CN101054683A - Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry - Google Patents
Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry Download PDFInfo
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- CN101054683A CN101054683A CN 200710037410 CN200710037410A CN101054683A CN 101054683 A CN101054683 A CN 101054683A CN 200710037410 CN200710037410 CN 200710037410 CN 200710037410 A CN200710037410 A CN 200710037410A CN 101054683 A CN101054683 A CN 101054683A
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Abstract
The present invention relates to a method for preparing anode catalyse electrodes for coal liquid electroanalysis for hydrogen making, especially to a method for preparing anode catalyse electrodes by depositing platinum, ruthenium and iridium catalysis layer on a nanometer porous titanic oxide thin film of substrate titanium through cyclic voltammetry, and belongs to the field of electrochemical deposition process engineering. Said preparation method in accordance with the present invention comprises the following steps: (1) pretreatment of metallic titanium substrate; (2) generation of titanium substrate surface layered porous TiO2 thin films; (3) cleaning processing of surfaces; (4) precious metal catalysis layer deposition on the TiO2 thin film; wherein the main process and step is that in the electrolytic tank, sulfuric acid is selected as supporting electrolyte, one or two of precious metal catalyzer solutions, such as H2PtCl66H2O, RuCl3 and IrCl3, are added therein. Within the electric potential range of -0.2-0.5 V, a scan with a scanning velocity of 50mV is performed under ultrasound shocking or magnetic stirring, wherein the deposition thickness of the catalysis layer is controlled by the number of scan turns. Composite electrodes such as Ti/TiO2-Pt-Ru and Ti/TiO2-Pt-Ir prepared in accordance with the present invention are catalysis electrodes of high activity and can improve the electrolysis electric current density and electrolysis electrical current efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of anode-catalyzed electrode of hydrogen by electrolyzing coal slurry, particularly adopt cyclic voltammetry on the nano porous titanium dioxide film, to deposit the preparation method of the anode-catalyzed electrode of platinum, ruthenium, iridium Catalytic Layer, belong to the electrochemical deposition process technical field.
Background technology
The electrolysis process technology of coal just has report the thirties in early days as far back as eighties of last century, in the later development process, owing to used expensive pure Pt sheet or Pt net as electrode, the electrolyzer of high resistance and low reaction speed or electrolyzer, not only the electrolytic reaction electric current is too small, and electrolytic efficiency is also lower, and the hydrogen manufacturing cost is improved.
On " Nature " magazine, once delivered coal at Coughlim in 1979 and Forooque and separated the paper of hydrogen manufacturing, and made the research of project enter substantial development period afterwards.
The reaction formula of coal slurry electrolytic hydrogen production is:
Positive C+2H
2O → CO
2+ 4H
++ 4e
Negative electrode 4H
++ 4e → 2H
2
Total reaction: C+2H
2O → CO
2+ 2H
2
The theoretical electrolytic potential of this reaction is 0.21V, far below traditional brine electrolysis theoretical electrolytic potential 1.23V, in the electrolytic process, elements such as the S in the coal, N are oxidized generation acid accordingly in electrolytic process, stay in the electrolytic solution, can not cause the pollution of the gas that produces when resembling coal burning environment.
At present, the coal slurry electrolytic hydrogen production mainly contains two classes with catalyticing anode: (1) continues to use tradition used pure Pt sheet or Pt net electrode.(2) Pt with doping certain proportion Ru, Ir is the binary metal alloy electrode.(3) be that the Pt of matrix is unit or binary catalyst electrode with the titanium.The two kinds of electrodes in front need to cause electrode to cost an arm and a leg with platinum, and electro catalytic activity is also lower, unsuitable large-scale application; The above-mentioned electrode of third kind is the electrode that preliminary stage is studied, though having significantly, reduces the electrode cost, but the sedimentary precious metal catalyst layer of titanium matrix surface specific surface area improves significantly, and electrolyte sulfuric acid is easy to cause the corrosion of titanium matrix, the work-ing life of reduction electrode.
Summary of the invention
The objective of the invention is to overcome the shortcoming that aforementioned catalysis electrode exists, a kind of preparation method of novel anode-catalyzed electrode is provided.
Characteristics of the present invention are to generate one deck stratiform, porous TiO at the metallic titanium matrix surface oxidation earlier
2Film is then at film surface and Kong Zhongyong cyclic voltammetry deposition preparation unit or binary catalyst layer.And TiO
2Film then is an intermediate barrier layers of precious metal catalyst layer and matrix titanium as Pt.
A kind of hydrogen by electrolyzing coal slurry of the present invention the preparation method of anode-catalyzed electrode, it is characterized in that it being that following technological process and step are arranged:
A. the pre-treatment of metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, be placed in the acetone ultrasonic wave oil removing subsequently 5 minutes, and used the redistilled water ultrasonic cleaning again, use certain density hydrofluoric acid treatment 1 minute then, the redistilled water of reusable heat cleans up, dry for standby.
B. the layered porous TiO of titanium-based surface
2The preparation of film: above-mentioned pretreated titanium matrix is placed in the electrolyzer, is oxidation 5 minutes in the electrolyte sulfuric acid of 1mol/L in concentration, controls certain current potential, and promptly volts DS 120V finally makes layered porous TiO
2Film, this is preparation attitude oxide film;
C. use the HF of lower concentration (5%) to handle for 10 seconds more above-mentioned preparation attitude oxide film, make the oxide film cleaning surfaces, the aperture also has change big slightly simultaneously.
D. at TiO
2Carry out the Catalytic Layer deposition on the film: in electrolyzer, with the platinized platinum electrode is counter electrode, and saturated calomel electrode is a reference electrode, with sulfuric acid is to support dielectric medium, add certain density Platinic chloride, chlorination nail or the iridium chloride precious metal catalyst agent solution for preparing in advance again.In-0.2V-0.5V potential range, scan under the condition that ultrasonic concussion or magnetic agitation are arranged with the sweep velocity of 50mV/S, the deposit thickness of Catalytic Layer is controlled by the scanning number of turns.Catalyzer noble metal granule size is controlled at 100 nanometers once; Finally make titanium-titanium oxide-precious metal catalyst layer compound anode-catalyzed electrode.
Above-mentioned TiO
2Added solution is H when carrying out the Catalytic Layer deposition on the film
2PtCl
66H
2O, RuCl
3, IrCl
3In one or both, described Catalytic Layer is Pt or Pt-Ru or Pt-Ir; Its both mol ratio of described Catalytic Layer Pt-Ru is 1: 1-1: 2; Its both mol ratio of Catalytic Layer Pt-Ir is 1: 1-1: 2
The characteristics of the inventive method are: owing between matrix titanium and the precious metal catalyst layer one deck TiO is arranged
2Film is as intermediate barrier layers, so reduced the corrosive nature of electrolyte sulfuric acid to a great extent to matrix, prolonged electrode life greatly, the matrix that has very big specific surface area stratiform, nano-porous structure simultaneously provides the precious metal catalyst layer sedimentary good environment, can hold more precious metal catalyst layer nano particle, this structure has improved the specific surface area of entire electrode greatly, has improved the catalytic activity of electrode to a great extent.
Description of drawings
Fig. 1 is TiO among the present invention
2The cyclic voltammetry curve figure of surface deposition Pt.
Fig. 2 is TiO among the present invention
2The cyclic voltammetry curve figure of surface deposition Pt-Ru.
Fig. 3 is TiO among the present invention
2The cyclic voltammetry curve figure of surface deposition Pt-Ir.
Fig. 4 is the I-V curve comparison diagrams of the different electrodes with other of anode-catalyzed electrode of the present invention in the electrolyzing coal slurry process.
Embodiment
After now embodiment of the present invention specifically being described in.
This example is Ti/TiO
2The preparation of-Pt anode-catalyzed electrode.Its preparation process is as follows:
(1) pre-treatment of metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, be placed in acetone the ultrasonic wave oil removing subsequently 5 minutes, and used the redistilled water ultrasonic cleaning again, use certain density hydrofluoric acid treatment 1 minute then, the redistilled water of reusable heat cleans up, dry for standby.
(2) the layered porous TiO of titanium-based surface
2The preparation of film: above-mentioned pretreated titanium matrix is placed in the electrolyzer, is oxidation 5 minutes in the electrolyte sulfuric acid of 1mol/L in concentration, controls certain current potential, and promptly volts DS 120V finally makes layered porous TiO
2Film, this is preparation attitude oxide film;
(3) use the HF of lower concentration (5%) to handle for 10 seconds more above-mentioned preparation attitude oxide film, make the oxide film cleaning surfaces, the aperture also has change big slightly simultaneously.
(4) at TiO
2Carry out Catalytic Layer deposition on the film: in electrolyzer, be counter electrode with the platinized platinum electrode, saturated calomel electrode is a reference electrode, serves as to support dielectric medium with the sulfuric acid of 0.5mol/L, and adding concentration again is the amino sodium sulfonate of organic additive of 50g/L; Reenter certain amount of H in addition
2PtCl
66H
2O solution makes its concentration arrive 5 * 10
-3Mol/L, sonic oscillation 5 minutes makes solution even; In-0.2V-0.5V potential range, under the condition that ultrasonic concussion or magnetic agitation are arranged, scan 80 circles with the sweep velocity of 50mV/S, the deposit thickness of Catalytic Layer is controlled by the scanning number of turns.
The TiO of present embodiment
2The cyclic voltammetry curve of surface deposition Pt is seen Fig. 1.
This example is Ti/TiO
2The preparation of-Pt-Ru anode-catalyzed electrode, wherein Pt is that 1: 2 its preparation process is identical with the front with the mol ratio of Ru in the plating bath.
The preparation process of present embodiment and the foregoing description 1 is identical.Different is in (4) step: plating procatalyst solution is concentration 5 * 10
-3The H of mol/L
2PtCl
66H
2O and 1 * 10
-2The RuCl of mol/L
3Mixing solutions.
The TiO of present embodiment
2(mol ratio Pt: Ru=1: cyclic voltammetry curve 2) is seen Fig. 2 to surface deposition Pt-Ru
This example is Ti/TiO
2The preparation of-Pt-Ir anode-catalyzed electrode, wherein Pt is that 1: 2 its preparation process is identical with the front with the mol ratio of Ir in the plating bath.
The preparation process of present embodiment and the foregoing description 1 is identical.Different is in (4) step: plating procatalyst solution is concentration 5 * 10
-3The H of mol/L
2PtCl
66H
2O and 1 * 10
-2The IrCl of mol/L
3Mixing solutions.
The TiO of present embodiment
2(mol ratio Pt: Ir=1: cyclic voltammetry curve 2) is seen Fig. 3 to surface deposition Pt-Ir
The anode-catalyzed electrode that the embodiment of the invention makes and the simultaneous test of other different electrodes; Test the I-V curve of different electrodes in the electrolyzing coal slurry process.
Concrete test conditions is: coal-water fluid concentration is 0.1g/ml, and dielectric medium is the sulfuric acid of 1mol/L, and temperature is 60 ℃; With the platinized platinum electrode is counter electrode, and test electrode is an anode, adopts two electrode systems; Adopt CHI660B electrochemistry comprehensive tester to test.
Test result is seen Fig. 4, and Fig. 4 is the I-V curve comparison diagrams of the different electrodes with other of anode-catalyzed electrode of the present invention in the electrolyzing coal slurry process.
Fig. 4: 1:Ti/TiO
2-Pt-Ru (the Pt-Ru mol ratio is 1: 2 in the plating bath)
2：Ti/TiO
2-Pt
3:Ti/Pt-Ru (the Pt-Ru mol ratio is 1: 2 in the plating bath)
4：Ti/Pt
5:(is pure) the Pt plate electrode.
As can be seen from Figure 4, the prepared Ti/TiO of the present invention
2-Pt-Ru and Ti/TiO
2-Pt electrode is to have higher electrode current density, and electrode current efficient is preferably arranged.
Claims (3)
1. the preparation method of the anode-catalyzed electrode of a hydrogen by electrolyzing coal slurry is characterized in that following technological process and step are arranged:
A. the pre-treatment of metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, be placed in the acetone ultrasonic wave oil removing subsequently 5 minutes, and used the redistilled water ultrasonic cleaning again, use certain density hydrofluoric acid treatment 1 minute then, the redistilled water of reusable heat cleans up, dry for standby;
B. the layered porous TiO of titanium-based surface
2The preparation of film: above-mentioned pretreated titanium matrix is placed in the electrolyzer, is oxidation 5 minutes in the electrolyte sulfuric acid of 1mol/L in concentration, controls certain current potential, and promptly volts DS 120V finally makes layered porous TiO
2Film;
C. use the HF of lower concentration (5%) to handle for 10 seconds more above-mentioned preparation attitude oxide film, make the oxide film cleaning surfaces, the aperture also has change big slightly simultaneously;
D. at TiO
2Carry out the Catalytic Layer deposition on the film: in electrolyzer, with the platinized platinum electrode is counter electrode, and saturated calomel electrode is a reference electrode, with sulfuric acid is to support dielectric medium, add certain density Platinic chloride, ruthenium chloride or the iridium chloride precious metal catalyst agent solution for preparing in advance again.In-0.2V-0.5V potential range, scan under the condition that ultrasonic concussion or magnetic agitation are arranged with the sweep velocity of 50mV/S, the deposit thickness of Catalytic Layer is controlled by the scanning number of turns.Catalyzer noble metal granule size is controlled at 100 nanometers once; Finally make titanium-titanium oxide-precious metal catalyst layer compound anode-catalyzed electrode.
2. as the preparation method of the anode-catalyzed electrode of claim 1 described a kind of hydrogen by electrolyzing coal slurry, it is characterized in that described TiO
2Added solution is H when carrying out the Catalytic Layer deposition on the film
2PtCl
66H
2O, RuCl
3, IrCl
3In one or both, described Catalytic Layer is Pt or Pt-Ru or Pt-Ir.
3. as the preparation method of the anode-catalyzed electrode of claim 2 described a kind of hydrogen by electrolyzing coal slurry, it is characterized in that its both mol ratio of described Catalytic Layer Pt-Ru is 1: 1-1: 2; Its both mol ratio of Catalytic Layer Pt-Ir is 1: 1-1: 2.
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703953A (en) * | 2012-06-07 | 2012-10-03 | 北京工业大学 | Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition |
| CN102899684A (en) * | 2012-09-11 | 2013-01-30 | 上海大学 | Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal |
| CN103255457A (en) * | 2013-04-28 | 2013-08-21 | 北京工业大学 | Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition |
| CN103668304A (en) * | 2012-09-24 | 2014-03-26 | 淮南师范学院 | Method for electrolyzing coal slurry to make hydrogen employing Ti/nano TiO2-ZrO2 electrode |
| CN104928708A (en) * | 2015-06-16 | 2015-09-23 | 沈阳磁力通能源技术有限公司 | Ultrasonic magnetic-heat device used for preparing nano battery material |
| CN105742652A (en) * | 2016-04-14 | 2016-07-06 | 华南理工大学 | Membrane electrode with bimetallic layer positive electrode for electrolysis water and preparation method of membrane electrode |
| CN107142491A (en) * | 2017-04-10 | 2017-09-08 | 广东卓信环境科技股份有限公司 | A kind of gas permeable electrode and preparation method thereof |
| CN109261146A (en) * | 2018-09-14 | 2019-01-25 | 大连理工大学 | A kind of preparation method for the hollow caged titanium oxide of nanoporous loading different metal |
-
2007
- 2007-02-09 CN CN 200710037410 patent/CN101054683A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703953B (en) * | 2012-06-07 | 2014-11-26 | 北京工业大学 | Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition |
| CN102703953A (en) * | 2012-06-07 | 2012-10-03 | 北京工业大学 | Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition |
| CN102899684A (en) * | 2012-09-11 | 2013-01-30 | 上海大学 | Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal |
| CN102899684B (en) * | 2012-09-11 | 2015-03-25 | 上海大学 | Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal |
| CN103668304A (en) * | 2012-09-24 | 2014-03-26 | 淮南师范学院 | Method for electrolyzing coal slurry to make hydrogen employing Ti/nano TiO2-ZrO2 electrode |
| CN103255457B (en) * | 2013-04-28 | 2016-07-06 | 北京工业大学 | A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium |
| CN103255457A (en) * | 2013-04-28 | 2013-08-21 | 北京工业大学 | Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition |
| CN104928708A (en) * | 2015-06-16 | 2015-09-23 | 沈阳磁力通能源技术有限公司 | Ultrasonic magnetic-heat device used for preparing nano battery material |
| CN104928708B (en) * | 2015-06-16 | 2017-04-12 | 沈阳磁力通能源技术有限公司 | Ultrasonic magnetic-heat device used for preparing nano battery material |
| CN105742652A (en) * | 2016-04-14 | 2016-07-06 | 华南理工大学 | Membrane electrode with bimetallic layer positive electrode for electrolysis water and preparation method of membrane electrode |
| CN105742652B (en) * | 2016-04-14 | 2018-06-22 | 华南理工大学 | It is a kind of for membrane electrode with double-metal layer anode of electrolysis water and preparation method thereof |
| CN107142491A (en) * | 2017-04-10 | 2017-09-08 | 广东卓信环境科技股份有限公司 | A kind of gas permeable electrode and preparation method thereof |
| CN109261146A (en) * | 2018-09-14 | 2019-01-25 | 大连理工大学 | A kind of preparation method for the hollow caged titanium oxide of nanoporous loading different metal |
| CN109261146B (en) * | 2018-09-14 | 2021-04-16 | 大连理工大学 | Preparation method of nano porous hollow cage-shaped titanium oxide loaded with different metals |
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Open date: 20071017 |