CN112456612A - Copper-doped carbon nitride electrode, preparation method and application thereof - Google Patents
Copper-doped carbon nitride electrode, preparation method and application thereof Download PDFInfo
- Publication number
- CN112456612A CN112456612A CN202011269253.0A CN202011269253A CN112456612A CN 112456612 A CN112456612 A CN 112456612A CN 202011269253 A CN202011269253 A CN 202011269253A CN 112456612 A CN112456612 A CN 112456612A
- Authority
- CN
- China
- Prior art keywords
- copper
- carbon nitride
- doped carbon
- acid
- electrode
- 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
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000006013 carbendazim Substances 0.000 claims abstract description 50
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims abstract description 45
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 25
- 150000001879 copper Chemical class 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract description 30
- 238000006731 degradation reaction Methods 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 7
- 239000007832 Na2SO4 Substances 0.000 abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 241000894007 species Species 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000005746 Carboxin Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GYSSRZJIHXQEHQ-UHFFFAOYSA-N carboxin Chemical compound S1CCOC(C)=C1C(=O)NC1=CC=CC=C1 GYSSRZJIHXQEHQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a copper-doped carbon nitride electrode, a preparation method and application thereof. The invention adopts the methods of precursor synthesis, calcination, coating and the like when preparing the copper-doped carbon nitride electrode, loads the synthesized copper-doped carbon nitride material on the surface of a graphite flake, does not need any template or catalyst in the preparation process, has simple process and low cost, takes the copper-doped carbon nitride electrode as a cathode, takes the graphite flake as an anode and contains Na2SO4The mixed solution of the carbendazim and the electrolyte solution forms a cathode electro-Fenton system for degrading the carbendazim, and the degradation efficiency is high.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a copper-doped carbon nitride electrode, a preparation method and application thereof.
Background
With the development of modern industry, the varieties of artificially synthesized refractory Organic Pollutants (POPs) are increasing, mainly come from the industries of petrochemical industry, medicine, pesticide synthesis, printing and dyeing and the like, and the toxicity is high, especially dyes, antibiotic medicines and the like can generate toxicity to a municipal sewage biological treatment system, so that the POPs are difficult to degrade by a biological method. Therefore, the exploration of an economical and effective treatment method for treating the POPs-containing wastewater from the source is urgent.
The electro-Fenton method combines electrochemistry with the Fenton reaction to reduce dissolved oxygen at the cathode to continuously produce H2O2And with Fe in solution2+The catalyst reacts to generate strong oxidant hydroxyl free radical (OH), which is a powerful technology for degrading and even mineralizing the organic pollutants. The electro-Fenton method has high degradation efficiency on pollutants, does not directly degrade the pollutants, but reduces dissolved oxygen to generate a strong oxidation substance to realize degradation, and simultaneously has low energy consumption and ideal economic cost because the content of the dissolved oxygen is not high. However, H2O2The yield of the product is low, and the product is one of the main factors restricting the application of the electro-Fenton method. In electro-Fenton's process H2O2The amount of the produced (C) depends on the cathode material, and therefore, the study of the cathode material is one of the most active fields of study of the electro-Fenton technique.
Graphite phase carbon nitride (g-C)3N4) Is the most stable carbon nitride allotrope, and in its structure, C, N atoms are all sp2The material is hybridized to form a plane conjugated structure, is a graphite-like two-dimensional layered material, and has the characteristics of good chemical thermal stability, acid and alkali resistance, no toxicity, easily obtained raw materials, convenience for modification and the like. In addition, in g-C3N4The abundance of "nitrogen basins" consisting of six nitrogen atoms in the sheet provides many active trapping sites to encapsulate metal ions. Thus, modified g-C3N4Is a cathode material with research significance.
Disclosure of Invention
Aiming at the defect of poor catalytic effect of the conventional cathode material in the electro-Fenton process, the invention provides a copper-doped carbon nitride electrode, a preparation method and application thereof.
In order to solve the problems, the invention adopts the technical scheme that:
the copper-doped carbon nitride electrode comprises a graphite sheet substrate electrode and copper-doped carbon nitride coated on the surface of the graphite sheet substrate electrode, wherein the copper-doped carbon nitride is prepared by calcining a precursor of the copper-doped carbon nitride.
Specifically, the preparation of the copper-doped carbon nitride precursor comprises the steps of dissolving a copper salt in strong acid to obtain a mixed solution, then adding the carbon nitride precursor into the mixed solution, filtering, washing and drying filter residues to obtain the copper-doped carbon nitride precursor, wherein the carbon nitride precursor comprises one or more of melamine or urea.
Specifically, the copper salt comprises one or more of copper chloride, copper nitrate and copper acetate, the strong acid comprises one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid and chloric acid, the molar ratio of the copper salt to the carbon nitride precursor is (0-4): 4, and the amount of the substance of the copper salt is not 0.
Specifically, the mass fraction of the strong acid is 35-39%, and the calcining temperature is 500-600 ℃.
A method for preparing a copper-doped carbon nitride electrode is used for preparing the copper-doped carbon nitride electrode, and comprises the following steps:
step 1: dissolving a copper salt in strong acid to obtain a mixed solution, then adding melamine into the mixed solution, filtering and washing, and drying filter residues to obtain a precursor of the copper-doped carbon nitride;
step 2: calcining the precursor of the copper-doped carbon nitride, and cooling to obtain the copper-doped carbon nitride;
and step 3: and adding a perfluorosulfonic acid polymer solution and absolute ethyl alcohol into the copper-doped carbon nitride, grinding the mixture into paste, coating the paste on a graphite sheet, and drying the graphite sheet to obtain the copper-doped carbon nitride electrode.
Further, the copper salt comprises one or more of copper chloride, copper nitrate and copper acetate, and the strong acid comprises one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid and chloric acid.
Furthermore, the molar ratio of the copper salt to the carbon nitride precursor is (0-4): 4, wherein the amount of the copper salt is not 0, the calcination temperature is 500-600 ℃, and the calcination time is 2-4 h.
Further, the mass fraction of the strong acid is 35-39%, the drying temperature is 79-93 ℃, and the drying time is more than 12 hours.
The application of the copper-doped carbon nitride electrode comprises the step of forming a cathode electro-Fenton system by using the copper-doped carbon nitride electrode as a cathode, using a graphite sheet as an anode and using carbendazim waste liquid as an electrolyte solution to degrade carbendazim.
The application of the copper-doped carbon nitride electrode prepared by the preparation method of the copper-doped carbon nitride electrode comprises the step of forming a cathode electro-Fenton system by using the copper-doped carbon nitride electrode as a cathode, a graphite sheet as an anode and carbendazim waste liquid as an electrolyte solution to degrade carbendazim.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) when the copper-doped carbon nitride electrode is prepared, the method of synthesizing a precursor, calcining, coating and the like is adopted, the synthesized copper-doped carbon nitride material is loaded on the surface of a graphite flake, no template or catalyst is needed in the preparation process, and the method has the advantages of simple process and low cost.
(2) The effective area of the copper-doped carbon nitride electrode prepared by the invention is 40 multiplied by 20 multiplied by 2mm, the prepared copper-doped carbon nitride electrode is taken as a cathode, a bare graphite sheet is taken as an anode, and the copper-doped carbon nitride electrode comprises 0.05 mol.L-1Na2SO4And 10 mg. L-1The mixed solution of the carbendazim is an electrolyte solution, and a cathode electro-Fenton system is formed.
(3) The invention firstly mixesThe copper carbon nitride is applied to the field of electrocatalysis, the persistent organic pollutant carbendazim is degraded by adopting the constructed cathode electro-Fenton system, and the optimal condition for degrading the carbendazim is explored. On the basis that the loading amount of the copper-doped carbon nitride is 0.01g, when the molar ratio of the copper-doped carbon nitride precursor to the copper-doped carbon nitride precursor is 3: 4, the pH of the solution was 3, and the degradation current density was 2.50mA cm-2The degradation efficiency of the system to carbendazim is highest, and can reach 95.4% in 180 min.
(4) The copper-doped carbon nitride is coated on the graphite sheet, so that the material is stably attached and is not easy to fall off.
Drawings
FIG. 1 is a graph showing the degradation rate of a CuCN-0.01/GF electrode on carbendazim in example 1 of the present invention;
FIG. 2 is a graph showing the degradation rate of a CuCN-0.02/GF electrode on carbendazim in example 2 of the present invention;
FIG. 3 is a graph showing the degradation rate of CuCN-0.03/GF electrode on carbendazim in example 3 of the present invention;
FIG. 4 is a graph showing the degradation rate of carbendazim by CuCN-0.04/GF electrodes in example 4 of the present invention;
FIG. 5 is a graph showing the degradation rate of carbendazim by CuCN-0.00/GF electrodes in example 5 of the present invention;
FIG. 6 is a graph summarizing the degradation rates of the copper-doped carbon nitride electrodes of examples 1 to 5 of the present invention to carbendazim;
Detailed Description
The copper-doped carbon nitride electrode prepared by the invention adopts a calcination method and a coating method to load the copper-doped carbon nitride on a graphite sheet, the graphite sheet is taken as a matrix electrode, and the copper-doped carbon nitride is taken as a hierarchical structure material of a load material.
The copper-doped carbon nitride is prepared by a calcination method, and is prepared by calcining a precursor of the copper-doped carbon nitride. The volume of the concentrated acid, the ratio of the copper salt to the amount of the carbon nitride precursor, the temperature rise time of calcination, the calcination time, the calcination temperature and other reaction factors are controlled.
The copper-doped carbon nitride electrode is obtained by adopting a coating method and controlling factors such as the loading capacity of the copper-doped carbon nitride, the volume of Nafion solution, the drying time and the temperature of the coating uniformity and the like, and the preparation process does not need any catalyst, has simple process, low cost and good degradation effect on carbendazim; the graphite flakes adopted by the invention are from Qingdao Baofeng graphite products Limited.
The Nafion solution is a perfluorosulfonic acid type polymer solution, forming a membrane electrode, and serves as a coating layer and a carrier of the catalyst.
Carbendazim, methyl-1H-2-benzimidazole carbamate, also known as cotton carboxin, benzimidazole number 44. The carbendazim bactericide is a broad-spectrum bactericide, can be used for foliar spraying, seed treatment, soil treatment and the like of crops, has a control effect on crop diseases caused by fungi (such as adelomycetes and polycystic fungi), generates process wastewater in condensation, centrifugation and dehydration processes of a carbendazim product, and mainly comprises water, a small amount of carbendazim and ammonia nitrogen (NH 3-N).
As the case may be, in the present invention, the carbendazim waste liquid is defined to contain Na2SO4And simulating the carbendazim waste liquid by using the mixed solution of the carbendazim and the carbendazim.
The preparation method of the copper-doped carbon nitride electrode comprises the following steps:
step 1: dissolving a copper salt in strong acid to obtain a mixed solution, then adding a carbon nitride precursor into the mixed solution, filtering and washing, and drying filter residues to obtain a copper-doped carbon nitride precursor;
step 2: calcining the precursor of the copper-doped carbon nitride, and cooling to obtain the copper-doped carbon nitride;
and step 3: and adding a perfluorosulfonic acid polymer solution and absolute ethyl alcohol into the copper-doped carbon nitride, grinding the mixture into paste, coating the paste on a graphite sheet, and drying the graphite sheet to obtain the copper-doped carbon nitride electrode.
The copper-doped carbon nitride represents the amount of Cu ion in the preparation process according to the different copper-doped amount of CuCN-x (x ranges from 0 to 0.04, and x is not 0), for example, in example 1, CuCl2·2H2The amount of O was 0.01mol and the amount of the carbon nitride precursor was 0.04mol, and the copper-doped carbon nitride obtained in this case was designated as CuCN-0.01.
In the specific application of the method, the adhesive is coated on the surface of the substrate,the prepared copper-doped carbon nitride electrode is taken as a cathode, a graphite sheet is taken as an anode, and Na is contained2SO4Mixed solution of carbendazim and carbendazim (0.05 mol. L)-1Na2SO4，10mg·L-1Carbendazim, pH 3) as electrolyte solution to form cathode electro-Fenton system for degrading carbendazim. The copper carbon nitride electrode promotes the generation of hydrogen peroxide, and then combines with ferrous ions to generate hydroxyl radicals, so that the degradation efficiency is improved. The Fenton method uses Fe2+And H2O2The reaction generates strong oxidizing OH which has high oxidation potential and no selectivity, so the OH can degrade and oxidize various organic pollutants.
In order to make the objects and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
the embodiment provides a preparation method of a copper-doped carbon nitride electrode, which specifically comprises the following steps:
step 1: pretreatment of graphite flakes
Sequentially polishing (100 × 20 × 2mm) graphite sheets (GF) with coarse and fine sand paper, ultrasonically cleaning with deionized water, concentrated acid, ethanol and deionized water for 4 times, 5min each time, and drying for later use;
step 2: preparation of copper-doped carbon nitride precursor
Dissolving a copper salt in strong acid (hydrochloric acid) to obtain a mixed solution, then adding a carbon nitride precursor (melamine) into the mixed solution, filtering and washing, and drying filter residues to obtain a copper-doped carbon nitride precursor;
the method specifically comprises the following steps: 0.01mol (1.7048g) of CuCl are added at room temperature22H2O was dissolved in 150mL 37% hydrochloric acid to form a dark green solution. Slowly adding 0.04mol (5.0488g) of melamine into the above solution under continuous stirring, gradually dissolving white melamine powder to obtain yellow powder, stirring thoroughly, filtering with 45 μm filter membrane and 37% hydrochloric acid, washing, and passing the obtained residue through filterDried overnight in a hood.
And step 3: preparation of copper-doped carbon nitride by calcination method
Loading the precursor of the copper-doped carbon nitride obtained in the step 2 into a porcelain boat with a cover, and carrying out air treatment at the temperature of 10 ℃ for min-1Heating to 500 ℃ from room temperature (30 ℃), keeping the temperature for 2 hours for calcination, and then cooling to room temperature at the same speed to obtain a black solid, namely the copper-doped carbon nitride, which is recorded as CuCN-0.01;
and 4, step 4: preparation of copper-doped carbon nitride electrode
And (3) weighing 0.01g of CuCN-0.01 prepared in the step (3) in an agate mortar, adding 30 mu L of Nafion solution and absolute ethyl alcohol, fully grinding the mixture to be pasty, then coating the paste on a graphite sheet, and drying the graphite sheet to obtain the copper-doped carbon nitride electrode. Specifically, the slurry was uniformly applied to a graphite sheet (100X 20X 2mm) with a brush pen in an area of 40X 20 mm. And drying the coated CuCN-0.01/GF electrode in an oven at the temperature of 80 ℃ for more than 12 hours.
The prepared copper-doped carbon nitride electrode is taken as a cathode, a graphite sheet is taken as an anode, and Na is contained2SO4Mixed solution of carbendazim and carbendazim (0.05 mol. L)-1Na2SO4，10mg·L-1Carbendazim, pH 3) as electrolyte solution to form cathode electro-Fenton system, and introducing oxygen (0.5 L.min)-1) Constant current (20mA) degradation is carried out, 2mL of samples are taken every 30min, the degradation result is shown in figure 1, and the degradation rate reaches 75.8% in 150 min.
Example 2:
step 1 is the same as in example 1
Step 2: preparation of copper-doped carbon nitride precursor
0.02mol (3.4096g) of CuCl are added at room temperature22H2O was dissolved in 150mL of 37% hydrochloric acid to form a dark green solution. 0.04mol (5.0488g) of melamine were slowly added to the above solution with continuous stirring. The white powder gradually dissolved, yielding a yellow powder. After stirring well, the mixture was washed by filtration through a 45 μm filter and 37% hydrochloric acid, and the resulting residue was dried overnight in a fume hood.
And step 3: preparation of copper-doped carbon nitride by calcination method
Loading the precursor in step 2 into a porcelain boat with a cover, and carrying out air treatment at 15 ℃ for min-1After calcination at a rate of 3h from room temperature (30 ℃) to 500 ℃ and cooling at the same rate to room temperature, a black solid was obtained, noted as CuCN-0.02.
And 4, step 4: preparation of copper-doped carbon nitride electrode
0.01g of CuCN-0.02 (0.01 g) prepared in step 3 was weighed in an agate mortar, 30. mu.L of Nafion solution and a certain amount of anhydrous ethanol were added, and the mixture was sufficiently ground into a paste. The slurry was uniformly applied to a graphite sheet (100X 20X 2mm) with a brush pen in an area of 40X 20 mm. And drying the coated CuCN-0.02/GF electrode in an oven at the temperature of 80 ℃ for more than 12 hours.
Taking the copper-doped carbon nitride electrode prepared in the step 4 as a cathode, taking a graphite sheet as an anode and taking Na2SO4Mixed solution of carbendazim and carbendazim (0.05 mol. L)-1Na2SO4，10mg·L-1Carbendazim, pH 3) as electrolyte solution to form cathode electro-Fenton system, and introducing oxygen (0.5 L.min)-1) Constant current (20mA) degradation is carried out, 2mL of samples are taken every 30min, the degradation result is shown in figure 2, and the degradation rate reaches 90.8% at 240 min.
Example 3:
step 1 is the same as in example 1
Step 2 differs from example 1 in that: CuCl22H2The amount of O species was 0.03mol (5.1144g) and the amount of melamine species was 0.04mol (5.0488 g).
Step 3 differs from example 1 in that: in air at 20 deg.C for min-1Heating from room temperature (30 ℃) to 500 ℃ for 4h, and cooling to room temperature at the same rate gave a black solid, noted CuCN-0.03.
Step 4 is the same as in example 1.
Taking the copper-doped carbon nitride electrode prepared in the step 4 as a cathode, taking a graphite sheet as an anode and taking Na2SO4Mixed solution of carbendazim and carbendazim (0.05 mol. L)-1Na2SO4，10mg·L-1Carbendazim, pH 3) as electrolyte solution to form cathode electro-Fenton systemOxygen conditions (0.5 L.min)-1) Constant current (20mA) degradation is carried out, 2mL of samples are taken every 30min, the degradation result is shown in figure 3, and the degradation rate reaches 95.4% in 180 min.
Example 4:
step 1 is the same as in example 1
Step 2 differs from example 1 in that: CuCl22H2The amount of O species was 0.04mol (6.8192g) and the amount of melamine species was 0.04mol (5.0488 g).
Step 3 differs from example 1 in that: in air at 5 deg.C for min-1Heating from room temperature (30 ℃) to 500 ℃ for 4h, and cooling to room temperature at the same rate gave a black solid, noted CuCN-0.04.
Step 4 is the same as in example 1.
Taking the copper-doped carbon nitride electrode prepared in the step 4 as a cathode, taking a graphite sheet as an anode and taking Na2SO4Mixed solution of carbendazim and carbendazim (0.05 mol. L)-1Na2SO4，10mg·L-1Carbendazim, pH 3) as electrolyte solution to form cathode electro-Fenton system, and introducing oxygen (0.5 L.min)-1) Constant current (20mA) degradation is carried out, 2mL of samples are taken every 30min, the degradation result is shown in figure 4, and the degradation rate reaches 88.6% at 150 min.
Example 5
The same as example 1, except that copper salt is cupric nitrate, strong acid is nitric acid, precursor of carbon nitride is urea, calcining temperature is 550 ℃, calcining time is 2.5h, and heating rate is 10 ℃ for min-1。
Example 6
The difference from the example 2 is that copper salt is copper acetate, strong acid is high manganese acid, carbon nitride precursor is urea, the calcining temperature is 580 ℃, the calcining time is 3.5h, and the heating rate is 15 ℃ for min-1。
Example 7
The difference from the example 2 is that copper salt is copper acetate, strong acid is perchloric acid, carbon nitride precursor is urea, the calcining temperature is 560 ℃, the calcining time is 2h, and the temperature rise rate is 18 ℃ for min-1。
Comparative example 1:
similar to example 1, but different from example 1, CuCl is not added in the synthesis of the precursor of copper-doped carbon nitride in step 222H2And O, the concentration of copper ions in the precursor is 0.
The degradation rate of the product to carbendazim is shown in figure 5, and the degradation rate of the system to carbendazim under the condition can be obviously reduced, and the degradation rate is only 60.6%.
Comparative example 2
Similar to example 1, but different from example 1, in step 2, CuCl was added to the synthesis of the copper-doped carbon nitride precursor22H2The amount of O species was 0.05 mol.
The degradation rate of the product to carbendazim is lower than that of the product CuCN-0.03 to carbendazim.
In conclusion, the calcining method and the coating method adopted by the invention have the advantages of simple preparation process, high yield, low cost and good degradation effect on carbendazim.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The copper-doped carbon nitride electrode is characterized by comprising a graphite sheet substrate electrode and copper-doped carbon nitride coated on the surface of the graphite sheet substrate electrode, wherein the copper-doped carbon nitride is prepared by calcining a precursor of the copper-doped carbon nitride.
2. The copper-doped carbon nitride electrode according to claim 1, wherein the preparation of the copper-doped carbon nitride precursor comprises dissolving a copper salt in a strong acid to obtain a mixed solution, adding a carbon nitride precursor into the mixed solution, filtering, washing, and drying filter residues, wherein the carbon nitride precursor comprises one or more of melamine or urea.
3. The copper-doped carbon nitride electrode according to claim 2, wherein the copper salt comprises one or more of copper chloride, copper nitrate and copper acetate, the strong acid comprises one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid and chloric acid, the molar ratio of the copper salt to the carbon nitride precursor is (0-4): 4, and the amount of the copper salt is different from 0.
4. The copper-doped carbon nitride electrode as claimed in claim 1, wherein the mass fraction of the strong acid is 35-39%, the calcination temperature is 500-600 ℃, and the calcination time is 2-4 h.
5. A method for preparing a copper-doped carbon nitride electrode, which is used for preparing the copper-doped carbon nitride electrode as claimed in any one of claims 1 to 4, and comprises the following steps:
step 1: dissolving a copper salt in strong acid to obtain a mixed solution, then adding a carbon nitride precursor into the mixed solution, filtering and washing, and drying filter residues to obtain a copper-doped carbon nitride precursor;
step 2: calcining the precursor of the copper-doped carbon nitride, and cooling to obtain the copper-doped carbon nitride;
and step 3: and adding a perfluorosulfonic acid polymer solution and absolute ethyl alcohol into the copper-doped carbon nitride, grinding the mixture into paste, coating the paste on a graphite sheet, and drying the graphite sheet to obtain the copper-doped carbon nitride electrode.
6. The method of claim 5, wherein the copper salt comprises one or more of copper chloride, copper nitrate, and copper acetate, and the strong acid comprises one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid, and chloric acid.
7. The copper-doped carbonitride electrode of claim 5The preparation method is characterized in that the molar ratio of the copper salt to the carbon nitride precursor is (0-4): 4, wherein the amount of the copper salt is not 0, the calcination temperature is 500-600 ℃, the calcination time is 2-4 h, and the heating rate is 3-20 ℃ for min-1。
8. The method for preparing the copper-doped carbon nitride electrode according to claim 5, wherein the mass fraction of the strong acid is 35-39%, the drying temperature is 79-93 ℃, and the drying time is more than 12 h.
9. The application of the copper-doped carbon nitride electrode as recited in any one of claims 1 to 4, wherein the application comprises the step of forming a cathode electro-Fenton system by using the copper-doped carbon nitride electrode as a cathode, using a graphite sheet as an anode and using carbendazim waste liquid as an electrolyte solution to degrade carbendazim.
10. The application of the copper-doped carbon nitride electrode prepared by the preparation method of the copper-doped carbon nitride electrode according to any one of claims 5 to 8 is characterized in that the application comprises the step of forming a cathode electro-Fenton system by using the copper-doped carbon nitride electrode as a cathode, using a graphite sheet as an anode and using carbendazim waste liquid as an electrolyte solution to degrade carbendazim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011269253.0A CN112456612A (en) | 2020-11-13 | 2020-11-13 | Copper-doped carbon nitride electrode, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011269253.0A CN112456612A (en) | 2020-11-13 | 2020-11-13 | Copper-doped carbon nitride electrode, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112456612A true CN112456612A (en) | 2021-03-09 |
Family
ID=74825639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011269253.0A Pending CN112456612A (en) | 2020-11-13 | 2020-11-13 | Copper-doped carbon nitride electrode, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112456612A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940532A (en) * | 2022-06-17 | 2022-08-26 | 燕山大学 | Modified carbon nitride/foam copper cathode, preparation method and application of modified carbon nitride/foam copper cathode in phenol wastewater treatment of electro-Fenton system |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103713030A (en) * | 2013-12-24 | 2014-04-09 | 江苏大学 | Preparation method and application of graphite type carbon nitride nano-rod modified electrode |
| CN105129921A (en) * | 2015-08-26 | 2015-12-09 | 中国科学院生态环境研究中心 | Preparation method for visible light responsive C3N4 thin film electrode |
| CN106404860A (en) * | 2016-08-30 | 2017-02-15 | 济南大学 | Production method and electrochemiluminescence sensing application of carbon nitride modified three-dimensional graphite electrode |
| CN106732741A (en) * | 2016-11-29 | 2017-05-31 | 滨州学院 | The visible light catalyst of dyestuff and its preparation and application in a kind of degrading waste water |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN107570190A (en) * | 2017-07-26 | 2018-01-12 | 湖南大学 | The preparation method of carbon doping carbon nitride films electrode |
| CN108993570A (en) * | 2018-07-30 | 2018-12-14 | 南京工业大学 | Preparation method and application of copper-doped graphite-phase carbon nitride composite material |
| CN109731603A (en) * | 2019-01-23 | 2019-05-10 | 河南师范大学 | A kind of universality method and its application of the nitrogen-doped carbon catalyst controllable with single pore-foaming agent preparation pore size |
| CN110773222A (en) * | 2019-11-13 | 2020-02-11 | 河南师范大学 | Universal preparation method and application of hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis |
| KR20200072288A (en) * | 2018-12-12 | 2020-06-22 | (주) 테크로스 | Method of reducing scale of cathode for electrolysis of ballast water |
-
2020
- 2020-11-13 CN CN202011269253.0A patent/CN112456612A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103713030A (en) * | 2013-12-24 | 2014-04-09 | 江苏大学 | Preparation method and application of graphite type carbon nitride nano-rod modified electrode |
| CN105129921A (en) * | 2015-08-26 | 2015-12-09 | 中国科学院生态环境研究中心 | Preparation method for visible light responsive C3N4 thin film electrode |
| CN106404860A (en) * | 2016-08-30 | 2017-02-15 | 济南大学 | Production method and electrochemiluminescence sensing application of carbon nitride modified three-dimensional graphite electrode |
| CN106732741A (en) * | 2016-11-29 | 2017-05-31 | 滨州学院 | The visible light catalyst of dyestuff and its preparation and application in a kind of degrading waste water |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN107570190A (en) * | 2017-07-26 | 2018-01-12 | 湖南大学 | The preparation method of carbon doping carbon nitride films electrode |
| CN108993570A (en) * | 2018-07-30 | 2018-12-14 | 南京工业大学 | Preparation method and application of copper-doped graphite-phase carbon nitride composite material |
| KR20200072288A (en) * | 2018-12-12 | 2020-06-22 | (주) 테크로스 | Method of reducing scale of cathode for electrolysis of ballast water |
| CN109731603A (en) * | 2019-01-23 | 2019-05-10 | 河南师范大学 | A kind of universality method and its application of the nitrogen-doped carbon catalyst controllable with single pore-foaming agent preparation pore size |
| CN110773222A (en) * | 2019-11-13 | 2020-02-11 | 河南师范大学 | Universal preparation method and application of hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis |
Non-Patent Citations (3)
| Title |
|---|
| 宋志伟等: "水污染控制工程", 31 July 2013, 中国矿业大学出版社, pages: 111 - 112 * |
| 张锋;李金兵;: "铜修饰的石墨氮化碳材料催化甲苯液相氧化反应", 广东化工, vol. 44, no. 12, pages 127 - 128 * |
| 赵一方: "电芬顿体系中阴极材料的制备及其对有机污染物的降解", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(月刊), no. 06, pages 1 - 3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940532A (en) * | 2022-06-17 | 2022-08-26 | 燕山大学 | Modified carbon nitride/foam copper cathode, preparation method and application of modified carbon nitride/foam copper cathode in phenol wastewater treatment of electro-Fenton system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | An etching and re-growth method for the synthesis of bismuth ferrite/MIL-53 (Fe) nanocomposite as efficient photocatalyst for selective oxidation of aromatic alcohols | |
| Gao et al. | Enhanced photocatalytic removal of amoxicillin with Ag/TiO 2/mesoporous gC 3 N 4 under visible light: property and mechanistic studies | |
| CN108786809B (en) | Titanium dioxide nanosheet photocatalyst and preparation method and application thereof | |
| WO2019223051A1 (en) | Method for promoting coking wastewater treatment by photocatalytic electrode coupled microbial fuel cell | |
| CN110639592B (en) | Boron and nitrogen doped carbon porous nanosheet supported transition metal nanoparticle material catalyst and preparation method and application thereof | |
| He et al. | Synergistic reduction of U (VI) and selective oxidation of benzyl alcohol to prepare benzaldehyde via WOx/g-C3N4 | |
| CN114669299B (en) | Mesoporous carbon-loaded copper-iron bimetallic catalyst and preparation method and application thereof | |
| Li et al. | Ammonia-nitrogen removal from water with gC3N4-rGO-TiO2 Z-scheme system via photocatalytic nitrification-denitrification process | |
| CN112517081B (en) | Composite photocatalyst of metallic tin porphyrin axial functionalization titanium dioxide and preparation method thereof | |
| CN115805072B (en) | Supported AgPt alloy photocatalyst and preparation method and application thereof | |
| CN113235113B (en) | Hollow carbon-coated copper oxide nanoparticle catalyst and preparation method and application thereof | |
| CN111992233A (en) | Core-shell nitrogen-doped iron metal nanoparticle, preparation method and electrocatalysis application thereof | |
| WO2023222142A1 (en) | Photocatalytic material for degrading pyridine, modified photocatalytic filler, and preparation methods therefor and use thereof | |
| CN112007677A (en) | Nitrogen-doped iron nanotube, and preparation method and application thereof | |
| CN110237853B (en) | Gadolinium chromate/silver phosphate composite photocatalyst and application thereof in VOCs purification | |
| CN115739103A (en) | Visible light photocatalytic material CuO x @BiVO 4 And preparation method and application thereof | |
| Barakat et al. | CoNi nanoparticles/CNT composite as effective anode for direct urea fuel cells | |
| CN112456612A (en) | Copper-doped carbon nitride electrode, preparation method and application thereof | |
| CN113198515B (en) | Ternary photocatalyst and preparation method and application thereof | |
| CN113968602A (en) | Method for removing nitrified nitrogen in water through electro-catalysis | |
| CN116713023A (en) | Preparation method and application of carbon nitride photocatalyst | |
| CN115805091B (en) | Preparation method of copper-silver double single-atom photocatalyst | |
| CN110902770A (en) | Fe based on carbon cloth3O4/C, Fe/C, preparation and application thereof | |
| CN111807474A (en) | Preparation method of phosphorus-doped cobalt nanowire array for nitrate-nitrogen reduction in water | |
| CN115569658A (en) | CABB/UCNT heterojunction composite photocatalyst and preparation method and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210309 |