CN110408952A - Molybdenum disulfide/NaY molecular sieve composite cathode is prepared and is applied in microorganism electrolysis cell - Google Patents
Molybdenum disulfide/NaY molecular sieve composite cathode is prepared and is applied in microorganism electrolysis cell Download PDFInfo
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- CN110408952A CN110408952A CN201910597320.2A CN201910597320A CN110408952A CN 110408952 A CN110408952 A CN 110408952A CN 201910597320 A CN201910597320 A CN 201910597320A CN 110408952 A CN110408952 A CN 110408952A
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- molecular sieve
- nay molecular
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- molybdenum disulfide
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 244000005700 microbiome Species 0.000 title claims description 14
- 238000005868 electrolysis reaction Methods 0.000 title claims description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229920000557 Nafion® Polymers 0.000 claims abstract description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 229960004756 ethanol Drugs 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 235000015097 nutrients Nutrition 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 241000208340 Araliaceae Species 0.000 claims description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000008434 ginseng Nutrition 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052613 tourmaline Inorganic materials 0.000 description 2
- 229940070527 tourmaline Drugs 0.000 description 2
- 239000011032 tourmaline Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 nickel cobalt metal oxide Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of molybdenum disulfide/NaY molecular sieve composite cathode material preparation methods, specifically, sodium molybdate and thiocarbamide and NaY molecular sieve are added in reaction kettle, deionized water is added, and are put into magneton and are placed in constant temperature blender with magnetic force and stir 1h；Magneton is taken out, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；Reaction kettle is taken out, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；Sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；Sample is taken, ethyl alcohol dissolution is added, after ultrasound is centrifuged 30min, is taken out；The sample of taking-up is uniformly applied on carbon paper, and uniformly smears Nafion solution, is dried, MEC cathode material is obtained.Operation of the present invention is simple, and experimental period is shorter, can stability and high efficiency production hydrogen.
Description
Technical field
The invention belongs to technical field of composite materials, specially a kind of molybdenum disulfide/NaY molecular sieve composite cathode material
Preparation method and its application in microorganism electrolysis cell.
Background technique
The energy is the important material base that development is social and uplifts the people's living standard, and is the strong of the promotion national economic development
Big power, economic growth and the raising of the level of economic development require the energy to support, and with current energy overview and ring
From the point of view of the situation of border, energy resources relative deficiency, problem of environmental pollution aggravation.Hydrogen Energy is as a kind of clean new energy and can completely
The blueprint of the renewable sources of energy, one completely new " hydrogen economy " is being formed.
In MEC, microorganism carries out metabolic process, and when electrode both ends are added with applied voltage, electronics is shifted from intracellular
Arrived extracellular anode, power supply provide potential difference effect under by external circuit reach cathode, in the cathodic compartment proton and
Electronics, which combines, generates hydrogen.To improve hydrogen generation efficiency, cathode material needs constantly selection and optimization.
Chinese patent (CN103413948A) has studied a kind of microorganism electrolysis cell modification biological cathode preparation method, will
MWNT/ tourmaline/PANI combination electrode tames biofilm as MFC anode, then moves to MEC cathode, finally construct
MWNT/ tourmaline/PANI modification biological cathode, the high conduction performance and Strong oxdiative of this research and utilization carbon nanotube and polyaniline
Reducing property realization chemical catalysis function simultaneously accelerates electron transmission, can highly effective hydrogen yield.But during preparing combination electrode
Use acetone as solvent, acetone is inflammable, and volatile, property is active, in addition, the period of biological domestication process is longer.
Chinese patent (CN107740136A) has studied a kind of order mesoporous cathode composite, with mesopore molecular sieve SBA-
15 be hard template, prepares nickel cobalt metal oxide, and mesopore metal oxide NiCo by hard template method2O4It is urged as MEC cathode
Agent increases the specific surface area of electrode, accelerates electron transmission.But when preparing mesopore molecular sieve, template need to be used, and
The source template P123 is rare, higher cost, during stirring is in HF solution to remove hard template SBA-15, it is possible to meeting
Cause the loss of Porous materials.
Chinese patent (CN109457269A) has studied a kind of MoS2/ graphene-nickel foam is adopted as MEC cathode material
It is prepared with hydro-thermal method, raw material environmental protection is cheap and easy to get, and is all nontoxic or hypotoxicity raw material, environmental pollution are small.But
Nickel foam is easily aoxidized by some foreign ions in the preprocessing process cleaned with hydrochloric ultrasonic wave, cannot function as support carrier, shadow
It rings and produces hydrogen effect.
Summary of the invention
It is an object of the present invention to provide a kind of novel MEC cathode materials, i.e. molybdenum disulfide/NaY molecular sieve composite cathode material
The preparation method of material and its application in microorganism electrolysis cell.
The present invention is achieved by the following technical scheme:
A kind of preparation method of molybdenum disulfide/NaY molecular sieve composite cathode material, includes the following steps:
Step 1: preparing reaction kettle；
Step 2: sodium molybdate and thiocarbamide and NaY molecular sieve are added in reaction kettle, deionized water is added, is put into magneton and is placed on
1h is stirred in constant temperature blender with magnetic force；Wherein, it is 5 by sodium molybdate and the ureagenetic molybdenum disulfide of sulphur and NaY molecular sieve mass ratio:
(1 ~ 3)；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking sample, ethyl alcohol dissolution is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper, and Nafion solution is uniformly smeared, dried, obtains MEC cathode material
Material.
Wherein, the NaY molecular sieve carries out synthetic reaction, specific preparation method in unsealed polytetrafluoroethylcontainer container
It is as follows:
It is Na by the mass ratio of the material step 1: preparing directed agents2O:Al2O3:SiO2:H2O=22:1:10:180, will be a certain amount of
Beaker is added in sodium hydroxide, sodium aluminate, deionized water, and sodium metasilicate is added under fast stirring, sufficiently dissolves, is aged at 70 DEG C
50min；
It is Na by the mass ratio of the material step 2: preparing mother liquor2O:Al2O3:SiO2:H2O=4.30:1:10:180, will be a certain amount of
Beaker is added in sodium hydroxide, sodium aluminate, deionized water, and silica solution is added under fast stirring, sufficiently dissolves；
Reaction system is formed step 3: the directed agents of first step preparation are added in mother liquor, is sufficiently stirred, is aged at 50 DEG C
1h, then the crystallization at 100 DEG C obtains NaY points by the product after crystallization through fast cooling, washing, suction filtration, drying, grinding steps
Son sieve.
About the application of molybdenum disulfide/NaY molecular sieve composite cathode material, in microorganism electrolysis cell, with molybdenum disulfide/
NaY molecular sieve composite material is cathode, using carbon felt as anode, using Ag/AgCl as reference electrode, with activated bacteria sludge and
(its constituent is electrolyte, the DC voltage of additional 0.7V, composition microorganism electricity with patent CN109136983A) to nutrient solution
Xie Chi.
The invention has the following advantages that
1, the raw material that the present invention uses are cheap and easy to get, easily manufacture.
2, operation of the present invention is simple, and experimental period is shorter, can stability and high efficiency production hydrogen.
3, the preparation of NaY molecular sieve and molybdenum disulfide is hydrothermal synthesis method, and reaction process is easy to control, reaction condition temperature
With, and during using NaY molecular sieve, template is not used.
4, the electrochemical catalysis activity of molybdenum disulfide is higher, and good dispersion does not bond, and coefficient of friction is lower, generates friction
Resistance is smaller, and stability is good, and NaY molecular sieve, which contains, has three-dimensional open-framework, increases the specific surface area of electrode, is conducive to two sulphur
Change the attachment of molybdenum, active site is more, accelerates electron transmission, and the two combines, and reaches highly effective hydrogen yield.
Detailed description of the invention
Fig. 1 shows MoS prepared by the embodiment of the present invention 22The scanning electron microscope (SEM) photograph of/NaY molecular sieve composite material.
Fig. 2 indicates the linear sweep voltammetry test chart of cathode material prepared by the embodiment of the present invention 1,2,3,4.
Fig. 3 a indicates the Ta Feier test chart of cathode material prepared by the embodiment of the present invention 1,2,3,4.
Fig. 3 b indicates the Tafel slope figure of cathode material prepared by the embodiment of the present invention 2,4.
Fig. 4 indicates that cathode material prepared by the embodiment of the present invention 1,2,3,4 generates the influence of electric current to microorganism electrolysis cell
Relational graph.
Fig. 5 indicates the gas generating component figure of cathode material prepared by the embodiment of the present invention 1,2,3,4.
Specific embodiment
Specific embodiments of the present invention are described in detail with reference to the accompanying drawing.
Embodiment 1
A kind of molybdenum disulfide/NaY molecular sieve composite cathode material is prepared by the following method:
Step 1: preparing the good reaction kettle of airtightness；
Step 2: 4mmol sodium molybdate and 20mmol thiocarbamide (the two, which is reacted, produces 0.4g molybdenum disulfide) are added in reaction kettle, with
And 0.08g NaY molecular sieve (molybdenum disulfide is 5:1 with NaY molecular sieve mass ratio), 60mL deionized water is added, after being put into magneton
It is placed in constant temperature blender with magnetic force and stirs 1h；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking 4mg sample, the dissolution of 0.5mL ethyl alcohol is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper (2cm × 2cm), and uniformly smear 10 μ L Nafion solutions
(fixed sample), dries, obtains MEC cathode material.
Embodiment 2
A kind of molybdenum disulfide/NaY molecular sieve composite cathode material is prepared by the following method:
Step 1: preparing the good reaction kettle of airtightness；
Step 2: 4mmol sodium molybdate and 20mmol thiocarbamide (the two, which is reacted, produces 0.4g molybdenum disulfide) are added in reaction kettle, with
And 0.16g NaY molecular sieve (molybdenum disulfide is 5:2 with NaY molecular sieve mass ratio), 60mL deionized water is added, after being put into magneton
It is placed in constant temperature blender with magnetic force and stirs 1h；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking 4mg sample, the dissolution of 0.5mL ethyl alcohol is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper (2cm × 2cm), and uniformly smear 10 μ L Nafion solutions
(fixed sample), dries, obtains MEC cathode material, scanning electron microscope (SEM) photograph is as shown in Figure 1.
Embodiment 3
A kind of molybdenum disulfide/NaY molecular sieve composite cathode material is prepared by the following method:
Step 1: preparing the good reaction kettle of airtightness；
Step 2: 4mmol sodium molybdate and 20mmol thiocarbamide (the two, which is reacted, produces 0.4g molybdenum disulfide) are added in reaction kettle, with
And 0.24g NaY molecular sieve (molybdenum disulfide is 5:3 with NaY molecular sieve mass ratio), 60mL deionized water is added, after being put into magneton
It is placed in constant temperature blender with magnetic force and stirs 1h；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking 4mg sample, the dissolution of 0.5mL ethyl alcohol is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper (2cm × 2cm), and uniformly smear 10 μ L Nafion solutions
(fixed sample), dries, obtains MEC cathode material.
Embodiment 4
A kind of molybdenum disulfide cathode material is prepared by the following method:
Step 1: preparing the good reaction kettle of airtightness；
Step 2: the sodium molybdate and thiocarbamide (the two reaction generates molybdenum disulfide) that the mass ratio of the material is 1:5 are added in reaction kettle, add
Enter 60mL deionized water, is put into magneton and is placed in constant temperature blender with magnetic force and stir 1h；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking 4mg sample, the dissolution of 0.5mL ethyl alcohol is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper (2cm × 2cm), and uniformly smear 10 μ L Nafion solutions
(fixed sample), dries, obtains MEC cathode material.
As shown in Figure 2, in ﹣ 1.5V-0V scanning range, the current density of cathode material prepared by embodiment 2 is connect
It is bordering on platinum guaze, higher than the cathode material and bare carbon paper of other embodiments preparation.
It is the Tafel curve of cathode material prepared by embodiment 1,2,3,4 by Fig. 3 a, Fig. 3 b is prepared by embodiment 2,4
Slope obtained by the strong polarized area linear fit in cathode flowpath part in the Tafel curve of cathode material, by Fig. 3 b it is found that embodiment 2
The Tafel slope of the composite material of preparation is minimum, is 34.4mV/dec.
As shown in Figure 4, the cathode material, platinum guaze of all embodiment preparations and the current density of bare carbon paper all increase at any time
Increase or tend towards stability greatly, and by comparison, it was found that the maximum current density of cathode material prepared by embodiment 2 is larger.
In microorganism electrolysis cell, using material prepared by above-mentioned different embodiments as the cathode of MEC reactor, with carbon
Felt is anode, and using Ag/AgCl as reference electrode, using activated bacteria sludge and nutrient solution as electrolyte, additional 0.7V's is straight
Galvanic electricity pressure forms microorganism electrolysis cell.
As shown in Figure 5, embodiment 2 prepare composite material gas production highest, be 14.9mL, and hydrogen proportion compared with
Height is 89.09%.
In short, as known from the above, MoS prepared by embodiment 22/ NaY molecular sieve composite property is best.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
It is described in detail according to the embodiment of the present invention, those skilled in the art should understand that, to technical solution of the present invention
It is modified or replaced equivalently, without departure from the spirit and scope of technical solution of the present invention, the present invention should all be covered by
In the protection scope of claims.
Claims (4)
1. a kind of molybdenum disulfide/NaY molecular sieve composite cathode material preparation method, characterized by the following steps:
Step 1: preparing reaction kettle；
Step 2: sodium molybdate and thiocarbamide and NaY molecular sieve are added in reaction kettle, deionized water is added, is put into magneton and is placed on
1h is stirred in constant temperature blender with magnetic force；Wherein, it is 5 by sodium molybdate and the ureagenetic molybdenum disulfide of sulphur and NaY molecular sieve mass ratio:
1~3；
Step 3: taking out magneton, reaction kettle is placed in 220 DEG C of baking ovens and is reacted for 24 hours；
Step 4: taking out reaction kettle, taking-up sample dehydrated alcohol, deionized water are washed after being cooled to room temperature, and filter to obtain sample；
Step 5: sample is placed in 70 DEG C ~ 80 DEG C baking ovens dry 12h；
Step 6: taking sample, ethyl alcohol dissolution is added, after ultrasound is centrifuged 30min, takes out；
Step 7: the sample of taking-up is uniformly applied on carbon paper, and Nafion solution is uniformly smeared, dried, obtains MEC cathode material
Material.
2. molybdenum disulfide according to claim 1/NaY molecular sieve composite cathode material preparation method, it is characterised in that:
The NaY molecular sieve the preparation method is as follows:
It is Na by the mass ratio of the material step 1: preparing directed agents2O:Al2O3:SiO2:H2O=22:1:10:180, by sodium hydroxide,
Beaker is added in sodium aluminate, deionized water, and sodium metasilicate is added under fast stirring, sufficiently dissolves, is aged 50min at 70 DEG C；
It is Na by the mass ratio of the material step 2: preparing mother liquor2O:Al2O3:SiO2:H2O=4.30:1:10:180, by sodium hydroxide,
Beaker is added in sodium aluminate, deionized water, and silica solution is added under fast stirring, sufficiently dissolves；
Reaction system is formed step 3: the directed agents of first step preparation are added in mother liquor, is sufficiently stirred, is aged at 50 DEG C
1h, then the crystallization at 100 DEG C obtains NaY points by the product after crystallization through fast cooling, washing, suction filtration, drying, grinding steps
Son sieve.
3. molybdenum disulfide according to claim 1/NaY molecular sieve composite cathode material preparation method, it is characterised in that:
It is 5:2 by sodium molybdate and the ureagenetic molybdenum disulfide of sulphur and NaY molecular sieve mass ratio in second step.
4. a kind of molybdenum disulfide/application of the NaY molecular sieve composite cathode material in microorganism electrolysis cell, it is characterised in that: In
It is ginseng with Ag/AgCl using carbon felt as anode using molybdenum disulfide/NaY molecular sieve composite material as cathode in microorganism electrolysis cell
Than electrode, using activated bacteria sludge and nutrient solution as electrolyte, the DC voltage of additional 0.7V, composition microorganism electrolysis
Pond.
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