CN107715881B - preparation method of carbon-point hybrid mesoporous nickel boride photocatalyst - Google Patents
preparation method of carbon-point hybrid mesoporous nickel boride photocatalyst Download PDFInfo
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- CN107715881B CN107715881B CN201711001262.XA CN201711001262A CN107715881B CN 107715881 B CN107715881 B CN 107715881B CN 201711001262 A CN201711001262 A CN 201711001262A CN 107715881 B CN107715881 B CN 107715881B
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- carbon
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- nickel boride
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- hybrid mesoporous
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- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000013335 mesoporous material Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 aromatic nitro compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
Abstract
the invention discloses a preparation method of a carbon-point hybrid mesoporous nickel boride photocatalyst, which comprises the following 5 steps of preparing a citric acid solution, adding nickel, carrying out hydrothermal reaction, adjusting the pH value, adding sodium borohydride for reaction and centrifuging to realize the preparation of the carbon-point hybrid mesoporous nickel boride photocatalyst. The preparation method of the carbon-point hybrid mesoporous nickel boride photocatalyst disclosed by the invention has the advantages of simple process, easiness in control, high yield and the like.
Description
Technical Field
the invention belongs to the technical field of nano materials and catalysis, and particularly relates to a preparation method of a carbon-point hybrid mesoporous nickel boride photocatalyst.
background
The mesoporous material is a porous material with the pore diameter between 2 nm and 50 nm. The pore canal of the mesoporous material is not only beneficial to improving the contact area of the reaction, but also beneficial to the adsorption and separation of organic molecules, thereby being taken as an efficient micro-reactor and playing an important role in the catalytic reaction. The novel hybrid material is formed by grafting or assembling nano-scale, uniform and stable functional nanoparticles in a pore channel of the mesoporous material, combines the attributes of the mesoporous material and the nano-material, and has super small-size effect, quantum size effect and the like, so that the novel hybrid material has more excellent performance.
the carbon dots are carbon nanoparticles mainly composed of carbon elements and having a fluorescence emission property. The carbon dot not only has the advantages of simple preparation process, low cost, non-toxic elements, greenness and the like, but also has the properties of quasi-semiconductor, photon absorption in a wide wavelength range, excellent electron transfer performance and the like, so that the carbon dot has important application value in the field of solar energy conversion and storage. The size of the carbon dots is less than 10nm and the carbon dots have a nearly spherical structure, so that the carbon dots are favorably filled in the pore channels of the mesopores, the agglomeration of the carbon dots is hindered, each carbon dot is favorably cooperated with the mesoporous material to participate in the energy conversion process, and the energy conversion efficiency is greatly improved.
compared with noble metals, nickel boride, which is a catalyst of the reduction type, has a lower cost, and thus has wide applications in the field of industrial catalysis. The nickel boride is made into a porous nano structure, so that the specific surface area can be obviously improved, more catalytic active points can be obtained, photons can be captured, and the utilization efficiency of solar energy can be improved. At present, a low-cost and efficient method for synthesizing mesoporous nickel boride is still lacked, and carbon dots are embedded into the pore channels of the mesoporous nickel boride in situ, so that formation of nano hybrid mesoporous nickel boride is more rarely reported.
Disclosure of Invention
Aiming at the problem that the existing nano hybrid mesoporous nickel boride lacks a low-cost and high-efficiency preparation method, the invention provides a preparation method of a carbon-point hybrid mesoporous nickel boride photocatalyst with simple process, easy control and high yield.
the preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst comprises the following steps:
(1) Preparing a mol/L citric acid solution, wherein a is 0.5-1;
(2) adding c mmol nickel powder or foam nickel into b mL of citric acid solution prepared in the step (1), heating to 60-80 ℃ to completely dissolve the nickel powder or the foam nickel, wherein b is 20-25, c is 4.5-10, and (a x b) c is 1-5.5;
(3) Putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 5-12 hours at the temperature of 175-225 ℃, and then cooling to room temperature;
(4) adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 7-9, then adding d mmol of sodium borohydride into the solution, and stirring the solution vigorously for 2-3 hours, wherein d is 4.5-11, and d: c is 1-1.1;
(5) And (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 3-5 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
The particle size of the nickel powder in the step (2) is less than 100 microns.
The preparation method of the carbon-point hybrid mesoporous nickel boride photocatalyst has the following advantages:
(1) The nickel boride in the prepared carbon-point hybrid mesoporous nickel boride photocatalyst is in an amorphous structure.
(2) The mesoporous size of the prepared carbon-point hybrid mesoporous nickel boride photocatalyst is 2-15 nm.
(3) The prepared carbon-point hybrid mesoporous nickel boride photocatalyst can efficiently catalyze and reduce organic matters such as aromatic nitro compounds, unsaturated hydrocarbons and the like.
(4) the photocatalytic conversion efficiency of the prepared carbon-point hybrid mesoporous nickel boride photocatalyst is more than 96%.
drawings
FIG. 1 is a low-power transmission electron microscope photograph of a carbon-dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention;
FIG. 2 is a transmission electron microscope photograph of the carbon dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention;
FIG. 3 is an x-ray diffraction spectrum of the carbon dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention;
FIG. 4 is a diagram showing the distribution of the pore diameter of the carbon-dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention;
FIG. 5 is an activity representation diagram of photocatalytic reduction of nitrophenol by the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the present invention;
FIG. 6 is an activity representation diagram of photocatalytic reduction of nitroaniline by the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the invention.
Detailed Description
The detailed technical scheme of the invention is described in the following with the accompanying drawings:
the preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst comprises the following steps:
(1) preparing a mol/L citric acid solution, wherein a is 0.5-1;
(2) adding c mmol nickel powder or foam nickel into b mL of citric acid solution prepared in the step (1), heating to 60-80 ℃ to completely dissolve the nickel powder or the foam nickel, wherein b is 20-25, c is 4.5-10, and (a x b) c is 1-5.5;
(3) putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 5-12 hours at the temperature of 175-225 ℃, and then cooling to room temperature;
(4) adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 7-9, then adding d mmol of sodium borohydride into the solution, and stirring the solution vigorously for 2-3 hours, wherein d is 4.5-11, and d: c is 1-1.1;
(5) And (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 3-5 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
the particle size of the nickel powder in the step (2) is less than 100 microns.
example 1
The preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst comprises the following steps:
(1) preparing 0.5mol/L citric acid solution;
(2) taking 20mL of the citric acid solution prepared in the step (1), adding 10mmol of nickel powder or foamed nickel, and heating to 60-80 ℃ to completely dissolve the nickel powder or foamed nickel;
(3) putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 5 hours at 175 ℃, and then cooling to room temperature;
(4) adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 7, then adding 11mmol of sodium borohydride into the solution, and stirring the solution vigorously for 2 hours;
(5) And (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 4 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
The prepared carbon-point hybrid mesoporous nickel boride photocatalyst is characterized and tested in performance, fig. 1 is a low-power transmission electron microscope photo of the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the invention, and the photo shows that the carbon-point hybrid mesoporous nickel boride photocatalyst presents a porous structure; FIG. 2 is a transmission electron micrograph of the carbon dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention, from which it can be seen that carbon dots are embedded in the pore channels of the mesoporous nickel boride; FIG. 3 is an x-ray diffraction spectrum of the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the present invention, and from the spectrum, it can be seen that the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the present invention is an amorphous structure; FIG. 4 is a distribution diagram of the pore diameter of the carbon-dot hybrid mesoporous nickel boride photocatalyst prepared by the present invention, wherein the size of the mesopores is 2-15 nm; fig. 5 is an activity characterization diagram of the photocatalytic reduction of nitrophenol by the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the present invention, and it can be seen that: under the irradiation of visible light, the nitrophenol is basically completely converted into the aminophenol within three minutes, and within 3 minutes, the efficiency of the visible light for irradiating the nitrophenol into the aminophenol exceeds 98 percent; fig. 6 is an activity characterization diagram of the photocatalytic reduction of nitroaniline by the carbon-point hybrid mesoporous nickel boride photocatalyst prepared by the invention, and it can be seen from the diagram that: the absorption peak of nitrophenol is gradually reduced along with the irradiation of visible light, the absorption peak of the product p-phenylenediamine is gradually enhanced, and the efficiency of converting nitrophenol into aminophenol is over 98 percent when the visible light is irradiated for 9 minutes.
example 2
the preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst comprises the following steps:
(1) preparing a 1mol/L citric acid solution;
(2) Taking 25mL of the citric acid solution prepared in the step (1), adding 4.5mmol of nickel powder or foamed nickel, and heating to 80 ℃ to completely dissolve the nickel powder or foamed nickel;
(3) putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 8 hours at 200 ℃, and then cooling to room temperature;
(4) Adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 8, then adding 4.5mmol of sodium borohydride into the solution, and violently stirring the solution for 3 hours;
(5) and (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 4 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
Example 3
The preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst comprises the following steps:
(1) preparing 0.5mol/L citric acid solution;
(2) Taking 25mL of the citric acid solution prepared in the step (1), adding 8mmol of nickel powder or foamed nickel, and heating to 70 ℃ to completely dissolve the nickel powder or the foamed nickel;
(3) Putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 12 hours at 225 ℃, and then cooling to room temperature;
(4) adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 9, then adding 8mmol of sodium borohydride into the solution, and violently stirring the solution for 2.5 hours;
(5) and (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 5 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
Claims (1)
1. The preparation method of the carbon dot hybrid mesoporous nickel boride photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a mol/L citric acid solution, wherein a is 0.5-1;
(2) adding c mmol of nickel foam into b mL of the citric acid solution prepared in the step (1), heating to 60-80 ℃ to completely dissolve the nickel foam, wherein b is 20-25, c is 4.5-10, and (a x b) c is 1-5.5;
(3) putting the solution obtained in the step (2) into a hydrothermal reaction kettle, preserving the heat for 5-12 hours at the temperature of 175-225 ℃, and then cooling to room temperature;
(4) adding sodium hydroxide into the solution obtained in the step (3) to enable the pH value of the solution to be 7-9, then adding d mmol of sodium borohydride into the solution, and stirring the solution vigorously for 2-3 hours, wherein d is 4.5-11, and d: c is 1-1.1;
(5) And (4) collecting black precipitates from the solution obtained in the step (4) by a centrifugal separation method, and washing the black precipitates for 3-5 times by using deionized water to finally obtain the carbon-point hybrid mesoporous nickel boride photocatalyst.
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| CN107715881B true CN107715881B (en) | 2019-12-17 |
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| CN108682857B (en) * | 2018-06-14 | 2020-11-06 | 商丘师范学院 | Preparation method of porous flower flake lithium battery positive electrode material |
| US10888845B1 (en) * | 2020-07-17 | 2021-01-12 | King Abdulaziz University | Graphene-tungsten oxide-metal boride/hydroxide photocatalysts, and methods for organic pollutant degradation and hydrogen production |
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| CN102560290A (en) * | 2010-12-24 | 2012-07-11 | 国家纳米技术与工程研究院 | Nano nickel boride (NiB) amorphous alloy and preparation method thereof |
| CN105056953B (en) * | 2015-08-26 | 2018-01-30 | 辽宁石油化工大学 | A kind of preparation method of magnetic spinel loading NiB catalyst |
| CN105478142B (en) * | 2015-11-19 | 2018-08-10 | 江苏大学 | A kind of indium sulfide meso-porous hollow microsphere photocatalyst and its preparation method and application |
| CN106521679A (en) * | 2016-11-22 | 2017-03-22 | 广州居安照明科技有限公司 | Application of carbon dot @ inorganic oxide to preparation of anti-ultraviolet product |
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