CN115722249A - Supported low-valence palladium monatomic material as well as preparation method and application thereof - Google Patents
Supported low-valence palladium monatomic material as well as preparation method and application thereof Download PDFInfo
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- CN115722249A CN115722249A CN202211484591.5A CN202211484591A CN115722249A CN 115722249 A CN115722249 A CN 115722249A CN 202211484591 A CN202211484591 A CN 202211484591A CN 115722249 A CN115722249 A CN 115722249A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 373
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 179
- 239000000463 material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 87
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 34
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 34
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000019253 formic acid Nutrition 0.000 claims abstract description 31
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 26
- 239000012498 ultrapure water Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
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- 230000002829 reductive effect Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
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- 239000010865 sewage Substances 0.000 claims description 3
- 239000002352 surface water Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 14
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- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
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- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 description 28
- 229960003760 florfenicol Drugs 0.000 description 28
- 125000004429 atom Chemical group 0.000 description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 8
- 210000002966 serum Anatomy 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 230000009467 reduction Effects 0.000 description 6
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- XUBOMFCQGDBHNK-JTQLQIEISA-N (S)-gatifloxacin Chemical compound FC1=CC(C(C(C(O)=O)=CN2C3CC3)=O)=C2C(OC)=C1N1CCN[C@@H](C)C1 XUBOMFCQGDBHNK-JTQLQIEISA-N 0.000 description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 5
- 230000010757 Reduction Activity Effects 0.000 description 5
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 5
- 229960005091 chloramphenicol Drugs 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 229960003923 gatifloxacin Drugs 0.000 description 5
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- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- 238000001514 detection method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 150000002367 halogens Chemical class 0.000 description 2
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- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a load type low valence palladium monatomic material and a preparation method and application thereof, cyanuric acid and melamine are dissolved in ultrapure water; dissolving palladium salt and organic acid in ultrapure water, and mixing with a cyanuric acid solution; adding phosphoric acid to the melamine solution; adding the mixed solution of cyanuric acid and an organic palladium polymer into the melamine phosphate polymer solution and stirring; adding a reducing agent into the mixed solution, and stirring until the reaction is complete; and washing and drying the obtained precipitate, and then placing the precipitate in a tubular furnace for calcining to obtain the load type low-valence palladium monatomic material. The invention prepares the load type low valence palladium monatomic material by introducing phosphorus and a reducing agent in the preparation process. The supported low-valence palladium monoatomic compound remarkably improves the utilization rate of palladium atoms and the activity of catalyzing formic acid to degrade halogenated hydrocarbon, and can be used for catalyzing and degrading halogenated organic pollutants in wastewater.
Description
Technical Field
The invention belongs to the technical field of treatment of halogen-containing organic polluted wastewater, and particularly relates to a supported low-valence palladium monatomic material as well as a preparation method and application thereof.
Background
The problem of contamination of halogenated organic compounds in the environment by abuses of halogen-containing organic solvents, pesticides, antibiotics and the like has received much attention in recent years, and it is difficult to effectively remove the above halogenated organic contaminants by conventional treatment processes. In recent years, researches show that the catalytic degradation of halogenated organic matters by using catalysts is one of effective ways for repairing the pollution of the halogenated organic matters in the environment. For example, catalytic Reduction Technology (CRT), represented by hydrogen catalyzed by palladium nanomaterial, can achieve rapid reductive degradation of various halogenated organic pollutants, and thus has been widely studied. However, the technology is complex to operate, and has the problems of difficult hydrogen storage and transportation, high cost of precious metal materials and the like, so that the technology is difficult to be applied in large-scale practical application. Currently, research suggests that the palladium monatomic catalytic material can improve the atom utilization efficiency and the reaction selectivity of atoms, so that the treatment effect on halogenated organic pollutants is expected to be improved while the material use cost is remarkably reduced. Therefore, the palladium monatomic catalyst has great application potential in the field of environmental remediation for efficiently removing halogenated organic matters in water and the like, and attracts the wide attention of researchers.
Since metal monoatomic groups such as palladium are thermodynamically unstable and easily aggregate into nanoclusters to lower the atom utilization rate, it is necessary to load the monoatomic groups on a carrier so as to maintain their atomic-level dispersibility. For example, carriers represented by carbon nitride contain a large number of nitrogen atoms with non-coordinated free electrons, which can serve as anchor sites for fixing dispersed metal atoms. However, a carrier such as carbon nitride anchors a metal monoatomic atom by a strong interaction with a metal atom such as palladium, copper, or the like, and at the same time, reduces an electron density of the metal atom, so that the metal atom is often supported on the carrier in a form of a metal cation having a high valence state. The high valence state of the metal atom obviously reduces the catalytic reduction activity of metal monoatomic atoms such as palladium and the like, and limits the application scene of the metal monoatomic atoms in the field of environmental remediation such as catalytic reduction degradation of halogenated organic matters and the like. Therefore, it is important to reduce the valence of the palladium monoatomic atom on the carrier to improve the catalytic reduction activity of the palladium monoatomic atom. However, how to realize the regulation of the valence of the supported metal monoatomic atom is a great challenge in the current preparation field of monoatomic materials.
Therefore, it is urgently needed to develop a preparation method of a supported low-valence palladium monatomic catalytic material, and to prepare the supported low-valence palladium monatomic catalytic material, so as to realize that palladium monatomic is dispersed on a carrier in a zero-valence state or low-valence state, thereby improving the utilization rate and catalytic reduction activity of palladium atoms, improving the removal effect of halogenated organic pollutants, reducing the use cost of materials, and meeting the practical application requirements of halogenated organic pollutant-containing wastewater treatment. As an electron rich element, phosphorus has a low electronegativity, and a coordinatable lone pair. Theoretically, the coordination environment of palladium atoms on the carrier can be regulated and controlled by doping phosphorus, and the electron density of palladium monoatomic atoms in the carrier is improved, so that the phosphorus atoms doped in the preparation process of the supported palladium monoatomic precursor is expected to realize regulation and control of the valence state of the supported palladium monoatomic atoms, and further the catalytic reduction activity of the supported palladium monoatomic atoms is improved. And reduction treatment is carried out on the carrier in the process of preparing the supported palladium monoatomic precursor, so that the palladium monoatomic can participate in coordination in a zero-valent form in the self-assembly process of the carrier and the palladium monoatomic precursor, and the supported low-valent palladium monoatomic material can be prepared.
Disclosure of Invention
The invention aims to provide a load type low-valence palladium monatomic material, and a preparation method and application thereof, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a supported lower valence palladium monatomic material, which comprises the following steps:
s1: respectively adding melamine and cyanuric acid into ultrapure water, heating to 80-90 ℃, and stirring to obtain a melamine solution and a cyanuric acid solution; the concentration of the melamine solution is 0-60mmol/L, and the concentration of the melamine solution is 0-60mmol/L;
s2: dissolving organic acid in ultrapure water, then adding water-soluble palladium salt into the organic acid solution and stirring for 0.5-1h to obtain an organic palladium polymer solution; the molar ratio of the water-soluble palladium salt to the organic acid is 1;
s3: adding the organic palladium polymer solution prepared in the step S2 into the cyanuric acid solution prepared in the step S1, and stirring for 0.5-1h to obtain a mixed solution of cyanuric acid and an organic palladium polymer; the molar ratio of the cyanuric acid to the water-soluble palladium salt is 50-1000;
s4: adding a palladium valence state regulator into the melamine solution prepared in the step S1 and stirring for 0.5-1h to obtain a melamine polymer solution; the molar ratio of the palladium valence regulator to the melamine is 0.1-1;
s5: adding the mixed solution of cyanuric acid and an organic palladium polymer prepared in the step S3 into the melamine polymer solution prepared in the step S4, and continuously stirring for 4-5h to obtain a supported palladium monoatomic precursor suspension;
s6: adding a reducing agent into the supported palladium monoatomic precursor suspension prepared in the step S5, and stirring for 0.5-1h to obtain a supported lower valence palladium monoatomic precursor suspension; the molar ratio of the reducing agent to the melamine is 0.005-0.1;
s7: and (3) filtering the supported low-valence palladium monatomic precursor suspension obtained in the step (S6), cleaning the suspension with deoxidized ultrapure water, then placing the suspension in a vacuum drying oven to be dried in vacuum at the temperature of 60-90 ℃, grinding the dried material into powder, placing the powder in a tubular furnace, heating the furnace to 500-700 ℃ at the heating rate of 5-10 ℃/min under the protection of argon, and then calcining the powder for 3-5 h to obtain the supported low-valence palladium monatomic material.
Further, the organic acid is oxalic acid or acetic acid.
Further, the water-soluble palladium salt is palladium nitrate or a hydrate thereof, potassium chloropalladite or a hydrate thereof, sodium chloropalladite or a hydrate thereof, or palladium chloride or a hydrate thereof.
Further, the palladium valence state regulator is phosphoric acid, phosphate or phosphate hydrate.
Further, the reducing agent is sodium borohydride or potassium borohydride.
Further, the flow rate of the argon is 5-50mL/min.
In a second aspect, the invention provides a supported lower valence palladium monatomic material.
In a third aspect, the invention provides an application of a supported low valence palladium monatomic material in removing halogenated organic pollutants in water by catalyzing reduction of formic acid, which comprises the following steps: adding the load type low valence palladium monatomic material and formic acid into water, reacting for 1h at the water temperature of 10-25 ℃, and finishing the removal of halogenated organic pollutants in the water.
Further, the water body is surface water, underground water, municipal sewage or industrial wastewater, the dosage of the load type low-valence palladium monatomic material is 0.1-1g/L, the dosage of the formic acid is 0.1-1g/L, and the concentration of the halogenated organic pollutant is 0-0.3mmol/L.
The invention has the beneficial effects that: the invention prepares the load type low valence palladium monatomic material taking carbon nitride as a carrier by doping phosphorus in the process of assembling the carbon nitride carrier precursor and the palladium monatomic precursor to form the load type palladium monatomic precursor and then carrying out reduction and calcination treatment on the load type palladium monatomic precursor. The material has good stability and reusability (recycling for more than 5 times, and activity is not reduced). The load type low-valence palladium monatomic material prepared by the invention improves the treatment capability of the halogenated organic pollution-containing wastewater and simultaneously obviously reduces the wastewater treatment cost.
Drawings
FIG. 1 is a flow chart of a method for preparing a supported lower valence palladium monatomic material;
FIG. 2 is a scanning electron microscope image of the supported palladium monatomic material in a low valence state prepared in example 1;
FIG. 3 is a dark field image of a transmission electron microscope of the supported palladium monatomic material in a lower valence state prepared in example 1;
FIG. 4 is a diagram of a carbon distribution of a supported palladium monatomic material in a low valence state prepared in example 1 after energy spectrum scanning;
FIG. 5 is a diagram of the nitrogen distribution after the energy spectrum scan of the supported palladium monatomic material in a low valence state prepared in example 1;
FIG. 6 is a diagram showing the distribution of palladium after energy spectrum scanning of the supported palladium monatomic material in a low valence state prepared in example 1;
FIG. 7 is an X-ray diffraction pattern of a supported lower palladium monatomic material in lower valence state as prepared in example 1;
FIG. 8 is a scanning electron microscope image of spherical aberration correction of the supported lower valence Pd monoatomic material prepared in example 1;
FIG. 9 is an X-ray photoelectron spectrum, wherein FIG. 9 (a) is an X-ray photoelectron spectrum of a conventional supported palladium monatomic material, and FIG. 9 (b) is an X-ray photoelectron spectrum of a supported lower valence palladium monatomic material prepared in example 1;
fig. 10 is a florfenicol degradation diagram, wherein fig. 10 (a) is a graph of the effect of a carbon nitride carrier, a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing degradation of florfenicol by formic acid, fig. 10 (b) is a graph of the comparison of the reaction rate of a conventional supported palladium monatomic and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing degradation of florfenicol by formic acid, fig. 10 (c) is a graph of the comparison of the dechlorination efficiency of a conventional supported palladium monatomic and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing degradation of florfenicol by formic acid, and fig. 10 (d) is a graph of the comparison of the defluorination efficiency of a conventional supported palladium monatomic and a supported low-valence palladium monatomic material prepared in example 3 in degradation of florfenicol by formic acid;
fig. 11 is a graph of recycling performance of the supported palladium monatomic material obtained in example 3, wherein fig. 11 (a) is a graph of effect of the supported palladium monatomic material obtained in example 3 in recycling catalytic formic acid to degrade florfenicol, and fig. 11 (b) is a graph of reaction rate of the supported palladium monatomic material obtained in example 3 in recycling catalytic formic acid to degrade florfenicol;
fig. 12 is a diagram showing the effect of a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing formic acid to remove various halogenated organic pollutants in water, wherein fig. 12 (a) is a diagram showing the effect of a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing formic acid to remove gatifloxacin in water, fig. 12 (b) is a diagram showing the effect of a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing formic acid to remove chloramphenicol from water, fig. 12 (c) is a diagram showing the effect of a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing formic acid to remove 4-chlorophenol in water, and fig. 12 (d) is a diagram showing the effect of a conventional supported palladium monatomic material and a supported low-valence palladium monatomic material prepared in example 3 in catalyzing formic acid to remove 2, 4-dichlorophenol from water.
Detailed Description
For purposes of promoting an understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings and examples, wherein the specific examples are described and illustrated in order to provide a more complete understanding of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Example 1
The invention provides a preparation method of a supported low-valence palladium monatomic material as shown in figure 1, which comprises the following steps:
s1: 3.026g of melamine and 2.9422g of cyanuric acid were weighed and added to 350mL and 400mL of ultrapure water, respectively, heated to 80 ℃ in a water bath, and stirred continuously to obtain a melamine solution and a melamine solution. The melamine and the cyanuric acid are both used as carbon nitride carrier precursors.
S2: 0.3mL of anhydrous acetic acid was measured, diluted with ultrapure water to 40mL, and 119.2mg of palladium nitrate dihydrate was weighed, added to the acetic acid solution and stirred for 1 hour to obtain a palladium acetate polymer solution. The palladium nitrate dihydrate is used as a palladium source.
S3: and (3) injecting the palladium acetate polymer solution prepared in the step (S2) into the cyanuric acid solution prepared in the step (S1) and stirring for 1h to obtain a mixed solution of cyanuric acid and a palladium acetate polymer.
S4: measuring 1mL of anhydrous phosphoric acid, diluting the anhydrous phosphoric acid to 10mL with ultrapure water, then adding the diluted phosphoric acid to the melamine solution prepared in the step S1, and stirring the solution for 1 hour to obtain a melamine phosphate polymer solution.
S5: and (4) adding the mixed solution of cyanuric acid and palladium acetate polymer prepared in the step (S3) into the melamine phosphate polymer solution prepared in the step (S4), and stirring for 5 hours to obtain the supported palladium monoatomic precursor suspension.
S6: and (4) weighing 89mg of sodium borohydride, dissolving the sodium borohydride into 20mL of ultrapure water, adding the sodium borohydride into the supported palladium monoatomic precursor suspension prepared in the step S5, and continuously stirring for 0.5h to obtain the supported lower valence palladium monoatomic precursor suspension.
S7: and (3) filtering the supported low-valence palladium monatomic precursor suspension prepared in the step (S6), washing the suspension for three times by using ultrapure water, then placing the suspension in a vacuum drying box, carrying out vacuum drying at 60 ℃, grinding the obtained material into powder after drying, placing the powder in a tubular furnace, heating the furnace to 600 ℃ at the heating rate of 10 ℃/min under the protection of argon with the flow of 5mL/min, and then calcining for 4 hours to obtain the supported low-valence palladium monatomic material.
Example 2
S1: 3.026g of melamine and 2.9422g of cyanuric acid were weighed and added into 400mL and 400mL of ultrapure water, respectively, heated to 85 ℃ in a water bath, and stirred continuously to obtain a melamine solution and a cyanuric acid solution. The melamine and the cyanuric acid are both used as carbon nitride carrier precursors.
S2: 27mg of oxalic acid was weighed and dissolved in 30mL of ultrapure water, and then 39mg of potassium chloropalladite was weighed and added to the oxalic acid solution and stirred for 0.5 hour to obtain a palladium oxalate polymer solution. The potassium chloropalladite is used as a palladium source.
S3: and (3) adding the palladium oxalate polymer solution prepared in the step (S2) into the cyanuric acid solution prepared in the step (S1) and stirring for 0.5h to obtain a mixed solution of cyanuric acid and a palladium oxalate polymer.
S4: 0.2mL of anhydrous phosphoric acid was dissolved in 10mL of ultrapure water, and then added to the melamine solution prepared in step S1 and stirred for 0.5h to obtain a melamine phosphate polymer solution.
S5: and (4) adding the mixed solution of cyanuric acid and palladium oxalate polymer prepared in the step (S3) into the melamine phosphate polymer solution prepared in the step (S4), and stirring for 4 hours to obtain the supported palladium monoatomic precursor suspension.
S6: and (3) weighing 20mg of sodium borohydride, dissolving the sodium borohydride into 20mL of ultrapure water, adding the sodium borohydride into the supported palladium monatomic precursor suspension prepared in the step (S5), and continuously stirring for 0.5h to obtain the supported low-valence palladium monatomic precursor suspension.
S7: and (3) filtering the supported low-valence palladium monatomic precursor suspension prepared in the step (S6), washing the suspension for three times by using deoxidized ultrapure water, then placing the suspension in a vacuum drying box, carrying out vacuum drying at 60 ℃, grinding the obtained material into powder after drying, placing the powder in a tubular furnace, heating the furnace to 600 ℃ at the heating rate of 10 ℃/min under the protection of argon with the flow of 10mL/min, and calcining the powder for 4 hours to obtain the supported low-valence palladium monatomic material.
Example 3
S1: 3.026g of melamine and 2.9422g of cyanuric acid were weighed and added to 350mL and 400mL of ultrapure water, respectively, heated to 85 ℃ in a water bath, and stirred continuously to obtain a melamine solution and a melamine solution. The melamine and cyanuric acid are both used as carbon nitride carrier precursors.
S2: 0.3mL of anhydrous acetic acid was measured and diluted with ultrapure water to 30mL to obtain an acetic acid solution, and then 85mg of palladium chloride was measured and added to the above acetic acid solution and stirred for 0.5h to obtain a palladium acetate polymer solution. The palladium chloride is used as a palladium source.
S3: and (3) adding the palladium acetate polymer solution prepared in the step (S2) into the cyanuric acid solution prepared in the step (S1) and stirring for 1h to obtain a mixed solution of cyanuric acid and a palladium acetate polymer.
S4: 1mL of anhydrous phosphoric acid was diluted to 10mL with ultrapure water, and then added to the melamine solution prepared in step S1 and stirred for 0.5h, to obtain a melamine phosphate polymer solution.
S5: and (4) adding the mixed solution of cyanuric acid and palladium acetate polymer prepared in the step (S3) into the melamine phosphate polymer solution prepared in the step (S4), and stirring for 5 hours to obtain the supported palladium monatomic precursor suspension.
S6: 89mg of sodium borohydride is weighed and dissolved in 40mL of ultrapure water, then the solution is added into the supported palladium monoatomic precursor suspension prepared in the step S5, and the stirring is continued for 1 hour to obtain the supported lower valence palladium monoatomic precursor suspension.
S7: and (3) filtering the supported low-valence palladium monatomic precursor suspension prepared in the step (S6), washing the suspension for three times by using deoxidized ultrapure water, then placing the suspension in a vacuum drying box, carrying out vacuum drying at 60 ℃, grinding the obtained material into powder after drying, placing the powder in a tubular furnace, heating the furnace to 550 ℃ at the heating rate of 10 ℃/min under the protection of argon with the flow of 50mL/min, and calcining the powder for 4 hours to obtain the supported low-valence palladium monatomic material.
FIG. 2 is a scanning electron microscope image of the supported low-valence palladium monatomic material prepared in example 1, wherein the morphology of the material is a tubular material with a diameter of about 2 μm. FIG. 3 shows a dark-field image of a partial region of the supported lower palladium monatomic tubular material prepared in example 1, on a 50nm scale. In fig. 3, only the local morphology of the carrier was observed, and no clear bright spots were observed, indicating that palladium was supported on the carrier in an atomic-scale dispersion. Fig. 4-6 are graphs showing the energy spectrum scan of the supported palladium monatomic material in the region shown in fig. 3, in which fig. 4 is a graph showing the carbon element distribution after the energy spectrum scan of the supported palladium monatomic material in the lower valence state shown in fig. 3, fig. 5 is a graph showing the nitrogen element distribution after the energy spectrum scan of the supported palladium monatomic material in the lower valence state shown in fig. 3, and fig. 6 is a graph showing the palladium element distribution after the energy spectrum scan of the supported palladium monatomic material in the lower valence state shown in fig. 3. The results of fig. 4-6 show that the main constituent elements of the carrier in the supported low valence palladium monatomic material prepared in example 3 are nitrogen element and carbon element, i.e. a carbon nitride carrier is formed, and palladium atoms are uniformly supported on the carrier.
FIG. 7 shows an X-ray diffraction pattern of a supported lower valence palladium monatomic material. As can be seen from FIG. 7, the carbon nitride support (g-C) 3 N 4 ) And the supported lower valence palladium monatomic material (Pd) prepared in example 1 1-red /g-C 3 N 4 ) Diffraction peaks of typical graphite-phase carbon nitride appear, and no diffraction peak of palladium is detected, which indicates that palladium in the prepared load-type low-valence palladium monatomic material does not form a crystal structure, and palladium element exists in a monatomic form.
FIG. 8 is a transmission electron micrograph of a supported palladium monatomic material in a lower valence state prepared in example 1, which shows a scale of 5nm, corrected by spherical aberration. It can be seen from fig. 8 that the palladium element is mainly dispersed on the carbon nitride support in a monoatomic form, further indicating that the palladium element is dispersedly supported on the carbon nitride support on an atomic scale.
FIG. 9 is an X-ray photoelectron spectroscopy (XPS) chart of palladium element in a supported palladium monatomic material, wherein FIG. 9a is a conventional supported palladium monatomic material (Pd) 1 /g-C 3 N 4 ) Fig. 9b is an X-ray photoelectron spectrum of the supported lower palladium monoatomic material prepared in example 1. As can be seen from fig. 9, compared with the conventional carbon nitride supported palladium monatomic material, most of the palladium atoms in the supported lower valence palladium monatomic material are dispersedly supported on the carbon nitride carrier in a zero valence state, i.e., the supported lower valence palladium monatomic material is successfully prepared by using the method of the present invention.
Application example 1
20mg of carbon nitride carrier (g-C) was weighed out separately 3 N 4 ) Conventional supported palladium monatomic material (Pd) 1 /g-C 3 N 4 ) And the supported lower valence palladium monatomic material (Pd) prepared in example 3 1-red /g-C 3 N 4 ) Adding into a 42mL serum bottle containing 17.5mL ultrapure water, and performing ultrasonic treatment for 10min; then 0.5mL of formic acid solution with the concentration of 1mol/L and 2mL of florfenicol solution with the concentration of 2.8mmol/L are respectively injected into the bottle, and then a rubber cover pad with a polytetrafluoroethylene lining is covered and mixed evenly, so that the reaction is carried outThe initial concentration of florfenicol in the system was 0.28mmol/L.
Placing the serum bottle on a rotary incubator, setting the rotating speed of the rotary incubator to be 50rpm, extracting 100 mu L of solution by using a glass sample injection needle at a preset time point, diluting the solution to 1mL, and then filtering the solution by using a filter membrane with the diameter of 0.22 mu m; and (3) carrying out liquid chromatography detection on the solution obtained by filtering, and detecting the content of the residual florfenicol in the solution. The florfenicol content profile during the reaction is shown in figure 10 a. As can be seen from fig. 10a, the supported low valence palladium monoatomic material has a significant removal effect on florfenicol compared to the carbon nitride support and the conventional supported palladium monoatomic material. And performing kinetic fitting on the reaction data to obtain the reaction rate constant of the conventional supported palladium monatomic material and the supported low-valence palladium monatomic material for catalyzing formic acid to degrade the florfenicol, as shown in fig. 10 b. As can be seen from FIG. 10b, the reaction rate of the conventional supported palladium monatomic material for catalyzing formic acid to degrade florfenicol is 0.7L-g -1 ·h -1 The reaction rate of the supported low-valence palladium monatomic material prepared in example 3 for catalyzing formic acid to degrade florfenicol is 1200L-g -1 ·h -1 The reaction rate is more than 1700 times faster than that of the conventional supported palladium monatomic material, which indicates that the reduction of the valence state of the palladium monatomic can obviously improve the catalytic reduction activity of the palladium monatomic.
After reacting for 1h, sampling 1mL of serum bottle, and then diluting to 10mL; filtering and pretreating the diluted solution by using a 0.22 mu m filter membrane, a C18 filter column and an NA filter column in sequence, and then carrying out ion chromatography detection to detect the content of chloride ions generated in a reaction system. The chlorine ion generation in the solution is shown in fig. 10c, and it can be seen from fig. 10c that the dechlorination efficiency of the conventional supported palladium monatomic material to florfenicol is only 7.3%, while the dechlorination efficiency of the supported low-valence palladium monatomic material prepared in example 3 to florfenicol reaches 100%.
After reacting for 5h, sampling 1mL of serum bottle, and then diluting to 10mL; filtering and pretreating the diluted solution by using a 0.22 mu m filter membrane, a C18 filter column and an NA filter column in sequence, and then carrying out ion chromatography detection to detect the content of the fluoride ions generated in the reaction system. The situation of generating fluorine ions in the solution is shown in fig. 10d, and it can be seen from fig. 10d that the defluorination of florfenicol cannot be realized by the conventional supported palladium monatomic material, while the defluorination efficiency of the supported low valence state monoatomic material prepared in example 3 to florfenicol after 5h of reaction reaches 35%.
Fig. 10 shows that, compared with a conventional supported palladium monatomic material, the supported low-valence palladium monatomic material prepared in example 3 significantly improves the reaction rate, dechlorination efficiency and defluorination efficiency of the florfenicol catalyzed by palladium monatomic, which indicates that the atom utilization rate of palladium and the reaction performance of the florfenicol degraded by formic acid reduction catalyzed by palladium monatomic can be significantly improved by reducing the valence of palladium monatomic on the carrier.
In order to verify the catalytic stability and the recycling performance of the supported low-valence palladium monatomic material, 5-time cycle tests for catalyzing formic acid to degrade florfenicol were performed on the supported low-valence palladium monatomic material prepared in example 3: after the load type low-valence palladium monatomic material catalyzes formic acid to degrade the florfenicol for 1h, carrying out centrifugal separation on the load type low-valence palladium monatomic material and the solution in the solution; after the centrifugation is finished, pouring out the supernatant, and adding 17.5mL of ultrapure water again and performing ultrasonic treatment for 10min; after completion of the sonication, 0.5mL of a 1mol/L formic acid solution and 2mL of a 2.8mmol/L florfenicol solution were again injected, and 100. Mu.L of the solution was sampled at a predetermined time point, diluted to 1mL, filtered through a 0.22 μm filter, and then the concentration of the florfenicol remaining in the solution was measured by a liquid chromatograph. The above experimental procedure was repeated 5 times. Fig. 11a shows the change of the residual florfenicol in the solution during the cycle test, and it can be known from fig. 11a that the supported low valence palladium monatomic material prepared in example 3 always maintains excellent degradation effect on the florfenicol. The change of the catalytic degradation reaction rate of the supported lower valence palladium monatomic prepared in example 3 on florfenicol in 5-cycle test is shown in fig. 11b, and as can be seen from fig. 11b, the reaction rates of the supported lower valence palladium monatomic material in 5-cycle test are all kept at 36L g -1 ·min -1 . FIG. 11 shows that the supported palladium monoatomic material with low valenceThe catalyst has good catalytic stability, so that the catalyst can be recycled to reduce the wastewater treatment cost in the practical wastewater treatment application.
Application example 2
Respectively weighing 20mg of a conventional supported palladium monoatomic material and the supported low-valence palladium monoatomic material prepared in the example 3, adding the materials into a 42 mL-specification serum bottle containing 11.5mL of ultrapure water, and carrying out ultrasonic treatment for 10min; then respectively injecting 0.5mL of 1mol/L formic acid solution into the bottles;
respectively injecting 2mL of gatifloxacin solution, chloramphenicol solution, 4-chlorophenol solution and 2, 4-dichlorophenol solution into a serum bottle, then covering a rubber cap pad with a polytetrafluoroethylene lining, and uniformly mixing to ensure that the initial concentrations of gatifloxacin, chloramphenicol, 4-chlorophenol and 2, 4-dichlorophenol in the reaction system are respectively 0.28mmol/L.
Placing the serum bottle on a rotary incubator, setting the rotating speed of the rotary incubator to be 50rpm, extracting 100 mu L of solution by using a glass sample injection needle at a preset time point, diluting the solution to 1mL, and then filtering the solution by using a filter membrane with the diameter of 0.22 mu m; and (4) carrying out liquid chromatography detection on the solution obtained by filtering, and detecting the content of the residual halogenated organic pollutants. The content of the halogenated organic matters remaining in the solution during the reaction is shown in fig. 12. Wherein, the content change curve of the residual gatifloxacin in the solution during the reaction is shown in fig. 12a, the content change curve of the residual chloramphenicol in the solution is shown in fig. 12b, the content change curve of the residual 4-chlorophenol in the solution is shown in fig. 12c, and the content change curve of the residual 2, 4-dichlorophenol in the solution is shown in fig. 12 d. As can be seen from fig. 12, compared with the conventional supported palladium monatomic material, the supported low-valence palladium monatomic material prepared in example 3 has a significant removal effect on four halogenated organic pollutants, namely gatifloxacin, chloramphenicol, 4-chlorophenol and 2, 4-dichlorophen, which indicates that the ability of palladium monatomic catalytic formic acid to degrade various halogenated organic pollutants in water can be significantly improved by reducing the valence of palladium monatomic on the carrier.
Application example 1 and application example 2 show that the supported low-valence palladium monatomic material can be used for catalyzing reduction of formic acid to remove halogenated organic pollutants in water, and is characterized by comprising the following steps: adding the load type low-valence palladium monatomic material and formic acid into a water body containing halogenated organic pollutants, wherein the temperature of the water body is 10-25 ℃, and reacting for 1h to finish the removal of the halogenated organic pollutants in the water body. The water body is surface water, underground water, municipal sewage or industrial wastewater, the dosage of the load type low valence palladium monatomic material is 0.1-1g/L, the dosage of the formic acid is 0.1-1g/L, and the concentration of the halogenated organic pollutant is 0-0.3mmol/L.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a supported low-valence palladium monatomic material is characterized by comprising the following steps:
s1: respectively adding melamine and cyanuric acid into ultrapure water, heating to 80-90 ℃, and stirring to obtain a melamine solution and a cyanuric acid solution; the concentration of the melamine solution is 0-60mmol/L, and the concentration of the melamine solution is 0-60mmol/L;
s2: dissolving organic acid in ultrapure water, adding water-soluble palladium salt into the organic acid solution, and stirring for 0.5-1h to obtain an organic palladium polymer solution; the molar ratio of the water-soluble palladium salt to the organic acid is 1;
s3: adding the organic palladium polymer solution prepared in the step S2 into the cyanuric acid solution prepared in the step S1, and stirring for 0.5-1h to obtain a mixed solution of cyanuric acid and an organic palladium polymer; the molar ratio of the cyanuric acid to the water-soluble palladium salt is 50-1000;
s4: adding a palladium valence state regulator into the melamine solution prepared in the step S1 and stirring for 0.5-1h to obtain a melamine polymer solution; the molar ratio of the palladium atomic valence regulator to the melamine is 0.1-1;
s5: adding the cyanuric acid-organic palladium polymer mixed solution prepared in the step S3 into the melamine polymer solution prepared in the step S4, and continuously stirring for 4-5h to obtain a supported palladium monoatomic precursor suspension;
s6: adding a reducing agent into the supported palladium monoatomic precursor suspension prepared in the step S5, and stirring for 0.5-1h to obtain a supported lower valence palladium monoatomic precursor suspension; the molar ratio of the reducing agent to the melamine is 0.005-0.1;
s7: and (3) filtering the supported low-valence palladium monatomic precursor suspension obtained in the step (S6), cleaning the suspension with deoxidized ultrapure water, then placing the suspension in a vacuum drying oven to be dried in vacuum at the temperature of 60-90 ℃, grinding the dried material into powder, placing the powder in a tubular furnace, heating the furnace to 500-700 ℃ at the heating rate of 5-10 ℃/min under the protection of argon, and then calcining the powder for 3-5 h to obtain the supported low-valence palladium monatomic material.
2. The method for preparing a supported palladium monatomic material in a reduced valence state according to claim 1, wherein the organic acid is oxalic acid or acetic acid.
3. The method for preparing a supported low-valence palladium monatomic material according to claim 1, wherein the water-soluble palladium salt is palladium nitrate or a hydrate thereof, potassium chloropalladite or a hydrate thereof, sodium chloropalladite or a hydrate thereof, or palladium chloride or a hydrate thereof.
4. The method for preparing a supported palladium monatomic material in a reduced valence state according to claim 1, wherein the palladium monatomic valence state modifier is phosphoric acid, phosphate, or phosphate hydrate.
5. The method for preparing a supported lower valence palladium monatomic material according to claim 1, wherein the reducing agent is sodium borohydride or potassium borohydride.
6. The method for preparing a supported palladium monatomic material in a reduced valence state according to claim 1, wherein the flow rate of argon is 5 to 50mL/min.
7. A supported, reduced-valence palladium monatomic material produced by the method of any of claims 1-6.
8. The use of the supported lower valence palladium monatomic material of claim 7 in the catalytic reduction of formic acid for the removal of halogenated organic contaminants in water, characterized in that it comprises the following steps: adding the load type low valence palladium monatomic material and formic acid into water, reacting for 1h at the water temperature of 10-25 ℃, and finishing the removal of halogenated organic pollutants in the water.
9. The use of claim 8, wherein the water body is surface water, underground water, municipal sewage or industrial wastewater, the dosage of the supported lower valence palladium monatomic material is 0.1-1g/L, the dosage of the formic acid is 0.1-1g/L, and the concentration of the halogenated organic pollutant is 0-0.3mmol/L.
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