CN103668304A - Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode - Google Patents
Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode Download PDFInfo
- Publication number
- CN103668304A CN103668304A CN201210374808.7A CN201210374808A CN103668304A CN 103668304 A CN103668304 A CN 103668304A CN 201210374808 A CN201210374808 A CN 201210374808A CN 103668304 A CN103668304 A CN 103668304A
- Authority
- CN
- China
- Prior art keywords
- electrode
- coal slurry
- zro
- coal
- tio
- 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
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003250 coal slurry Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract 4
- 238000002360 preparation method Methods 0.000 claims abstract 4
- 239000000758 substrate Substances 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000003245 coal Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 46
- 238000000034 method Methods 0.000 abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- -1 salt compounds Chemical class 0.000 abstract description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 229960000935 dehydrated alcohol Drugs 0.000 description 14
- 229910052726 zirconium Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005498 polishing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 235000011194 food seasoning agent Nutrition 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明涉及一种Ti/nanoTiO2-ZrO2电极电解煤浆制取氢气的方法，所涉及的关键问题之一是制备Ti/nanoTiO2-ZrO2电极并采用此电极电解煤浆制取氢气的电解工艺。本发明采用在钛酸丁酯中分别加入锆金属的盐类化合物，直接水解钛酸丁酯分别得到锆金属掺杂的复合纳米TiO2溶胶，选用纯钛金属，采用提拉法将锆金属掺杂的复合纳米TiO2溶胶涂覆在表面洁净的Ti基体上，煅烧后制成Ti/TiO2-ZrO2膜修饰电极。采用Ti/TiO2-ZrO2膜修饰电极为煤浆电解的阳极，DSA电极为对电极，以H2SO4为电解液，在Fe3+作为溶液催化剂的条件下，控制槽压1.2V以内，得到氢气为：6mL/cm2，电流密度为：17.35mA/cm2。The present invention relates to a Ti/nanoTiO 2 -ZrO 2 electrode electrolytic coal slurry production method for hydrogen, one of the key issues involved is the preparation of the Ti/nanoTiO 2 -ZrO 2 electrode and the use of this electrode electrolytic coal slurry to produce hydrogen electrolytic process. In the present invention, salt compounds of zirconium metal are respectively added to butyl titanate, and the butyl titanate is directly hydrolyzed to obtain composite nano- TiO sol doped with zirconium metal, and pure titanium metal is selected, and zirconium metal is mixed with The mixed composite nano-TiO 2 sol is coated on the Ti substrate with a clean surface, and then calcined to make a Ti/TiO 2 -ZrO 2 film modified electrode. Using Ti/TiO 2 -ZrO 2 membrane modified electrode as the anode of coal slurry electrolysis, DSA electrode as the counter electrode, H 2 SO 4 as the electrolyte, under the condition of Fe 3+ as the solution catalyst, the tank pressure is controlled within 1.2V , the obtained hydrogen gas is: 6mL/cm 2 , and the current density is: 17.35mA/cm 2 .
Description
Technical field
The invention belongs to coal slurry hydrogen making technical field, relate to a kind of high catalytic activity Ti/nanoTiO for preparing
2-ZrO
2electrode also adopts the electrolysis process of this catalysis electrode electrolyzing coal slurry hydrogen making.
Background technology
The electrolysis of coal utilizes technology approximately from twentieth century mid-term, just to have report, but because efficiency is low Arrested Development.Until Cougmin in 1979 and Famoq have delivered after the article of coal electrolyzing hydrogen manufacturing on the magazines such as Nature, the research of this respect just has large development. in the acidic medium that he proposes, the method for electrolyzing coal slurry liquid hydrogen making belongs to electrochemistry hydrogen manufacturing.He finds that the bath voltage of electrolyzing coal slurry liquid hydrogen manufacturing is only half of water electrolysis hydrogen production bath voltage, has greatly reduced the energy consumption of whole process in acidic medium.
1985, the people such as Lalvanl adopted first three-electrode system and control potentiometry and studied the anodic oxidation of U.S. NorthDakota brown coal in NaOH solution, and the anode that they use is Pt electrode.The electrolysate of anolyte compartment mainly contains humic acids, CO
2with a small amount of O
2, cathode compartment produces H
2.Under different anode potentials, carry out electrolysis, find that humic acids and water-soluble carboxylic acid's yield are the highest, under the experiment condition adopting at them when anode potential is 2.7V (SCE), cathode hydrogen evolution current efficiency is 80%-90%, and the transformation efficiency of brown coal reaches 50%.
Nineteen eighty-two park etc. is studied the oxidation mechanism of coal, and they think that coal electrolyzing oxidation and the impurity F e ion in charcoal have very large relation, Fe
3+by chemical reaction, carbon is oxidized.The related researcher of Ohio State University since 2004 headed by Botte professor is doing a large amount of research work aspect coal slurry electrolysis feasibility, obtained good achievement, made this research topic of coal slurry electrolytic hydrogen production in practicalization, stride forward major step.Major objective is agreed to subsidize for the project of the novel coal electrolyzing device for producing hydrogen of design in November, 2004 U.S. Edison material technology center (Edison Materials Technology Center (EMTEC)).The hydrogen that this device produces finally can be for the fuel cell operation of 5 kilowatts a year.
Within 2006, Botte study group is at solution Fe
3+/ Fe
2+effect under, obtained when decomposition voltage 1.1V, produce hydrogen speed and can reach 18mL/hcm
2achievement.
Electrochemical method utilizes coal resources, and makes hydrogen simultaneously, and this technology meets the energy development strategy of China very much.Because electrochemical method utilizes coal technology, not only coal can be converted into methane, ethene, ethane, carboxylic acid, the useful Chemicals such as humic acid, but also can obtain high-purity hydrogen, especially along with the development of fuel cell electric vehicle, for Hydrogen Energy utilization provides space widely.
Research and develop highly active catalysis electrode and be coal slurry electrolytic hydrogen production the key issue that must solve, the anodic reaction of coal slurry electrolytic hydrogen production is actually depolarize reaction, play reduction anode potential, reduce the effect that coal slurry electrolytic hydrogen production reacts required impressed voltage, to seek to develop highly active anode-catalyzed electrode, reduce anode overpotential, accelerate anodic reaction speed, improving electrolytic reaction electric current is the practical key issue of coal slurry electrolytic reaction.Up to the present, coal slurry electrolytic hydrogen production mainly contains following a few class with catalyticing anode: (1) pure Pt sheet or Pt net electrode used in traditional coal electrolyzing process.(2) Pt of doping certain proportion Ru, Ir metallic element is binary metal alloy electrode.(3) Pt that carbon cloth is matrix is precious metal catalyst electrode.The electrolyte solution of coal slurry electrolytic hydrogen production is sulfuric acid, so the anode of using as coal slurry electrolytic hydrogen production is except possessing the most basic requirement of electrolytic anode material, also has harsher requirement, above-mentioned various types of electrodes all can not thoroughly meet the requirement of the anode material of coal slurry electrolytic hydrogen production, and be all to take precious metal as main raw material, expensive, from practical, still have very large gap.
Hydrogen Energy as a kind of cleaning, efficient, can store and the reproducible energy is with a wide range of applications, hydrogen manufacturing is compared with coal high-temperature gasification, and the needed processing unit of hydrogen by electrolyzing coal slurry is simple, mild condition, thereby also can greatly reduce hydrogen manufacturing cost, and technological process easy handling.Employing has the nano-TiO of high catalytic activity and stability
2-ZrO
2the hydrogen manufacturing of complex film modified electrolysis coal slurry, is to take coal as main energy structure feature according to China, and development be take coal as waste hydrogen source is hydrogen manufacturing route with Chinese characteristics, is also current most economical route.
Summary of the invention
The present invention relates to prepare high catalytic activity Ti/nanoTiO
2-ZrO
2electrode also adopts the electrolysis process of this catalysis electrode electrolyzing coal slurry hydrogen making.The present invention adopts the salt compounds that adds zirconium metal in butyl (tetra) titanate, and direct hydrolysis butyl (tetra) titanate obtains respectively the metal-doped composite Nano TiO of zirconium
2colloidal sol, selects pure titanium metal, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the clean Ti matrix in surface, makes Ti/TiO after calcining
2-ZrO
2film modified electrode.Adopt Ti/TiO
2-ZrO
2film modified electrode is the anode of coal slurry electrolysis, and DSA electrode is to electrode, with H
2sO
4for electrolytic solution, at Fe
3+under condition as solution catalyst, control flume is pressed in 1.2V, and Electrowinning is to hydrogen.
Ti/nanoTiO
2-ZrO
2electrolysis coal slurry hydrogen making takes following technical scheme to realize:
(1) first by Ti matrix use respectively different meshes sand papering polishing, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid clean.With acetone deoiling, dehydrated alcohol, clean subsequently, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, is placed in retort furnace roasting, and cooling rear taking-up, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, with the electrolyzer of barrier film.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, electrolytic medium solution: 1～4mol/LH
2sO
4; The Fe of catalyzer: 60mmol/L
3+.
Described acetone deoiling, dehydrated alcohol supersound washing time are 15min.
Described sand paper is 250 orders, 500 orders, 1000 orders and 2000 orders
Described is containing the solution of zirconium nitrate, and zirconium nitrate content is zirconium nitrate 0.5～1mol/l.
Described Ti metal adopts TA
1the pure titanium metal of type (purity is 99.5%).
Described ethanol is dehydrated alcohol and the treating processes that removes minor amount of water through 4A molecular sieve.
The described diaphragm for electrolytic cell with barrier film adopts Nafion 117.
Described coal slurry adopts sulfuric acid to prepare coal slurry, coal-water fluid concentration: 0.02/mL～0.12/mL.
Described catalyzer is ferric sulfate.
Described electrolytic reaction temperature is 75 ℃.
The particle diameter of described coal particle: a coal 12 μ m～115 μ m that obtain different-grain diameter with ball mill ball milling.
Described coal particle ball mill Ball-milling Time is 2h.
Embodiment
Embodiment 1
(1) first by Ti matrix use respectively 250 orders, 500 orders, 1000 orders and 2000 order sand papering polishings, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid and ethylene glycol (volume ratio is 1: 4) to clean.Use subsequently acetone deoiling, dehydrated alcohol supersound washing 5 minutes, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, heats 5min, is placed in 450 ℃ of roasting 30min of retort furnace constant temperature, cooling rear taking-up.Said process repeats 4～5 times, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, with the electrolyzer of barrier film.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, coal-water fluid concentration: 0.02/mL, temperature is 75 ℃, and anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, electrolytic medium solution: 1mol/L H
2sO
4; The Fe of catalyzer: 60mmol/L
3+, obtain hydrogen and be: 1mL/cm
2h, current density is: 11.35mA/cm
2.
Embodiment 2
(1) first by Ti matrix use respectively 250 orders, 500 orders, 1000 orders and 2000 order sand papering polishings, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid and ethylene glycol (volume ratio is 1: 4) to clean.Use subsequently acetone deoiling, dehydrated alcohol supersound washing 5 minutes, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, heats 5min, is placed in 450 ℃ of roasting 30min of retort furnace constant temperature, cooling rear taking-up.Said process repeats 4～5 times, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, with the electrolyzer of barrier film.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, coal-water fluid concentration: 0.08/mL, temperature is 75 ℃, and anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, electrolytic medium solution: 1mol/L H
2sO
4; The Fe of catalyzer: 60mmol/L
3+, obtain hydrogen and be: 4mL/cm
2h, current density is: 14.35mA/cm
2.
Embodiment 3
(1) first by Ti matrix use respectively 250 orders, 500 orders, 1000 orders and 2000 order sand papering polishings, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid and ethylene glycol (volume ratio is 1: 4) to clean.Use subsequently acetone deoiling, dehydrated alcohol supersound washing 5 minutes, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, heats 5min, is placed in 450 ℃ of roasting 30min of retort furnace constant temperature, cooling rear taking-up.Said process repeats 4～5 times, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, H type diaphragm sell.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, coal-water fluid concentration: 0.12/mL, temperature is 75 ℃, and anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, dielectric solution: 1mol/L H
2sO
4; The Fe of catalyzer: 60mmol/L
3+, obtain hydrogen and be: 6mL/cm
2h, current density is: 17.35mA/cm
2.
Embodiment 4
(1) first by Ti matrix use respectively 250 orders, 500 orders, 1000 orders and 2000 order sand papering polishings, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid and ethylene glycol (volume ratio is 1: 4) to clean.Use subsequently acetone deoiling, dehydrated alcohol supersound washing 5 minutes, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, heats 5min, is placed in 450 ℃ of roasting 30min of retort furnace constant temperature, cooling rear taking-up.Said process repeats 4～5 times, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, with the electrolyzer of barrier film.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, coal-water fluid concentration: 0.12/mL, temperature is 75 ℃, and anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, electrolytic medium solution: 2mol/L H
2sO
4; The Fe of catalyzer: 60mmol/L
3+, obtain hydrogen and be: 6.7mL/cm
2h, current density is: 18.23mA/cm
2.
Embodiment 5
(1) first by Ti matrix use respectively 250 orders, 500 orders, 1000 orders and 2000 order sand papering polishings, make it to present argenteous metalluster.The object of polishing is to make Rough Metal Surface smooth, smooth.Then with distilled water, dehydrated alcohol, rinse well, then use hydrofluoric acid and ethylene glycol (volume ratio is 1:4) to clean.Use subsequently acetone deoiling, dehydrated alcohol supersound washing 5 minutes, remove the greasy dirt of Ti matrix surface.
(2) direct hydrolysis butyl (tetra) titanate obtains the metal-doped composite Nano TiO of zirconium
2colloidal sol, adopts crystal pulling method by the metal-doped composite Nano TiO of zirconium
2colloidal sol is coated on the Ti matrix of cleaning, after seasoning, under infrared lamp, heats 5min, is placed in 450 ℃ of roasting 30min of retort furnace constant temperature, cooling rear taking-up.Said process repeats 4～5 times, makes Ti/TiO
2-ZrO
2film modified electrode.
(3) adopt two electrode systems, with the electrolyzer of barrier film.Utilize Potentiostat 1.2V groove to depress the reaction of carrying out coal slurry electrooxidation, coal-water fluid concentration: 0.12/mL, temperature is 75 ℃, and anode is commercially available DSA electrode, and negative electrode is Ti/TiO
2-ZrO
2film modified electrode, electrolytic medium solution: 4mol/L H
2sO
4; The Fe of catalyzer: 60mmol/L
3+, obtain hydrogen and be: 6.84mL/cm
2h, current density is: 18.76mA/cm
2.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention, all should fall in the definite protection domain of the claims in the present invention book.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374808.7A CN103668304A (en) | 2012-09-24 | 2012-09-24 | Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210374808.7A CN103668304A (en) | 2012-09-24 | 2012-09-24 | Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103668304A true CN103668304A (en) | 2014-03-26 |
Family
ID=50307060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210374808.7A Pending CN103668304A (en) | 2012-09-24 | 2012-09-24 | Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103668304A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938836A (en) * | 2018-09-21 | 2020-03-31 | 中国科学院大连化学物理研究所 | A method for improving the stability of electrodes for CO2 electrochemical reduction |
| CN114574879A (en) * | 2022-03-02 | 2022-06-03 | 大连理工大学 | Method for improving yield of humic acid prepared by coal electrolysis by coating film on surface of coal particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226683A (en) * | 1979-08-09 | 1980-10-07 | Vaseen Vesper A | Method and apparatus for hydrogen production in an absorber liquid by electrochemical of coal and water |
| CN101054683A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry |
| CN102477565A (en) * | 2010-11-29 | 2012-05-30 | 淮南师范学院 | Ti-based electrode with high catalytic activity, Ti/nano TiO2-RE2O3;Ti/nanoTiO2-ZrO2Preparation of |
-
2012
- 2012-09-24 CN CN201210374808.7A patent/CN103668304A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226683A (en) * | 1979-08-09 | 1980-10-07 | Vaseen Vesper A | Method and apparatus for hydrogen production in an absorber liquid by electrochemical of coal and water |
| CN101054683A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry |
| CN102477565A (en) * | 2010-11-29 | 2012-05-30 | 淮南师范学院 | Ti-based electrode with high catalytic activity, Ti/nano TiO2-RE2O3;Ti/nanoTiO2-ZrO2Preparation of |
Non-Patent Citations (1)
| Title |
|---|
| 印仁和等: "电解煤浆制取氢气的工艺研究", 《现代化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938836A (en) * | 2018-09-21 | 2020-03-31 | 中国科学院大连化学物理研究所 | A method for improving the stability of electrodes for CO2 electrochemical reduction |
| CN110938836B (en) * | 2018-09-21 | 2022-05-06 | 中国科学院大连化学物理研究所 | A method for improving the stability of electrodes for CO2 electrochemical reduction |
| CN114574879A (en) * | 2022-03-02 | 2022-06-03 | 大连理工大学 | Method for improving yield of humic acid prepared by coal electrolysis by coating film on surface of coal particles |
| CN114574879B (en) * | 2022-03-02 | 2023-09-22 | 大连理工大学 | A method of coating the surface of coal particles to improve the yield of humic acid produced by coal electrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jourdin et al. | High acetic acid production rate obtained by microbial electrosynthesis from carbon dioxide | |
| Feng et al. | TiO2 nanotube arrays modified titanium: a stable, scalable, and cost-effective bioanode for microbial fuel cells | |
| CN103014752B (en) | A kind of TiO 2nano-tube array load is containing the preparation method of ruthenium coating catalyzer | |
| CN102732910B (en) | The organic method of coal slurry electrolytic preparation is strengthened under a kind of alkaline system | |
| CN106958033B (en) | Magn é li phase TinO2n-1The preparation method of nanotube electrode | |
| CN102517601A (en) | A preparation method of Cu2O/TiO2 nanotube array electrode with graphene assembled on the surface | |
| CN103334142A (en) | A self-doping modified high-conductivity TiO2 nanotube array preparation method | |
| CN105304910B (en) | Carbon dioxide electrochemical reduction hydrocarbon electrode and its preparation and application | |
| CN103603008A (en) | A Nano TiO2 Electrode Doped with Rare Earth Lanthanum and Its Electrocatalytic Reduction of Furfural | |
| CN102477565A (en) | Ti-based electrode with high catalytic activity, Ti/nano TiO2-RE2O3;Ti/nanoTiO2-ZrO2Preparation of | |
| Su et al. | Emerging applications of nanodiamonds in photocatalysis | |
| CN103132120A (en) | Method for preparing photoelectrocatalysis electrode material capable of efficiently degrading organic pollutants | |
| CN102899683A (en) | A kind of preparation method of Ti-based nano CeO2/PbO2 modified electrode | |
| CN101642714A (en) | Preparation method of core-shell Fe/Pd bimetallic nano-catalyst | |
| CN104195588A (en) | Method for preparing hydrogen and oxygen by decomposing pure water through photoelectrochemistry | |
| CN206244890U (en) | A kind of titanic oxide nanometer tube modified tin dioxide coating on titanium antimony electrode of high stability | |
| CN106567102A (en) | A preparation method of TiO2/carbon nanotube/Ni photoelectrically active composite electrode | |
| CN103290424A (en) | Preparation method of TiC powder | |
| CN108722437A (en) | The preparation method and ferronickel composite catalyst of ferronickel composite catalyst | |
| CN103668304A (en) | Production of Hydrogen by Electrolyzing Coal Slurry with Ti/nanoTiO2-ZrO2 Electrode | |
| CN110499515A (en) | A method for electrochemically preparing ferric oxide-graphene composite | |
| CN104022289A (en) | A RuNi/TiO2 nanotube electrode for direct methanol fuel cell and its preparation method | |
| CN101407924A (en) | In-situ electrochemistry preparation for Ti/TiO2 membrane electrode | |
| Jiang et al. | Efficient conversion of greenhouse gas of CO2 into carbon products with desirable structures via molten carbonates electrolysis | |
| CN106498437A (en) | A kind of Carbon dioxide electrochemical reduction electrode preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |