CN116726934A - LDH composite catalytic material and preparation method and application thereof - Google Patents
LDH composite catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116726934A CN116726934A CN202310693925.8A CN202310693925A CN116726934A CN 116726934 A CN116726934 A CN 116726934A CN 202310693925 A CN202310693925 A CN 202310693925A CN 116726934 A CN116726934 A CN 116726934A
- Authority
- CN
- China
- Prior art keywords
- catalytic material
- mxene
- composite catalytic
- salt
- ldh
- 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
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 30
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- -1 salt nickel salt Chemical class 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 239000002872 contrast media Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 34
- 230000015556 catabolic process Effects 0.000 abstract description 30
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- YVPYQUNUQOZFHG-UHFFFAOYSA-N amidotrizoic acid Chemical compound CC(=O)NC1=C(I)C(NC(C)=O)=C(I)C(C(O)=O)=C1I YVPYQUNUQOZFHG-UHFFFAOYSA-N 0.000 description 37
- 229960005223 diatrizoic acid Drugs 0.000 description 37
- 230000004913 activation Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000012425 OXONE® Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 9
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000009303 advanced oxidation process reaction Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000003642 reactive oxygen metabolite Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910019233 CoFeNi Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012216 imaging agent Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003589 nefrotoxic effect Effects 0.000 description 1
- 210000000944 nerve tissue Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an LDH composite catalytic material and a preparation method and application thereof, wherein the composite catalytic material comprises a carrier MXene and metal hydroxide loaded on the carrier, and the metal is nickel, cobalt and iron; the preparation method comprises the following steps: (1) Dissolving metal salt nickel salt, cobalt salt, ferric salt and urea in an alcohol solution, uniformly stirring, then adding MXene, and continuously and uniformly stirring to obtain a suspension; (2) Carrying out solvothermal synthesis reaction on the suspension, and filtering, washing and drying after the reaction is finished to obtain a product; the MXene is introduced into the LDH, the LDH grows between and on the surface of the MXene layer, so that the LDH composite catalytic material has a stabilizing effect, metal ions are reduced from precipitating, metal hydroxide aggregation is avoided, the stability and catalytic activity of the catalytic material are improved, the efficient degradation of organic pollutants in wastewater is realized through a free radical and non-free radical path, and the persulfate catalytic activity and the stability of the material are superior to those of the LDH.
Description
Technical Field
The invention relates to a catalytic material, in particular to an LDH composite catalytic material and a preparation method and application thereof.
Background
More and more studies have demonstrated the widespread presence of drugs in the aquatic environment over the last decades, raising concerns about their impact on the aquatic ecosystem and on human health. Among them, iodinated X-ray contrast agents (ICMs) as medical imaging agents are frequently detected in hospital and domestic sewage, wastewater from treatment plants, surface water, groundwater and even drinking water. To ensure imaging contrast, ICMs are designed as inert and highly soluble drugs that are widely used due to their stable imaging properties and low toxicity to vessel walls and nerve tissue. However, such drugs may be the major sources of iodine for iodotrihalomethanes (iodo-THMs) and iodo disinfection byproducts (I-DBPs), which are harmful to mammals due to their high genotoxicity and cytotoxicity, and their long-term accumulation will adversely affect human health. Diatrizoic acid (DTZ), one of the most widely used ICMs at present, is a pharmaceutical compound for organ or vessel imaging. DTZ has been used as a control compound since the 50 s of the 20 th century, and is excreted from organisms within a few hours after administration, but is not metabolized, explaining that it can be detected in an aqueous environment. DTZ is very resistant to biodegradation and has high polarity and high biochemical stability, and is difficult to remove from water by conventional sewage treatment processes and drinking water plants. There is little current research data on the environmental risk of ICMs, but there have been studies showing that DTZ may have nephrotoxic effects on animals and humans.
Advanced oxidation techniques (AOPs) are used to produce free radicals (e.g., hydroxyl radicals (. OH), superoxide radicals (. O) 2 - ) Sulfate radical (. SO) 4 - ) For effectively eliminating pollutants, the method has received attention because of the advantages of simple operation, mild reaction conditions, high efficiency and the like. AOPs degrade organic contaminant molecules into small non-toxic compounds by the action of Reactive Oxygen Species (ROS). In recent years, various AOPs technology such as Fenton/Fenton-like reaction, electrocatalytic, ozone oxidation and the like have been developed in the field of water treatment. However, the disadvantages of the traditional AOPs such as poor stability, acid and alkali resistance, poor adaptability and the like prevent the wide applicability. To overcome the above disadvantages, the method comprises activating the peroxide disulphate (S 2 O 8 2- PDS) or peroxomonosulphate (HSO) 5 - PMS) persulfate advanced oxidation processes (PS-AOPs) are receiving increasing attention. With sulfate radicals (. SO) 4 - ) The main radical route has a higher redox potential (2.5-3.1V), a longer service life (30-40. Mu.s) and a wider pH range, and is of great interest (2.0-9.0). On the other hand, three main non-radical pathways such as electron transfer processes, singlet oxygenation 1 O 2) And high-valence metal induced oxidation have also been widely studied and reported. With free radicals to oxidizeIn comparison, it has several advantages: (1) Electron rich organic contaminants tend to be highly selective in catalytic degradation; (2) When wastewater with complex components is treated, the catalytic efficiency of a non-radical oxidation system is still high despite the coexistence of inorganic anions and Natural Organic (NOMs); (3) In comparison with conventional AOPs, peroxide can be effectively utilized during the non-radical reaction, and the stoichiometric ratio between the consumed persulfate and the target organic pollutant is very low (4) by adjusting the structure and composition of the catalyst, the reaction pathway and redox potential of the non-radical system can be further optimized. In general, PMS with longer O-O bonds and asymmetric structures are more easily activated than PDS, producing more active species, but the activation efficiency is still low. Most of the current activation methods are generally long, inefficient, complex to operate and require a large amount of energy, limiting their application. Heterogeneous transition metals are considered to be effective catalysts for activating PMS because of their low energy consumption, simple reaction configuration, and rich earth resources. To date, various transition metal ions (activation performance: ni 2+ <Fe 3+ <Mn 2+ <V 3+ <Ce 3+ <Fe 2+ <Ru 3+ <Co 2+ ) It has been demonstrated that PMS can be activated effectively. However, the catalytic performance of these metal ions is greatly affected by pH, and is still difficult to recycle during PMS activation, which is prone to secondary pollution.
Layered Double Hydroxides (LDHs) are a typical transition metal-based material, consisting of a layered structure of two layers of metal hydroxides, the layers of which are made up of positively charged octahedral divalent and trivalent metal hydroxides, wherein anions are sandwiched in a repetitive manner in the positively charged metal layers, keeping them electrically neutral. The general structural formula is [ M ] 2+ (1-x) M 3+ x (OH) 2 ] x+ ·[A n- x/n ]·mH 2 O, where M 2+ And M 3+ Are divalent and trivalent metal cations coordinated to hydroxide anions, A n- Represents an interlayer anion, and x represents a proportion of a trivalent metal cation (generally in the range of 0.2 to 0.33). Due to its unique advantages: (1) Low cost and production processThe process is simple; (2) Flexible chemical composition (e.g., number of layers, metal species, metal ratio, etc.); (3) The structure is stable, and the fixing effect on toxic metal ions is good; (4) The diversity of morphology may expose more active sites. LDHs have been tried to degrade environmental pollutants by making various heterogeneous catalysts that are efficient and structurally stable, and have been explored for many environmental applications such as adsorption, catalysis, photoelectrocatalysis, etc.
However, although a variety of conventional synthetic methods exist, such as: anion exchange, co-precipitation, solution mixing and hydrothermal reactions have been used for LDHs production, but the uncontrollability and complexity of these techniques make it difficult to obtain homogeneous catalysts with controlled morphology, and therefore a simple and efficient method is needed to synthesize well organized layer structures and controlled morphology. Furthermore, LDHs have the unavoidable disadvantage: (1) metal precipitation, secondary pollution; (2) single material and low efficiency; (3) Electrostatic agglomeration and low electron conductivity are still considered inherent drawbacks of LDHs, which greatly reduce the exposed sites and overall catalytic activity of the material. The above disadvantages limit the use of LDHs in PS-AOPs.
Disclosure of Invention
The invention aims to: a first object of the present invention is to provide an LDH composite catalytic material which enhances the catalytic activity of an LDH material for activating persulfate; a second object of the present invention is to provide a process for the preparation of the LDH composite catalytic material; a third object of the present invention is to provide the use of said LDH composite catalytic material for activating persulfate to degrade organic dyestuffs.
The technical scheme is as follows: the LDH composite catalytic material comprises a carrier MXene and metal hydroxide loaded on the MXene.
Preferably, the MXene material is Ti 3 C 2 . The MXene material is purchased from Nanjing Mingchun new material technology Co.
Preferably, the metals are nickel, cobalt and iron, wherein the molar ratio of the nickel, the cobalt and the iron is 1:1-5:3.
The preparation method of the LDH composite catalytic material comprises the following steps:
(1) Dissolving metal salt nickel salt, cobalt salt, ferric salt and urea in an alcohol solution, uniformly stirring, then adding MXene, and continuously and uniformly stirring to obtain a suspension;
(2) And (3) carrying out solvothermal synthesis reaction on the suspension obtained in the step (1), and filtering, washing and drying after the reaction is finished to obtain the layered metal hydroxide composite catalytic material.
Preferably, in the step (1), the mass ratio of the metal salt to the MXene is 30:1-5. The enhancement effect of the catalyst is not obvious by the smaller content of MXene, and the metal catalytic center of the layered metal hydroxide is covered; higher amounts of MXene added will result in uneven growth of layered metal hydroxides on the MXene, resulting in reduced catalytic performance.
Preferably, in the step (1), the mass ratio of the urea to the metal salt is 1-5:1. Urea is used as precipitant and decomposed at high temperature to provide OH - And CO 3 2- ，CO 3 2- As interlayer anions, the composite material keeps electric neutrality, the stability of the LDH composite material is enhanced, and the insufficient urea content can lead to OH - And CO 3 2- The production amount is insufficient, and the synthesis of the layered metal hydroxide is incomplete.
Preferably, in the step (1), the nickel salt is one of nickel chloride, nickel sulfate, nickel nitrate or nickel hydroxide; the cobalt salt is one of cobalt nitrate, cobalt sulfate or cobalt chloride; the ferric salt is one of ferric chloride, ferric sulfate or ferric nitrate.
Preferably, in step (1), the alcohol solution is ethanol or methanol.
Preferably, in the step (2), the temperature of the solvothermal synthesis reaction is 100-150 ℃. In the solvothermal synthesis reaction process, MXene with negatively charged surface adsorbs metal ions in solution and OH generated at high temperature - Reacts with the metal of the surface of the MXene to form a metal hydroxide, so that the MXene serves as a substrate, and the layered metal hydroxide grows between and in the surface thereof.
Preferably, in the step (2), the drying temperature is 40-80 ℃.
The LDH composite catalytic material is applied to the degradation of organic pollutants by activated persulfate.
The organic contaminant is an iodinated X-ray contrast agent.
The mechanism of the invention is as follows: the invention takes MXene as a substrate, and the layered metal hydroxide can grow on the surface and between layers. As the high-conductivity MXene is used as a substrate, the conductivity of the catalytic material can be enhanced, and as the MXene has larger specific surface area, developed pore structure and rich functional groups including hydroxyl radicals, carboxyl radicals, epoxy radicals and the like, metal ions can be adsorbed by oxygen-containing groups such as hydroxyl radicals on the surface of the MXene in the LDH synthesis process so as to grow, the LDH grows between the MXene layers and on the surface, the MXene has a stabilizing effect, the arrangement of metal active sites is optimized, the precipitation of the metal ions is reduced, the stability and the catalytic activity of the catalytic material are improved, and the efficient activation of persulfate can be realized so as to improve the degradation rate of pollutants. The CoFeNi layered metal hydroxide is uniformly distributed by the good pore structure and mechanical strength of MXene to avoid agglomeration, so that the recycling is facilitated.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The MXene is introduced into the layered metal hydroxide, and the MXene interlayer and surface are grown by the LDH to play a role in stabilizing, so that the precipitation of metal ions is reduced, the agglomeration of the metal hydroxide is avoided, and the stability and catalytic activity of the catalytic material are improved; (2) The preparation method is simple, green and environment-friendly, and is easy for industrialization; (3) The catalyst material is used for activating persulfate to degrade organic pollutants, and high-efficiency activation of persulfate is realized, so that the degradation rate of the pollutants is improved.
Drawings
FIG. 1 is Ti 3 C 2 Scanning electron microscope images of the material;
FIG. 2 is a scanning electron microscope image of the catalytic material prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the catalytic material prepared in example 1;
FIG. 4 shows the different Ti's prepared in examples 1-3 3 C 2 The effect of the catalytic material prepared by the addition amount for degrading pollutants by activating the peroxymonosulfate is compared with a graph;
FIG. 5 is a graph showing the comparison of the pollutant degradation effects of the activation of peroxymonosulfate by different catalytic materials;
FIG. 6 is a graph showing the effect of the catalytic material prepared in example 1 on the degradation of pollutants by cyclic activation of peroxymonosulfate;
FIG. 7 is a graph showing the catalytic activation effect of different mass catalytic materials on peroxymonosulfate;
FIG. 8 is a graph showing the catalytic activation effect of the same mass of catalytic material on monosulfate at different concentrations.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
The LDH composite catalytic material of the invention, the carrier MXene is a multilayer Ti 3 C 2 The molar ratio of nickel, cobalt and iron in the metal hydroxide is 1:3:3, the preparation method comprises the following steps:
(1) 36.35mg (2.5 mM) of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、109.14mg(7.5mM)Co(NO 3 ) 2 ·6H 2 O and 151.5mg (7.5 mM) Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 50ml of ethanol solution, 0.99g of urea is added, the mixture is stirred until the urea is completely dissolved, 30mg of MXene is added, and the mixture is stirred uniformly for standby;
(2) Adding the mixed solution obtained in the step (1) into an autoclave, carrying out hydrothermal synthesis reaction at 120 ℃ for 12 hours, taking out the composite material obtained in the process after the reaction is finished, filtering, repeatedly cleaning with ethanol solution, and putting into an oven for drying at 60 ℃ for 10 hours to obtain the LDH composite catalytic material.
Example 2
On the basis of example 1, ti in step (1) was changed 3 C 2 The mass of (2) was 10mg, the remaining conditions were unchanged.
Example 3
On the basis of example 1, ti in step (1) was changed 3 C 2 The mass of (2) was 50mg, the remaining conditions were unchanged.
Example 4
The layered metal hydroxide composite catalytic material of the invention, the carrier MXene is a multilayer Ti 3 C 2 The molar ratio of nickel, cobalt and iron in the metal hydroxide is 1:1:3, the preparation method comprises the following steps:
(1) 36.35mg (2.5 mM) of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、36.38mg(2.5mM)Co(NO 3 ) 2 ·6H 2 O and 151.5mg (7.5 mM) Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 50ml of ethanol solution, 0.99g of urea is added, the mixture is stirred until the urea is completely dissolved, 30mg of MXene is added, and the mixture is stirred uniformly for standby;
(2) Adding the mixed solution obtained in the step (1) into an autoclave, carrying out hydrothermal synthesis reaction at 100 ℃ for 12 hours, taking out the composite material obtained in the process after the reaction is finished, filtering, repeatedly cleaning with ethanol solution, and putting into an oven for drying at 40 ℃ for 10 hours to obtain the LDH composite catalytic material.
Example 5
The layered metal hydroxide composite catalytic material of the invention, the carrier MXene is a multilayer Ti 3 C 2 The molar ratio of nickel, cobalt and iron in the metal hydroxide is 1:5:3, the preparation method comprises the following steps:
(1) 36.35mg (2.5 mM) of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、181.9mg(12.5mM)Co(NO 3 ) 2 ·6H 2 O and 151.5mg (7.5 mM) Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 50ml of ethanol solution, 0.99g of urea is added, the mixture is stirred until the urea is completely dissolved, 30mg of MXene is added, and the mixture is stirred uniformly for standby;
(2) Adding the mixed solution obtained in the step (1) into an autoclave, carrying out hydrothermal synthesis reaction at 150 ℃ for 12 hours, taking out the composite material obtained in the process after the reaction is finished, filtering, repeatedly cleaning with ethanol solution, and putting into an oven for drying at 80 ℃ for 10 hours to obtain the LDH composite catalytic material.
Comparative example 1
Based on example 1, no Ti was added 3 C 2 The remaining conditions are unchanged.
Comparative example 2
On the basis of example 1, ti in step (1) was changed 3 C 2 The mass of (2) was 70mg, the remaining conditions were unchanged.
Structural characterization
For unreacted Ti 3 C 2 The catalytic material prepared in example 1 and the catalytic material prepared in comparative example 1 were characterized and the results are shown in fig. 1.
From FIG. 1, unreacted Ti 3 C 2 Is an accordion-like irregular block (length and width are about 20×15×10 μm).
As can be taken from FIG. 2, the single layered metal hydroxide prepared in comparative example 1 was a regular sphere composed of a layered structure, with a diameter of about 4. Mu.m.
As can be taken from FIG. 3, the layered metal hydroxide in the catalytic material prepared in example 1 successfully grows on Ti 3 C 2 And the growth of layered metal hydroxide does not destroy Ti 3 C 2 Is accordion-like, the addition of the layered metal hydroxide being such that Ti 3 C 2 The interlayer spacing increases, which provides a larger specific surface area for peroxymonosulfate activation, increasing the reactive sites.
Characterization of Performance
(1) Activity of catalytically activated persulfates of the LDH composite catalytic material of the present invention
The testing method comprises the following steps: preparing a simulated wastewater solution containing 10mg/LDTZ, taking 100mL of simulated wastewater into a reactor, adding 0.03g of potassium monopersulfate powder, and then adding 0.003g of the catalytic material prepared in examples 1-3, wherein the magnetic stirring speed is 800r/min, and the reaction time is 15min. The concentration of DTZ was analyzed by high performance liquid chromatography during the reaction, and the test results are shown in FIG. 2.
As can be seen from fig. 4, the time required for the catalytic materials of examples 1 to 3 to activate the potassium monopersulfate persulfate to degrade DTZ to 100% is 8min, 15min, and 12min, respectively.
Using the catalytic materials prepared in example 1, comparative example 1 and comparative example 2, comparative group 1 was set to equal mass of Ti 3 C 2 The powder was used to replace the catalytic material, the control group 2 was not added with potassium monopersulfate, the control group 3 was not added with any substance that activates persulfate, the degradation effect on DTZ was tested, the test method was the same as above, and the test results are shown in fig. 3.
As can be taken from fig. 5, the degradation rate of DTZ reaches 100% when the catalytic material of example 1 activates the degradation reaction of potassium monopersulfate for 8 min; the degradation rate of DTZ is 78.50% when the catalytic material prepared in comparative example 1 activates the degradation reaction of potassium monopersulfate for 15 min; the degradation rate of DTZ can reach 100% when the catalytic material prepared in comparative example 2 activates the potassium monopersulfate to degrade for 15 min; ti (Ti) 3 C 2 The degradation rate of DTZ is only 83.8% when the powder activates the potassium monopersulfate to degrade for 15 min; the degradation rate of DTZ is only 2.65% when potassium monopersulfate is not added for degradation reaction for 15 min; the degradation rate of DTZ is only 2.25% when the potassium monopersulfate is activated for 15min without any substance. Compared with comparative example 1, no Ti was added 3 C 2 Metal hydroxide catalytic material of (2) comparative example 2 with addition of excess Ti 3 C 2 Metal hydroxide catalytic material of (2) and pure Ti of control group 1 3 C 2 Layered metal hydroxide prepared by the invention and Ti 3 C 2 The composite catalyst is used for activating the peroxymonosulfate and has higher removal efficiency on DTZ wastewater. Layered metal hydroxide and Ti 3 C 2 On the one hand, the specific surface area of the material is increased after the composition, so that more active sites are provided for the activation of the peroxymonosulfate; on the other hand, ti having high conductivity 3 C 2 The electron transfer performance of the composite material can be improved, and the activation of the peroxymonosulfate is facilitated, so that the degradation rate of the DTZ is accelerated; in addition, ti 3 C 2 The amount of metal precipitated as a substrate can be reduced to improve the stability of the material. The composite catalyst has good application potential in the field of treating iodized X-ray contrast agent wastewater by activating the peroxymonosulfate.
(2) Cycle test
To verify the stability of the composite catalytic material synthesized according to the present invention, repeated experiments were performed, using the catalytic material prepared in example 1, washed with ultra pure water after use, and dried at 60 ℃ in a vacuum oven before the next cycle.
As shown in fig. 6, the catalytic material prepared in example 1 was examined for its effect on degradation of DTZ in four runs. The result shows that the composite catalyst has good stability in the degradation process, and can reach 100% degradation rate within 15min in four times of cyclic use.
(3) Catalytic activation effect of different catalytic material masses on persulfate
The degradation effect of the catalyst material prepared in example 1 on DTZ was tested by using the materials for catalyzing and activating persulfate, the test method was the same as above, and the addition amounts of the catalysts were changed to 0.001g,0.002g, 0.003g, 0.004g and 0.005g, respectively, and the test results are shown in FIG. 7.
As can be seen from fig. 7, the addition amounts of the catalytic materials were 0.001g, respectively, and the degradation rate of DTZ was 68.25% at 15 min; the addition amount of the catalytic materials is 0.002g respectively, and the degradation rate of the DTZ is 83.00% when the reaction is carried out for 15 min; the addition amount of the catalytic materials is 0.003g respectively, and the degradation rate of the DTZ is 100% in 8min of reaction; the addition amount of the catalytic materials is 0.004g respectively, and the degradation rate of the DTZ is 84.00% when the reaction is carried out for 15 min; the addition amount of the catalytic materials is 0.005g respectively, and the degradation rate of the DTZ is 88.85% when the reaction is carried out for 15min. The increase of the adding amount of the catalyst provides more reactive sites for the system, which is beneficial to the activation of persulfate to generate free radicals (such as SO 4 - OH, etc.), thus increasing the degradation rate of DTZ. However, when the catalyst dosage is increased from 0.003g/L to 0.005g/L, the reaction rate is not further improved, and the degradation efficiency is reduced. It is possible that PMS is rapidly activated due to excessive catalyst amount, a large amount of active material is generated, and PMS vs. SO4 is generated - Quenching of (2) and SO4 - Is self-quenched.
(4) Catalytic activation effect of equal mass catalytic material mass on persulfates with different concentrations
The degradation effect of the catalytic material prepared in example 1 on DTZ was tested by using the same method as above, and the initial concentration of DTZ was changed to 5mg/L, 10mg/L, 15mg/L, 20mg/L and 30mg/L, and the test results are shown in FIG. 8.
As can be obtained from FIG. 8, the initial concentration of DTZ is 5mg/L, and the degradation rate of DTZ can reach 100% in 2min of reaction; the initial concentration of the DTZ is 10mg/L, and the degradation rate of the DTZ can reach 100% in 8min of reaction; the initial concentration of the DTZ is 15mg/L, and the degradation rate of the DTZ can reach 96.20% in 15min of reaction; the initial concentration of the DTZ is 25mg/L, and the degradation rate of the DTZ can reach 92.40% when the reaction is carried out for 15min. With increasing initial concentration of DTZ, the system generates insufficient reactive oxygen species to react with the excess contaminants, and the large amount of intermediate products generated during the reaction may compete with DTZ for free radicals, and further, at higher concentrations of ATZ, intimate contact between the catalyst active sites and PMS is hindered, so that the percentage of DTZ removed per unit time is reduced as a function of the initial concentration.
Claims (10)
1. An LDH composite catalytic material comprising a support MXene and a metal hydroxide supported on MXene.
2. The LDH composite catalytic material of claim 1, wherein the MXene material is Ti 3 C 2 。
3. The LDH composite catalytic material of claim 1, wherein the metals are nickel, cobalt, and iron, and wherein the molar ratio of nickel, cobalt, and iron is from 1:1 to 5:3.
4. A method of preparing an LDH composite catalytic material in accordance with claim 1, comprising the steps of:
(1) Dissolving metal salt nickel salt, cobalt salt, ferric salt and urea in an alcohol solution, uniformly stirring, then adding MXene, and continuously and uniformly stirring to obtain a suspension;
(2) And (3) carrying out solvothermal synthesis reaction on the suspension obtained in the step (1), and filtering, washing and drying after the reaction is finished to obtain the layered metal hydroxide composite catalytic material.
5. The method for producing an LDH composite catalytic material according to claim 4, wherein in step (1), the mass ratio of the metal salt to MXene is 30:1 to 5.
6. The process for preparing an LDH composite catalytic material according to claim 4, wherein in step (2), the temperature of the solvothermal synthesis reaction is 100 to 150 ℃.
7. The process for preparing an LDH composite catalytic material according to claim 4, wherein in step (1), the mass ratio of urea to metal salt is 1 to 5:1.
8. The method for producing an LDH composite catalytic material according to claim 4, wherein in step (1), the nickel salt is one of nickel chloride, nickel sulfate, nickel nitrate or nickel hydroxide; the cobalt salt is one of cobalt nitrate, cobalt sulfate or cobalt chloride; the ferric salt is one of ferric chloride, ferric sulfate or ferric nitrate.
9. Use of an LDH composite catalytic material according to any of claims 1-3 for activating persulfate to degrade organic contaminants.
10. The use according to claim 9, wherein the organic contaminant is an iodinated X-ray contrast agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310693925.8A CN116726934A (en) | 2023-06-12 | 2023-06-12 | LDH composite catalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310693925.8A CN116726934A (en) | 2023-06-12 | 2023-06-12 | LDH composite catalytic material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116726934A true CN116726934A (en) | 2023-09-12 |
Family
ID=87900648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310693925.8A Pending CN116726934A (en) | 2023-06-12 | 2023-06-12 | LDH composite catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116726934A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118006195A (en) * | 2024-03-11 | 2024-05-10 | 国网吉林省电力有限公司四平供电公司 | Preparation method of anti-friction self-repairing conductive anticorrosive paint and paint |
-
2023
- 2023-06-12 CN CN202310693925.8A patent/CN116726934A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118006195A (en) * | 2024-03-11 | 2024-05-10 | 国网吉林省电力有限公司四平供电公司 | Preparation method of anti-friction self-repairing conductive anticorrosive paint and paint |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Roy et al. | Mechanistic investigation of photocatalytic degradation of Bisphenol-A using MIL-88A (Fe)/MoS2 Z-scheme heterojunction composite assisted peroxymonosulfate activation | |
| Zhang et al. | High-efficiency removal of tetracycline by carbon-bridge-doped g-C3N4/Fe3O4 magnetic heterogeneous catalyst through photo-Fenton process | |
| Tao et al. | In-situ construction of Co (OH) 2 nanoparticles decorated urchin-like WO3 for highly efficient degradation of sulfachloropyridazine via peroxymonosulfate activation: Intermediates and DFT calculation | |
| Gao et al. | Solar photocatalytic abatement of tetracycline over phosphate oxoanion decorated Bi2WO6/polyimide composites | |
| Xiang et al. | Accelerated photocatalytic degradation of iohexol over Co3O4/g-C3N4/Bi2O2CO3 of pn/nn dual heterojunction under simulated sunlight by persulfate | |
| Liu et al. | Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: Insight into the increase of Cu+ triggered by Co doping | |
| Pelalak et al. | State-of-the-art recent applications of layered double hydroxides (LDHs) material in Fenton-based oxidation processes for water and wastewater treatment | |
| Li et al. | Facile fabrication of ZnO decorated ZnFe-layered double hydroxides@ biochar nanocomposites for synergistic photodegradation of tetracycline under visible light | |
| Jing et al. | Enhanced defect oxygen of LaFeO3/GO hybrids in promoting persulfate activation for selective and efficient elimination of bisphenol A in food wastewater | |
| Xie et al. | Heterogeneous fenton-like degradation of amoxicillin using MOF-derived Fe0 embedded in mesoporous carbon as an effective catalyst | |
| CN110801839B (en) | Co2FeAl-LDH, preparation method thereof and method for degrading pollutants | |
| CN113231105B (en) | Manganese dioxide loaded metal phthalocyanine composite material, preparation and application in degradation of antibiotics | |
| CN116726934A (en) | LDH composite catalytic material and preparation method and application thereof | |
| CN111790399A (en) | Catalyst for treating wastewater by cooperating with low-temperature plasma technology, preparation and application thereof, and method for treating phenol wastewater | |
| Xu et al. | One-step solvothermal synthesis of wood flour carbon fiber/BiOBr composites for photocatalytic activation of peroxymonosulfate towards sulfadiazine degradation: Mechanisms comparison between photo, chemical and photo-chemical oxidation processes | |
| Zhao et al. | Investigation of the degradation and dehalogenation properties of florfenicol by heterogeneous Fenton reaction activated with MIL-53 (Al)-supported nano zero-valent iron | |
| Yang et al. | Microwave synthesis of Fe–Cu diatomic active center MOF: synergistic cyclic catalysis of persulfate for degrading norfloxacin | |
| JP2021112728A (en) | Heterogeneous fenton reaction catalyst, method for producing heterogeneous reaction catalyst, and method for decomposing organic matter | |
| CN108927172B (en) | Preparation and application of gold nanoparticle-loaded magnetic biomass carbon material | |
| Gahrouei et al. | From wastewater to clean water: Recent advances on the removal of metronidazole, ciprofloxacin, and sulfamethoxazole antibiotics from water through adsorption and advanced oxidation processes (AOPs) | |
| Yang et al. | Efficient degradation of antibiotics by heterojunction photocatalysts driving peroxydisulfate activation under visible light irradiation | |
| Nguyen et al. | Enhanced degradation of cefalexin using Co2SnO4@ rGO as an effective peroxymonosulfate activator in hybrid ozonation system | |
| CN112657555B (en) | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof | |
| Jiang et al. | A highly dispersed magnetic polymetallic catalyst to activate peroxymonosulfate for the degradation of organic pollutants in wastewater | |
| Pan et al. | (1 1 1) Facet-dominant peracetic acid activation by octahedral CoO anchored hollow carbon microspheres for tetracycline degradation |
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 |