ZnWO4 photocatalytic material with oxygen vacancy and preparation method thereof

Abstract

The invention belongs to the field of novel photocatalytic materials, and particularly relates to a ZnWO4 photocatalytic material containing oxygen vacancy. According to the material, absorption exists in a near infrared region of an ultraviolet-visible light diffuse reflection spectrum, wherein the wavelength range of the near infrared region is 780-2500 nm. The invention further relates to a preparation method of the ZnWO4 photocatalytic material containing oxygen vacancy. Na2WO4 and soluble zinc salt are used as raw materials, ZnWO4 crystals are formed through a hydrothermal crystallization reaction and then roasted in the presence of hydrogen so as to achieve partial reduction of ZnWO4, and then the ZnWO4 photocatalytic material containing oxygen vacancy is obtained.

Claims

1. A preparation method of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy, comprising: reacting Na.sub.2WO.sub.4 and a soluble zinc salt in a solution to form a reaction product; subjecting the reaction product to a hydrothermal crystallization reaction to obtain ZnWO.sub.4 crystals; and roasting the obtained ZnWO.sub.4 crystals in the presence of hydrogen so as to achieve partial reduction of ZnWO.sub.4 to obtain the ZnWO.sub.4 photocatalytic material containing oxygen vacancy.

2. The preparation method of claim 1, wherein the soluble zinc salt is ZnCl.sub.2, Zn(CH.sub.3COO).sub.2, or Zn(NO.sub.3).sub.2, and the soluble zinc salt has a concentration range in a hydrothermal crystallization mother liquor of 0.001-0.1 mol/L.

3. The preparation method of claim 1, wherein the hydrothermal crystallization reaction is carried out at a temperature of 120-200 C. for 12-36 hrs.

4. The preparation method of claim 1, wherein an amount of oxygen vacancy in the ZnWO.sub.4 photocatalytic material is changed by regulating a temperature and a reduction time of the roasting step.

5. The preparation method of claim 1, wherein the obtained ZnWO.sub.4 crystals are roasted in the presence of hydrogen at a temperature of 350-600 C. for a roasting time of 1-4 hrs.

6. The preparation method of claim 1, wherein the ZnWO.sub.4 photocatalytic material containing oxygen vacancy has light absorption in a near infrared region of an ultraviolet-visible light diffuse reflection spectrum, wherein a wavelength range of the near infrared region is 780-2500 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an X-ray diffraction spectrogram of a ZnWO.sub.4 photocatalytic material containing oxygen vacancy.

(2) FIG. 2 is an ultraviolet-visible light diffuse reflection spectrum (UV-VIS spectrum) of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy.

(3) FIG. 3 shows the photocatalytic hydrogen production performance of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy in a lactic acid solution.

DETAILED DESCRIPTION OF THE INVENTION

(4) The invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and all used drugs are from commercial sources.

Example 1

(5) (1) Synthesis of a typical ZnWO.sub.4 photocatalytic material by a hydrothermal process: by taking deionized water as a solvent, 4 mmol Zn(CH.sub.3COO).sub.2 and 4 mmol Na.sub.2WO.sub.4 are dissolved in 40 mL deionized water respectively, and a solution A and a solution B are obtained; the solution B is dropwise added to the solution A with stirring, the stirring is carried out continuously for 30 min, and then a white suspension is obtained; the obtained white suspension is put in a 100 mL hydrothermal reaction kettle, the hydrothermal reaction kettle is put in an oven, a thermostatic reaction undergoes at 180 DEG C. for 24 h, and then cooling to temperature is carried out; and then, a solid product in the hydrothermal reaction kettle is separated out by centrifugation and is washed with deionized water and ethanol for three times respectively, and subsequently drying and grinding are carried out, so that a corresponding ZnWO.sub.4 photocatalytic material is obtained; and (2) preparation of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy by roasting and reducing in the presence of hydrogen: the obtained typical ZnWO.sub.4 photocatalytic material is put in a crucible, and is roasted in an atmosphere furnace under a hydrogen atmosphere at 400 DEG C. for 2 h, with the temperature increasing rate during roasting being 2 DEG C./min, and finally an obtained product is the ZnWO.sub.4 photocatalytic material containing oxygen vacancy.

Example 2

(6) (1) Synthesis of a typical ZnWO.sub.4 photocatalytic material by a hydrothermal process: by taking deionized water as a solvent, 2 mmol ZnCl.sub.2 and 2 mmol Na.sub.2WO.sub.4 are dissolved in 40 mL deionized water respectively, and a solution A and a solution B are obtained; the solution B is dropwise added to the solution A with stirring, the stirring is carried out continuously for 30 min, and then a white suspension is obtained; the obtained white suspension is put in a 100 mL hydrothermal reaction kettle, the hydrothermal reaction kettle is put in an oven, a thermostatic reaction undergoes at 150 DEG C. for 24 h, and then cooling to temperature is carried out; and then, a solid product in the hydrothermal reaction kettle is separated out by centrifugation and is washed with deionized water and ethanol for three times respectively, and subsequently drying and grinding are carried out, so that a corresponding ZnWO.sub.4 photocatalytic material is obtained; and (2) preparation of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy by roasting and reducing in the presence of hydrogen: the obtained typical ZnWO.sub.4 photocatalytic material is put in a crucible, and is roasted in an atmosphere furnace under a hydrogen atmosphere at 500 DEG C. for 4 h, with the temperature increasing rate during roasting being 2 DEG C./min, and finally an obtained product is the ZnWO.sub.4 photocatalytic material containing oxygen vacancy.

Example 3

(7) Example 3 is a spectroscopy characterization and activity experiment on the ZnWO.sub.4 photocatalytic material containing oxygen vacancy and a common ZnWO.sub.4 photocatalytic material.

(8) FIG. 1 is an X-ray diffraction spectrogram of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy and the common ZnWO.sub.4 photocatalytic material which are prepared on the conditions of the example 1 and the example 2. It can be observed that the X-ray diffraction peak intensity after the oxygen vacancy is introduced is weakened generally.

(9) FIG. 2 is an ultraviolet-visible light diffuse reflection spectrum of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy and the common ZnWO.sub.4 photocatalytic material which are prepared on the conditions of the example 1 and the example 2. It can be observed that absorption of ZnWO.sub.4 with the oxygen vacancy exists in a near infrared region, which shows that the oxygen vacancy exist in the material.

(10) FIG. 3 is a performance evaluation experiment on the ZnWO.sub.4 photocatalytic material containing oxygen vacancy and the common ZnWO.sub.4 photocatalytic material, prepared on the conditions of the example 1 and the example 2, applied to a lactic acid photocatalytic hydrogen production reaction. The horizontal axis is reaction time and the longitudinal axis is a hydrogen evolution rate. Obviously, the activity of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy in the example 1 is increased by about 4 times compared with that of the typical ZnWO.sub.4 photocatalytic material, and the activity of the ZnWO.sub.4 photocatalytic material containing oxygen vacancy in the example 2 is increased by about 6 times compared with that of the typical ZnWO.sub.4 photocatalytic material, which shows that after the oxygen vacancy is introduced, the ZnWO.sub.4 photocatalytic activity is improved greatly.