CN112337464A - Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst - Google Patents
Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst Download PDFInfo
- Publication number
- CN112337464A CN112337464A CN202011109889.9A CN202011109889A CN112337464A CN 112337464 A CN112337464 A CN 112337464A CN 202011109889 A CN202011109889 A CN 202011109889A CN 112337464 A CN112337464 A CN 112337464A
- Authority
- CN
- China
- Prior art keywords
- metal
- light
- precursor
- porous carbon
- doped porous
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005118 spray pyrolysis Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 239000012159 carrier gas Substances 0.000 claims abstract description 8
- 238000000889 atomisation Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 21
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical group [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 9
- 229940012189 methyl orange Drugs 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000004408 titanium dioxide Substances 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a spray pyrolysis preparation method of a metal-doped porous carbon-based visible-light-induced photocatalyst, which comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving in deionized water to form a precursor solution; carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas, and pyrolyzing for 1-2s to form a material precursor; cooling the material precursor and collecting; the invention also discloses a synthesis system for implementing the method and application of the photocatalytic material prepared by the method in catalytic degradation treatment of the dye. The catalyst material has the advantages that the raw materials required by the preparation of the catalyst material are cheap and easy to obtain, the subsequent large-scale utilization is facilitated, the synthesis steps are simple, and the catalyst material can be prepared by one-step pyrolysis after the precursor solution is prepared; the catalyst material can also greatly improve the utilization rate of sunlight, reduce the occurrence of light corrosion and greatly improve and maintain the specific surface area of the catalyst material.
Description
Technical Field
The invention relates to the field of preparation of porous carbon material photocatalysts, in particular to a spray pyrolysis preparation method, a synthesis system and application of a metal-doped porous carbon-based visible-light-induced photocatalyst.
Background
The photocatalyst is a generic name for a semiconductor material having a photocatalytic function represented by nano-sized titanium dioxide. In the case of titanium dioxide, it can generate a substance having a strong oxidizing property (e.g., hydroxyl radical, oxygen gas, etc.) under light irradiation, and can be used for decomposing organic compounds, partially inorganic compounds, bacteria, viruses, etc. However, the existing photocatalytic materials have the following disadvantages: (1) the existing photocatalytic material has low light utilization efficiency, for example, the traditional titanium dioxide-based photocatalyst can only well utilize the light in an ultraviolet band; (2) the existing photocatalytic material has photo-corrosion, and the material can be decomposed and damaged after being used for a period of time, so that the service life of the catalyst is greatly reduced; (3) the specific surface area of the existing photocatalyst material is insufficient, and the specific surface area is also greatly reduced after agglomeration, so that the catalyst cannot be fully and effectively utilized.
In addition, a carbon-based porous material hydrothermal method can be adopted to prepare the photocatalytic material, but the conventional hydrothermal method for synthesizing the carbon-based porous material is that all raw materials are directly put into a reaction kettle for reaction, subsequent carbon materials are required to be cleaned, ground, sieved and the like, so that the stability and uniformity of a sample cannot be ensured, and an additional modification step is required to be carried out during subsequent metal and heteroatom doping, which is very tedious.
Disclosure of Invention
The invention aims to provide a spray pyrolysis preparation method, a synthesis system and application of a metal-doped porous carbon-based visible-light-induced photocatalyst.
The invention realizes the purpose through the following technical scheme:
a spray pyrolysis preparation method of a metal-doped porous carbon-based visible-light-induced photocatalyst comprises the following steps
The method comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving in deionized water to form a precursor solution;
step two: carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas, and pyrolyzing for 1-2s to form a catalyst material precursor;
step three: and cooling the catalyst material precursor, collecting, cleaning and modifying to obtain the metal-doped porous carbon-based visible-light-induced photocatalyst material.
The further improvement is that the mass ratio of each component in the precursor solution is 0.5-5% of carbon source material, 0.5-5% of pore-forming agent and 0.1-2% of metal salt solution.
The further improvement is that the carbon source material is sucrose.
In a further improvement, the pore-forming agent is sodium carbonate or sodium chloride.
In a further improvement, the metal salt solution is copper sulfate.
The further improvement is that the carrier gas adopts nitrogen with the flow rate of 0.1-5L/min.
The further improvement is that the temperature of the pyrolysis is 600-800 ℃.
The further improvement is that in the third step, the collected catalyst material precursor is soaked and washed by dilute hydrochloric acid to adjust the surface potential, and after the soaking and washing are completed, the catalyst material precursor is separated, cleaned and dried.
The invention provides a synthesis system for implementing the method, which comprises a spraying device, a pyrolysis device and a collection device, wherein the spraying device consists of a spraying container, an ultrasonic atomizer arranged in the spraying container and a nitrogen tank connected with the spraying container, the collection device is connected with the spraying container through a pipeline, the pyrolysis device is a tubular furnace, and the tubular furnace is arranged on a connecting pipeline between the collection device and the spraying container.
The invention provides an application of a metal-doped porous carbon-based visible-light-induced photocatalyst prepared by the method in catalytic degradation of a dye, wherein the dye is methyl orange, methylene blue or Congo red and the like.
The invention has the beneficial effects that:
1) the synthesis steps are simple, the photocatalyst material can be prepared by one-step pyrolysis after the precursor solution is prepared, and the subsequent operations of cleaning, grinding, sieving and the like and the additional modification operation during the doping of metal and heteroatom are omitted;
2) the traditional photocatalyst mostly utilizes titanium dioxide, the band gap of the titanium dioxide is 3.1-3.2eV, only ultraviolet band light can be utilized, the sunlight utilization efficiency is low, the method loads copper oxide and cuprous oxide nanoparticles with the band gap of 1.2-2.2eV on the surface of the nano-scale porous carbon material through a one-step pyrolysis synthesis method, so that the band gap of the prepared catalyst material is reduced, and the utilization rate of sunlight is greatly improved;
3) the carbon material has a stable structure, and the carbon material is used as a catalyst substrate, so that the occurrence of light corrosion can be greatly reduced, the stable work of the catalyst is ensured, and the service life is prolonged;
4) the nanoscale porous carbon has rich porous structures, the specific surface area of the catalyst material can be greatly increased, and the surface electronegativity of the catalyst material particles can be improved through the loading of metal and corresponding modification adjustment, so that the catalyst material is prevented from agglomerating, and the higher specific surface area is kept in the whole reaction process;
5) the catalyst material can be used for harmless degradation treatment of dyes and other organic pollutants;
6) the raw materials required by the preparation of the catalyst material are cheap and easy to obtain, and the catalyst material is convenient for subsequent large-scale utilization.
Drawings
FIG. 1 is a TEM image of a visible-light-induced photocatalyst prepared by the one-step pyrolysis method of the present invention;
FIG. 2 is a schematic diagram of a spray pyrolysis preparation system of a metal-doped porous carbon-based visible light catalyst;
FIG. 3 is a graph showing the degradation curve of a visible light catalyst methyl orange;
in the figure: 1. a pyrolysis device; 2. a collection device; 3. a spray container; 4. an ultrasonic atomizer; 5. a nitrogen tank; 6. a pipeline.
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst comprises the following steps:
the method comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving the mixture in deionized water to form a precursor solution, wherein the mass ratio of each component in the precursor solution is 0.5% of the carbon source material, 0.5% of the pore-forming agent and 0.1% of the metal salt solution;
step two: carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas (nitrogen with the flow rate of 0.1L/min), and pyrolyzing the precursor liquid for 1.5s at 700 ℃ to form a catalyst material precursor;
step three: and cooling the material precursor, collecting, and soaking and washing the collected material precursor by using dilute hydrochloric acid to adjust the surface potential, improve the dispersibility and prevent subsequent aggregation, and separating, cleaning and drying the precursor material after the soaking and washing are finished.
Example 2
The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst comprises the following steps:
the method comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving the mixture in deionized water to form a precursor solution, wherein the mass ratio of each component in the precursor solution is 5% of the carbon source material, 5% of the pore-forming agent and 1% of the metal salt solution;
step two: carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas (nitrogen with the flow rate of 2L/min), and pyrolyzing the precursor liquid for 2s at 600 ℃ to form a catalyst material precursor;
step three: and cooling the material precursor, collecting, and soaking and washing the collected material precursor by using dilute hydrochloric acid to adjust the surface potential, improve the dispersibility and prevent subsequent aggregation, and separating, cleaning and drying the precursor material after the soaking and washing are finished.
Example 3
The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst comprises the following steps:
the method comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving the mixture in deionized water to form a precursor solution, wherein the mass ratio of each component in the precursor solution is 2% of the carbon source material, 2% of the pore-forming agent and 2% of the metal salt solution;
step two: carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas (nitrogen with the flow rate of 5L/min), and pyrolyzing the precursor liquid for 1s at 800 ℃ to form a catalyst material precursor;
step three: cooling and collecting the material precursor, soaking and washing the collected material precursor with dilute hydrochloric acid to adjust surface potential, improving dispersibility and preventing subsequent aggregation, separating, cleaning and drying the precursor material after soaking and washing, and obtaining a TEM image of the photocatalyst sample as shown in FIG. 1
In the above embodiment, the carbon source material is sucrose, the pore-forming agent is sodium carbonate, and the metal salt solution is copper sulfate. Of course, in the implementation process of the present invention, the carbon source material, the pore-forming agent, and the metal salt solution may be selected from other substances as needed, for example, the carbon source material may also be selected from glucose, maltose, glycerol, and the like, the pore-forming agent may also be selected from ammonium bicarbonate, calcium carbonate, and the like, and the metal salt solution may also be selected from cerium nitrate, zinc chloride, manganese sulfate, iron nitrate, lanthanum nitrate, praseodymium nitrate, and the like, all of which are within the protection scope of the present invention.
Example 4
As shown in fig. 2, a synthesis system for implementing the above method comprises a spraying device, a pyrolysis device 1 and a collection device 2, wherein the spraying device is composed of a spraying container 3, an ultrasonic atomizer 4 arranged in the spraying container 3 and a nitrogen tank 5 connected to the spraying container 3, the collection device 2 is connected with the spraying container 3 through a pipeline 6, the pyrolysis device 1 is a tubular furnace, and the tubular furnace is arranged on the connecting pipeline 6 between the collection device 2 and the spraying container 3.
This synthesis system is at the during operation, pack into spray container 3 with the prepared precursor liquid earlier, start ultrasonic atomizer 4, become the liquid droplet with precursor liquid ultrasonic atomization, open the discharge valve of nitrogen gas jar 5 simultaneously, in nitrogen gas lets in spray container 3 with certain speed, in nitrogen gas can carry the atomizing liquid droplet and get into pyrolysis device 1 through pipeline 6, pyrolysis device 1 heats the pyrolysis, forms the catalyst material precursor, is cooled down and is collected by collection device 2 at last.
Example 5
The application of the metal-doped porous carbon-based visible-light-induced photocatalyst prepared by the method in catalytic degradation of dyes is methyl orange, methylene blue, Congo red or the like, and can be used for degrading other organic pollutants.
In order to verify the catalytic degradation efficiency of the catalyst material prepared by the invention, a photocatalytic degradation contrast test of methyl orange is carried out as follows:
preparing a catalyst sample prepared in example 2, titanium dioxide and methyl orange into 0.01g/L of dispersion liquid a, b and c respectively;
mixing 5ml of the dispersion liquid a and b with 5ml of the solution c to obtain samples d and e;
thirdly, the solution d and the solution e are subjected to dark ultrasound for 60min to achieve adsorption balance;
exposure to 150000Lx sunlight after 60 min;
sampling at intervals, centrifuging, taking supernatant, filtering and measuring the concentration of methyl orange.
The degradation curve prepared based on the measured concentration of methyl orange is shown in fig. 3, and the experimental results show that the catalyst material prepared in example 2 (i.e., the "sample" curve in the figure) has better photocatalytic effect than titanium dioxide, mainly indicated that the catalyst material prepared in example 2 can degrade methyl orange faster, the time required for reaching 30% degradation rate is about 200min shorter than that of titanium dioxide, and the final degradation rate is 32% higher than that of titanium dioxide.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst is characterized by comprising the following steps of: the method comprises the steps of
The method comprises the following steps: mixing a carbon source material, a pore-forming agent and a metal salt solution, and dissolving in deionized water to form a precursor solution;
step two: carrying out ultrasonic atomization on the precursor liquid, then sending the precursor liquid into pyrolysis equipment along with carrier gas, and pyrolyzing for 1-2s to form a catalyst material precursor;
step three: and cooling the catalyst material precursor, collecting, cleaning and modifying to obtain the metal-doped porous carbon-based visible-light-induced photocatalyst material.
2. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the mass ratio of each component in the precursor solution is 0.5-5% of carbon source material, 0.5-5% of pore-forming agent and 0.1-2% of metal salt solution.
3. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the carbon source material is sucrose.
4. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the pore-forming agent is sodium carbonate or sodium chloride.
5. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the metal salt solution is copper sulfate.
6. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the carrier gas adopts nitrogen with the flow rate of 0.1-5L/min.
7. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: the temperature of the pyrolysis is 600-800 ℃.
8. The spray pyrolysis preparation method of the metal-doped porous carbon-based visible-light-induced photocatalyst according to claim 1, characterized in that: and in the third step, the collected material precursor is soaked and washed by dilute hydrochloric acid to adjust the surface potential, and after the soaking and washing are finished, the catalyst material precursor is separated, cleaned and dried.
9. A synthesis system for carrying out the method of any one of claims 1 to 8, wherein: the synthesis system comprises a spraying device, a pyrolysis device and a collecting device, wherein the spraying device comprises a spraying container, an ultrasonic atomizer arranged in the spraying container and a nitrogen tank connected to the spraying container, the collecting device is connected with the spraying container through a pipeline, the pyrolysis device selects a tubular furnace, and the tubular furnace is arranged on a connecting pipeline between the collecting device and the spraying container.
10. Use of a metal-doped porous carbon-based visible-light-induced photocatalyst prepared by the method according to any one of claims 1 to 8 in dye-catalyzed degradation, wherein: the dye is methyl orange, methylene blue or Congo red.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011109889.9A CN112337464A (en) | 2020-10-16 | 2020-10-16 | Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011109889.9A CN112337464A (en) | 2020-10-16 | 2020-10-16 | Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112337464A true CN112337464A (en) | 2021-02-09 |
Family
ID=74360950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011109889.9A Pending CN112337464A (en) | 2020-10-16 | 2020-10-16 | Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112337464A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282973A (en) * | 2022-08-11 | 2022-11-04 | 中国科学院上海高等研究院 | 3D printing-based monolithic catalyst, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107138A (en) * | 2009-12-25 | 2011-06-29 | 中国科学院海洋研究所 | Photocatalyst, preparation method and application thereof |
| CN103240089A (en) * | 2013-05-21 | 2013-08-14 | 淮北师范大学 | Solid-phase mechanical-chemical preparation method of nano Cu2O photocatalyst |
| KR20150033338A (en) * | 2013-09-24 | 2015-04-01 | 서강대학교산학협력단 | Carbon-doped metal oxide-containing porous structure, preparing method of the same, and photocatalyst including the same |
| CN107754797A (en) * | 2017-11-29 | 2018-03-06 | 山东大学 | A kind of nanometer Cu2O@porous carbon composite photocatalyst materials and preparation method thereof |
| CN110790254A (en) * | 2019-11-12 | 2020-02-14 | 湖南大学 | Method for preparing porous carbon materials with different morphologies by ultrasonic spray pyrolysis regulation and control |
| CN110921647A (en) * | 2019-12-10 | 2020-03-27 | 合肥工业大学 | Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof |
-
2020
- 2020-10-16 CN CN202011109889.9A patent/CN112337464A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107138A (en) * | 2009-12-25 | 2011-06-29 | 中国科学院海洋研究所 | Photocatalyst, preparation method and application thereof |
| CN103240089A (en) * | 2013-05-21 | 2013-08-14 | 淮北师范大学 | Solid-phase mechanical-chemical preparation method of nano Cu2O photocatalyst |
| KR20150033338A (en) * | 2013-09-24 | 2015-04-01 | 서강대학교산학협력단 | Carbon-doped metal oxide-containing porous structure, preparing method of the same, and photocatalyst including the same |
| CN107754797A (en) * | 2017-11-29 | 2018-03-06 | 山东大学 | A kind of nanometer Cu2O@porous carbon composite photocatalyst materials and preparation method thereof |
| CN110790254A (en) * | 2019-11-12 | 2020-02-14 | 湖南大学 | Method for preparing porous carbon materials with different morphologies by ultrasonic spray pyrolysis regulation and control |
| CN110921647A (en) * | 2019-12-10 | 2020-03-27 | 合肥工业大学 | Hard carbon microsphere with adjustable morphology and pore structure, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张爱健，: ""多孔碳基固体磺酸颗粒的可控制备与应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 谢艳春，: ""纳米Cu2O及其复合材料的制备及性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282973A (en) * | 2022-08-11 | 2022-11-04 | 中国科学院上海高等研究院 | 3D printing-based monolithic catalyst, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015149499A1 (en) | Low-temperature and highly efficient denitration catalyst and preparation method therefor | |
| CN108554412B (en) | Preparation method and application of large-size high-porosity Fe-doped photocatalytic magnetic porous microspheres | |
| CN106944092B (en) | A kind of preparation method of the Fe-MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs | |
| CN110124660A (en) | A kind of Z- mechanism Bi rich in Lacking oxygen2O3@CeO2Photochemical catalyst and the preparation method and application thereof | |
| CN109174141A (en) | A kind of preparation method of composite Nano catalysis material | |
| CN104772110A (en) | Visible-light response type air purifier photo-catalyst filter screen and preparation method thereof | |
| CN110575832A (en) | Preparation method and application of silver-titanium dioxide-nano diamond composite photocatalyst | |
| WO2022047813A1 (en) | Organic wastewater treatment method based on multi-element co-doped tio2 nano photocatalytic material | |
| CN105148972A (en) | Preparation method and application of novel catalyst for reducing nitrate nitrogen in water under visible light condition | |
| CN106475125A (en) | Graphite phase carbon nitride and nano titanium oxide composite coating additive and preparation method | |
| CN106031869A (en) | A BiVO4/TiO2 composite nanorod having visible light activity, and preparation and applications thereof | |
| CN108479762A (en) | A kind of manganese oxide catalyst and its preparation method and application | |
| CN108722464A (en) | It is a kind of using nitrogen-doped titanium dioxide as Pd triple effect low temperature catalysts of carrier and its preparation method and application | |
| CN113000046A (en) | Modified manganese-based mullite catalyst for synergistic purification of nitrogen oxides and volatile organic compounds, and preparation method and application thereof | |
| CN105771953A (en) | Preparation method of zinc titanate and titanium dioxide composite nano material | |
| CN111974374A (en) | Preparation method of biochar modified nano ZnO composite powder | |
| CN112337464A (en) | Spray pyrolysis preparation method, synthesis system and application of metal-doped porous carbon-based visible-light-induced photocatalyst | |
| WO2020093517A1 (en) | Photocatalytic material for efficient and selective reduction and removal of nitrate nitrogen in water, and preparation method thereof | |
| CN110354845A (en) | A kind of bismuth tungstate photocatalyst and its preparation method and application of carbon nano dot modification | |
| CN110124648A (en) | A kind of surface Lacking oxygen TiO2The preparation method of/carbon composite nanotube | |
| CN108993501A (en) | A kind of silver-silver oxide-zinc oxide photocatalysis material preparation method | |
| CN114471707B (en) | Hydrogel sphere containing catalyst, preparation method thereof and application thereof in photocatalytic treatment of organic pollutants | |
| CN107321361B (en) | Denitration catalyst for improving low-temperature activity and preparation method thereof | |
| CN100377778C (en) | Titanium oxide photocatalyst stimulated by visible light and synthesis method thereof | |
| CN111013622B (en) | Z-type graphitized carbon nitride/carbon/sulfur-doped graphitized carbon nitride composite material and preparation method thereof |
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 |