CN111974374A - Preparation method of biochar modified nano ZnO composite powder - Google Patents
Preparation method of biochar modified nano ZnO composite powder Download PDFInfo
- Publication number
- CN111974374A CN111974374A CN202010841461.7A CN202010841461A CN111974374A CN 111974374 A CN111974374 A CN 111974374A CN 202010841461 A CN202010841461 A CN 202010841461A CN 111974374 A CN111974374 A CN 111974374A
- Authority
- CN
- China
- Prior art keywords
- biochar
- modified nano
- nano zno
- zno composite
- composite powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VFHDWENBWYCAIB-UHFFFAOYSA-M hydrogen carbonate;tetramethylazanium Chemical compound OC([O-])=O.C[N+](C)(C)C VFHDWENBWYCAIB-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 abstract description 17
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 116
- 239000011787 zinc oxide Substances 0.000 description 57
- 239000003054 catalyst Substances 0.000 description 16
- 244000025254 Cannabis sativa Species 0.000 description 15
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 15
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 15
- 235000009120 camo Nutrition 0.000 description 15
- 235000005607 chanvre indien Nutrition 0.000 description 15
- 239000011487 hemp Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- -1 hydroxyl free radical Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229910016411 CuxO Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/60—
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010841461.7A CN111974374A (en) | 2020-08-20 | 2020-08-20 | Preparation method of biochar modified nano ZnO composite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010841461.7A CN111974374A (en) | 2020-08-20 | 2020-08-20 | Preparation method of biochar modified nano ZnO composite powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111974374A true CN111974374A (en) | 2020-11-24 |
Family
ID=73442369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010841461.7A Pending CN111974374A (en) | 2020-08-20 | 2020-08-20 | Preparation method of biochar modified nano ZnO composite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111974374A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452320A (en) * | 2020-12-15 | 2021-03-09 | 浙江海洋大学 | Catalyst for degrading pollutants by natural light and preparation method thereof |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877961A (en) * | 2014-03-05 | 2014-06-25 | 北京大学 | Carbon-based zinc oxide nanosphere composite material and preparation method thereof |
| CN109499563A (en) * | 2017-09-15 | 2019-03-22 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of zinc oxide-active carbon composite catalyst |
| CN109731546A (en) * | 2019-01-29 | 2019-05-10 | 蚌埠学院 | Zinc oxide/ferroso-ferric oxide/active carbon nanometer waste water treating agent preparation and application |
-
2020
- 2020-08-20 CN CN202010841461.7A patent/CN111974374A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877961A (en) * | 2014-03-05 | 2014-06-25 | 北京大学 | Carbon-based zinc oxide nanosphere composite material and preparation method thereof |
| CN109499563A (en) * | 2017-09-15 | 2019-03-22 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of zinc oxide-active carbon composite catalyst |
| CN109731546A (en) * | 2019-01-29 | 2019-05-10 | 蚌埠学院 | Zinc oxide/ferroso-ferric oxide/active carbon nanometer waste water treating agent preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| M. VINAYAGAM ET AL.: ""Photocatalytic degradation of orange G dye using ZnO/biomass activated carbon nanocomposite"", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
| N. SOBANA ET AL.: ""Synergism and effect of operational parameters on solar photocatalytic degradation of an azo dye(Direct Yellow 4) using activated carbon-loaded zinc oxide"", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》 * |
| 宫晓磊: ""生物炭基复合材料吸附有机污染物的机制研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452320A (en) * | 2020-12-15 | 2021-03-09 | 浙江海洋大学 | Catalyst for degrading pollutants by natural light and preparation method thereof |
| CN112452320B (en) * | 2020-12-15 | 2023-02-28 | 浙江海洋大学 | Catalyst for degrading pollutants by natural light and preparation method thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zalfani et al. | Novel 3DOM BiVO 4/TiO 2 nanocomposites for highly enhanced photocatalytic activity | |
| CN105800674B (en) | A kind of preparation method and application for vulcanizing tin material | |
| CN111437867B (en) | Composite photocatalyst containing tungsten oxide and preparation method and application thereof | |
| CN111974374A (en) | Preparation method of biochar modified nano ZnO composite powder | |
| Yang et al. | Self-assembly Z-scheme heterostructured photocatalyst of Ag 2 O@ Ag-modified bismuth vanadate for efficient photocatalytic degradation of single and dual organic pollutants under visible light irradiation | |
| CN111036189B (en) | ZnO/CuO or ZnO/CuO/Cu loaded on activated carbon2Preparation method of O photocatalytic composite powder | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| Reddy et al. | Highly efficient hydrogen production using Bi2O3/TiO2 nanostructured photocatalysts under led light irradiation | |
| Huang et al. | Synergetic adsorption and photocatalysis performance of g-C3N4/Ce-doped MgAl-LDH in degradation of organic dye under LED visible light | |
| Tian et al. | Visible light enhanced Fe–I–TiO2 photocatalysts for the degradation of gaseous benzene | |
| CN110327932B (en) | Cu2Preparation method of O/ZnO composite photocatalyst | |
| Chen et al. | The BiOBr/Bi/Bi2WO6 photocatalyst with SPR effect and Z-scheme heterojunction synergistically degraded RhB under visible light | |
| Yosefi et al. | Sequential precipitation design of p-BiOCl-p-Mn3O4 binary semiconductor nanoheterojunction with enhanced photoactivity for acid orange 7 removal from water | |
| Yu et al. | Significant improvement of photocatalytic hydrogen evolution rate over g-C3N4 with loading CeO2@ Ni4S3 | |
| Yan et al. | Construction of novel ternary dual Z-scheme Ag3VO4/C3N4/reduced TiO2 composite with excellent visible-light photodegradation activity | |
| Feng et al. | Two-step construction of WO3@ TiO2/CS-biochar S-scheme heterojunction and its synergic adsorption/photocatalytic removal performance for organic dye and antibiotic | |
| Wang et al. | A novel 2D nanosheets self-assembly camellia-like ordered mesoporous Bi12ZnO20 catalyst with excellent photocatalytic property | |
| CN108273539B (en) | Ta3N5Nanoparticle hybrid TiO2Hollow sphere composite photocatalyst and preparation method and application thereof | |
| Zhang et al. | Fabrication and study of a novel TiO2/g-C3N5 material and photocatalytic properties using methylene blue and tetracycline under visible light | |
| Li et al. | A simple synthetic strategy toward recyclable polyurethane foam supported defective CoFeAl-layered double hydroxides for antibiotics photocatalytic degradation | |
| CN108837840B (en) | A kind of Ag/g-C3N4Modify bismuth tungstate mixed crystal composite material and preparation method and application | |
| CN107961785B (en) | Preparation method and application of high-activity bismuth chromate nano photocatalyst | |
| Cui et al. | Synthesis of CdS/m-TiO 2 mesoporous spheres and their application in photocatalytic degradation of rhodamine B under visible light | |
| Lal et al. | Enhancing photocatalytic, photoelectrochemical hydrogen evolution, and dye degradation using p-type NiCo2O4 spinel photocatalyst synthesized via tapioca leaf extract mediated process | |
| CN113893839B (en) | Preparation method of photocatalytic material for purifying indoor air |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201124 |