CN117899936A - Composite material of palladium-loaded bimetal organic framework compound modified foam nickel and preparation method and application thereof - Google Patents
Composite material of palladium-loaded bimetal organic framework compound modified foam nickel and preparation method and application thereof Download PDFInfo
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- CN117899936A CN117899936A CN202310526328.6A CN202310526328A CN117899936A CN 117899936 A CN117899936 A CN 117899936A CN 202310526328 A CN202310526328 A CN 202310526328A CN 117899936 A CN117899936 A CN 117899936A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 318
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 159
- 239000006260 foam Substances 0.000 title claims abstract description 145
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 93
- 239000013384 organic framework Substances 0.000 title claims abstract description 90
- 150000001875 compounds Chemical class 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000009467 reduction Effects 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000015556 catabolic process Effects 0.000 claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 claims abstract description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 238000004070 electrodeposition Methods 0.000 claims description 41
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 24
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 17
- 238000004729 solvothermal method Methods 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- -1 compound modified nickel Chemical class 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 37
- 239000000243 solution Substances 0.000 description 30
- 238000005406 washing Methods 0.000 description 14
- 238000006298 dechlorination reaction Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007306 turnover Effects 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
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- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of electrodes, and particularly relates to a palladium-loaded bimetal organic framework compound modified foam nickel composite material, and a preparation method and application thereof. The palladium-loaded bimetal organic framework compound modified foam nickel composite material comprises foam nickel and a palladium-loaded bimetal organic framework compound layer attached to holes and surfaces of the foam nickel; the palladium-loaded bimetallic organic framework compound comprises a bimetallic organic framework compound and nano palladium; the bimetal organic framework compound is formed by coordination self-assembly of metal nickel, iron and terephthalic acid; the nano palladium is loaded into the bimetallic organic framework compound and distributed on the surface of the bimetallic organic framework compound. Test results show that the palladium-loaded bimetal organic framework compound modified foam nickel composite material is used as a working electrode in electrocatalytic hydrogenation reduction, and has high TCAA removal rate and high stability in electrochemical reduction degradation of TCAA.
Description
Technical Field
The invention belongs to the technical field of electrodes, and particularly relates to a palladium-loaded bimetal organic framework compound modified foam nickel composite material, and a preparation method and application thereof.
Background
Trichloroacetic acid (TCAA) is a common disinfection by-product of drinking water and is the most hazardous component of chloroacetic acid. Is widely distributed in nature and is difficult to degrade, and has proved to have cancerogenic, teratogenic and mutagenic risks. It is worth noting that the chloro group in the TCAA molecule is the root cause of toxicity, so that the research on the efficient and rapid dechlorination method has important practical application value.
Currently, there are various methods for removing chlorine-containing organics in wastewater treatment. The electrochemical reduction method has the advantages of high reaction speed, high selectivity, mild reaction condition, no secondary pollution and the like, becomes a very promising dechlorination technology, and attracts more and more environmental researchers' attention in the world. The technology is a method for removing chlorine in the pollutant in the form of Cl - by utilizing electrochemical reduction reaction, and comprises direct electron transfer and electrocatalytic hydrodechlorination reaction. In general, direct electron transfer to accomplish dechlorination requires a large amount of energy, so electrocatalytic hydrodechlorination plays a major role in the reaction process. Palladium is considered the most efficient electrocatalytic hydrodechlorination catalyst because its special external electronic configuration (4 d10s 2) tends to adsorb active hydrogen (H, a strong reducing agent) generated by electrolysis of water on the surface, which attacks the positively charged C atoms of chlorinated organics, resulting in the cleavage of the C-CI bond to complete the dechlorination. In addition, palladium also has excellent H-storage capacity, so that H-and chloroacetic acid continuously interact in an aqueous medium, and the sustainability and stability of the electrode are ensured.
In order to reduce industrial cost to the greatest extent and improve the electrocatalytic hydrodechlorination efficiency of palladium catalysts, the most commonly used method at present is to load the catalysts on base materials with different properties, such as carbon materials, foam metals, graphene and the like. The study selects porous foam nickel with good conductivity as a substrate, but the agglomeration and instability of palladium catalyst affect the practical application. This is mainly due to the low specific surface area of the nickel foam which limits the dispersion of palladium nanoparticles with high specific surface energy. Therefore, the addition of an intermediate layer between the nickel foam and the metal catalyst has great academic research value. The metal-organic frameworks are self-assemblies of organic and inorganic hybrid materials, whose high porosity, adjustable pore structure and high specific surface area have become a popular choice for catalyst supports. With the increasing manifestation of the defects of single function, weak catalytic performance and the like of a single metal-organic framework, the application of the metal-organic framework material is greatly limited. Therefore, finding new methods to develop high performance metal organic framework materials has significant research value.
Disclosure of Invention
In view of the above, the present invention aims to provide a composite material of palladium-supported bimetal organic framework compound modified foam nickel, which has high TCAA removal rate and good TCAA removal stability.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a palladium-loaded bimetal organic framework compound modified foam nickel composite material, which comprises foam nickel and a palladium-loaded bimetal organic framework compound layer attached to holes and surfaces of the foam nickel; the palladium-loaded bimetallic organic framework compound comprises a bimetallic organic framework compound and nano palladium; the bimetal organic framework compound is formed by coordination self-assembly of metal nickel, iron and terephthalic acid; the nano palladium is loaded into the bimetallic organic framework compound and distributed on the surface of the bimetallic organic framework compound.
Preferably, the bimetallic organic framework compound is in the form of a sheet;
the particle size of the nano palladium is 5-10nm;
The load of nano palladium in the composite material is 7-139mg/g.
The invention also provides a preparation method of the palladium-loaded bimetal organic framework compound modified foam nickel composite material, which comprises the following steps:
Performing metal nickel and ferroelectric chemical deposition by taking the foam nickel as a negative electrode to obtain nickel-iron bimetal pre-deposition foam nickel;
placing the nickel-iron bimetal pre-deposited foam nickel into solvent thermal reaction raw material liquid to perform solvent thermal reaction to obtain bimetal organic framework compound modified foam nickel; the solvent thermal reaction raw material liquid comprises nickel chloride, ferric trichloride, terephthalic acid and a mixed solvent, wherein the mixed solvent comprises N, N-dimethylformamide, ethanol and water;
Placing the bimetal organic framework compound modified foam nickel into a palladium-containing solution for adsorption treatment, and performing electrochemical reduction on the obtained adsorption electrode to obtain the palladium-loaded bimetal organic framework compound modified foam nickel composite material; solutes in the palladium-containing solution include palladium chloride and sodium chloride.
Preferably, the conditions for electrochemical deposition of nickel include: the electrolyte comprises nickel chloride, ferric trichloride and ammonium chloride; the concentration of nickel chloride in the electrolyte is 0.02-0.07mol/L, the concentration of ferric trichloride is 0.07-0.12mol/L, and the concentration of ammonium chloride is 2-2.5mol/L; the current in the electrochemical deposition of the ferronickel bimetal is 0.2-2A, and the time is 100-500s.
Preferably, the mass ratio of the nickel chloride, the ferric trichloride and the terephthalic acid in the solvothermal reaction raw material liquid is (0.05-0.15): (0.18-0.26): (0.08-0.16); the ratio of the mass of the nickel chloride and the ferric trichloride to the volume of the mixed solvent is (0.05-0.15): (0.18-0.26) g: (25-50) mL.
Preferably, the solvothermal reaction is carried out at a temperature of 120-180 ℃ for 12-24 hours.
Preferably, the concentration of palladium chloride in the palladium-containing solution is 0.5-10mmol/L, and the concentration of sodium chloride is 30-300mmol/L.
Preferably, the temperature of the adsorption treatment is 25-30 ℃.
Preferably, the electrochemical reduction conditions include: the electrolyte is sodium chloride solution; the cathode current density is 2-2.5mA cm -2, and the time is 30-50min.
The invention relates to an electrochemical deposition device for ferronickel bimetal, which comprises an electrolytic cell, wherein a working cavity is arranged in the electrolytic cell;
Still including high-efficient electrode replacement subassembly, high-efficient electrode replacement subassembly includes positive electrode support, lift cylinder, negative pole support, rotating electrical machines and negative pole seat, the bottom right side of positive electrode support is connected with the top right side of electrolytic cell, the top left side of electrolytic cell is provided with the mounting hole, lift cylinder cooperation is installed in the mounting hole, the negative pole support is installed at the output of lift cylinder, the rotating electrical machines is installed in the left end of negative pole support, the left end middle part of negative pole support is provided with the through-hole, the output of rotating electrical machines passes the through-hole and is connected with the left end of negative pole seat, the top and the bottom of negative pole seat all are provided with the locating hole.
The device can more conveniently feed and discharge the foamed nickel, improves the preparation efficiency of the nickel-iron bimetallic foamed nickel, and is beneficial to improving the TCAA removal rate.
The invention relates to an electrochemical deposition device for ferronickel bimetal, which further comprises four groups of springs and four groups of clamping plates, wherein round grooves are formed in the inner ends of two groups of positioning holes, the four groups of clamping plates are respectively and laterally connected with the left side and the right side of the two groups of round grooves, and the inner ends and the outer ends of the four groups of springs are respectively connected with the outer ends of the four groups of clamping plates and the outer ends of the two groups of round grooves.
According to the electrochemical deposition device for the ferronickel bimetal, the top ends of the two groups of clamping plates on the upper side and the bottom ends of the two groups of clamping plates on the lower side are respectively provided with a first chamfer.
According to the electrochemical deposition device for the ferronickel bimetal, the top end of the upper side positioning hole and the bottom end of the lower side positioning hole are respectively provided with the second chamfer.
The invention relates to an electrochemical deposition device for nickel-iron bimetal, wherein the inner ends of four groups of clamping plates are provided with anti-skid patterns.
The invention relates to an electrochemical deposition device for ferronickel bimetal, which also comprises a concentration detector, wherein the concentration detector is arranged at the front end of an electrolytic cell.
The invention relates to an electrochemical deposition device for ferronickel bimetal, which also comprises an alarm, wherein the alarm is arranged at the front end of an electrolytic cell and is electrically connected with a concentration detector.
The invention relates to an electrochemical deposition device for ferronickel bimetal, which also comprises a liquid supplementing pipe and a liquid discharging pipe, wherein the output end of the liquid supplementing pipe and the input end of the liquid discharging pipe are respectively communicated with the top and the bottom of the right end of a working cavity.
Compared with the prior art, the invention has the beneficial effects that: when the electrochemical deposition device for the nickel-iron bimetal foam nickel is used, two groups of foam nickel can be inserted into two groups of positioning holes respectively, at the moment, the lifting cylinder can be operated to retract to drive the lower side foam nickel to be inserted into the electrolytic cell to start electrochemical deposition reaction, after the foam nickel is plated, the lifting cylinder is operated to output to drive the negative electrode bracket to rise, meanwhile, the rotating motor is operated to output to drive the negative electrode seat to turn over 180 degrees, at the moment, the lifting cylinder can be operated to retract to drive the lower side foam nickel to be inserted into the electrolytic cell to perform electrochemical deposition reaction again, at the same time, the foam nickel plated on the upper side can be manually removed and replaced with the foam nickel to be plated, and the operations above are repeated, so that the nickel-iron bimetal foam nickel can be more efficiently prepared and produced; through the device, can be more convenient go up the unloading to foam nickel and change, improve the preparation efficiency of ferronickel bimetal foam nickel to the practicality has been strengthened.
The invention also provides application of the palladium-loaded bimetal organic framework compound modified foam nickel composite material in electrochemical reduction degradation of TCAA as a working electrode in electrocatalytic hydrogenation reduction.
The invention provides a palladium-loaded bimetal organic frame compound modified foam nickel composite material, which comprises foam nickel, foam nickel holes and a palladium-loaded bimetal organic frame compound layer attached to the surface; the palladium-loaded bimetallic organic framework compound comprises a bimetallic organic framework compound and palladium; the bimetal organic framework compound is formed by coordination self-assembly of metal nickel, iron and terephthalic acid; the palladium is loaded into the bimetallic organic framework compound and distributed on the surface of the bimetallic organic framework compound. In the invention, the surface of the composite material is a palladium-loaded bimetal organic framework compound layer, palladium is loaded into the bimetal organic framework compound and distributed on the surface of the bimetal organic framework compound, meanwhile, foam nickel and the foam nickel holes are tightly combined with the palladium-loaded bimetal organic framework compound layer attached to the surface, so that the bonding strength of palladium in the composite material is improved, and palladium is not easy to fall off; in addition, the bimetal organic framework compound structure has high specific surface area, improves the number of adsorption sites on the surface of the composite material, is beneficial to adsorbing more TCAA on the surface of the composite material in the application process, and promotes the dechlorination reaction; palladium nanoparticles are supported in the bimetallic organic framework compound to promote the generation of more H to participate in the dechlorination reaction.
When the composite material provided by the invention is used for TCAA dechlorination, the highly dispersed palladium nano particles can provide more H, and the surface concentration of TCAA in the dechlorination reaction is increased; can optimize the constant potential dechlorination effect of TCAA and improve the maximum dechlorination rate. In addition, the structure of the bimetal organic framework compound layer composite foam nickel of the composite material can strengthen the adsorption of TCAA, improve the dispersion of palladium nano particles and improve the activity, the selectivity and the stability of an electrode.
The test results of the examples show that the composite material of the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel has high roughness; when the composite material of the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel is used as a working electrode in electrochemical reduction and degradation of TCAA in electrocatalytic hydrogenation, the composite material continuously works for 1mg/L of TCAA for 2.5 hours under the condition of-1.2V, the TCAA is completely removed, the continuous four-time degradation efficiency is basically unchanged, and the stability is high.
Drawings
FIG. 1 is an SEM image of the product of each stage of preparation of example 1, wherein in FIG. 1, (a) is nickel foam, (b) is nickel pre-deposited nickel foam, (c) and (d) are nickel foam modified by a bimetallic organic framework compound, and (e) and (f) are composite materials of palladium-loaded bimetallic organic framework compound modified nickel foam;
FIG. 2 is a TCAA degradation graph of application example 1 and comparative application example 1;
FIG. 3 is a TCAA degradation graph showing four continuous degradations of a composite material modified with a palladium-loaded bimetallic organic framework compound in application example 1;
FIG. 4 is a TCAA degradation graph of application example 2;
FIG. 5 is a schematic view of the structure of the present invention;
FIG. 6 is a schematic top view of the negative electrode base of the present invention;
FIG. 7 is a schematic view of the splint structure of the present invention;
FIG. 8 is a schematic diagram of the front view of the present invention;
The reference numerals in the drawings: 1. an electrolytic cell; 2. a working chamber; 3. a positive electrode support; 4. a lifting cylinder; 5. a negative electrode support; 6. a rotating electric machine; 7. a negative electrode base; 8. positioning holes; 9. a spring; 10. a clamping plate; 11. a first chamfer; 12. a second chamfer; 13. anti-skid lines; 14. a concentration detector; 15. an alarm; 16. a fluid supplementing pipe; 17. and a liquid discharge tube.
Description of the embodiments
The invention provides a palladium-loaded bimetal organic framework compound modified foam nickel composite material, which comprises foam nickel and a palladium-loaded bimetal organic framework compound layer attached to holes and surfaces of the foam nickel; the palladium-loaded bimetallic organic framework compound comprises a bimetallic organic framework compound and nano palladium; the bimetal organic framework compound is formed by coordination self-assembly of metal nickel, iron and terephthalic acid; the nano palladium is loaded into the bimetallic organic framework compound and distributed on the surface of the bimetallic organic framework compound.
In the present invention, the bimetal organic framework compound is in a sheet form.
In the present invention, the particle diameter of the nano palladium is preferably 5 to 10nm, more preferably 6 to 10nm.
In the invention, the loading of nano palladium in the composite material is preferably 7-139mg/g, more preferably 20-120mg/g.
The invention also provides a preparation method of the palladium-loaded bimetal organic framework compound modified foam nickel composite material, which comprises the following steps:
performing nickel-iron bimetal electrochemical deposition by taking the foam nickel as a negative electrode to obtain metal nickel and iron pre-deposited foam nickel;
Placing the metal nickel and iron pre-deposited foam nickel into solvent thermal reaction raw material liquid to carry out solvent thermal reaction to obtain the bimetal organic framework compound modified foam nickel; the solvent thermal reaction raw material liquid comprises nickel chloride, ferric trichloride terephthalic acid and a mixed solvent, wherein the mixed solvent comprises N, N-dimethylformamide, ethanol and water;
Placing the bimetal organic framework compound modified foam nickel into a palladium-containing solution for adsorption treatment, and performing electrochemical reduction on the obtained adsorption electrode to obtain the palladium-loaded bimetal organic framework compound modified foam nickel composite material; solutes in the palladium-containing solution include palladium chloride and sodium chloride.
In the present invention, each component in the preparation method is a commercially available product well known to those skilled in the art unless specified otherwise.
The invention takes foam nickel as a negative electrode to carry out nickel-iron bimetal electrochemical deposition to obtain nickel-iron bimetal pre-deposition foam nickel.
In the present invention, the porosity of the nickel foam is preferably 95-98%; the density is preferably 0.2-0.3g/cm 3; the thickness is preferably 0.10-0.15cm. The source of the foam nickel is not particularly limited, and the foam nickel is commercially available.
The invention preferably pre-treats the nickel foam prior to electrochemical deposition of the ferronickel bimetal; the pretreatment comprises acid leaching, acetone washing and ethanol washing which are sequentially carried out. In the present invention, the acid for acid leaching is preferably dilute sulfuric acid; the mass percentage concentration of the dilute sulfuric acid is preferably 10wt%. In the present invention, the acid leaching time is preferably 60 to 90min, more preferably 70 to 80min. The invention removes the oxide layer on the surface of the foam nickel by acid leaching.
In the present invention, the time of the acetone washing and the ethanol washing is preferably independently 10 to 30 minutes, more preferably 15 to 25 minutes. In the present invention, the acetone washing and the ethanol washing are preferably performed under ultrasonic conditions; the present invention is not particularly limited to the above ultrasound, and ultrasound well known to those skilled in the art may be used.
After pretreatment, the invention takes the pretreated foam nickel as a negative electrode to carry out nickel-iron bimetal electrochemical deposition to obtain the nickel-iron bimetal pre-deposition foam nickel.
In the invention, the positive electrode in the nickel-iron bimetallic electrochemical deposition is preferably a platinum sheet. In the present invention, the electrolyte in the electrochemical deposition of the ferronickel bimetal preferably comprises nickel chloride, ferric trichloride and ammonium chloride. In the present invention, the concentration of nickel chloride in the electrolyte is preferably 0.02 to 0.08mol/L, more preferably 0.02 to 0.07mol/L; the concentration of ferric trichloride is 0.07-0.12mol/L, more preferably 0.08-0.11mol/L; the concentration of ammonium chloride is preferably 2 to 2.5mol/L, more preferably 2 to 2.4mol/L. In the present invention, the nickel-iron bimetal electrochemical deposition is preferably constant current deposition. In the invention, the current in the electrochemical deposition of the ferronickel bimetal is preferably 0.2-2A, more preferably 0.2-1.7A; the time is preferably 100 to 500s, more preferably 150 to 450s.
After the nickel-iron bimetal pre-deposition nickel foam is obtained, the nickel-iron bimetal pre-deposition nickel foam is placed in solvent thermal reaction raw material liquid to carry out solvent thermal reaction, and the bimetal organic framework compound modified nickel foam is obtained.
In the invention, the solvothermal reaction raw material liquid comprises nickel chloride, ferric trichloride, terephthalic acid and a mixed solvent, wherein the mixed solvent comprises N, N-dimethylformamide, ethanol and water.
In the present invention, the mass ratio of nickel chloride, ferric trichloride and terephthalic acid in the solvothermal reaction raw material liquid is preferably (0.05-0.15): (0.18-0.26): (0.08-0.16), more preferably (0.05-0.11): (0.18-0.22): (0.10-0.16). In the present invention, the ratio of the mass of the nickel chloride and the ferric trichloride to the volume of the mixed solvent is preferably (0.05-0.15): (0.18-0.26) g: (25-50) mL, more preferably (0.05-0.11): (0.18-0.22) g: (30-50) mL. In the invention, the volume ratio of the N, N-dimethylformamide, the ethanol and the water in the mixed solvent is preferably 14:1:1.
In the present invention, the temperature of the solvothermal reaction is preferably 125 to 180 ℃, more preferably 140 to 170 ℃; the time is preferably 12 to 24 hours, more preferably 16 to 24 hours.
The invention prepares a bimetallic organic framework compound by a solvothermal method, uses nickel or iron as an inorganic metal center and is mutually connected with a bridged terephthalic acid organic ligand through self-assembly, thus forming a crystalline porous material with a periodic reticular structure.
After the solvothermal reaction, the invention preferably further comprises: and (3) carrying out solid-liquid separation on the solid-liquid mixture obtained by the solvothermal reaction, and washing and drying the obtained solid substance in sequence. The solid-liquid separation is not particularly limited, and solid-liquid separation well known to those skilled in the art may be employed, and specifically, filtration may be employed. In the present invention, the washing is preferably ethanol and water alternate washing; the number of times of washing with each of the ethanol and water is preferably 3. In the present invention, the temperature of the drying is preferably 80 ℃; the time is preferably 2 hours. In the present invention, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably-1X 10 2kPa--0.5×102 kPa.
After the bi-metal organic framework compound modified foam nickel is obtained, the bi-metal organic framework compound modified foam nickel is placed in a palladium-containing solution for adsorption treatment, and the obtained adsorption electrode is subjected to electrochemical reduction, so that the palladium-loaded bi-metal organic framework compound modified foam nickel composite material is obtained.
In the present invention, the solutes in the palladium-containing solution include palladium chloride and sodium chloride. In the present invention, the concentration of palladium chloride in the palladium-containing solution is preferably 0.5 to 10mmol/L, more preferably 1 to 9.5mmol/L, still more preferably 1.5 to 9mmol/L. In the present invention, the concentration of sodium chloride in the palladium-containing solution is preferably 30 to 300mmol/L, more preferably 50 to 280mmol/L, still more preferably 80 to 250mmol/L.
In the present invention, the temperature of the adsorption treatment is preferably 25 to 30 ℃, more preferably 28 to 30 ℃. In the present invention, the time of the adsorption treatment is based on the change of the palladium-containing solution from yellow to colorless. In the present invention, the adsorption treatment apparatus is preferably a shaker. In the invention, the yellow divalent palladium in the palladium-containing solution is continuously adsorbed to the adsorption site of the metal organic framework compound modified foam nickel during the adsorption treatment.
In the present invention, the electrolyte in the electrochemical reduction is preferably a sodium chloride solution. In the present invention, the concentration of the sodium chloride solution is preferably 2g/L. In the present invention, the cathode current density in the electrochemical reduction is preferably 2 to 2.5mA cm -2, more preferably 2.1 to 2.5mA cm -2; the time is preferably 30 to 50min, more preferably 30 to 45min.
The invention also provides application of the palladium-loaded bimetal organic framework compound modified foam nickel composite material in electrochemical reduction degradation of TCAA as a working electrode in electrocatalytic hydrogenation reduction.
The application of the invention is not particularly limited, and the electrochemical reduction degradation method of TCAA, which is well known to those skilled in the art, can be adopted.
In the present invention, the voltage in the electrochemical reduction degradation of TCAA is preferably-1.0 to 1.5V. In the invention, the concentration of TCAA in the electrochemical reduction degradation of TCAA is preferably 1-5mg/L. In the invention, the temperature of the electrochemical reduction degradation of the TCAA is preferably room temperature, more preferably 18-26 ℃; the temperature of the electrochemical reduction degradation of TCAA is preferably controlled by a constant temperature cooling water tank.
In the present invention, the electrode in the electrochemical reduction degradation of TCAA is preferably a three-electrode system. In the invention, the electrocatalytic hydrogenation reduction electrode (cathode, working electrode) in the electrochemical reduction degradation of TCAA is the composite material of the palladium-loaded bimetallic organic framework compound modified foam nickel in the technical scheme. In the present invention, the anode in the electrochemical reduction degradation of TCAA is preferably a platinum electrode. In the invention, the reference electrode in the electrochemical reduction degradation of TCAA is preferably an Ag/AgCl electrode. In the present invention, the TCAA electrochemical reduction degradation is preferably performed under stirring; the invention prevents the polarization of the TCAA solution system by stirring.
In order to further illustrate the present invention, the following describes in detail, with reference to examples, a palladium-supported bimetallic organic framework compound modified foam nickel composite material, and a preparation method and application thereof, which are not to be construed as limiting the scope of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
Placing 2cm multiplied by 0.12cm of foam nickel in 10wt% dilute sulfuric acid for pickling for 30min to remove a surface oxide layer, then performing ultrasonic cleaning in 25mL of acetone for 10min, and performing ultrasonic cleaning in 25mL of ethanol for 10min to obtain pretreated foam nickel;
The pre-deposition experiment adopts an invention device for electrochemical deposition of nickel-iron bimetal, when the device works, two groups of foam nickel can be inserted into two groups of positioning holes respectively, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel pretreated at the lower side to be inserted into an electrolytic cell to start electrochemical deposition reaction, after the foam nickel is plated, the lifting cylinder is operated to output to drive the negative electrode bracket to rise, meanwhile, the rotating motor is operated to output to drive the negative electrode bracket to turn over 180 degrees, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel at the lower side to be inserted into the electrolytic cell to perform electrochemical deposition reaction again, wherein the electrolyte is a mixed solution of nickel chloride, ferric chloride and ammonium chloride (the concentration of nickel chloride is 0.03mol/L, the concentration of ferric chloride is 0.08 mol/L), and the concentration of ammonium chloride is 2 mol/L), and the electrochemical deposition of nickel-iron bimetal is performed for 300s under the condition of constant current of 0.2A, so as to obtain the nickel-iron bimetal pre-deposition foam nickel. Meanwhile, the foam nickel plated on the upper side can be manually removed and replaced by the foam nickel to be plated, and the operations are repeated, so that the nickel-iron bimetal foam nickel can be more efficiently prepared and produced;
preparing 0.055g of nickel chloride, 0.187g of ferric trichloride, 0.16g of terephthalic acid and 50mL of mixed solvent (the mixed solvent is a mixture of N, N-dimethylformamide, ethanol and water according to the volume ratio of 14:1:1) to obtain solvothermal reaction raw material liquid, placing the nickel-iron bimetallic pre-deposited foam nickel into the solvothermal reaction raw material liquid, carrying out solvothermal reaction for 16h at 140 ℃, filtering the obtained solid-liquid mixture, alternately carrying out ethanol washing and water washing on the obtained solid substance for 3 times, and drying at 80 ℃ for 2h to obtain the bimetallic organic framework compound modified foam nickel;
Preparing a palladium-containing solution with the concentration of palladium chloride of 10mmol/L and the concentration of sodium chloride of 30mmol/L, placing the metal organic framework compound modified foam nickel into the palladium-containing solution, and carrying out adsorption treatment at the temperature of 30 ℃ until the palladium-containing solution becomes colorless; and placing the obtained adsorption electrode in 2g/L sodium chloride solution, and carrying out electrochemical reduction for 30min under the condition that the cathode current density is preferably 2.5mA cm -2, so as to obtain the palladium-loaded bimetal organic framework compound modified foam nickel composite material.
Scanning electron microscopy tests were performed on the nickel foam, nickel-iron bimetal pre-deposited nickel foam, the bimetal organic framework compound modified nickel foam and the palladium supported bimetal organic framework compound modified nickel foam composite material in example 1, and the SEM images obtained are shown in fig. 1, in which (a) is nickel foam, (b) is nickel-iron bimetal pre-deposited nickel foam, (c) and (d) are bimetal organic framework compound modified nickel foam, and (e) and (f) are palladium supported bimetal organic framework compound modified nickel foam composite materials. As can be seen from fig. 1, the foam nickel has a smoother surface and a small specific surface area; after nickel electrochemical deposition, the surface structure of the foam nickel is changed, and a large amount of nickel and iron atoms are loaded on the original smooth surface, so that the surface is roughened; after solvothermal reaction, the surface structure of the electrode is further changed, and a large number of sheet structures are stacked together, so that the specific surface area of the electrode is further increased, and the roughness is obviously improved; after adsorption treatment and electrochemical reduction, palladium nano-particles can be uniformly supported on the surface of the electrode, and the palladium is less shed after reaction.
The composite material of the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel obtained in the example 1 is used as a working electrode in electrocatalytic hydrogenation reduction to carry out TCAA electrochemical reduction degradation, and the conditions are as follows: before the electrolytic reduction dechlorination, adding 100mL of mixed solution into a cathode chamber, wherein the chemical composition of the mixed solution is 2mmol/L Na 2SO4 and 1mg/L aqueous solution of TCAA, and 100mL of aqueous solution of Na 2SO4 with the concentration of 2mmol/L is respectively added into an anode chamber; the composite material prepared in the embodiment 1 is used as a cathode working electrode to be connected with a power supply cathode, a platinum sheet is used as an anode to be connected with a power supply anode, an Ag/AgCl electrode is selected as a reference electrode, the potential is applied to be-1.2V, the temperature is controlled to be 30 ℃ through a constant-temperature cooling water tank, and a magnetic stirrer is continuously used for stirring in the reaction process to prevent solution polarization; electrochemical reduction degradation for 2.5h.
Examples
Placing 2cm multiplied by 0.12cm of foam nickel in 10wt% dilute sulfuric acid for pickling for 30min to remove a surface oxide layer, then performing ultrasonic cleaning in 25mL of acetone for 10min, and performing ultrasonic cleaning in 25mL of ethanol for 10min to obtain pretreated foam nickel;
The pre-deposition experiment adopts an invention device for electrochemical deposition of nickel-iron bimetal, when the device works, two groups of foam nickel can be inserted into two groups of positioning holes respectively, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel pretreated at the lower side to be inserted into an electrolytic cell to start electrochemical deposition reaction, after the foam nickel is plated, the lifting cylinder is operated to output to drive the negative electrode bracket to rise, meanwhile, the rotating motor is operated to output to drive the negative electrode bracket to turn over 180 degrees, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel at the lower side to be inserted into the electrolytic cell to perform electrochemical deposition reaction again, wherein the electrolyte is a mixed solution of nickel chloride, ferric chloride and ammonium chloride (the concentration of nickel chloride is 0.03mol/L, the concentration of ferric chloride is 0.08 mol/L), and the concentration of ammonium chloride is 2 mol/L), and the electrochemical deposition of nickel-iron bimetal is performed for 500s under the condition of constant current of 0.2A, so as to obtain the nickel-iron bimetal pre-deposition foam nickel. Meanwhile, the foam nickel plated on the upper side can be manually removed and replaced by the foam nickel to be plated, and the operations are repeated, so that the nickel-iron bimetal foam nickel can be more efficiently prepared and produced;
Preparing 0.055g of nickel chloride, 0.187g of ferric trichloride, 0.16g of terephthalic acid and 50mL of mixed solvent (the mixed solvent is a mixture of N, N-dimethylformamide, ethanol and water according to the volume ratio of 14:1:1) to obtain solvothermal reaction raw material liquid, placing the nickel-iron bimetallic pre-deposited foam nickel into the solvothermal reaction raw material liquid, carrying out solvothermal reaction for 24 hours at 140 ℃, filtering the obtained solid-liquid mixture, alternately carrying out ethanol washing and water washing on the obtained solid matters for 3 times, and drying at 80 ℃ for 2 hours to obtain the bimetallic organic framework compound modified foam nickel;
Preparing palladium-containing solution with palladium chloride concentration of 10mmol/L and sodium chloride concentration of 30mmol/L, placing the bimetal organic framework compound modified nickel foam into the palladium-containing solution, carrying out adsorption treatment at 30 ℃ until the palladium-containing solution becomes colorless, placing the obtained adsorption electrode into 2g/L of sodium chloride solution, and carrying out electrochemical reduction for 30min under the condition that the cathode current density is preferably 2.5mA cm -2, so as to obtain the palladium-loaded bimetal organic framework compound modified nickel foam composite material.
The composite material of the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel obtained in the example 2 is used as a working electrode in electrocatalytic hydrogenation reduction to carry out TCAA electrochemical reduction degradation, and the conditions are as follows:
Before the electrolytic reduction dechlorination, adding 100mL of mixed solution into a cathode chamber, wherein the chemical composition of the mixed solution is 2mmol/L Na 2SO4 and 1mg/L aqueous solution of TCAA, and 100mL of aqueous solution of Na 2SO4 with the concentration of 2mmol/L is respectively added into an anode chamber; the composite material prepared in the example 2 is used as a cathode working electrode to be connected with a power supply cathode, a platinum sheet is used as an anode to be connected with a power supply anode, an Ag/AgCl electrode is selected as a reference electrode, the potential is applied to be-1.2V, the temperature is controlled to be 30 ℃ through a constant-temperature cooling water tank, and a magnetic stirrer is continuously used for stirring in the reaction process to prevent the solution from being polarized; electrochemical reduction degradation for 2.5h.
Placing 2cm multiplied by 0.12cm of foam nickel in 10wt% dilute sulfuric acid for pickling for 30min, then ultrasonically cleaning for 30min in 25mL of acetone, and then ultrasonically cleaning for 10min in 25mL of ethanol to obtain pretreated foam nickel;
The pre-deposition experiment adopts an invention device for electrochemical deposition of nickel-iron bimetal, when the device works, two groups of foam nickel can be inserted into two groups of positioning holes respectively, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel pretreated at the lower side to be inserted into an electrolytic cell to start electrochemical deposition reaction, after the foam nickel is plated, the lifting cylinder is operated to output to drive the negative electrode bracket to rise, meanwhile, the rotating motor is operated to output to drive the negative electrode bracket to turn over 180 degrees, at the moment, the lifting cylinder can be operated to retract to drive the foam nickel at the lower side to be inserted into the electrolytic cell to perform electrochemical deposition reaction again, wherein the electrolyte is a mixed solution of nickel chloride, ferric chloride and ammonium chloride (the concentration of nickel chloride is 0.03mol/L, the concentration of ferric chloride is 0.08 mol/L), and the concentration of ammonium chloride is 2 mol/L), and the electrochemical deposition of nickel-iron bimetal is performed for 300s under the condition of constant current of 0.2A, so as to obtain the nickel-iron bimetal pre-deposition foam nickel. Meanwhile, the foam nickel plated on the upper side can be manually removed and replaced by the foam nickel to be plated, and the operations are repeated, so that the nickel-iron bimetal foam nickel can be more efficiently prepared and produced;
Preparing a palladium-containing solution with the concentration of palladium chloride of 10mmol/L and the concentration of sodium chloride of 30mmol/L, placing the nickel-iron bimetal pre-deposited foam nickel into the palladium-containing solution, and carrying out adsorption treatment at the temperature of 30 ℃ until the palladium-containing solution becomes colorless; and (3) placing the obtained adsorption electrode in a sodium chloride solution with the concentration of 2g/L, and carrying out electrochemical reduction for 30min under the condition that the current density of a cathode is preferably 2.5mA cm -2, so as to obtain the palladium-containing foam nickel composite material.
According to the method of application example 1, TCAA electrochemical reduction degradation is carried out by taking the composite material containing palladium foam nickel obtained in comparative example 1 as a cathode.
The TCAA degradation profiles of application example 1 and comparative application example 1 are shown in fig. 2. As can be seen from FIG. 2, the composite material of palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel provided by the invention has the advantages that 1mg/L TCAA is dechlorinated at 2.5h under the condition of 1.2V, and the removal efficiency in comparative example 1 also reaches 55.6%.
Five times of degradation are continuously carried out on the composite material of the nickel foam modified by the palladium-embedded nickel/iron bimetallic organic framework compound in application example 1, and the degradation curve chart of the obtained TCAA is shown in figure 3. The lifetime of an electrode is generally considered to be an important parameter for the practical application of the electrode. As shown in fig. 3, the degradation efficiency of TCAA reaches 96.03% after 1h in the first degradation experiment, and the composite material with nickel/iron bimetal organic framework compound modified foam nickel embedded in palladium still maintains good degradation effect after five repeated experiments. This demonstrates that the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel composite material provided by the invention can keep running for a long time under constant voltage and maintain relatively stable dechlorination efficiency.
The TCAA degradation profile of application example 2 is shown in fig. 4. As can be seen from FIG. 4, the composite material of the palladium-embedded nickel/iron bimetal organic framework compound modified foam nickel provided by the invention has 94.03% of TCAA removal rate of 1mg/L under the condition that the deposition time is 500s and the applied cathode potential is-1.2V, and has high TCAA removal rate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The composite material of palladium-loaded bimetal organic framework compound modified foam nickel is characterized by comprising foam nickel and a palladium-loaded bimetal organic framework compound layer attached to holes and surfaces of the foam nickel; the palladium-loaded bimetallic organic framework compound comprises a bimetallic organic framework compound and nano palladium; the bimetal organic framework compound is formed by coordination self-assembly of metal nickel, iron and terephthalic acid; the nano palladium is loaded into the bimetallic organic framework compound and distributed on the surface of the bimetallic organic framework compound.
2. The palladium-supported bimetallic organic framework compound modified nickel foam composite of claim 1, wherein the bimetallic organic framework compound is in the form of a sheet;
the particle size of the nano palladium is 5-10nm;
The load of nano palladium in the composite material is 7-139mg/g.
3. The method for preparing the palladium-supported bimetallic organic framework compound modified foam nickel composite material as claimed in claim 1 or 2, which is characterized by comprising the following steps:
performing nickel-iron bimetal electrochemical deposition by taking the foam nickel as a negative electrode to obtain nickel-iron bimetal pre-deposition foam nickel;
placing the nickel-iron bimetal pre-deposited foam nickel into solvent thermal reaction raw material liquid to perform solvent thermal reaction to obtain bimetal organic framework compound modified foam nickel; the solvent thermal reaction raw material liquid comprises nickel chloride, ferric trichloride, terephthalic acid and a mixed solvent, wherein the mixed solvent comprises N, N-dimethylformamide, ethanol and water;
Placing the bimetal organic framework compound modified foam nickel into a palladium-containing solution for adsorption treatment, and performing electrochemical reduction on the obtained adsorption electrode to obtain the palladium-loaded bimetal organic framework compound modified foam nickel composite material; solutes in the palladium-containing solution include palladium chloride and sodium chloride.
4. A method of preparing as claimed in claim 3, wherein the ferronickel bi-metal electrochemical deposition conditions comprise: the electrolyte comprises nickel chloride, ferric trichloride and ammonium chloride; the concentration of nickel chloride in the electrolyte is 0.02-0.07mol/L, the concentration of ferric trichloride is 0.07-0.12mol/L, and the concentration of ammonium chloride is 2-2.5mol/L; the current in the electrochemical deposition of the ferronickel bimetal is 0.1-2A, and the time is 100-500s.
5. The method according to claim 3, wherein the mass ratio of nickel chloride, ferric trichloride and terephthalic acid in the solvothermal reaction raw material solution is (0.05-0.15): (0.18-0.26): (0.08-0.16); the ratio of the mass of the nickel chloride and the ferric trichloride to the volume of the mixed solvent is (0.05-0.15): (0.18-0.26) g: (25-50) mL.
6. The method according to claim 3 or 5, wherein the solvothermal reaction is carried out at a temperature of 120-180 ℃ for a period of 12-24 hours;
The concentration of palladium chloride in the palladium-containing solution is 0.3-10mmol/L, and the concentration of sodium chloride is 30-300mmol/L;
The electrolyte is sodium chloride solution; the cathode current density is 2-2.5mA cm -2, and the time is 30-50min.
7. The preparation method according to claim 3 or 4, wherein the electrochemical deposition of the ferronickel bimetal adopts an electrochemical deposition device for the ferronickel bimetal, and comprises an electrolytic cell (1), wherein a working cavity (2) is arranged inside the electrolytic cell (1);
The high-efficiency electrode replacement device is characterized by further comprising a high-efficiency electrode replacement assembly, wherein the high-efficiency electrode replacement assembly comprises an anode support (3), a lifting cylinder (4), a cathode support (5), a rotating motor (6) and a cathode seat (7), the right side of the bottom end of the anode support (3) is connected with the right side of the top end of the electrolytic cell (1), the left side of the top end of the electrolytic cell (1) is provided with a mounting hole, the lifting cylinder (4) is matched and mounted in the mounting hole, the cathode support (5) is mounted at the output end of the lifting cylinder (4), the rotating motor (6) is mounted at the left end of the cathode support (5), the middle part of the left end of the cathode support (5) is provided with a through hole, the output end of the rotating motor (6) penetrates through the through hole to be connected with the left end of the cathode seat (7), and the top end and the bottom end of the cathode seat (7) are provided with positioning holes (8).
8. The method according to claim 7, wherein the electrochemical deposition device for nickel-iron bimetal further comprises four groups of springs (9) and four groups of clamping plates (10), wherein circular grooves are formed in the inner ends of the two groups of positioning holes (8), the four groups of clamping plates (10) are respectively connected with the left sides and the right sides of the two groups of circular grooves in a sliding manner, and the inner ends and the outer ends of the four groups of springs (9) are respectively connected with the outer ends of the four groups of clamping plates (10) and the outer ends of the two groups of circular grooves.
9. The preparation method according to claim 7, wherein the electrochemical deposition device for ferronickel bimetal further comprises a liquid supplementing pipe (16) and a liquid discharging pipe (17), and the output end of the liquid supplementing pipe (16) and the input end of the liquid discharging pipe (17) are respectively communicated with the top and the bottom of the right end of the working cavity (2); the top ends of the two groups of clamping plates (10) on the upper side and the bottom ends of the two groups of clamping plates (10) on the lower side are respectively provided with a first chamfer angle (11); the top end of the upper side locating hole (8) and the bottom end of the lower side locating hole (8) are both provided with second chamfers (12).
10. Use of a palladium-supported bimetallic organic framework compound modified foam nickel composite material according to claim 1 or 2 as a working electrode in electrocatalytic hydrogenation reduction in TCAA electrochemical reduction degradation.
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