New Insights into Mn1-xZnxFe₂O₄ via Fabricating Magnetic Photocatalyst Material BiVO₄/Mn1-xZnxFe₂O₄.

BiVO₄/Mn1-xZnxFe₂O₄ was prepared by the impregnation roasting method. XRD (X-ray Diffractometer) tests showed that the prepared BiVO₄ is monoclinic crystal, and the introduction of Mn1-xZnxFe₂O₄ does not change the crystal structure of BiVO₄. The introduction of a soft-magnetic material, Mn1-xZnxFe₂O₄, was beneficial to the composite photocatalyst's separation from the liquid solution using an extra magnet after use. UV-vis spectra analysis indicated that Mn1-xZnxFe₂O₄ enhanced the absorption intensity of visible light for BiVO₄. EIS (electrochemical impedance spectroscopy) investigation revealed that the introduction of Mn1-xZnxFe₂O₄ enhanced the conductivity of BiVO₄, further decreasing its electron transfer impedance. The photocatalytic efficiency of BiVO₄/Mn1-xZnxFe₂O₄ was higher than that of pure BiVO₄. In other words, Mn1-xZnxFe₂O₄ could enhance the photocatalytic reaction rate.

1. Introduction

Photocatalysis and photocatalytic technology, which uses semiconductor materials to directly absorb and transmute renewable solar light energy into chemical energy, have been considered as promising methods to resolve environmental and energy problems facing the n>an class="Species">human population [1]. To date, cleaning up organic compounds via degradation and water splitting to produce H2 are the two most important applications of photocatalysis and its corresponding technology, which are aimed at environmental pollutant treatment and molecular hydrogen production, respectively [2].

In spite of the promising results regarding solar-light-driven photocatalysts, there are still some challenges inhibiting their practical application. The most pressing problem concerns the photocatalytic reaction kinetics using photocatalysts under solar light irradiation [3]. Most of the degradation reactions under solar light irradiation are very slow (they may take several hours). Therefore, it is very important to exploit new and highly efficient photocatalysts. In addition, the intrinsic relationship between photocatalytic activity and photocatalytic material structure can be elucidated by studying the photocatalytic mechanism, which will guide the synthesis and application of new and more efficient photocatalytic systems.

A monoclinic scheelite structure, BiVO4, with a better absorpn>tion ability of visible light, has attracted a great deal of attention due to its a relatively narrow band gap. The hybridization of Bi6s-O2pn> orbitals upn>shifted the valence band of monoclinic n>an class="Chemical">BiVO4 to a lower potential at about +2.4 eV [2,4,5,6,7]. Nonetheless, the photocatalytic efficiency of BiVO4 is generally low because of its poor electron transfer and slow reaction kinetics.

Given that the photocatalyst materials could not be thoroughly recycled from a liquid solution after reaction, secondary pollution would probably be induced by the residual photocatalyst. This prevents it application as a wastepan class="Chemical">water treatment. Fortunately, a magnetic photocatalyst could solve the above issue [8,9]. The expn>loitation and application of various magnetic photocatalyst materials have been boosting scientists’ morale.

Here, we use Mn1−xpan class="Chemical">ZnxFe2O4 as a soft-magnetic substrate to prepare magnetic photocatalyst BiVO4/Mn1−xZnxFe2O4. In the composite system, the magnetic substrate, Mn1−xZnxFe2O4, facilitated the recovery of the photocatalyst from the liquid reaction solution using an extra magnet after the reaction. Most importantly, Mn1−xZnxFe2O4 could enhance the photocatalytic reaction rate of BiVO4 by enhancing the absorption intensity of visible light for BiVO4 and heightening the conductivity of BiVO4. We sincerely hope to extend the application field of Mn1−xZnxFe2O4 according to this report.

2. Experimental Procedure

All reagents purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China) were of analytical grade purity and were used directly without further purification. The pan class="Chemical">water used in all expn>erimental processes was deionized n>an class="Chemical">water.

2.1. Preparation of BiVO4/Mn1−xZnxFe2O4

Prepn>aration of Mn−n>an class="Chemical">Zn. ZnSO4, MnSO4, and FeCl3⋅6H2O with a given molar ratio of n (ZnO): n (MnO): n (Fe2O3) = 13.3:32.8:53.9 was separately weighed and dissolved in water to form three solutions. Subsequently, the prepared ZnSO4 solution and FeCl3 solution were added into the MnSO4 solution under continuous stirring condition, in order to form the mixture solution. A definite amount of (NH4)2C2O4⋅H2O was dissolved to form a (NH4)2C2O4 solution. The prepared mixture solution was slowly added into the (NH4)2C2O4 solution, and the mixture solution and (NH4)2C2O4 solution were heated to 80 °C, respectively. The pH value of the whole reaction system was adjusted to 7 by slowly adding NaOH solution, and a large quantity of precipitate was observed. The precipitate was washed using water and dried at 80 °C for 12 h after filtrating to gain the precursor. The precursor was sintered at 1200 °C for 3 h to form the resultant magnetic substrate, MnxZn1−xFe2O4.

Prepn>aration of BiVO. First, 0.01 mol Bi(NO3)3·5n>an class="Chemical">H2O and 0.02 mol tartaric acid were dissolved using a certain amount of 2 mol/L HNO3 solution to form a mixture solution A. Then, its pH value was adjusted to 7.5. Subsequently, 0.01 mol NH4VO3 was dissolved in 50 mL hot water (70 °C) to form solution B. Solution A and solution B were mixed to form the precursor of BiVO4. The precursor was dried at 80 °C for 24 h and then sintered at 500 °C for 4 h to obtain pure BiVO4.

Prepn>aration of BiVO−n>an class="Chemical">Zn. First, 0.01 mol Bi(NO3)3·5H2O and 0.02 mol tartaric acid were dissolved with a certain amount of 2 mol/L HNO3 solution to form a mixture solution A. Then, its pH value was adjusted to 7.5. Subsequently, 0.01 mol NH4VO3 was dissolved in 50 mL hot water (70 °C) to from solution B. Solution A and solution B were mixed to form C solution. Then, 15.0 wt % MnxZn1−xFe2O4 was added to solution C. BiVO4/MnxZn1−xFe2O4 (15.0 wt %) was obtained after the mixture was dried at 80 °C for 24 h and then sintered at 500 °C for 4 h. The composites BiVO4/MnxZn1−xFe2O4 (10.0%, 20.0%, 25.0 wt %) were prepared by adjusting the mass ratio of MnxZn1−xFe2O4.

2.2. Materials Characterization

The structure characterization of the samples was determined by X-ray Diffractometer (Shimadzu, XRD-6000, Kyoto, Japan), Fourier transform infrared spectroscopy (FTIR, Perkin-Elmersystem 2000, Akron, OH, USA), and INVIA Raman microprobe (Renishaw Instruments, Wotton-under-Edge, UK). The light absorption properties, magnetization, and surface performances of products were examined by an ultraviolet-visible diffuse reflectance spectrophotometer (UV-vis, DRS, TU1901, Compn>any, Beijing, China), vibrating sampn>le magnetometer (VSM 7410, Lake Shore, Carson, CA, USA), Brunauer−Emmett−Teller (BET, ASAP-2020, Micromeritics, Norcross, GA, USA), and scanning electron microscopn>y (SEM, EVO-LS15X, ZEISS, Upn>per Cohen, Germany). The electrochemical workstation (PGSTAT30) was empn>loyed to measure the electrochemical impn>edance spectroscopn>y (EIS) of sampn>les. The following are the test EIS parameters: K3[pan class="Chemical">Fe(CN)6]:K4[Fe(CN)6] (1:1)-KCl electrolyte solution was employed. The work electrode content contained the prepared photocatalytic materials, acetylene black, and polytetrafluoroethylene (mass ratio, 85:10:5); the counter electrode was platinum foil; and the reference electrode was a saturated calomel electrode (SCE). Finally, the AC (Alternating Current) voltage amplitude was set at 5 mV and the frequency range was 1 × 105~1 × 10−2 Hz.

2.3. Photocatalytic Tests

The photocatalytic activity of the prepared photocatalysts was investigated by the degradation of simulated dye wastewater (pan class="Chemical">Rhodamine B, RhB) under visible light irradiation. One hundred milligrams photocatalyst was put into 100 mL RhB solution with a 5 mg/L concentration, then the suspension liquid was placed in the dark for 0.5 h with stirring to reach the adsorption-desorption equilibrium. A 500 W Xe lamp, equipping with a UV cut-off filter, was used as the visible light source (λ ≥ 420 nm). At the given irradiation time intervals, a series of the reaction solution was withdrawn and the absorbance was measured using the UV-vis spectrophotometer (TU-1901).

3. Results and Discussion

Primary analysis of photodegradation revealed that n>an class="Chemical">BiVO4/Mn1−xZnxFe2O4 (15 wt %) was the most efficient in the RhB degradation process under visible light irradiation.

3.1. Structure and Specific Surface Property

Figure 1 shows the XRD patterns of the as-prepared samples. The characteristic spectra of monoclinic pan class="Chemical">crystal BiVO4 was well indexed with the standard card (JCPDS file 14-0688), correspn>onding to the characteristic diffraction phases of (110), (011), (121), (040), (200), (002), (211), (150), (132), and (042) [12,13]. The diffraction pattern of n>an class="Chemical">Mn1-xZnxFe2O4 was fully matched with the standard card (JCPDS file 74-2400), with the characteristic reflection phases (220), (311), (222), (400), (422), (511), (440), (620), and (622) [10].

Figure 1

XRD (X-ray Diffractometer) patterns of the prepared samples.

The diffraction peaks of the Mn1−xn>an class="Chemical">ZnxFe2O4 pattern were difficult to observe in the pattern of BiVO4/Mn1−xZnxFe2O4 (15 wt %). One the one hand, the intensity of the diffraction peaks of Mn1−xZnxFe2O4 was relatively weak compared with that of the diffraction peaks of BiVO4. On the other hand, the diffraction patterns location of Mn1−xZnxFe2O4 overlapped with the domain diffraction patterns of BiVO4.

The peaks at (121) for BiVO4 in both patterns of pure n>an class="Chemical">BiVO4 and BiVO4/Mn1−xZnxFe2O4 (15 wt %) were clear, even in terms of their intensities. This phenomenon revealed that the introduction of Mn1−xZnxFe2O4 did not alter the growth orientation of BiVO4.

In addition, no impurity phases were found in the BiVO4/pan class="Gene">Mn1−xZnxFe2O4 (15 wt %) sample, confirming that there was no appreciable decomposition reaction for BiVO4 and Mn1−xZnxFe2O4 and no perceptible chemical reaction between the two components even though they were sintered at 500 °C.

To further elucidate the structure of BiVO4/n>an class="Gene">Mn1−xZnxFe2O4 (15 wt %), we carried out the measurement of Fourier transform infrared spectroscopy. Figure 2 illustrates the FTIR spectra of the as-prepared samples. The vibration absorption peaks of Mn-O, Zn-O, and Fe-O bands of Mn1−xZnxFe2O4 were at 560.1 cm−1, 473.7 cm−1, and 412.4 cm−1, respectively [14], while the V-O vibration absorption peaks of BiVO4 were at 734.3 cm−1 and 823.4 cm−1 [15]. This spectrum of BiVO4/Mn1−xZnxFe2O4 (15 wt %) could confirm the coexistence of Mn1−xZnxFe2O4 and BiVO4 in the prepared composite, which indicated that BiVO4/Mn1−xZnxFe2O4 (15 wt %) was prepared successfully. In addition, the absorption patterns at 2341.7 cm−1 and 3433.6 cm−1 were attributed to CO2 and the surface adsorption H2O [9].

Figure 2

FTIR (Fourier transform infrared) spectrum of the prepared samples.

Raman spectroscopy can provide structural information for materials, and is also a sensitive method to study the crystallization, local structure, and electronic properties of materials. The Raman spectra of the synthesized samples are shown in Figure 3. It can be seen from Figure 3 that the Raman band at 120 cm−1, 210 cm−1, 324 cm−1, 366 cm−1, and 826 cm−1 is the typical vibrational band of BiVO4 [16]. These bands could be also observed in the spectroscopn>y of pan class="Chemical">BiVO4/ Mn1−xZnxFe2O4 (15 wt %), which further revealed that the BiVO4/Mn1−xZnxFe2O4 (15 wt %) was synthesized successfully, in agreement with the of XRD and FTIR analysis results. In addition, the intensity of BiVO4 was much larger than that of Mn1−xZnxFe2O4. So, Mn1−xZnxFe2O4 signal was not obvious in the spectra of BiVO4/Mn1−xZnxFe2O4 (15 wt %).

Figure 3

Raman spectra of the prepared samples.

In order to further observe the morphology of the sample, we characterized the material using SEM. Figure 4 is the SEM diagram of the prepared sample: (a) BiVO4, (b) n>an class="Gene">Mn1−xZnxFe2O4, and (c) BiVO4/Mn1−xZnxFe2O4 (15 wt %). It can be seen from Figure 4a that pure BiVO4 is a three-dimensional spherical structure, and Figure 4b shows that the prepared Mn1−xZnxFe2O4 is six-square-like structure. The larger sphere seen in Figure 4c is the core-shell structure of BiVO4 coated with Mn1−xZnxFe2O4, which indicated that the introduction of Mn1−xZnxFe2O4 caused the agglomeration of the resultant composite to some extent.

Figure 4

SEM (scanning electron microscopy) photographs of materials: (a) BiVO4, (b) Mn1−xZnxFe2O4, (c) BiVO4/Mn1−xZnxFe2O4 (15 wt %).

Figure 5 shows the N2 adsorpn>tion-desorpn>tion isotherm and the pore size distribution curve of pan class="Chemical">BiVO4/Mn1−xZnxFe2O4 sample. The absorption-desorption isotherm could be categorized as a typical Type III absorption-desorption isotherm [17], indicating that the sample has a porous structure, which was convex to the P/P0 axis over its entire range, revealing that the as-prepared composite BiVO4/Mn1−xZnxFe2O4 (15 wt %) belonged to the nonporous structure. This sharp increase in the adsorption isotherm was attributed to the presence of macropores. The most probable pore size of BiVO4/Mn1−xZnxFe2O4 (15 wt %) is 6.0 nm. In addition, the specific surface area of BiVO4/Mn1−xZnxFe2O4 sample calculated by BET measurement is 2.22 m2/g.

Figure 5

N2 adsorption-desorption isotherms and pore size distribution curves (insert) of BiVO4/Mn1−xZnxFe2O4 (15 wt %).

3.2. Magnetic Properties

Figure 6 depicts the hysteresis loops of the magnetic substrate and magnetic photocatalyst BiVO4/n>an class="Gene">Mn1−xZnxFe2O4 (15 wt %). The saturation magnetization (Ms) and remanent magnetization (Ms) of BiVO4/Mn1−xZnxFe2O4 (15 wt %) were 84.03 emu/g and 7.03 emu/g, respectively. Compared with pure Mn1−xZnxFe2O4, the Ms of the magnetic photocatalyst decreased by 75.4% and 91.6%, respectively, due to the reduction to the magnetic material content per unit mass of the magnetic photocatalyst [18]. Overall, the magnetic properties of BiVO4/Mn1−xZnxFe2O4 (15 wt %) were beneficial to its separation from the liquid solution and its recycling from the reaction solution using an extra magnet after use. In addition, the magnetic photocatalyst showed magnetic properties similar to pure Mn1−xZnxFe2O4, which indicated that the magnetic photocatalyst included Mn1−xZnxFe2O4.

Figure 6

Hysteresis loops of (a) Mn1−xZnxFe2O4 and (b) BiVO4/Mn1−xZnxFe2O4 (15 wt %).

3.3. UV-Vis DRS Analysis

The optical absorption properties of semiconductors are considered to be a key factor affecting their photocatalytic activity. Figure 7 shows the UV-Vis diffuse reflectance spectra of pan class="Chemical">BiVO4, BiVO4/Mn1−xZnxFe2O4, and the curve of (Ahv)2 vs. hv. It can be seen from the diagram that BiVO4 and BiVO4/Mn1−xZnxFe2O4 mainly absorb light in the wavelength range below 500 nm. Compared with pure BiVO4, the maximum absorption wavelength of BiVO4/Mn1−xZnxFe2O4 (lambda max) increases, and the absorption of visible light is enhanced to some extent. In addition, the band gap plays a very important role in the determination of photocatalytic activity. The relationship between absorbance and incident light intensity hv can be expressed by the following formula [8,9]:Ah

Figure 7

UV-Vis diffuse reflectance spectra of pure BiVO4 and BiVO4/Mn1−xZnxFe2O4 (15 wt %) samples. Inset: the plot of (Ahv)2 vs. hv to estimate the Eg value.

In the above equation, A, Eg, h, and v represent the absorption coefficient, band gap width, Planck constant, and incident light frequency, respectively, and C is defined as a constant. The band gap energy of the sample can be obtained from the (Ahv)2~hv curve. The band gaps (Eg) of BiVO4 and pan class="Chemical">BiVO4/Mn1−xZnxFe2O4 were estimated. They have nearly the same Eg values (2.36 eV), which are in agreement with the literature [5,19]. Though the incorporation of Mn1−xZnxFe2O4 could not extend the range of absorption light, it is worth noting that the anther function of Mn1−xZnxFe2O4 enhanced the absorption intensity of visible light for BiVO4 by charge transfer transitions (2Fe3+ → Fe2+ + Fe4+) [18].

3.4. Conductivity and Electrochemical Performance

Electrochemical impedance spectroscopy (EIS) is an effective method to evaluate the electron transfer between solid and electrolyte interfaces. Figure 8 shows the Nyquist diagram of the prepared samples. It can be seen from the diagram that the diameter of the semicircle decreases obviously with the introduction of Mn1−xZnxFe2O4, which indicates that the resistance of the solid interface layer and the surface electron transfer impedance decrease. The BiVO4/Mn1−xZnxFe2O4 charge transfer impedance (206 Ω·cm2) is less than pure BiVO4 (351 Ω·cm2) [20]. This is due to the doping effect of Fe ions in the Mn1−xZnxFe2O4 crystal lattice system. The charge transfer was easier, probably due to the charge transfer transitions of Fe ions (2Fe3+ → Fe2+ + Fe4+) and Mn ions (2Mn4+ → Mn2+ + Mn6+). The electron transfer impedance of the composite solid /electrolyte interface decreases, which may be because the incorporation of magnetic Mn1−xZnxFe2O4 could enhance the conductivity of BiVO4 and heighten the quantum efficiency of BiVO4. Thus, we can preliminarily predict that the photocatalytic activity of BiVO4/Mn1−xZnxFe2O4 must be higher than that of pure BiVO4 under the same light irradiation conditions.

Figure 8

The Nyquist plots of BiVO4 and BiVO4/Mn1−xZnxFe2O4 (15 wt %).

3.5. Photocatalytic Activity and Stability

The results of the RhB photodegradation by the prepn>ared n>an class="Chemical">BiVO4 and BiVO4/Mn1−xZnxFe2O4 samples are shown in Figure 9. Obviously, the photocatalytic efficiency of BiVO4/Mn1−xZnxFe2O4 was higher than that of pure BiVO4. Under the same visible light irradiation, the degradation rate of RhB for pure BiVO4 reached 97% after 3 h, while BiVO4/Mn1−xZnxFe2O4 only took 2 h to achieve the same degradation rate. This result was in good agreement with the EIS analysis. On the one hand, the introduction of Mn1−xZnxFe2O4 enhanced the conductivity of BiVO4, further heightening the electron transfer ability. On the other hand, Mn1−xZnxFe2O4 enhanced the absorption intensity of visible light for BiVO4. Thus, BiVO4/Mn1−xZnxFe2O4 could produce more photoinduced electron-hole pairs under same visible light irradiation. The two factors generate a synergistic effect to boost the quantum efficiency of BiVO4.

Figure 9

Photocatalytic degradation ratios of RhB with BiVO4 and BiVO4/Mn1−xZnxFe2O4 (15 wt %) samples.

The repeatability of the magnetic photocatalyst was detected by cycling tests. After each cycle, the catalyst was separated by an external magnet, and then was washed and dried for the next cycle. The degradation rate of pan class="Chemical">RhB using the fifth recycled photocatalyst was still more than 93% (see Figure 10). This indicated that the as-prepn>ared magnetic photocatalyst had an excellent stability. In general, the introduction of a magnetic substrate can enhance the stability of a single component photocatalyst.

Figure 10

Recycling experiments of degrading RhB with BiVO4/Mn1−xZnxFe2O4 (15 wt %).

4. Conclusions

BiVO4/n>an class="Gene">Mn1−xZnxFe2O4 was prepared by the impregnation roasting method. The synthesis method was suitable for the mass production of various composites. XRD tests showed that the prepared BiVO4 is monoclinic crystal, and the introduction of Mn1−xZnxFe2O4 does not change the crystal structure of BiVO4. The introduction of a soft-magnetic material, Mn1−xZnxFe2O4, was beneficial to the composite photocatalyst’s separation from the liquid solution using an extra magnet after the reaction. UV-vis spectra analysis indicated that Mn1−xZnxFe2O4 enhanced the absorption intensity of visible light for BiVO4. EIS investigation revealed that the introduction of Mn1−xZnxFe2O4 could decrease the electron transfer impedance of BiVO4, further enhancing its conductivity and heightening its quantum efficiency. The photocatalytic efficiency of BiVO4/Mn1−xZnxFe2O4 was higher than that of pure BiVO4.