CN115420841B - Online catalytic membrane reactor-high performance liquid chromatography combined system and preparation method and application thereof - Google Patents
Online catalytic membrane reactor-high performance liquid chromatography combined system and preparation method and application thereof Download PDFInfo
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- 229910016528 CuMOF Inorganic materials 0.000 claims abstract description 100
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- 239000002699 waste material Substances 0.000 claims abstract description 12
- 238000004811 liquid chromatography Methods 0.000 claims abstract description 9
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 229920001690 polydopamine Polymers 0.000 claims description 101
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000011068 loading method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012621 metal-organic framework Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000004401 flow injection analysis Methods 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 238000010223 real-time analysis Methods 0.000 claims description 4
- 238000011897 real-time detection Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 239000004696 Poly ether ether ketone Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 229920002530 polyetherether ketone Polymers 0.000 description 9
- 238000004626 scanning electron microscopy Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 7
- 239000012279 sodium borohydride Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
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- 239000012071 phase Substances 0.000 description 6
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- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
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- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- 238000005067 remediation Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
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- 239000012456 homogeneous solution Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an on-line catalytic membrane reactor-high performance liquid chromatography combined system and a preparation method and application thereof. The combined system comprises a catalytic membrane reactor, a liquid chromatography six-way valve sample injector and a high performance liquid chromatograph which are connected in sequence; wherein: the catalytic membrane reactor comprises a pre-column sleeve and a pre-column core, wherein NH is filled in the pre-column core 2 -a CuMOF/PDA/CF composite nano catalytic membrane; a sample switching device is arranged between an outlet of the catalytic membrane reactor and a sample inlet of the liquid chromatography six-way valve sample injector; the outlet of the catalytic membrane reactor is communicated with the sample inlet of the six-way valve sample injector through a sample switching device, or is communicated with the waste liquid outlet of the sample switching device through the sample inlet of the sample switching device. The system has high reactivity and good stability, and can realize long-term real-time monitoring of the catalytic degradation process; meanwhile, the catalyst also has high mass and heat transfer efficiency, improves the recoverability and the reactivity of the catalyst, and has industrial application prospect.
Description
Technical Field
The invention relates to the field of water pollution remediation, in particular to an online NH (NH) 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined system, and preparation method and application thereof.
Background
In recent years, researchers have focused on preparing high-activity non-noble metal-based catalysts to catalytically reduce p-nitrophenol (4-NP) which is relatively toxic in water environments to p-aminophenol (4-AP) which has a wide commercial application value. Among them, metal Organic Frameworks (MOFs) are receiving extensive attention from researchers due to their large specific surface area, special porous structure, and abundant reaction sites. However, MOF-based catalysts are usually present in the form of fine powders, which are difficult to recycle during the reaction process and have poor operability. Therefore, it is severely limited in practical applications of environmental remediation.
Therefore, how to realize the MOF-based catalyst for relieving the pollution problem of p-nitrophenol in water environment and realizing the real-time and long-term detection of the catalytic reaction process has great market application prospect.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides an online NH 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined system, preparation method thereof and application thereof in the field of water environment pollutant treatment.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides an online catalytic membrane reactor-high performance liquid chromatography combined system, which comprises a catalytic membrane reactor, a liquid chromatography six-way valve sample injector and a high performance liquid chromatograph which are connected in sequence; wherein:
the catalytic membrane reactor comprises a pre-column sleeve and a pre-column core, wherein a catalytic membrane is filled in the pre-column core, and is made of metal organic framework/polydopamine/copper foam (NH) 2 -CuMOF/PDA/CF) composite nano-catalytic membrane;
the catalytic membrane reactor comprises a catalytic membrane reactor body, wherein a sample switching device is arranged between an outlet of the catalytic membrane reactor and a sample inlet of a liquid chromatography six-way valve sample injector, the sample switching device is provided with two circulation branches, and the two circulation branches can be switched, wherein: a first flow-through branch: the outlet of the catalytic membrane reactor is communicated with a sample inlet of a six-way valve sample injector through a sample switching device; a second circulation branch: and the outlet of the catalytic membrane reactor is communicated with the waste liquid port of the sample switching device through the sample inlet of the sample switching device.
According to the scheme, the combined system further comprises a constant flow injection pump which is communicated with the sample inlet of the catalytic membrane reactor and used for injecting liquid into the catalytic membrane reactor.
According to the scheme, the filling amount of the catalytic film is 1-4 sheets; preferably 2-4 tablets.
According to the scheme, the catalytic membrane is filled in the pre-column core along the axial direction.
According to the scheme, the diameter of the pre-column core is 4.6-5 mm, and the length is 10-12 mm.
According to the scheme, the sample switching device is a six-way valve.
According to the scheme, the NH 2 The diameter of the CuMOF/PDA/CF catalytic membrane is 4.5-5 mm, and the CuMOF/PDA/CF catalytic membrane is round.
According to the scheme, the NH 2 In the-CuMOF/PDA/CF composite nano catalytic film, NH 2 -a CuMOF thickness of 5-10 microns.
According to the scheme, the NH 2 In the-CuMOF/PDA/CF composite nano catalytic film, NH 2 The organic ligand of CuMOF is 2-amino terephthalic acid (NH) 2 -H 2 BDC)。
According to the scheme, the NH 2 The preparation of the CuMOF/PDA/CF composite nano catalytic film comprises the following steps:
(1) immersing the pretreated copper foam in a dopamine hydrochloride solution, and carrying out self-polymerization on dopamine on the surface of the copper foam at room temperature to obtain a PDA/CF catalytic membrane;
(2) copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) and 2-amino terephthalic acid (NH) 2 -H 2 BDC) is added into N, N-dimethylformamide solvent (DMF) together, a uniform solution is obtained after ultrasonic dispersion, and then the solution is mixed with the PDA/CF catalytic film obtained in the step 1) to carry out hydrothermal reaction, thus obtaining NH 2 -a CuMOF/PDA/CF composite catalytic membrane.
Preferably, in the step (1), the copper foam pretreatment step is as follows: commercial copper foam was cut into round shapes, ultrasonically cleaned with hydrochloric acid, absolute ethanol, acetone, ultrapure water in this order, and then vacuum dried at 55-65 ℃. More preferably, the hydrochloric acid solution concentration is 0.9 to 1.1 mol/liter; more preferably, the ultrasound time is 5 to 6 minutes.
Preferably, in the step (1), the concentration of dopamine in the dopamine hydrochloride solution is 2-3 mg/ml. More preferably, the dopamine hydrochloride solution is prepared by a mixed solvent of Tris buffer solution and methanol; the concentration of the Tris buffer solution is 10mM, the pH value is 8.5, and the volume ratio of the Tris buffer solution to the methanol is 1:1-1:1.2.
Preferably, in the step (1), the self-polymerization time is 12 to 24 hours;
preferably, in the uniform solution obtained in the step (2), the mass volume ratio of the copper nitrate trihydrate, the 2-amino terephthalic acid and the DMF is 20-22 mg: 15-16.5 mg:1mL.
Preferably, in the step (2), the hydrothermal synthesis time is 3-12 hours, and the hydrothermal synthesis temperature is 100-120 ℃.
Providing the online NH 2 The construction method of the combined system of the CuMOF/PDA/CF catalytic membrane reactor and the high performance liquid chromatography comprises the following steps:
1) NH is added to 2 The CuMOF/PDA/CF composite nano catalytic membrane is filled into the pretreated pre-column core, and then is filled into a matched pre-column sleeve to obtain a catalytic membrane reactor;
2) Then, a six-way valve sample injector and a sample switching device of the high performance liquid chromatograph are arranged between a chromatographic column and a catalytic membrane reactor of the high performance liquid chromatograph to finish online NH 2 -building of a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined system.
According to the scheme, in the step 1), pretreatment of the pre-column core is carried out: sequentially ultrasonically cleaning the pre-column core with methanol and ultrapure water, and drying.
According to the scheme, in the step 2), the chromatographic column, the six-way valve sampler, the sample switching device and the catalytic membrane reactor are connected through a 1/16 inch polyether ether ketone (PEEK) pipe and a nut.
Providing the online NH 2 The application of the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined system in removing water environment pollutant p-nitrophenol.
According to the scheme, the application is specifically as follows:
delivery of p-nitrophenol and NaBH using constant flow syringe pump 4 To NH 2 The CuMOF/PDA/CF catalytic membrane reactor carries out chemical reaction, and effluent after the reaction is conveyed to a high performance liquid chromatograph for real-time monitoring.
Preferably, the liquid flows through the sample switching device after reacting in the catalytic membrane reactor, then enters the quantitative ring in the six-way valve sampler to finish loading, and the effluent liquid reserved in the quantitative ring is introduced into the chromatographic column of the high performance liquid chromatograph to enter the real-time analysis and detection of the subsequent detector.
Preferably, when real-time monitoring of the effluent of the catalytic membrane reactor is not required, the solution after reaction in the catalytic membrane reactor is directly discharged from the waste liquid port of the sample switching device and does not enter the six-way valve sampler and the high performance liquid chromatograph.
Preferably, p-nitrophenol and NaBH 4 NaBH in the mixed solution of (2) 4 The concentration ratio of the p-nitrophenol to the p-nitrophenol is 1:20 to 40, preferably 1: 30-40; the concentration of the p-nitrophenol is 0.5-1 mmol/L; naBH 4 The concentration is 0.01 to 0.04 mol/liter.
Preferably, constant flow syringe pumps are used to deliver p-nitrophenol and NaBH 4 The flow rate of the mixed solution is 0.1 to 2 ml/min, preferably 0.1 to 1 ml/min.
Preferably, a chromatographic column in high performance liquid chromatography is an XDB-C18 column with the thickness of 5 microns and the thickness of 4.6X106 mm, the volume ratio of methanol to water in a mobile phase is 3:7-7:3, the flow rate is 0.8-1.0 ml/min, the detection wavelength is 317 nm, the sample injection volume is 20 microlitres, and the column temperature is 30 ℃.
The Catalytic Membrane Reactor (CMR) is a novel continuous flow reactor capable of fixing heterogeneous catalysts, has the inherent characteristics of high activity, high stability, accurate regulation and control and the like, and has great potential in the fields of fine chemical synthesis, environmental engineering and the like. The catalytic membrane reactor can be used as a good carrier of MOF powder, prevents loss and stabilizes the performance of the MOF powder, has high-efficiency mass and heat transfer rate, and can effectively improve the selectivity and the reactivity of the catalyst to a substrate. The invention constructs the supported catalytic membrane reactor and is combined with the high performance liquid chromatograph, thereby not only solving the activity and stability of the MOF-based catalyst and effectively relieving the pollution problem of p-nitrophenol in water environment, but also realizing the real-time and long-term detection of the catalytic reaction process and having huge market application prospect.
In the invention, the online NH 2 The method for using the combined system of the CuMOF/PDA/CF catalytic membrane reactor and the high performance liquid chromatography comprises the following steps: firstly, pumping mixed solution of p-nitrophenol and sodium borohydride into a catalytic membrane reactor at a certain flow rate by using a constant flow injection pump to perform catalytic reaction, then switching a sample switching device to a sample injection state, and switching an automatic sample injection device (namely a liquid chromatography six-way valve sample injector) to a sample injection state to ensure thatThe effluent liquid after the reaction enters a quantitative ring of an automatic sample feeding device along a PEEK tube from a sample switching device to finish sample feeding; after loading, rapidly switching the sample switching device to a loading state and switching the automatic sample feeding device to a sampling state, and introducing the retained effluent in the quantitative loop into a chromatographic column of the high performance liquid chromatograph from a mobile phase to enter a subsequent detector for real-time analysis and detection; when the effluent of the catalytic membrane reactor is not required to be monitored in real time, the sample switching device can be switched to the loading position, and at the moment, the solution after reaction is directly discharged from the No. 3 waste liquid port of the sample switching device and does not enter the automatic sample feeding device and the high performance liquid chromatograph.
The beneficial effects of the invention are as follows:
1. the invention provides an online NH 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system, wherein NH 2 The construction of the CuMOF/PDA/CF catalytic membrane reactor not only improves the operability and stability of the powdery catalyst, but also has high mass and heat transfer efficiency and reactivity, is easy to expand the scale and is environment-friendly.
2. The invention uses NH 2 The CuMOF/PDA/CF catalytic membrane reactor is combined with the high performance liquid chromatography on-line detection technology, has high automation degree and simple and convenient operation, can realize long-term and real-time monitoring of the catalytic degradation process, and has wide application prospect.
3. The invention provides on-line NH 2 The CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system can efficiently remove p-nitrophenol pollutants in water environment, and has high catalytic efficiency and good stability.
Drawings
FIG. 1 is NH according to example 1 of the present invention 2 -preparation flow chart of the CuMOF/PDA/CF catalytic membrane.
FIG. 2 is an online NH in an embodiment of the invention 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system, wherein FIG. 2a is sample switching device and six-way valve sample injector loading state, FIG. 2b is sample switching device sample loading and six-way valve sample injector loading state, FIG. 2c is sample switching device loading state, six-way valve sample injector loading stateAnd (5) sampling state of the valve sampler.
FIG. 3 is a graph of the morphology of the material of example 1 of the present invention: FIG. 3a is a scanning electron microscope image of a commercial copper foam at 500 Xmagnification; FIG. 3b is a scanning electron microscope image at 2000 Xmagnification of the PDA/CF catalytic film; FIG. 3c is NH 2 Scanning electron microscopy at 5000 Xmagnification of the CuMOF/PDA/CF catalytic membrane.
FIG. 4 shows the CF, PDA/CF, NH according to example 1 of the present invention 2 XRD spectra of CuMOF/PDA/CF.
FIG. 5 is an online NH produced in example 1 of the present invention 2 The degradation performance of p-nitrophenol under different sodium borohydride concentration, catalytic membrane number and flow rate of a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system is examined.
FIG. 6 is an online NH produced in example 1 of the present invention 2 -CuMOF/PDA/CF catalytic film reactor-high performance liquid chromatography system and control group on-line NH 2 -CuMOF/CF catalytic membrane reactor-high performance liquid chromatography system stability comparative investigation.
FIG. 7 is a topographical view of a material of example 1 of the present invention: wherein FIG. 7a is NH prior to use 2 -scanning electron microscopy at 5000 x magnification of the CuMOF/PDA/CF catalytic membrane; FIG. 7b is NH prior to use 2 -scanning electron microscopy at 5000 x magnification of the CuMOF/CF catalytic membrane; FIG. 7c is NH after use 2 -scanning electron microscopy at 5000 x magnification of the CuMOF/PDA/CF catalytic membrane; FIG. 7d is NH after use 2 Scanning electron microscopy at 5000 Xmagnification of the CuMOF/CF catalytic membrane.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
As shown in fig. 2, the embodiment of the invention provides an online catalytic membrane reactor-high performance liquid chromatography combined system, which comprises a catalytic membrane reactor, a liquid chromatography six-way valve sample injector and a high performance liquid chromatograph which are connected in sequence; wherein:
the catalytic membrane reactor comprises a pre-column sleeve and a pre-column core, wherein a catalytic membrane is filled in the pre-column core, and the catalytic membrane is a metal organic framework/polydopamine/copper foamFoam (NH) 2 -CuMOF/PDA/CF) composite nano-catalytic membrane;
the catalytic membrane reactor comprises a catalytic membrane reactor body, wherein a sample switching device is arranged between an outlet of the catalytic membrane reactor and a sample inlet of a liquid chromatography six-way valve sample injector, the sample switching device is provided with two circulation branches, and the two circulation branches can be switched, wherein: a first flow-through branch: the outlet of the catalytic membrane reactor is communicated with a sample inlet of a six-way valve sample injector through a sample switching device; a second circulation branch: and the outlet of the catalytic membrane reactor is communicated with the waste liquid port of the sample switching device through the sample inlet of the sample switching device.
In one embodiment, the combined system further comprises a constant flow injection pump which is communicated with the sample inlet of the catalytic membrane reactor and used for injecting liquid into the catalytic membrane reactor.
In one embodiment, the filling amount of the catalytic film is 1-4 sheets; in a preferred embodiment, 2-4 tablets.
In one embodiment, the catalytic membrane is axially filled within the pre-column core.
In one embodiment, the sample switching apparatus is a six-way valve.
In one embodiment, the diameter of the pre-column core is 4.6-5 mm, and the length is 10-12 mm.
In one embodiment, the NH 2 The diameter of the CuMOF/PDA/CF catalytic membrane is 4.5-5 mm, and the CuMOF/PDA/CF catalytic membrane is round.
In one embodiment, the NH 2 In the-CuMOF/PDA/CF composite nano catalytic film, NH 2 -a CuMOF thickness of 5-10 microns.
In one embodiment, the NH 2 In the-CuMOF/PDA/CF composite nano catalytic film, NH 2 The organic ligand of CuMOF is 2-amino terephthalic acid (NH) 2 -H 2 BDC)。
Example 1
Providing an online NH 2 A process for preparing a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system, the preparation flow is as shown in figures 1 and 2, comprising the steps of:
(1) Pretreatment of commercial copper foam: commercial copper foam was cut into a circular shape having a diameter of 4.5 mm, ultrasonically cleaned sequentially with 1 mol/liter of hydrochloric acid, absolute ethanol, acetone, ultra-pure water for 5 minutes, and then vacuum-dried at 60 degrees centigrade for 1 hour;
(2) Preparation of PDA/CF catalytic film: the copper foam in the step (1) is completely immersed in 10 milliliters of dopamine hydrochloride solution, and dopamine is self-polymerized on the surface of the copper foam at room temperature. Wherein the dopamine hydrochloride solution is 2 mg/ml dopamine hydrochloride solution prepared by taking Tris buffer solution (10 mmol, pH=8.5) and methanol (1:1, v/v) as mixed solvents, and the self-polymerization reaction time is 24 hours; after the polymerization reaction is finished, cleaning the PDA/CF catalytic film with ultrapure water for several times, and vacuum drying at 60 ℃ for 2 hours;
(3)NH 2 preparation of a CuMOF/PDA/CF composite catalytic film: 203 mg of copper nitrate trihydrate (Cu (NO 3 ) 2 ·3H 2 O) and 152.5 mg of 2-aminoterephthalic acid (NH) 2 -H 2 BDC) was added together to 10 ml of N, N-dimethylformamide solvent (DMF) and sonicated for 15 minutes to give a homogeneous solution. Then mixing the catalyst with the PDA/CF catalytic film obtained in the step (2), transferring the mixture into a high-pressure reaction kettle, and reacting for 12 hours at 120 ℃ to prepare NH 2 -a CuMOF/PDA/CF composite catalytic membrane. Finally, removing MOF particles deposited on the surface of the catalytic film by ultrasonic cleaning in ultrapure water for 30s, and drying in vacuum at 60 ℃ for 2 hours;
(4) Pretreatment of a pre-column core: sequentially carrying out ultrasonic cleaning on the air pre-column core by methanol and ultrapure water for 5 minutes respectively, and drying;
(5) Online NH 2 -assembly of a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system: NH is added to 2 The CuMOF/PDA/CF composite nano catalytic membrane is filled into the pre-column core pretreated in the step (4), then is filled into a matched column sleeve to obtain a catalytic membrane reactor, then a high performance liquid chromatograph six-way valve sampler and a sample switching device are arranged between the chromatographic column of the high performance liquid chromatograph and the catalytic membrane reactor, and the chromatographic column, the six-way valve sampler, the sample switching device and the catalytic membrane are reacted by using a 1/16 inch polyether ether ketone (PEEK) pipe and a nutThe devices are directly connected to finish on-line NH 2 Construction of a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system.
In FIG. 2, the resulting online NH is shown 2 The using method of the combined system of the CuMOF/PDA/CF catalytic membrane reactor and the high performance liquid chromatography is as follows:
first, the following are respectively stated with respect to the loading state and the sampling state:
sample switching device sample injection state: and the outlet of the catalytic membrane reactor is communicated with a sample inlet of the six-way valve sample injector through a sample switching device.
Sample switching device loading state: namely, the outlet of the catalytic membrane reactor is communicated with the waste liquid port of the sample switching device through the sample inlet of the sample switching device, and liquid directly enters the waste liquid barrel through the waste liquid port.
Sample introduction state of six-way valve sample injector: and introducing the effluent liquid reserved in the quantitative ring into the chromatographic column from the mobile phase under the drive of a high-pressure pump of the high-performance liquid chromatograph.
Sample loading state of six-way valve sample injector: and after the reaction of the catalytic membrane reactor, the effluent enters a quantitative ring of the six-way valve sampler along the PEEK pipe by a sample switching device to finish loading.
Secondly, the specific operation is as follows: pumping mixed solution of p-nitrophenol and sodium borohydride into a catalytic membrane reactor at a certain flow rate by using a constant flow injection pump to perform catalytic reaction, then switching a sample switching device to a sample feeding state, switching the sample feeding device to a sample feeding state, and enabling effluent after the reaction to enter a quantitative ring of a six-way valve sample feeder along a PEEK tube by the sample switching device to finish sample feeding, as shown in FIG. 2 b; after loading, rapidly switching the sample switching device to a loading state, switching the six-way valve sampler to the loading state, introducing the effluent liquid reserved in the quantitative loop into the chromatographic column from the mobile phase under the drive of the high-pressure pump of the high-performance liquid chromatograph, and entering a subsequent detector for real-time analysis and detection, as shown in fig. 2 c; when the effluent of the catalytic membrane reactor is not required to be monitored in real time, the sample switching device can be switched to the loading position, and at the moment, the solution after the reaction is directly discharged from the No. 3 waste liquid port of the sample switching device without entering the six-way valve sampler and the high performance liquid chromatograph, as shown in fig. 2 a.
Fig. 3 is a topography of a material. FIG. 3a is a scanning electron microscope image of a commercial copper foam at 500 Xmagnification, from which it can be seen that the commercial copper foam exhibits a smooth-surfaced three-dimensional network structure; FIG. 3b is a scanning electron microscope image of a PDA/CF catalytic film at 2000 x magnification, showing that the self-polymerized growing Polydopamine (PDA) coating exhibits a crescent structure, tightly wrapping the surface of the copper foam substrate; FIG. 3c is NH 2 Scanning electron microscopy of-CuMOF/PDA/CF catalytic membrane at 5000 times magnification, it can be observed that NH is supported 2 After CuMOF, the surface of the catalytic film presents a nano flower-like structure formed by a nano sheet array, and the outer layer NH 2 -a CuMOF thickness of 5-10 microns.
FIG. 4 is an XRD spectrum of a material in which diffraction peaks at 10.9 °, 12.5 °, 12.8 °, 14.1 °, 17.6 °, 18.9 °, 21.3 ° and 25.4 ° belong to NH 2 Characteristic diffraction peaks of CuMOF, whereas Jiang Yanshe peaks at 43.7 °, 50.8 ° and 74.5 ° are derived from zero valent copper in the base copper foam, the above characterization results demonstrate NH 2 Successful preparation of a CuMOF/PDA/CF composite nano catalytic membrane.
Example 2
NH 2 The CuMOF/PDA/CF catalytic membrane is compared with the other self-made catalytic membranes for the degradation efficiency of p-nitrophenol.
Determination of NH produced in example 1 of the present invention 2 CuMOF/PDA/CF catalytic film and self-made CF, PDA/CF (i.e. intermediate product prepared in example 1), NH 2 Comparison of the degradation efficiency of p-nitrophenol by CuMOF/CF catalytic membrane.
NH 2 The CuMOF/CF catalytic membrane is as NH in example 1 2 -preparation of a CuMOF/PDA/CF catalytic film preparation procedure wherein step (2) was omitted and the remaining steps were identical to example 1.
P-nitrophenol degradation experiments: a mixture of 30 ml of 1 mmol/l p-nitrophenol and 0.04 mol/l sodium borohydride was prepared and placed in a 100 ml beaker and stirred well. At room temperature, a piece of catalytic film of different types is respectively added for catalytic degradation reaction, and the mixed solution is continuously stirred in the reaction process. At the 6 th minute, 0.5 ml of the reaction solution was taken out from the reaction system, diluted with ultrapure water, and then examined by using an ultraviolet-visible spectrophotometer to obtain the degradation efficiency of each catalytic film in the bulk reaction, and the results are shown in Table 1.
The catalytic properties of the four catalytic films are shown in Table 1, wherein the pure CF catalytic film and the PDA/CF catalytic film have poorer degradation properties of p-nitrophenol, namely 17.3 percent and 39.5 percent (the scanning electron microscope images of the two catalytic films are respectively shown in fig. 3a and 3 b), and NH 2 -CuMOF/CF and NH 2 The catalytic activity of the CuMOF/PDA/CF catalytic membrane is as high as 92.4% and 99.8%, compared with NH without polydopamine coating modification 2 -CuMOF/CF catalytic membrane vs NH 2 The activity of the CuMOF/PDA/CF catalytic membrane is improved by 7.4%, which is presumably related to the more abundant reactive sites formed on the surface of the catalytic membrane after the polydopamine coating is modified.
TABLE 1 comparison of the degradation Properties of p-nitrophenol by four different catalytic films
Example 3
Providing an on-line NH obtained in example 1 2 -use of a cumofpda/CF catalytic membrane reactor-high performance liquid chromatography system for removing p-nitrophenol, a water environmental contaminant, comprising the steps of:
the standard p-nitrophenol solution was prepared in ultrapure water. Delivery of 1 mmole/liter of p-nitrophenol and NaBH using a constant flow syringe pump 4 Through NH 2 The reaction effluent is conveyed to a high performance liquid chromatograph by using a 1/16 inch PEEK tube, a sample switching device and a six-way valve injector to monitor the reaction degradation efficiency in real time, and the result is shown in figure 5.
Wherein, the reaction system conditions are set as follows:
when the number of the filling sheets of the catalytic film is 1, the flow rate is 0.1-2 ml/min, and the NaBH 4 The results are shown in FIG. 5a when the concentration is 20 to 40 times that of p-nitrophenol.
When NaBH 4 The result is shown in FIG. 5b when the concentration is 30 times that of p-nitrophenol, the flow rate is 0.1-2 ml/min, and the number of filling sheets of the catalytic film is 1-4.
The test conditions were as follows: the chromatographic column is an XDB-C18 column with the size of 5 microns and the volume ratio of 4.6X150 mm, the volume ratio of mobile phase methanol to water is 7:3, the flow rate is 1.0 ml/min, the detection wavelength is 317 nm, the sample injection volume is 20 microliters, and the column temperature is 30 ℃.
Screening to obtain online NH 2 The reaction conditions matched with the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system are as follows: naBH 4 The concentration is 20 to 40 times, preferably 30 to 40 times of the concentration of the p-nitrophenol; the filling amount of the catalytic film is 1-4 sheets, preferably 2-4 sheets; the flow rate is 0.1-2 ml/min, preferably 0.1-1 ml/min.
Example 4
Online NH 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system and online NH 2 -comparison of stability of CuMOF/CF catalytic membrane reactor-high performance liquid chromatography system.
Determination of the on-line NH produced in example 1 of the present invention 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system and online NH prepared in example 2 2 -long-term stability of a CuMOF/CF catalytic membrane reactor-high performance liquid chromatography system to remove p-nitrophenol, a water environmental pollutant, the apparatus diagram of which is shown in FIG. 2, comprising the steps of:
firstly, ultrasonic cleaning is sequentially carried out on an empty solid phase extraction column core (10 multiplied by 4.6 mm) for five minutes by using methanol and water, then a catalytic membrane is filled into the column core, and the catalytic membrane is assembled into a column sleeve to form the catalytic membrane reactor. Next, as shown in fig. 2, a constant flow injection pump, a catalytic membrane reactor, a sample switching device, and a six-way valve injector were directly connected to a high performance liquid chromatograph through a 1/16 inch polyetheretherketone tube and a nut. After the catalytic reaction starts, the reaction effluent is monitored in real time by a high performance liquid chromatograph every 20 minutes:
(1) The sample switching device and the six-way valve injector are in the loading state within 0-20 minutes, as shown in fig. 2a, at the moment, the reaction solution (1 mmol/L p-nitrophenol and 0.04 mol/L sodium borohydride mixed solution) is pumped into the catalytic membrane reactor by a constant flow injection pump at the flow rate of 0.1 ml/minute for reaction, and effluent is discharged from the waste liquid outlet of the six-way valve 1;
(2) When 20 minutes, the sample switching device is switched to a sample injection state, the six-way valve sample injector is kept in the sample injection state, and as shown in fig. 2b, the reaction liquid enters a quantitative ring of the six-way valve sample injector from the sample switching device to finish sample injection;
(3) After loading is completed, the sample switching device is rapidly switched to a loading state of the six-way valve sampler, and as shown in fig. 2c, the effluent in the quantitative ring is brought into a chromatographic column of the high performance liquid chromatograph by a mobile phase for analysis and detection;
(4) After a few seconds, both the sample switching device and the six-way valve injector are switched to Loading state, and the state setting in the step (1) is restored, as shown in fig. 2 a; the operation is circulated once every 20 minutes, thus realizing online NH 2 The results of the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system and its stability test are shown in FIG. 6.
FIG. 6 shows that when the number of the catalytic membrane filling sheets is 1, the catalytic membrane filling sheets are in-line NH without polydopamine coating modification 2 Comparison between CuMOF/CF catalytic membrane reactor and high performance liquid chromatography system, the online NH prepared by the invention 2 After the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system is continuously operated for 300 minutes, the degradation rate of more than 70 percent of p-nitrophenol in the ultra-pure water environment can still be realized, and the degradation rate can be more than 90 percent within the first 60 minutes. While online NH without polydopamine modification 2 The CuMOF/CF catalytic membrane reactor-high performance liquid chromatography system has the catalytic activity of only 36% after 300 minutes of operation, which indicates that the loading of the polydopamine coating in the catalytic membrane successfully improves the stability of the MOF catalyst and gives higher reaction activity and good stability to an online system. When the number of the filling sheets of the catalytic film is 4, NH is online 2 The CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system still maintains the degradation activity of more than 94% after 300 minutes of continuous operation, which shows that the system is in the presence ofThe water environment restoration field has potential application prospect.
FIGS. 7a and 7b are NH before use, respectively 2 -CuMOF/PDA/CF and NH 2 Scanning electron microscopy at 5000 Xmagnification of the CuMOF/CF catalytic membrane, FIGS. 7c and 7d being NH after use respectively 2 -CuMOF/PDA/CF and NH 2 Scanning electron microscopy at 5000 Xmagnification of the CuMOF/CF catalytic membrane. By comparing SEM images of the catalytic membrane before and after use, it can be seen that NH functionalized with PDA 2 After the catalytic reaction is completed, the CuMOF/PDA/CF catalytic film has the surface NH of 2 The nano-platelet array structure of the CuMOF is preserved, and a large amount of active nano-particles are generated simultaneously; while NH not functionalized by PDA 2 After use of the CuMOF/CF catalytic membrane, NH on the surface 2 The CuMOF coating was significantly detached and the stability was poor, which is consistent with the performance results of the two catalytic membranes in FIG. 6.
Comparative example 1
Online NH 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system-off-line batch mode NH 2 Comparison of the degradation efficiency of p-nitrophenol by CuMOF/PDA/CF catalytic membrane.
Determination of on-line NH produced in example 1 of the present invention 2 -CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system and NH in off-line batch mode 2 Comparison of the degradation efficiency of p-nitrophenol by CuMOF/PDA/CF catalytic membrane.
P-nitrophenol degradation experiment in offline batch mode: a mixture of 30 ml of 1 mmol/l p-nitrophenol and 0.03 mol/l sodium borohydride was prepared and placed in a 100 ml beaker and stirred well. At room temperature, add a slice of NH 2 The CuMOF/PDA/CF catalytic membrane carries out catalytic degradation reaction, and the mixed solution is continuously stirred in the reaction process. Taking out 0.5 ml of reaction solution from the reaction system within a preset time interval (1 minute), diluting with ultrapure water, detecting with an ultraviolet-visible spectrophotometer to obtain catalytic degradation efficiency at different moments, and calculating a first-order reaction rate constant.
Online NH 2 The reaction conditions of the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system are set as follows: the number of the filling sheets of the catalytic film is 1,the flow rate was 0.2 ml/min, the p-nitrophenol concentration was 1 mmol/l, and the sodium borohydride concentration was 0.03 mol/l.
In off-line intermittent mode, NH 2 The first order reaction rate constant of the-CuMOF/PDA/CF catalytic membrane is 0.3049min -1 While on-line NH 2 The first-order reaction rate constant of the-CuMOF/PDA/CF catalytic film reactor-high performance liquid chromatography system is up to 76.7min -1 . Compared with the traditional off-line intermittent mode, the invention prepares the on-line NH 2 The reaction rate of the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system is improved by 2-3 orders of magnitude due to the efficient mass and heat transfer rate and the high activity MOF-based catalyst loading of the continuous flow mode. At the same time, compared with batch mode, online NH 2 The CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography system mode does not require additional separation and recovery steps for the catalytic membrane, and is simpler, faster, more labor-saving and more economical.
Claims (10)
1. Online NH 2 The combined device comprises a catalytic membrane reactor, a liquid chromatography six-way valve sample injector and a high performance liquid chromatograph which are connected in sequence; wherein:
the catalytic membrane reactor comprises a pre-column sleeve and a pre-column core, wherein a catalytic membrane is filled in the pre-column core, and is a metal organic framework/polydopamine/copper foam composite nano catalytic membrane, namely NH 2 -a CuMOF/PDA/CF composite nano catalytic membrane; the NH is 2 In the CuMOF/PDA/CF composite nano catalytic film, the self-polymerized and grown polydopamine coating presents a crescent structure and is tightly coated on the surface of the copper foam substrate, which is marked as PDA/CF; loading NH on PDA/CF 2 -cumorf; the catalytic film surface presents a nano flower-like structure formed by a nano sheet array;
the catalytic membrane reactor comprises a catalytic membrane reactor body, wherein a sample switching device is arranged between an outlet of the catalytic membrane reactor and a sample inlet of a liquid chromatography six-way valve sample injector, the sample switching device is provided with two circulation branches, and the two circulation branches can be switched, wherein: a first flow-through branch: the outlet of the catalytic membrane reactor is communicated with a sample inlet of a six-way valve sample injector through a sample switching device; a second circulation branch: and the outlet of the catalytic membrane reactor is communicated with the waste liquid port of the sample switching device through the sample inlet of the sample switching device.
2. The combination device according to claim 1, wherein the catalytic membrane is filled in an amount of 1 to 4 sheets in the axial direction in the pre-column core.
3. The combination according to claim 1, wherein the NH 2 In the-CuMOF/PDA/CF composite nano catalytic film, NH 2 -a CuMOF thickness of 5-10 microns.
4. The combination according to claim 1, wherein the NH 2 The preparation of the CuMOF/PDA/CF composite nano catalytic film comprises the following steps:
(1) immersing the pretreated copper foam in a dopamine hydrochloride solution, and carrying out self-polymerization on dopamine on the surface of the copper foam at room temperature to obtain a PDA/CF catalytic membrane;
(2) adding copper nitrate trihydrate and 2-amino terephthalic acid into N, N-dimethylformamide solvent together, performing ultrasonic dispersion to obtain a uniform solution, and then mixing with the PDA/CF catalytic film obtained in the step (1) to perform hydrothermal reaction to obtain NH 2 -a CuMOF/PDA/CF composite nano catalytic membrane.
5. The combination according to claim 4, wherein in the step (1), the self-polymerization time is 12 to 24 hours; in the step (2), the hydrothermal synthesis time is 3-12 hours, and the hydrothermal synthesis temperature is 100-120 ℃.
6. An NH as claimed in any one of claims 1 to 5 2 The construction method of the online catalytic membrane reactor-high performance liquid chromatography combined device of the CuMOF/PDA/CF is characterized by comprising the following steps:
1) NH is added to 2 -CuMOF/PDA/CF composite nano-catalysisFilling the membrane into the pretreated pre-column core, and then filling the pre-column core into a matched pre-column sleeve to obtain a catalytic membrane reactor;
2) Then, a six-way valve sample injector and a sample switching device of the high performance liquid chromatograph are arranged between a chromatographic column and a catalytic membrane reactor of the high performance liquid chromatograph to finish online NH 2 Construction of a CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined device.
7. An online NH as claimed in any one of claims 1 to 5 2 The application of the CuMOF/PDA/CF catalytic membrane reactor-high performance liquid chromatography combined device in removing water environment pollutant p-nitrophenol.
8. The use according to claim 7, characterized in that it is in particular:
delivery of p-nitrophenol and NaBH using constant flow syringe pump 4 To NH 2 The CuMOF/PDA/CF catalytic membrane reactor carries out chemical reaction, and effluent after the reaction is conveyed to a high performance liquid chromatograph for real-time monitoring.
9. The use according to claim 7, wherein,
when real-time monitoring is needed, liquid flows through a sample switching device after reacting in a catalytic membrane reactor, then enters a quantitative ring in a six-way valve sampler to finish loading, and effluent liquid reserved in the quantitative ring is introduced into a chromatographic column of a high performance liquid chromatograph to enter a real-time analysis and detection of a subsequent detector;
when real-time monitoring is not needed, the solution after reaction in the catalytic membrane reactor is directly discharged from the waste liquid port of the sample switching device and does not enter the six-way valve sample injector and the high performance liquid chromatograph.
10. The use according to claim 7, wherein p-nitrophenol and NaBH 4 NaBH in the mixed solution of (2) 4 The concentration ratio of the p-nitrophenol to the p-nitrophenol is 1: 20-40, wherein the concentration of p-nitrophenol is 0.5-1 mmol/L; usingConstant flow injection pump for delivering p-nitrophenol and NaBH 4 The flow rate of the mixed solution is 0.1-2 ml/min.
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