CN111974374A - Preparation method of biochar modified nano ZnO composite powder - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a preparation method of biochar modified nano ZnO composite powder, belonging to the technical field of photocatalysts. According to the invention, a mixed solution of biochar and a zinc salt is subjected to a hydrothermal reaction at a temperature of 100-160 ℃ under an alkaline condition to obtain the biochar modified nano ZnO composite photocatalyst. The biochar modified nano ZnO composite photocatalyst has the advantages of large specific surface area and strong adsorption capacity, responds to visible light, and has the efficiency of degrading Methylene Blue (MB) pollutants under ultraviolet-visible light for 100min reaching 98.71 percent; the method utilizes renewable natural resource biochar to modify ZnO, has high catalytic activity, can be repeatedly utilized, and has no secondary pollution; meanwhile, the preparation method is simple, the production cost is low, and the method can be applied to industrial production.
Description
Technical Field
The invention relates to a preparation method of biochar modified nano ZnO composite powder, belonging to the technical field of photocatalysts.
Background
In recent years, ZnO has been widely used and developed as a photocatalyst, because of its advantages of low price, no toxicity, high stability, etc. ZnO has wide energy gap (3.37ev), only responds to ultraviolet light, and only has less than 5 percent of ultraviolet light in sunlight, so the utilization rate of visible light is low; and the photogenerated photon electron-hole generated in the photocatalysis process is easy to recombine, the photocatalysis efficiency is influenced, and the photochemical corrosion phenomenon is also generated, so that the practical application of ZnO is greatly limited.
In order to improve the photocatalytic efficiency of ZnO, increase its utilization rate, and reduce the recombination of electrons and holes, the ZnO is modified by a calcination method, a chemical precipitation method, a sol-gel method, a hydrothermal method, and the like, including noble metal doping, introduction of a carbon-based material, and recombination of a semiconductor oxide. The synthesized Ag/ZnO, Au/ZnO, Pt-ZnO and other composite photocatalysts improve the stability of the catalysts to a certain extent, broaden the absorption of visible light, but have too high cost and secondary pollution; the introduced carbon-based materials such as graphene, carbon nanotube and the like also have the defects of high cost and poor catalytic effect; binary catalyst ZnO/TiO synthesized by utilizing semiconductor oxide2、ZnO/Fe2O3、ZnO/Cu2O, the general process is complex, the visible light response range is narrow, the catalytic performance cannot reach the best, and the environment is not friendly.
Disclosure of Invention
The invention provides a preparation method of a biochar modified nano ZnO composite powder aiming at the problems of high cost and poor catalytic effect of the existing ZnO photocatalyst, and the invention utilizes renewable natural resources biochar to modify ZnO, has high catalytic activity, can be repeatedly utilized and has no secondary pollution; meanwhile, the preparation method is simple, the production cost is low, and the method can be applied to industrial production.
The biochar is prepared by thermally decomposing an organic raw material in a specific low-temperature (<700 ℃) anoxic environment, the high carbon content, the high specific surface area and the conductive property of the biochar are beneficial to mineralization of organic pollutants, and the biochar in the catalyst of the biochar modified ZnO can obviously inhibit rapid recombination of photo-generated electron pairs in a photocatalysis process so as to achieve efficient degradation.
A preparation method of biochar modified nano ZnO composite powder comprises the following specific steps:
(1) dispersing biochar in ethanol to obtain a mixed solution A, dissolving zinc salt in the mixed solution A, and stirring for pretreatment for 1-2 hours to obtain a mixed solution B;
(2) dropwise adding the aqueous alkali into the mixed solution B to react until a system does not precipitate, and performing ultrasonic treatment for 30-60 min to obtain a precursor;
(3) reacting the precursor for 8-12 h at the temperature of 100-160 ℃, carrying out solid-liquid separation, washing the solid until the washing liquid is neutral, and drying to obtain the biochar modified nano ZnO composite photocatalyst;
the preferred biochar is hemp stalk activated carbon, and the preparation method comprises the following steps: crushing hemp stalks to an average particle size of about 10 microns to obtain hemp stalk fine materials, washing the hemp stalk fine materials by deionized water to remove impurities, and drying the hemp stalk fine materials at the temperature of 60 ℃ for 10 hours to remove moisture; at Ar2Under the protection of atmosphere, carbonizing the hemp stalk fine material in a tube furnace at the aeration rate of 0.1L/min and the temperature of 650 ℃ for 3 h; cooling to room temperature in the same atmosphere, grinding, and sieving with 300 mesh sieve to obtain charcoal;
the biochar in the step (1) and Zn in zinc salt2+The molar ratio of (A) to (B) is 1: 0.5-3;
the zinc salt in the step (1) is Zn (CH)3COO)2Or Zn (NO)3)2.6(H2O)；
The alkali solution in the step (2) is potassium hydroxide, sodium hydroxide or tetramethyl ammonium bicarbonate solution;
preferably, the concentration of the alkali solution is 0.1-0.5 mol/L;
preferably, the stirring speed in the step (1) is 200-500 rpm;
preferably, the drying temperature in the step (3) is 40-60 ℃, and the drying time is 8-12 h.
According to the biochar modified nano ZnO composite photocatalyst, under the irradiation of visible light, electrons generated by a ZnO Valence Band (VB) are excited to migrate to a Conduction Band (CB), and a hole (h) is left in the valence band+) Electron-hole pairs and H generated under illumination2O、O2The reaction generates hydroxyl free radical (OH), superoxide free radical (O)2) Active species with strong oxidation reduction property, wherein the active species can mineralize and decompose organic pollutants into H2O、CO2And other inorganic small molecular substances, in the catalysis process, the biochar with high specific surface area and developed aperture rapidly adsorbs pollutants and transfers to the surface of ZnO to generate concentration difference so as to improve the photocatalysis efficiency; in addition, ZnO is attached to the surface of the biochar, so that the specific surface area of the whole catalyst is improved, active sites are increased, meanwhile, the biochar has good electron shuttling capability, and the synergistic effect with ZnO reduces the recombination of photo-generated electrons and holes, so that the efficiency of the catalyst is improved.
The invention has the beneficial effects that:
(1) the biochar modified nano ZnO catalyst has the advantages of large specific surface area, more catalytic active sites, strong adsorption capacity, stable chemical property, low cost and sustainable use, and the introduction of the biochar realizes waste utilization;
(2) the charcoal modified nano ZnO catalyst has high catalytic efficiency and strong activity, can strongly absorb ultraviolet light within a spectral range from less than 400nm, greatly improves the absorption within a visible light range, realizes the response to the visible light, and has good stability;
(3) the biochar modified nano ZnO catalyst is prepared by a one-step hydrothermal method, the operation is simple and convenient, no pollutant is introduced in the hydrothermal synthesis, and no secondary pollution is caused by using the catalyst; in the catalysis process, the biochar with high specific surface area and developed aperture rapidly adsorbs pollutants and transfers to the surface of ZnO to generate concentration difference so as to improve the photocatalysis efficiency; in addition, ZnO is attached to the surface of the biochar, so that the specific surface area of the whole catalyst is improved, active sites are increased, meanwhile, the biochar has good electron shuttling capability, and the synergistic effect with ZnO reduces the recombination of photo-generated electrons and holes, so that the efficiency of the catalyst is improved.
Drawings
FIG. 1 is an XRD pattern of the composite powder of nano ZnO modified by biochar in examples 1 and 2;
FIG. 2 is SEM images of composite powder of nano ZnO modified by biochar of examples 1 and 2;
FIG. 3 is a diagram of the ultraviolet-visible diffuse reflectance spectrum (UV-vis) of the biochar-modified nano ZnO composite powder in example 1;
FIG. 4 is a graph of the degradation efficiency of the biochar-modified nano ZnO composite powder in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of biochar modified nano ZnO composite powder comprises the following specific steps:
(1) dispersing biochar (hemp stalk activated carbon) in ethanol to obtain a mixed solution A, dissolving zinc salt (zinc nitrate) in the mixed solution A, and stirring for pretreatment for 1h to obtain a mixed solution B; wherein hemp stalk biochar (C) and zinc nitrate (Zn (NO)2)·6H2O) is 1:0.5, and the stirring speed is 200 rmp;
(2) dropwise adding an alkali solution (a potassium hydroxide solution) into the mixed solution B to react until a system does not precipitate, and performing ultrasonic treatment for 60min to obtain a precursor; wherein the concentration of the potassium hydroxide solution is 0.1 mol/L;
(3) reacting the precursor at 100 ℃ for 12h, carrying out solid-liquid centrifugal separation, washing the solid with deionized water until the washing liquid is neutral, and drying at 40 ℃ for 12h to obtain the biochar modified nano ZnO composite photocatalyst;
the XRD pattern of the composite photocatalyst of nano ZnO modified by biochar in the embodiment is shown in figure 1, and the product is zinc oxide with a hexagonally plumbite structure as can be seen from figure 1. As shown by PDF #99-0111, ZnO has peak positions at 31.76 °, 34.41 °, 36.25 °, 47.53 °, 56.59 °, 62.85 °, 66.37 °, 67.94 ° and 69.08 ° for the (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes, respectively. The amorphous biochar has no obvious steamed bread peak in XRD. The average grain size of the composite catalyst was calculated from the Scherrer formula: dcK λ/(Bcos θ) (λ); wherein K is 0.89 of Scherrer constant, D is the average thickness of crystal grains vertical to the crystal plane direction, B is the full width at half maximum of a sample diffraction peak, theta is a diffraction angle, gamma is an X-ray wavelength (0.154056nm), and the calculation result shows that the average size of the composite catalyst is 31 nm;
the SEM morphology of the composite photocatalyst modified by biochar nano ZnO according to this embodiment is characterized in that, as shown in fig. 2a, the composite photocatalyst is a composite photocatalyst in which nano ZnO particles form a 3D structure which is uniformly deposited on the surface of hemp stalk biochar and which exhibits crystallographic characteristics of preferred orientation in the (002) direction; as can be seen from the ultraviolet-visible diffuse reflection spectrum analysis of the composite photocatalyst, the composite photocatalyst has stronger absorption in the ultraviolet-visible light region (see figure 3);
the photocatalytic activity of the composite catalyst was evaluated by degrading the cationic contaminant Methylene Blue (MB) under uv-visible light, as follows: putting 50mg of the biochar-modified nano ZnO composite photocatalyst prepared in the embodiment into 200mL of Methylene Blue (MB) solution with the concentration of 30mg/L, taking 4mL of suspension solution every 10min, testing the absorption concentration of the MB solution after solid-liquid separation, and calculating the degradation rate; irradiating for 100min under 300W xenon lamp irradiation, wherein the catalytic efficiency can reach 98.71.8% after 100min, and the degradation rate is 96.23% after 3 times of repeated degradation (see figure 4).
Example 2: a preparation method of biochar modified nano ZnO composite powder comprises the following specific steps:
(1) dispersing biochar (hemp stalk activated carbon) in ethanol to obtain a mixed solution A, dissolving zinc salt (zinc acetate) in the mixed solution A, and stirring for pretreatment for 2h to obtain a mixed solution B(ii) a Wherein the hemp stalk biochar (C) and the zinc acetate Zn (CH)3COO)2The molar ratio of (1: 3) and the stirring speed of 500 rmp;
(2) dropwise adding an alkali solution (tetramethylammonium bicarbonate) into the mixed solution B to react until the system does not precipitate, and performing ultrasonic treatment for 120min to obtain a precursor; wherein the concentration of the potassium hydroxide solution is 0.5 mol/L;
(3) the precursor reacts for 8 hours at the temperature of 160 ℃, solid-liquid centrifugal separation is carried out, the solid is washed by deionized water until the washing liquid is neutral, and the charcoal modified nano ZnO composite photocatalyst is obtained after drying for 10 hours at the temperature of 80 ℃;
the XRD pattern of the composite photocatalyst of nano ZnO modified by biochar in the embodiment is shown in figure 1, and as can be seen from figure 1, the product is zinc oxide (ZnO) with a stable structure of hexaplumbite; after the proportion is adjusted, the XRD result shows that the peak position of ZnO is not changed, but the peak intensity is increased;
in the representation of the SEM morphology of the biochar-modified nano ZnO composite photocatalyst of this embodiment, as shown in fig. 2b, nano ZnO particles form a 3D structure and are deposited on the surface of hemp stalk biochar, and ZnO nanocrystals are preferentially distributed on the surface of biochar;
the photocatalytic activity of the composite catalyst was evaluated by degrading the cationic contaminant Methylene Blue (MB) under uv-visible light, as follows: putting 30mg of the biochar-modified nano ZnO composite photocatalyst prepared in the embodiment into 200mL of Methylene Blue (MB) solution with the concentration of 30mg/L, taking 4mL of suspension solution every 10min, testing the absorption concentration of MB after solid-liquid separation, and calculating the degradation rate; irradiating for 100min under 300W xenon lamp, wherein the catalytic efficiency can reach 95.8% after 100min, and the degradation rate is 94.35% after 2 times of repeated degradation.
Example 3: a preparation method of biochar modified nano ZnO composite powder comprises the following specific steps:
(1) dispersing biochar (hemp stalk activated carbon) in ethanol to obtain a mixed solution A, dissolving zinc salt (zinc nitrate) in the mixed solution A, and stirring for pretreatment for 2 hours to obtain a mixed solution B; wherein hemp stalk biochar (C) and zinc nitrate (Zn (NO)2)·6H2O) in a molar ratio of 1:1, stirringThe stirring speed is 350 rmp;
(2) dropwise adding an alkali solution (tetramethylammonium bicarbonate) into the mixed solution B to react until the system does not precipitate, and performing ultrasonic treatment for 80min to obtain a precursor; wherein the concentration of the potassium hydroxide solution is 0.2 mol/L;
(3) reacting the precursor at 130 ℃ for 10h, carrying out solid-liquid centrifugal separation, washing the solid with deionized water until the washing liquid is neutral, and drying at 70 ℃ for 8h to obtain the biochar modified nano ZnO composite photocatalyst;
in the embodiment, the product of the activated carbon loaded ZnO/CuxO photocatalytic composite powder is zinc oxide (ZnO) with a stable structure of hexagonal lead-zinc ore, and after the proportion is adjusted, an XRD result shows that the position of a ZnO peak is not changed, but the peak intensity is weakened;
the morphology of the biochar modified nano ZnO composite photocatalyst is that 3D structures formed by nano ZnO particles are deposited on the surface of hemp stalk biochar, and the nano ZnO composite photocatalyst is uniformly dispersed and preferentially oriented and distributed along the (002) direction;
the photocatalytic activity of the composite catalyst was evaluated by degrading the cationic contaminant Methylene Blue (MB) under uv-visible light, as follows: putting 10mg of the biochar-modified nano ZnO composite photocatalyst prepared in the embodiment into 200mL of Methylene Blue (MB) solution with the concentration of 10mg/L, irradiating for 100min under the projection of a 300W xenon lamp, taking 4mL of suspension solution at intervals of 10min, testing the absorption concentration of MB after solid-liquid separation, and calculating the degradation rate; after 100min, the catalytic efficiency can reach 97.6%, and the degradation rate is 94% after 3 times of repeated degradation.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of biochar modified nano ZnO composite powder is characterized by comprising the following specific steps:
(1) dispersing biochar in ethanol to obtain a mixed solution A, dissolving zinc salt in the mixed solution A, and stirring for pretreatment for 1-2 hours to obtain a mixed solution B;
(2) dropwise adding the aqueous alkali into the mixed solution B to react until a system does not precipitate, and performing ultrasonic treatment for 30-60 min to obtain a precursor;
(3) and (3) reacting the precursor for 8-12 h at the temperature of 100-160 ℃, carrying out solid-liquid separation, washing the solid until the washing liquid is neutral, and drying to obtain the biochar modified nano ZnO composite photocatalyst.
2. The method for preparing the biochar modified nano ZnO composite powder according to claim 1, which is characterized by comprising the following steps: step (1) adding Zn into the biochar and the zinc salt2+The molar ratio of (A) to (B) is 1: 0.5-3.
3. The method for preparing the biochar modified nano ZnO composite powder according to claim 1, which is characterized by comprising the following steps: the zinc salt in the step (1) is Zn (CH)3COO)2Or Zn (NO)3)2.6(H2O)。
4. The method for preparing the biochar modified nano ZnO composite powder according to claim 1, which is characterized by comprising the following steps: the alkali solution in the step (2) is potassium hydroxide, sodium hydroxide or tetramethyl ammonium bicarbonate solution.
5. The method for preparing the biochar modified nano ZnO composite powder according to claim 4, which is characterized by comprising the following steps: the concentration of the alkali solution is 0.1-0.5 mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113926444A (en) * | 2021-11-17 | 2022-01-14 | 厦门理工学院 | Zinc oxide nano-rod ternary composite material and preparation method and application thereof |
| CN115007130A (en) * | 2021-11-30 | 2022-09-06 | 昆明理工大学 | Preparation method and application of zinc oxide/zinc silicate/biochar composite material |
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