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.


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 human population [1]. To date, cleaning up organic compounds via degradation and water splitting to produce H 2 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.

Photocatalytic Tests
The photocatalytic activity of the prepared photocatalysts was investigated by the degradation of simulated dye wastewater (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).

Results and Discussion
Primary analysis of photodegradation revealed that BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (15 wt %) was the most efficient in the RhB degradation process under visible light irradiation.  (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 × 10 5~1 × 10 −2 Hz.

Photocatalytic Tests
The photocatalytic activity of the prepared photocatalysts was investigated by the degradation of simulated dye wastewater (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).

Results and Discussion
Primary analysis of photodegradation revealed that BiVO4/Mn1−xZnxFe2O4 (15 wt %) was the most efficient in the RhB degradation process under visible light irradiation.    The diffraction peaks of the Mn1−xZnxFe2O4 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.

Structure and Specific Surface Property
The peaks at (121) for BiVO4 in both patterns of pure 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/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/Mn1−xZnxFe2O4 (15 wt %), we carried out the measurement of Fourier transform infrared spectroscopy. Figure [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]. 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 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 BiVO 4 [16]. These bands could be also observed in the spectroscopy of BiVO 4 / Mn 1−x Zn x Fe 2 O 4 (15 wt %), which further revealed that the BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (15 wt %) was synthesized successfully, in agreement with the of XRD and FTIR analysis results. In addition, the intensity of BiVO 4 was much larger than that of Mn 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 spectroscopy of 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 %). 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) 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.  In order to further observe the morphology of the sample, we characterized the material using SEM. Figure  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 spectroscopy of 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 %). 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) 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 5 shows the N 2 adsorption-desorption isotherm and the pore size distribution curve of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 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/P 0 axis over its entire range, revealing that the as-prepared composite BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (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 BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (15 wt %) is 6.0 nm. In addition, the specific surface area of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 sample calculated by BET measurement is 2.22 m 2 /g. Materials 2018, 11, x FOR PEER REVIEW 6 of 11 Figure 5 shows the N2 adsorption-desorption isotherm and the pore size distribution curve of 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 m 2 /g.  Figure 6 depicts the hysteresis loops of the magnetic substrate and magnetic photocatalyst BiVO4/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. vspace-6pt  Figure 6 depicts the hysteresis loops of the magnetic substrate and magnetic photocatalyst BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (15 wt %). The saturation magnetization (Ms) and remanent magnetization (Ms) of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (15 wt %) were 84.03 emu/g and 7.03 emu/g, respectively. Compared with pure Mn 1−x Zn x Fe 2 O 4 , 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 BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (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 Mn 1−x Zn x Fe 2 O 4 , which indicated that the magnetic photocatalyst included Mn 1−x Zn x Fe 2 O 4 .

Magnetic Properties
Materials 2018, 11, x FOR PEER REVIEW 6 of 11 Figure 5 shows the N2 adsorption-desorption isotherm and the pore size distribution curve of 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 m 2 /g.  Figure 6 depicts the hysteresis loops of the magnetic substrate and magnetic photocatalyst BiVO4/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.

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 BiVO 4 , BiVO 4 /Mn 1−x Zn x Fe 2 O 4 , and the curve of (Ahv) 2 vs. hv. It can be seen from the diagram that BiVO 4 and BiVO 4 /Mn 1−x Zn x Fe 2 O 4 mainly absorb light in the wavelength range below 500 nm. Compared with pure BiVO 4 , the maximum absorption wavelength of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 (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]: 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~h v curve. The band gaps (Eg) of BiVO 4

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 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]: 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~h v curve. The band gaps (Eg) of BiVO4 and 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 (2Fe 3+ → Fe 2+ + Fe 4+ ) [18].

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·cm 2 ) is less than pure BiVO4 (351 Ω·cm 2 ) [20]. This is due to the doping effect of Fe

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 Mn 1−x Zn x Fe 2 O 4 , which indicates that the resistance of the solid interface layer and the surface electron transfer impedance decrease. The BiVO 4 /Mn 1−x Zn x Fe 2 O 4 charge transfer impedance (206 Ω·cm 2 ) is less than pure BiVO 4 (351 Ω·cm 2 ) [20]. This is due to the doping effect of Fe ions in the Mn 1−x Zn x Fe 2 O 4 crystal lattice system. The charge transfer was easier, probably due to the charge transfer transitions of Fe ions (2Fe 3+ → Fe 2+ + Fe 4+ ) and Mn ions (2Mn 4+ → Mn 2+ + Mn 6+ ). The electron transfer impedance of the composite solid /electrolyte interface decreases, which may be because the incorporation of magnetic Mn 1−x Zn x Fe 2 O 4 could enhance the conductivity of BiVO 4 and heighten the quantum efficiency of BiVO 4 . Thus, we can preliminarily predict that the photocatalytic activity of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 must be higher than that of pure BiVO 4 under the same light irradiation conditions. Materials 2018, 11, x FOR PEER REVIEW 8 of 11 ions in the Mn1−xZnxFe2O4 crystal lattice system. The charge transfer was easier, probably due to the charge transfer transitions of Fe ions (2Fe 3+ → Fe 2+ + Fe 4+ ) and Mn ions (2Mn 4+ → Mn 2+ + Mn 6+ ). 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.

Photocatalytic Activity and Stability
The results of the RhB photodegradation by the prepared 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.

Photocatalytic Activity and Stability
The results of the RhB photodegradation by the prepared BiVO 4 and BiVO 4 /Mn 1−x Zn x Fe 2 O 4 samples are shown in Figure 9. Obviously, the photocatalytic efficiency of BiVO 4

Photocatalytic Activity and Stability
The results of the RhB photodegradation by the prepared 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.  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 RhB using the fifth recycled photocatalyst was still more than 93% (see Figure 10). This indicated that the as-prepared magnetic photocatalyst had an excellent stability. In general, the introduction of a magnetic substrate can enhance the stability of a single component photocatalyst. 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 RhB using the fifth recycled photocatalyst was still more than 93% (see Figure  10). This indicated that the as-prepared magnetic photocatalyst had an excellent stability. In general, the introduction of a magnetic substrate can enhance the stability of a single component photocatalyst.

Conclusions
BiVO4/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.

Conclusions
BiVO 4 /Mn 1−x Zn x Fe 2 O 4 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 BiVO 4 is monoclinic crystal, and the introduction of Mn 1−x Zn x Fe 2 O 4 does not change the crystal structure of BiVO 4 . The introduction of a soft-magnetic material, Mn 1−x Zn x Fe 2 O 4 , 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 Mn 1−x Zn x Fe 2 O 4 enhanced the absorption intensity of visible light for BiVO 4 . EIS investigation revealed that the introduction of Mn 1−x Zn x Fe 2 O 4 could decrease the electron transfer impedance of BiVO 4 , further enhancing its conductivity and heightening its quantum efficiency. The photocatalytic efficiency of BiVO 4 /Mn 1−x Zn x Fe 2 O 4 was higher than that of pure BiVO 4 .