2.3. Synthesis of (Ag2O/BiVO4/Eu2O3)
3.2. SEM and EDX analysis
Firstly add 1.17 g of Eu2O3 in 20 ml of HNO3 and 0.33 g of AgNO3
dissolved in 20 ml H2O. Both suspensions added in 1.08 g of BiVO4. Now The SEM images in Fig. 2(a) exhibits the grain size and morphology
take 10 ml water and yogurt mix it vigorously and combine with the of synthesized sample Ag2O/BiVO4. The SEM image shows plate like
prepared suspension, placed this sample on a hot plate and raised the morphology of prepared sample [25]. The grain size is 70 nm The Fig. 2
temperature up to 400 ◦ C under magnetic stirring. Add 25 ml NaOH, (b) shows the prepared sample (Ag2O/BiVO4/Eu2O3) have dipole-dipole
5 ml EDA, and 2 ml hydrazine to solution. Put this sample in an auto­ interaction causingagglomeration in sample [36] calculated grain size is
clave and dry the sample in the oven for 14 h at 130 ◦ C.Filter the 63.5 nm.
attained precipitates and after filtration dry the sample again in the oven The composite was analyzed by EDX in order to confirm the
for 24 h at 80 ◦ C. composition of (Ag2O/BiVO4/Eu2O3).The corresponding peaks

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T. Shahid et al. Next Materials 4 (2024) 100191

Fig. 1. (a) XRD of (Ag2O/BiVO4) (b)XRD of (Ag2O/BiVO4/Eu2O3).

Fig. 2. (a)SEM image of (Ag2O/BiVO4) (b) SEM image of (Ag2O/BiVO4/Eu2O3).

observed during the EDX measurement as shown in Fig. 3. The peaks of 3.3. Analysis of FTIR spectrum
O, Ag, V and Eu with apparent concentration 12.14, 3.53, 4.41, 20.63
respectively and wt%age 5.76, 2.19, 2.92, 15.88 respectively confirm Fig. 4(a-b) shows the FTIR results of composites and detected in the
presence in all element of the synthesized sample(Ag2O/BiVO4/Eu2O3) range 600–4000 cm− 1. Fig. 4(a) exhibit (Ag2O/BiVO4) IR spectra broad
as shown in Table 1. band at peak 3294.03 cm− 1 observed due to hydrogen O-H band. The
strong stretching of N-O observed at sharp peaks 1524.48 cm− 1,
1637.23 cm− 1 and 1019.42 cm− 1, 1109.81 cm− 1 shows single bond

Fig. 3. EDX of (Ag2O/BiVO4/Eu2O3).

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Table 1 calculated band gap is 1.65 eV as comparison to (Ag2O/BiVO4) band gap

EDX weight %age of (Ag2O/BiVO4/Eu2O3). is small that’s why it is more suitable for dye degradation as compare to
Fig. 2(c) Apparent %age wt%age (Ag2O/BiVO4) in the sunlight irradiation. So (Ag2O/BiVO4/Eu2O3) is
more capable as sunlight driven photocatalyst [40].
(Ag2O/BiVO4/Eu2O3) O 12.14 5.76
Ag 3.53 2.19
V 4.41 2.92
Eu 20.63 15.88 3.5. UV Spectroscopy analysis

Fig. 6(a-b) shows the UV graph spectrum of both composite on a

stretching of C-O. The peaks at 667.01 cm− 1, 697.19 cm− 1shows the Methylene blue dye under sunlight in 400–800 nm wavelength range.
stretching of V-O band [37].Fig. 4(b) describe (Ag2O/BiVO4/Eu2O3) Plotted graph shown in Fig. 6(a) wavelength versus absorbance shows
composite IR spectra a large band from 4000 to 2800 cm− 1mainly the absorption rate of composite (Ag2O/BiVO4). In the sunlight absor­
ascribe hydroxyl group O-H the absorption of water at composite surface bance decreases gradually as reaction time increased after added a dye
[38]. The characteristic peak 3333.17 cm− 1 exhibit Eu2O3 phase [39]. MB in solution. The composite (Ag2O/BiVO4) degraded the dye MB 38%
At peak 1637.23 cm− 1 and 1537.52 cm− 1 observed C– –C and C– –O age. The composite (Ag2O/BiVO4/Eu2O3) degraded the dye MB up-to
double bond stretching. The C-O single bond stretching observed at peak 41%age under the sunlight irradiation as shown in Fig. 6(b). This is
1248.65 cm− 1. The peaks 1068.81 cm− 1, 1000.79 cm− 1 shows C– –O because of decreases of absorption on the catalyst surface with the in­
stretching of acetate. creases in concentration of dye it leads to hydroxyl radical’s reduction
which plays important role in system for degradation of dye. Another
3.4. Band gap reason could be in lower degradation rate of MB at higher concentration
is because of sedimentation and aggregation of catalyst particles, which
Using UV spectrophotometry studythe optical properties of synthe­ causes enhancementscattering of light. This scenario decreases photo­
sized samples. Fig. 5(a-b) shows that the band gap of prepared com­ catalytic active sites [41–43]. As a comparison of MB another dye
posite is calculated using Tauc plot and its graph peaked between Congo-red used on both synthesized composites. Fig. 6(c-d) exhibit the
photon energy in eV and (αhʋ)2 curve. UV spectrum of composite at wavelength 350–750 nm on dye CR. Fig. 6
(c) shows composite (Ag2O/BiVO4) act as photocatalyst and degraded
(a h υ) = B (h υ − E g)n (2)
the dye Congo-red 82%age and composite (Ag2O/BiVO4/Eu2O3)
In this equation α is the coefficient of absorbance, h is planks con­ degraded dye 99%age as shown in Fig. 6(d). Clear differences in pho­
stant, ʋ is the light frequency, hʋ is light energy, Eg band gap energy. tocatalytic degradation of both dyes MB and CR indicate that composites
Fig. 5(a) is the estimated band gap of composite (Ag2O/BiVO4) 1.84 eV have attribute to high rate of recombination of charge carries towards
and Fig. 5(b) is the Tauc plot of composite (Ag2O/BiVO4/Eu2O3) and Congo-red [44]. This indicate that composites have lower photocatalytic

Fig. 4. (a) FTIR graph of (Ag2O/BiVO4) (b) FTIR graph of (Ag2O/BiVO4/Eu2O3).

Fig. 5. (a)Tauc plot of (Ag2O/BiVO4), (b)Tauc plot of (Ag2O/BiVO4/Eu2O3).

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Fig. 6. (a) Absorbance spectra of (Ag2O/BiVO4) for MB (b) Absorbance spectra of (Ag2O/BiVO4/Eu2O3)for MB (c) Absorbance spectra of (Ag2O/BiVO4) for CR (d)
Absorbance spectra of (Ag2O/BiVO4/Eu2O3) for CR.

activity for dye MB and act as an active light driven photocatalyst to­
C0 − Ct
wards dye Congo-red. It is evident that in present study composites are %age degradation(D) = × 100 (3)
C0
beneficial and shows excellent photocatalytic activity for acidic dye
(Congo-red) and less effective for basic dye (Methylene blue) [45–47]. Where D is the efficiency of degradation, Co is the concentration of
The crystalline size has been recognized as an important factor that dye at initial time, Ct is the concentration for the complete time interval
influences the photocatalytic activity because it dictates many physical absorbance. The results show as band gap of (Ag2O/BiVO4/Eu2O3)is
properties (i.e., surface area, surface energy, light absorptivity, and small as compare to (Ag2O/BiVO4) has appreciable performance in the
lattice distortion). By addition of Eu2O3 the crystalline size decreased sunlight irradiation. The behavior of graph shows photocatalytic
and it may enhance the specific surface area of the synthesized com­ degradation of dyes increases when light fall on catalyst surface.
posite and due to this the increase in photocatalytic degradation takes Fig. 8 shows that Co/Ct and lnCo/Ct vs time graphs of composite
place. Generally, for a single-phase crystal, there is strong evidence that (Ag2O/BiVO4/Eu2O3) has increasing curve as compare to (Ag2O/BiVO4)
increasing crystalline size enhances photocatalytic activity. Amend­ for CR. So the reaction follows the Pseudo-first order kinetics.
ments have been made in conclusion and process mechanism section.
ln C0 /Ct = kt (4)
The comparison of synthesized composite with different literature of
rare earth composites is given in Table 2. Co and Ct are introductory concentration and concentration at time t
Fig. 7 shows the %age degradation of CR increases over the time for respectively and K is first order rate invariable. The values of rate con­
(Ag2O/BiVO4/Eu2O3) as compared to (Ag2O/BiVO4). The %age of dye stants for CR dye are Ag2O/BiVO4=0.030/min and Ag2O/BiVO4/
degradation is calculated by using (3) Eu2O3=0.074/min. similarly for MB dye are Ag2O/BiVO4=0.006/min

Table 2
Comparison of different rare earth composite with synthesized composite (Ag2O/BiVO4) (Ag2O/BiVO4/Eu2O3).
Ref. Material Source Band gap Dye Time Percentage degradation

[17] WO3 Visible light 2.83 eV to 2.46 eV Rhodamine B 100 min 70%
[18] (La, Nd, Sm and Dy) doped UV light 3.23 eV, 3.17 eV, 3.19 eV, MB 25 min Nd doped ZnO shows 98%
ZnO 3.18 eV degradation
[20] Er3+/TiO2 Visible light 2.88 eV MB 60 min 77%
[48] Eu2O3 Visible light 3.60 eV Atrazine 60 min 73%
irradiation
[29] Eu2O3/Ta2O5 UV light 3.0 eV Rhodamine B 300 min 90.8%
[34] ZnO/Eu2O3/NiO Visible light 3.69 eV MB 160 min 97%
Present Ag2O/BiVO4 Sunlight 1.84 eV MB, CR 60 min 38% MB
work 82% CR
Present (Ag2O/BiVO4/Eu2O3) Sunlight 1.65 eV MB,CR 60 min 41% MB
work 99% CR

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Fig. 7. %age degradation versus time graph of synthesized composites.

Fig. 8. Co/Ct vs time behavior of synthesized photocatalysts for dye MB and CR (b) Pseudo-first order kinetics in the presence of specimens as photo catalysts.

and Ag2O/BiVO4/Eu2O3=0.007/min.
2h+ + 2H2O → H2O2 + 2H+ (7)
3.6. Proposed mechanism In the conduction band reduction reaction take place when dissolved
oxygen react with electron e- resultant superoxide radical (•O2) formed.
When sunlight with plentiful energy fall on the photocatalyst
e−CB + O2 → • O−2 (8)
aqueous solution electron-hole pair created by the excitation of electron
from valance band (VB) to conduction band (CB) as shown in Fig. 9. The The generated hydroxyl radical and superoxide highly reactive spe­
photon energy becomes equal or more than the band gap energy of cies oxidize the dye (MB and CR) which is present on the active sites of
photocatalyst. The electron-hole (e-h) pair take part in photocatalytic photocatalyst. Final product H2O and CO2 obtained [49,50].
reaction.
•O-2 + OH + photocatalyst + dye molecules → CO2 + H2O (9)
Photocatalyst + hʋ(sunlight)→e−CB + h+
VB (5)

The hydroxyl radical (•OH) formed in oxidation reaction when

absorbed water molecule react with hole h+ in the valence band.

h+ +
VB + H2 O→H + • OH (6)

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T. Shahid et al. Next Materials 4 (2024) 100191

Fig. 9. Proposed mechanism of photocatalysis.

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functionalized xerogel for removal of methylene blue and lead ions from aqueous
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photocatalysts for degradation of dyes, RSC Adv. 8 (2018) 17582.
[19] E. Regulska, J. Breczko, A. Basa, A.T. Dubis, Rare-earth metals-doped nickel
The authors declare that they have no known competing financial aluminate spinels for photocatalytic degradation of organic pollutants, Catalysts
interests or personal relationships that could have appeared to influence (2020).
[20] R.A. El-Kholy, H. Isawi, E. Zaghloo, E.A. Soliman, M.M.H. Khalil, M.M. Said, M.El-
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