CN111952606A - Fe/HKUST-1 catalyst, and preparation method and application thereof - Google Patents
Fe/HKUST-1 catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111952606A CN111952606A CN202010810014.5A CN202010810014A CN111952606A CN 111952606 A CN111952606 A CN 111952606A CN 202010810014 A CN202010810014 A CN 202010810014A CN 111952606 A CN111952606 A CN 111952606A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hkust
- cathode
- preparation
- microbial fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000446 fuel Substances 0.000 claims abstract description 43
- 230000000813 microbial effect Effects 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000010865 sewage Substances 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- -1 Polytetrafluoroethylene Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 210000003097 mucus Anatomy 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 241000863430 Shewanella Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a Fe/HKUST-1 catalyst, a preparation method and application thereof. The Fe/HKUST-1 catalyst is prepared by the HKUST-1 and an iron source through simple combination and doping reactions. Compared with the preparation method of noble metal platinum and the alloy material thereof, the preparation method of the Fe/HKUST-1 catalyst provided by the invention has the advantages of low raw material and preparation cost and simple process. The invention also discloses the Fe/HKUST-1 catalyst material prepared by the preparation method. The prepared Fe/HKUST-1 catalyst has better conductivity and electron mobility. The invention also discloses application of the Fe/HKUST-1 catalyst in a microbial fuel cell catalytic material or sewage treatment. The invention also discloses a cathode catalyst layer of the microbial fuel cell. The carbon composite cathode catalyst layer prepared by the prepared Fe/HKUST-1 catalyst has the characteristics of wide raw material source, high stability, high conductivity and electrocatalytic activity, low operation cost, simple maintenance and the like.
Description
Technical Field
The invention belongs to the field of bioelectrochemistry, and particularly relates to a preparation method of a Fe/HKUST-1 catalyst and application of the catalyst as a catalytic layer in a microbial fuel cell.
Background
The energy crisis and the environmental problem are two major problems facing all mankind, and are one of the problems to be solved urgently in the modern industrial development. Nowadays, the traditional chemical fuel energy source cannot meet the requirements of modern society, and the environmental damage caused by the development of the energy source is increasingly intensified. On the other hand, the method can effectively develop and utilize biomass energy which is an energy source in a new field, can effectively solve the problems of environmental pollution and energy shortage, and has important significance for realizing social sustainable development, wherein the microbial fuel cell is expected to improve the problems of environment and energy in the field of wastewater treatment.
Microbial Fuel Cells (MFCs) are a novel and multifunctional bioelectrochemical technology that can convert chemical energy in sewage into electrical energy by the activity of electrogenic microorganisms. Microbial fuel cells are typically constructed of an anode and a cathode and a sheet of proton exchange membrane. The working principle of the microbial fuel cell is as follows: the microorganisms decompose the oxygenated fuel at the anode and produce electrons, which can reach the cathode via an external electricity, and protons, which pass through the proton exchange membrane to the cathode, where they are consumed and combine with oxygen to produce water. Compared with the traditional fuel cell, the microbial fuel cell can effectively treat organic wastewater while providing power supply, does not bring secondary pollution, has the advantages of good treatment effect, clean renewable energy, simple maintenance and the like, is a novel efficient technology, and is widely concerned by scholars at home and abroad.
Although the potential of microbial fuel cells has good application in future development, the development of the technology is limited by many factors such as microbial activity, performance of electrode materials and matching of proton exchange membranes, so that the technology cannot meet the requirements of modern industries. The prepared cathode catalyst with high catalytic activity for the microbial fuel cell not only can obviously improve the electricity generation performance of the microbial fuel cell, but also can replace a Pt/C catalyst of noble metal, thereby greatly reducing the overall cost and improving the stability, and having important significance for large-scale application of the microbial fuel cell.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a preparation method of the iron-doped non-noble metal Fe/HKUST-1 catalyst with simple preparation process. The prepared catalyst can replace the traditional noble metal catalyst and is beneficial to improving the electricity generation performance of the microbial fuel cell.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a Fe/HKUST-1 catalyst comprises the following steps: adding an iron source into the HKUST-1, and calcining in an inert atmosphere to obtain the Fe/HKUST-1 catalyst.
HKUST-1 has the chemical formula: cu3(BTC)2As one of metal organic framework Materials (MOFs), the compound was first synthesized by Chui doctor of hong kong science and technology university in 1999, and has shown good application prospects in the fields of gas storage, biomedicine, magnetic composite materials, catalysis, fluorescence, and the like. The HKUST-1 can be prepared by the existing synthetic method, and can also be directly purchased in the market.
The Fe/HKUST-1 catalyst is prepared by calcining an iron source and HKUST-1, and has better conductivity and electron mobility, compared with precious metal platinum and alloy materials thereof, the prepared raw materials have low price, simple process and wide raw material sources, and have unusual performance compared with the precious metal platinum and the alloy materials thereof, and the preparation method of the Fe/HKUST-1 catalyst is simple, has moderate reaction conditions and is suitable for industrial mass production.
The inert atmosphere can be nitrogen, argon, helium and the like, and preferably nitrogen is adopted. The iron source can be iron sulfate, ferric nitrate nonahydrate, ferric chloride and the like, and is preferably ferric chloride.
Preferably, the preparation method of HKUST-1 comprises the following steps: dissolving a copper source, water and trimesic acid in an organic solvent, carrying out hydrothermal reaction to obtain a product, washing and drying to obtain the HKUST-1. The preparation method of HKUST-1 disclosed by the invention is preferably prepared by adopting the preparation process.
Preferably, the iron source is at least one of ferric chloride and ferric nitrate nonahydrate; the copper source is copper nitrate trihydrate; the conditions of the hydrothermal reaction are as follows: reacting for 6-18 h at 110-130 ℃; the molar ratio of the copper atoms to the trimesic acid is as follows: 2:1.
Preferably, the molar ratio of Cu atoms in the HKUST-1 to Fe atoms in the iron source is: cu: fe is 1:1 to 1:3. The Fe/HKUST-1 catalyst prepared in the molar ratio range has excellent oxidation-reduction activity and catalytic activity.
Preferably, the molar ratio of Cu atoms in the HKUST-1 to Fe atoms in the iron source is: cu: fe ═ 1: 2. The Fe/HKUST-1 catalyst prepared under the molar ratio has better catalytic activity, and the electricity generation performance of the battery is better when the catalyst is used as a battery catalyst.
Preferably, the calcination conditions are: heating at 700-900 ℃ for 1-3 h. More preferably, the conditions of the calcination are: heating at 800 deg.C for 2 h.
Compared with the traditional preparation method of noble metal platinum and alloy materials thereof, the preparation method of the Fe-doped non-noble metal Fe/HKUST-1 catalyst has the advantages of low raw material cost, simple and convenient preparation process and controllable yield.
The invention also aims to provide the Fe/HKUST-1 catalyst prepared by the preparation method of the Fe/HKUST-1 catalyst.
The invention also aims to provide an application of the Fe/HKUST-1 catalyst in a microbial fuel cell catalytic material or sewage treatment.
The invention also aims to provide a microbial fuel cell cathode catalyst which comprises the Fe/HKUST-1 catalyst. The Fe/HKUST-1 catalyst is applied to the cathode catalyst of the microbial fuel cell, has low cost and simple maintenance, and can ensure that the cathode has good conductivity, high electro-catalytic activity, stable output and high power.
The invention also aims to provide a cathode catalyst layer of the microbial fuel cell, which comprises carbon cloth, and a carbon base layer and a Fe/HKUST-1 catalyst layer which are respectively arranged at two sides of the carbon cloth; the Fe/HKUST-1 catalytic layer contains the Fe/HKUST-1 catalyst.
Preferably, the content of the Fe/HKUST-1 catalyst in unit area of the Fe/HKUST-1 catalyst layer is 0.4-0.6 mg/cm2。
Preferably, the Fe/HKUST-1 catalyst layer comprises an Fe/HKUST-1 catalyst, acetylene black and a binder; the weight ratio of the Fe/HKUST-1 catalyst to the acetylene black is as follows: Fe/HKUST-1 catalyst: acetylene black is 1:3.9 to 4.1.
The invention also aims to provide a microbial fuel cell, which comprises a reactor shell, an anode chamber, a cathode chamber and a proton exchange membrane arranged between the anode chamber and the cathode chamber; the reactor comprises a reactor shell, an anode chamber, a cathode chamber, a lead, a resistor, an anode catalyst, a cathode catalyst and a Fe/HKUST-1 catalyst, wherein the anode chamber and the cathode chamber are arranged in the reactor shell and are connected through the lead, the lead is provided with the resistor, the anode chamber is internally provided with the anode catalyst, the cathode chamber is internally provided with the cathode catalyst, and the cathode catalyst contains the Fe/HKUST-1. The microbial fuel cell provided by the invention adopts the Fe/HKUST-1 catalyst as a cathode catalyst, and has the advantages of stable output and higher power.
The invention has the beneficial effect that the invention provides a preparation method of the Fe/HKUST-1 catalyst. The Fe/HKUST-1 catalyst is prepared by calcining an iron source and HKUST-1, and has better conductivity and electron mobility, and compared with noble metal platinum and alloy materials thereof, the prepared raw materials of the Fe/HKUST-1 catalyst have low price and wide source, and have unusual performance compared with the noble metal platinum and alloy materials thereof, and the preparation method of the Fe/HKUST-1 catalyst is simple, has moderate reaction conditions, and is suitable for industrial batch production. The invention also provides the Fe/HKUST-1 catalyst prepared by the preparation method of the Fe/HKUST-1 catalyst. The invention also provides application of the Fe/HKUST-1 catalyst in a microbial fuel cell catalytic material or sewage treatment. The invention also provides a microbial fuel cell cathode catalyst containing the Fe/HKUST-1 catalyst, a microbial fuel cell cathode catalyst layer and a microbial fuel cell. The Fe/HKUST-1 catalyst is applied to the cathode catalytic material of the microbial fuel cell, compared with the traditional microbial fuel cell adopting noble metal platinum and alloy materials thereof as the cathode catalytic material, the catalytic material has the advantages of low preparation cost, simple steps, high conductivity and electrocatalytic activity, low cost, simple maintenance, stable output and high power, and the performance of the cell is greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of a microbial fuel cell prepared by using the Fe/HKUST-1 catalyst of the present invention; the number 1 is marked as a reactor plastic shell, one side of the reactor plastic shell is opened, and the rest positions are sealed; the No. 2 is marked as anode carbon felt and is soaked in anolyte; number 3, labeled as cathode catalyst layer, separated from the side in contact with the reactor by a PEM membrane; no. 4 is marked as a plate which is made of the same material as the shell of the reactor, and the middle part of the plate is hollowed out; no. 5 is marked as the resistance (1000 omega) of the anode and cathode connection, and the connecting lead is a polished titanium wire. Wherein the cathode catalyst layer comprises carbon cloth, a carbon base layer and a Fe/HKUST-1 catalyst layer which are respectively arranged at two sides of the carbon cloth.
FIG. 2 is a plot of cyclic voltammetry measurements for a microbial fuel cell MFC cell, with the solid line curve being the plot of cyclic voltammetry measurements for an MFC cell with the Fe/HKUST-1 catalyst prepared in example 1; the dashed curve is the plot of the cyclic voltammetry measurements for the MFC cells for the Fe/HKUST-1 catalyst prepared in example 2.
Fig. 3 is a graph of cyclic voltammetry tests of MFC cells of microbial fuel cells prepared with Pt/C as catalyst.
FIG. 4 is a plot of a linear sweep voltammetry test for a microbial fuel cell MFC cell, in which the solid line curve is a plot of a linear sweep voltammetry test for an MFC cell with the Fe/HKUST-1 catalyst prepared in example 1; the dashed curve is the plot of the linear sweep voltammetry test of the MFC cells for the Fe/HKUST-1 catalyst prepared in example 2.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
Example 1
In one embodiment of the preparation method of the Fe/HKUST-1 catalyst of the present invention, the preparation method of the Fe/HKUST-1 catalyst of the present embodiment comprises the following steps:
(1) 1.45g (6.00mol) of copper nitrate trihydrate and 30ml of deionized water are added into 1.4g (6.67mol) of trimesic acid and 30ml of ethanol and stirred evenly;
(2) magnetically stirring the mixed solution obtained in the step (1) in a water bath at 25 ℃ at the rotating speed of 500rpm for 30min to form a mixed solution;
(3) placing the mixed solution obtained in the step (2) in a reaction kettle, and reacting at 120 ℃ for 12 hours to form a blue mixed solution;
(4) washing the mucus obtained in the step (3) with absolute ethyl alcohol, and then placing the mucus in a vacuum drying oven for drying for 12h at the temperature of 80 ℃ until the liquid in the mixture is completely evaporated to obtain a blue solid HKUST-1;
(5) taking 0.5g of the blue solid HKUST-1 obtained in the step (4) as Cu: mixing Fe with 0.162g of ferric chloride in a molar ratio of 1: 1;
(6) and (5) placing the solid matter obtained in the step (5) in a tubular furnace, introducing high-purity nitrogen, and heating at 800 ℃ for 2h at the heating rate of 5 ℃/min to obtain the Fe/HKUST-1 catalyst.
The Fe-doped Fe/HKUST-1 catalyst is used for preparing a cathode catalyst layer of a microbial fuel cell.
A microbial fuel cell is shown in figure 1, wherein No. 1 is marked as a reactor plastic shell, one side of the reactor plastic shell is provided with an opening, and the rest positions are sealed; no. 2 is marked as anode carbon felt and is soaked in anolyte, and the anolyte contains gram-negative bacteria (Shewanella); number 3, labeled as cathode catalyst layer, separated from the side in contact with the reactor by a PEM membrane; no. 4 is marked as a plate which is made of the same material as the shell of the reactor, and the middle part of the plate is hollowed out; no. 5 is marked as the resistance (1000 omega) of the anode and cathode connection, and the connecting lead is a polished titanium wire. The cathode catalyst layer comprises carbon cloth, a carbon base layer and a Fe/HKUST-1 catalyst layer, wherein the carbon base layer and the Fe/HKUST-1 catalyst layer are respectively arranged on two sides of the carbon cloth, and the preparation method comprises the following steps:
(1) preparing a carbon base layer:
firstly, cutting off carbon cloth with the specification of 9.4cm multiplied by 9.4 cm;
weighing 0.1378g of acetylene black;
measuring 2.5ml of 40% Polytetrafluoroethylene (PTFE) solution;
fourthly, the acetylene black in the third step is placed into a sample bottle, 6 glass beads are added, 40% Polytetrafluoroethylene (PTFE) solution in the third step is added, a plug is screwed, and the mixture is swirled for 20s, so that black suspension is obtained;
covering the carbon black suspension on one side of the carbon cloth by using a small brush, and lightly and uniformly coating the carbon black suspension to prevent the carbon black suspension from being coated on the other side;
sixthly, drying the coated carbon cloth by using a blower, wherein the drying distance is moderate to prevent the high temperature from damaging the structure;
and placing the carbon cloth on a high-temperature ceramic plate in a muffle furnace, and calcining for 30min at 370 ℃ to obtain the required carbon-based layer.
(2) Preparation of the catalytic layer:
weighing 0.1767g of acetylene black;
weighing 0.0442g of the prepared catalyst Fe/HKUST-1;
thirdly, pouring the Fe/HKUST-1 catalyst to the surface of the acetylene black, and repeatedly stirring to fully and uniformly mix the catalyst;
fourthly, pouring the mixed powder obtained in the third step into a sample bottle and dropwise adding 0.5ml of deionized water;
fifthly, sequentially adding 1.5ml of 5% Nafion solution and 1.5ml of pure isopropanol solution into the sample bottle in the fourth step;
sixthly, adding 6 glass beads into the sample bottle, and whirling for 20s to fully and uniformly mix the glass beads to obtain a catalyst suspension;
seventhly, covering the other side of the carbon cloth obtained in the step (1) with a catalyst suspension by using a small brush, and slightly and uniformly coating the catalyst suspension to prevent the catalyst suspension from being coated on the other side;
and blowing the coated carbon cloth to dry by using a blower, and drying in the air for 24 hours to obtain the Fe-Cu-N-C composite cathode catalyst layer.
Examples 2 to 3
Examples 2 to 3 differ from example 1 only in the content of iron chloride incorporated in step (5) of the production method, and example 2 was carried out in terms of Cu: fe molar ratio 1:2 (i.e. 0.5g HKUST-1 mixed with 0.324g ferric chloride), example 3 as Cu: the Fe molar ratio was 1:3 (i.e., 0.5g of HKUST-1 mixed with 0.486g of ferric chloride).
The microbial fuel cells prepared in examples 1 and 2 were subjected to Cyclic Voltammetry (CV) at a sweep rate of 10mV/s using an Ag/AgCl electrode as a reference electrode in a voltage range of-0.8 to 0.2V, and the results are shown in FIG. 2. When the microbial fuel cells prepared by the conventional Pt/C catalyst are tested under the same conditions, it is apparent that the redox peak positions of examples 1 and 2 are more significant compared to the microbial fuel cells prepared by the conventional Pt/C catalyst, indicating that the electrochemical activity of the microbes in the microbial fuel cells is higher.
The microbial fuel cells prepared in examples 1 and 2 were subjected to a Linear Sweep Voltammetry (LSV) test at a sweep rate of 10mV/s using an Ag/AgCl electrode as a reference electrode in a voltage range of-0.8 to 0.2V, and the results are shown in FIG. 4.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a Fe/HKUST-1 catalyst is characterized by comprising the following steps: adding an iron source into the HKUST-1, and calcining in an inert atmosphere to obtain the Fe/HKUST-1 catalyst.
2. The method for preparing a Fe/HKUST-1 catalyst according to claim 1, wherein the molar ratio of Cu atoms in the HKUST-1 to Fe atoms in the iron source is: cu: fe is 1:1 to 1:3.
3. The method for preparing the Fe/HKUST-1 catalyst according to claim 1, wherein the calcination conditions are as follows: heating at 700-900 ℃ for 1-3 h.
4. The method for preparing the Fe/HKUST-1 catalyst according to claim 1, wherein the HKUST-1 catalyst is prepared by the method comprising the steps of: dissolving a copper source, water and trimesic acid in an organic solvent, carrying out hydrothermal reaction to obtain a product, washing and drying to obtain the HKUST-1.
5. The method of preparing the Fe/HKUST-1 catalyst according to claim 4, wherein the iron source is at least one of ferric chloride and ferric nitrate nonahydrate; the copper source is copper nitrate trihydrate; the conditions of the hydrothermal reaction are as follows: reacting for 6-18 h at 110-130 ℃; the molar ratio of the copper atoms to the trimesic acid is as follows: 2:1.
6. The Fe/HKUST-1 catalyst prepared by the preparation method of the Fe/HKUST-1 catalyst as claimed in any one of claims 1 to 5.
7. The use of the Fe/HKUST-1 catalyst of claim 6 in the catalysis of materials in microbial fuel cells and in sewage treatment.
8. A microbial fuel cell cathode catalyst comprising the Fe/HKUST-1 catalyst of claim 6.
9. The cathode catalyst layer of the microbial fuel cell is characterized by comprising carbon cloth, a carbon base layer and a Fe/HKUST-1 catalyst layer, wherein the carbon base layer and the Fe/HKUST-1 catalyst layer are respectively arranged on two sides of the carbon cloth; the Fe/HKUST-1 catalyst layer comprises the Fe/HKUST-1 catalyst as claimed in claim 6, and the catalyst content per unit area of the catalyst layer is 0.4-0.6 mg/cm2。
10. A microbial fuel cell comprising a reactor housing, an anode compartment, a cathode compartment and a proton exchange membrane disposed between the anode and cathode compartments; the anode chamber and the cathode chamber are arranged in a reactor shell, the anode chamber and the cathode chamber are connected through a lead, a resistor is arranged on the lead, an anode catalyst is arranged in the anode chamber, a cathode catalyst is arranged in the cathode chamber, and the cathode catalyst contains the Fe/HKUST-1 catalyst as claimed in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010810014.5A CN111952606A (en) | 2020-08-12 | 2020-08-12 | Fe/HKUST-1 catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010810014.5A CN111952606A (en) | 2020-08-12 | 2020-08-12 | Fe/HKUST-1 catalyst, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111952606A true CN111952606A (en) | 2020-11-17 |
Family
ID=73332479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010810014.5A Pending CN111952606A (en) | 2020-08-12 | 2020-08-12 | Fe/HKUST-1 catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111952606A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725403A (en) * | 2022-04-19 | 2022-07-08 | 华南理工大学 | Microbial fuel cell anode material and preparation method and application thereof |
| CN114878662A (en) * | 2022-05-20 | 2022-08-09 | 中南大学 | Application of Cu-HHB or Cu-BTC in pyocin detection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868109A (en) * | 2015-05-04 | 2015-08-26 | 南开大学 | Tin oxide and porous carbon composite lithium ion battery anode materials |
| US20180280949A1 (en) * | 2016-05-13 | 2018-10-04 | King Fahd University Of Petroleum And Minerals | Trans-metallated mof catalyst |
| CN109524645A (en) * | 2018-11-07 | 2019-03-26 | 河南师范大学 | A kind of chelating agent auxiliary prepares tin/copper/carbon composite method |
| CN109772394A (en) * | 2019-01-16 | 2019-05-21 | 盐城工学院 | Phosphorus doping carbon/cuprous oxide composite catalyst and its preparation method and application |
-
2020
- 2020-08-12 CN CN202010810014.5A patent/CN111952606A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868109A (en) * | 2015-05-04 | 2015-08-26 | 南开大学 | Tin oxide and porous carbon composite lithium ion battery anode materials |
| US20180280949A1 (en) * | 2016-05-13 | 2018-10-04 | King Fahd University Of Petroleum And Minerals | Trans-metallated mof catalyst |
| CN109524645A (en) * | 2018-11-07 | 2019-03-26 | 河南师范大学 | A kind of chelating agent auxiliary prepares tin/copper/carbon composite method |
| CN109772394A (en) * | 2019-01-16 | 2019-05-21 | 盐城工学院 | Phosphorus doping carbon/cuprous oxide composite catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| YU QIAO,等: "Pyrolytic Carbon-coated Cu-Fe Alloy Nanoparticles with High Catalytic Performance for Oxygen Electroreduction", 《CHEMISTRY - AN ASIAN JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725403A (en) * | 2022-04-19 | 2022-07-08 | 华南理工大学 | Microbial fuel cell anode material and preparation method and application thereof |
| CN114878662A (en) * | 2022-05-20 | 2022-08-09 | 中南大学 | Application of Cu-HHB or Cu-BTC in pyocin detection |
| CN114878662B (en) * | 2022-05-20 | 2023-02-28 | 中南大学 | Application of Cu-HHB or Cu-BTC in detection of pyocin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| Yue et al. | Surface engineering of hierarchical Ni (OH) 2 nanosheet@ nanowire configuration toward superior urea electrolysis | |
| CN106868563B (en) | A kind of preparation method and applications of selenide thin film modifying foam nickel electrode | |
| CN109718822B (en) | Method for preparing metal-carbon composite catalytic material and application thereof | |
| CN106784877B (en) | Preparation method of microbial fuel cell cathode composite material and microbial fuel cell reactor | |
| CN112958116B (en) | Bi2O2.33-CdS composite photocatalyst and preparation process thereof | |
| CN110048134A (en) | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN111501062A (en) | Preparation method of ruthenium-doped carbon nanotube composite material and application of ruthenium-doped carbon nanotube composite material in aspect of microbial electrolysis cell cathode | |
| CN111952606A (en) | Fe/HKUST-1 catalyst, and preparation method and application thereof | |
| CN114477163A (en) | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof | |
| CN115896841B (en) | Iridium-supported metal oxide core-shell catalyst, preparation method and application thereof | |
| CN113174609B (en) | Preparation method and application of ultrahigh-performance hydrogen evolution water electrolysis catalyst | |
| CN110065932B (en) | Lithium insertion type selenium compound, and preparation method and application thereof | |
| CN114824331A (en) | Layered double-metal oxide negative electrode material and preparation method and application thereof | |
| CN114622243A (en) | Fe-doped Ni3S2Preparation method and application of electrode material | |
| CN113026031A (en) | Electrode material, preparation method and application thereof, and assembled water electrolysis device | |
| CN113186558A (en) | Sponge nickel/octa-sulfide nine-nickel composite material and preparation method and application thereof | |
| CN111841567A (en) | Preparation method and application of nickel-manganese oxyhydroxide film with Tuoling structure | |
| CN111013618A (en) | Phosphorus-doped cobalt-iron-vanadium trimetal catalyst and preparation method thereof | |
| CN112221506B (en) | Catalyst, preparation method and application thereof | |
| CN115198304B (en) | Nickel selenide sulfide composite seawater electrocatalyst and preparation method and application thereof | |
| CN108155390A (en) | It is a kind of for the nitridation catalyzed by ruthenium complexes agent of fuel cell and preparation method | |
| CN213304173U (en) | Nickel carbide cathode capable of enhancing power generation and nickel carbide cathode microbial fuel cell reactor | |
| CN114420957B (en) | Method for constructing porous iron nanocomposite carbon material based on saccharomycete carbon template | |
| CN107611462A (en) | A kind of anolyte and preparation method thereof, the biobattery containing anolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201117 |
|
| RJ01 | Rejection of invention patent application after publication |