CN101717950B - Method for preparing anode-catalyzed electrode for electrolyzing slurry coal - Google Patents
Method for preparing anode-catalyzed electrode for electrolyzing slurry coal Download PDFInfo
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- CN101717950B CN101717950B CN2009101995410A CN200910199541A CN101717950B CN 101717950 B CN101717950 B CN 101717950B CN 2009101995410 A CN2009101995410 A CN 2009101995410A CN 200910199541 A CN200910199541 A CN 200910199541A CN 101717950 B CN101717950 B CN 101717950B
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Abstract
The invention relates to a method for preparing an anode-catalyzed electrode for electrolyzing slurry coal, i.e. a method for preparing an alloy electrode of which the metallic titanium base material is coated with cobalt and nickel oxides and platinum, belonging to the technical field of chemical material preparation process. The method comprises the following steps of: (1) pretreating a metallic titanium substrate; (2) generating a platinum-cobalt-nickel alloy catalyst layer on the titanium substrate by a constant-current and stepped electrolytic deposition method; and (3) after the electrolytic deposition of the metal on the titanium substrate, heat-pretreating in an oven and heat-posttreating in a muffle furnace with a treating temperature of 400-600 DEG C. The main electrolytic deposition process is carried out in an electrolytic bath, and main salts for depositing platinum, cobalt and nickel are respectively H2PtCl6.6H2O, CoSO4.6H2O and NiSO4.7H2O. Ti/Pt-CO3O4, Ti/Pt-NiO and Ti/Pt-CO3O4-NiO catalyzed electrodes prepared by the method can provide the current density and the current efficiency in the electrolytic process and have higher catalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of anode-catalyzed electrode of electrolyzing coal slurry, that is to say that plating has the method for the alloy electrode of cobalt-nickel oxide and platinum on a kind of metal titanium base material of preparation, genus electrochemical material fabricating technology field.
Background technology
The electrolysis of coal utilizes technology approximately from twentieth century report just to be arranged mid-term, but because efficient is low Arrested Development.Behind the article of having delivered the coal electrolytic hydrogen production on the magazines such as Nature, the research of this respect just has large development up to Coughlin in 1979 and Farooque.He finds that the bath voltage of hydrogen by electrolyzing coal slurry only is half of water electrolysis hydrogen production bath voltage, has significantly reduced the energy consumption of whole process in acidic medium.
People such as Clarke have carried out Fe
3+/ Fe
2+Redox couple is in comparatively high temps (80～180 ℃) research of hydrogen by electrolyzing coal slurry down.He thinks if oxidation of coal is talked about completely.Reaction formula is as follows:
Chemical reaction in anolyte compartment's solution:
4Fe
3++C
X+2H
2O＝4Fe
2++CO
2+4H
+
Anodic reaction: Fe
2+=Fe
3++ e
-
Cathodic reaction: 2H
++ 2e
-=H
2
Total reaction: C
X+ 2H
2O=2H
2+ CO
2
Carry out the electrolysis coal under acidic conditions, be lower than under the 1.3V condition at voltage, anode mainly is that coal participates in reaction, do not have tangible oxygen and separate out, from the angle of Conversion of energy, an electric energy part changes into Hydrogen Energy, another part energy is used for oxidized coal, and energy is fully used, not waste.But voltage is during greater than 1.3V, along with the increase of voltage, and the reaction of the existing coal of anode, the aerobic air elutriation goes out again, is equivalent to brine electrolysis, has wasted electric energy, can not realize producing hydrogen and can efficiently utilize coal again.
The beginning of the seventies and the beginning of the eighties, people such as Yen and Senftle make anode to hard coal, use two electrode systems to carry out constant-current electrolysis in alkaline medium.The result shows: product is mainly humic acids and part water-soluble carboxylic acid.At present, carry out the electrolysis coal under alkaline condition, used anode-catalyzed electrode is metal electrodes such as copper, nickel, lead, platinum, but its catalytic activity is not high, unsuitable large-scale application, and because catalyticing anode all is a metal, in the life-time service process, be corroded easily, the work-ing life of electrode is not long.
Summary of the invention
The objective of the invention is to overcome the shortcoming that the aforesaid anode catalysis electrode exists, a kind of preparation method of anode-catalyzed electrode of durable and efficient electrolyzing coal slurry is provided.
The present invention be a kind of under alkaline condition the preparation method of the anode-catalyzed electrode of electrolyzing coal slurry.
The preparation method of the anode-catalyzed electrode of a kind of electrolyzing coal slurry of the present invention is characterized in that having following technological process and step:
A. the pre-treatment of electrode metal titanium matrix: at first use metallographic phase sand papering from coarse to fine to light, even; Use deionized water rinsing, be put in ultrasonic cleaning in ethanol or the acetone again, removing degreasing, and then use deionized water rinsing, then remove the oxide compound foreign material with 4%HF, the redistilled water of reusable heat is placed in the ethanol after washing, and is standby;
B. in the enterprising row metal galvanic deposit of metallic titanium matrix: in electrolyzer, being anode with the platinized platinum electrode, is working electrode with above-mentioned treated metallic titanium matrix; On metallic titanium matrix, carry out the Catalytic Layer galvanic deposit; The Catalytic Layer electrodeposition adopts method of fractional steps galvanostatic deposition; The steps include:
(1) deposit the platinum film layer earlier: under continuous current, electroplate liquid is to contain certain density sulfuric acid and certain density organic additive NH as supporting electrolyte
2SO
3Na, and certain density H
2PtCl
66H
2O; Under ultrasonic concussion or magnetic agitation condition, carry out galvanostatic deposition; Current density is controlled at 0.21A/dm
2, electrodeposition time is 8～12 minutes; Described vitriolic concentration is 0.5mol/L; Described organic additive NH
2SO
3The concentration of Na is 50g/L; Described H
2PtCl
66H
2The concentration of O is 5 * 10
-3Mol/L;
(2) deposit cobalt or nickel or deposit two kinds of metals simultaneously again: the electroplate liquid of employing is the mixing solutions of certain density cobalt sulfate solution or nickel sulfate solution or rose vitriol and single nickel salt, be added with the mixing solutions of certain density boric acid and sodium-chlor in addition again, regulate pH value to 5.0～5.6, current density is 0.21A/dm
2, electrodeposition time is 4～8 minutes; The concentration of described rose vitriol is 20g/L; The concentration of described single nickel salt is 200g/L;
C. after the enterprising row metal galvanic deposit of metallic titanium matrix, the titanium electrode of preparation is placed on earlier carries out pre-treatment 10～15 minutes in the baking oven, be put in the horse expense stove aftertreatment then 1～2 hour, Heating temperature is 400～600 ℃; Naturally cool to room temperature then, finally make the titanium substrate anode catalysis electrode.
Deposition used rose vitriol and single nickel salt mixing solutions during two kinds of metals in the time of above-mentioned, wherein the mass ratio of rose vitriol and single nickel salt is 1: 10.
The advantage and the characteristics of the inventive method are as described below:
(1) catalysis electrode of the inventive method preparation has nanometer globular structure, has big specific surface area, can increase the area that reacts with coal, has improved the catalytic activity of electrode to a great extent.
(2) the catalysis electrode composition of the inventive method preparation is the oxide compound and the noble metal platinum of cobalt nickel, compares with the metal electrode that tradition is used, has corrosion resistance nature preferably, has prolonged the work-ing life of electrode greatly.
(3) catalysis electrode of the inventive method preparation is used for the electrolysis coal, and under higher voltage, anode does not produce oxygen, and so both can obtain the hydrogen energy source of clean and effective, can efficiently utilize coal again simultaneously, thereby realize the comprehensive utilization to product.
(4) carrier of the anode catalyst efficiently of the inventive method preparation is non-carbonaceous metal titanium, titanium has very high stability, can not participate in electrode reaction, in the time of can avoiding making carrier with gac, graphite etc. like this, gac, graphite etc. are by the shortcoming of simultaneous oxidation and the influence of foreign material introducing is arranged when anodic product is analyzed.
Description of drawings
Fig. 1 is the Ti/Pt-Co of the inventive method preparation
3O
4Surface topography scanning electron microscope (SEM) figure of electrode.
Fig. 2 is surface topography scanning electron microscope (SEM) figure of the Ti/Pt-NiO electrode of the inventive method preparation.
Fig. 3 is the Ti/Pt-Co of the inventive method preparation
3O
4X-ray diffraction (XRD) figure.Wherein, ● expression: Ti,
Expression: Pt, ■ represents: Co
3O
4
Fig. 4 is X-ray diffraction (XRD) figure of the Ti/Pt-NiO of the inventive method preparation.Wherein, ● expression: Ti,
Expression: Pt, ☆ represents: NiO.
Fig. 5 is for scheming for the I-V in the anode-catalyzed electrode of the inventive method preparation and the traditional platinum electrode electrolyzing coal slurry.
Embodiment
After now specific embodiments of the invention being described in.
Present embodiment is the preparation of Ti/Pt-CO3O4 anode-catalyzed electrode, and its preparation process is as follows:
(1) pre-treatment of electrode metal titanium matrix: at first use metallographic phase sand papering from coarse to fine to light, even; Use deionized water rinsing, be put in ultrasonic cleaning in ethanol or the acetone again, removing degreasing, and then use deionized water rinsing, then remove the oxide compound foreign material with 4%HF, the redistilled water of reusable heat is placed in the ethanol after washing, and is standby;
(2) in the enterprising row metal galvanic deposit of metallic titanium matrix: in electrolyzer, being anode with the platinized platinum electrode, is working electrode with above-mentioned treated metallic titanium matrix; On metallic titanium matrix, carry out the Catalytic Layer galvanic deposit; The Catalytic Layer electrodeposition adopts method of fractional steps galvanostatic deposition; The steps include:
The first step is deposition platinum film layer earlier: the H2SO4 that adopts 0.5mol/L adds the organic additive NH of 50g/L again as supporting electrolyte
2SO
3Na; Add certain amount of H in addition again
2PtCl
66H
2O makes its concentration reach 5 * 10
-3Mol/L; Ultrasonic concussion 5 minutes makes solution even, constitutes electroplate liquid; Under 20～30 ℃, carry out galvanostatic deposition under the sonic oscillation condition; Current density is controlled at 0.21A/dm
2, electrodeposition time is 10 minutes;
Second goes on foot deposit cobalt again: the electroplate liquid of employing is the mixing solutions of the sodium-chlor of the boric acid of heptahydrate, 30g/L of concentration 20g/L and 15g/L; Regulate pH value to 5.4, current density is 0.21A/dm
2, electrodeposition time is 6 minutes;
(3) after the enterprising row metal galvanic deposit of metallic titanium matrix, the titanium electrode of preparation is placed on earlier and carries out pre-treatment 12 minutes in the baking oven, be put in the horse expense stove aftertreatment then 1.5 hours, Heating temperature is 500 ℃; Naturally cool to room temperature then, finally make titanium substrate anode catalysis electrode Ti/Pt-CO
3O
4
Embodiment 2
Present embodiment is the preparation of the anode-catalyzed electrode of Ti/Pt-NiO, and its preparation process is as follows:
(1) pre-treatment of metallic titanium matrix is with above-mentioned embodiment 1.
(2) identical in the enterprising row metal galvanic deposit of metallic titanium matrix and the foregoing description 1.Different is: in second step is again nickel deposited, and the electroplate liquid of employing is the mixing solutions of the sodium-chlor of the boric acid of seven water single nickel salts, 30g/L of concentration 200g/L and 15g/L.
(3) heat pre-treatment after the enterprising row metal galvanic deposit of metallic titanium matrix and heating aftertreatment and the foregoing description 1 are identical.
Finally make titanium substrate anode catalysis electrode Ti/Pt-NiO.
Embodiment 3
Present embodiment is Ti/Pt-CO
3O
4The preparation of-NiO anode-catalyzed electrode, its preparation process is as follows:
(1) pre-treatment of metallic titanium matrix is with above-mentioned embodiment 1.
(2) identical in the enterprising row metal galvanic deposit of metallic titanium matrix and the foregoing description 1.Different is: be again while deposit cobalt and two kinds of metals of nickel in second step; The electroplate liquid that adopts is the mixing solutions of the sodium-chlor of the boric acid of seven water single nickel salts, 30g/L of heptahydrate, the concentration 200g/L of concentration 20g/L and 15g/L.
(3) heat pre-treatment after the enterprising row metal galvanic deposit of metallic titanium matrix and heating aftertreatment and the foregoing description 1 are identical.
Finally make titanium substrate anode catalysis electrode Ti/Pt-CO
3O
4-NiO.
To the instrument detecting result that the foregoing description product is done, the detection and the test of I-V variation characteristic etc. when each titanium substrate anode catalysis electrode of gained among the embodiment has been made SEM, XRD and electrolyzing coal slurry, it the results are shown in the accompanying drawing 1～5.
The anode-catalyzed electrode that the embodiment of the invention makes compares experiment with traditional used platinum electrode, tests different electrodes electric current-groove in the electrolyzing coal slurry process and presses (I-V) curve.Concrete experiment condition is: coal-water fluid concentration is 0.06g/mL, and ionogen is the sodium hydroxide solution of 1mol/L, and temperature is 75 ℃; The platinized platinum electrode adopts two electrode systems as counter electrode; Adopt CHI660B electrochemistry comprehensive tester to test.Test result is seen Fig. 5, and Fig. 5 is the prepared anode-catalyzed electrode of the present invention and the traditional comparison of platinum electrode in the electrolyzing coal slurry process.As can be seen from Figure 5, in electrolyzing coal slurry, the anode-catalyzed electrode that the present invention makes all platinum electrode current density than traditional is big, catalytic activity height, wherein Zhi Bei Ti/Pt-Co
3O
4-NiO, Ti/Pt-NiO electrode catalyst activity are best.
Claims (2)
1. the preparation method of the anode-catalyzed electrode of an electrolyzing coal slurry is characterized in that having following technological process and step:
A. the pre-treatment of electrode metal titanium matrix: at first use metallographic phase sand papering from coarse to fine to light, even; Use deionized water rinsing, be put in ultrasonic cleaning in ethanol or the acetone again, removing degreasing, and then use deionized water rinsing, then remove the oxide compound foreign material with 4%HF, the redistilled water of reusable heat is placed in the ethanol after washing, and is standby;
B. in the enterprising row metal galvanic deposit of metallic titanium matrix: in electrolyzer, being anode with the platinized platinum electrode, is working electrode with above-mentioned treated metallic titanium matrix; On metallic titanium matrix, carry out the Catalytic Layer galvanic deposit; The Catalytic Layer electrodeposition adopts method of fractional steps galvanostatic deposition; The steps include:
(1) deposit the platinum film layer earlier: under continuous current, electroplate liquid is to contain certain density sulfuric acid and certain density organic additive NH as supporting electrolyte
2SO
3Na, and certain density H
2PtCl
66H
2O; Under ultrasonic concussion or magnetic agitation condition, carry out galvanostatic deposition; Current density is controlled at 0.21A/dm
2, electrodeposition time is 8～12 minutes; Described vitriolic concentration is 0.5mol/L; Described organic additive NH
2SO
3The concentration of Na is 50g/L; Described H
2PtCl
66H
2The concentration of O is 5 * 10
-3Mol/L;
(2) deposit cobalt or nickel or deposit two kinds of metals simultaneously again: the electroplate liquid of employing is the mixing solutions of certain density cobalt sulfate solution or nickel sulfate solution or rose vitriol and single nickel salt, be added with the mixing solutions of the sodium-chlor of the boric acid of 30g/L concentration and 15g/L concentration in addition again, regulate pH value to 5.0～5.6, current density is 0.21A/dm
2, electrodeposition time is 4～8 minutes; The concentration of described heptahydrate is 20g/L; The concentration of described seven water single nickel salts is 200g/L;
C. after the enterprising row metal galvanic deposit of metallic titanium matrix, the titanium electrode of preparation is placed on earlier carries out pre-treatment 10～15 minutes in the baking oven, be put in the horse expense stove aftertreatment then 1～2 hour, Heating temperature is 400～600 ℃; Naturally cool to room temperature then, finally make the titanium substrate anode catalysis electrode.
2. the preparation method of the anode-catalyzed electrode of a kind of electrolyzing coal slurry as claimed in claim 1 is characterized in that described rose vitriol and single nickel salt mixing solutions used when depositing two kinds of metals simultaneously, and wherein the mass ratio of rose vitriol and single nickel salt is 1: 10.
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| CN102477564B (en) * | 2010-11-23 | 2014-11-19 | 中国科学院大连化学物理研究所 | Method for preparing SPE (solid polymer electrolyte) anodic oxygen evolution catalysts for water electrolysis |
| CN103055853B (en) * | 2011-10-20 | 2014-09-03 | 中国科学院大连化学物理研究所 | Method for preparation of water electrolysis oxygen evolution catalyst with silicon oxide molecular sieve as template |
| CN105148920A (en) * | 2015-08-18 | 2015-12-16 | 中国科学院长春应用化学研究所 | Self-supporting transition metal-metal alloy catalyst as well as preparation method and application of self-supporting transition metal-metal alloy catalyst |
| CN106757142B (en) * | 2016-11-21 | 2020-07-03 | 沈阳化工大学 | Preparation method and application of carbon fiber loaded nanoscale bimetal PtCo catalytic electrode |
| CN113529132A (en) * | 2021-08-09 | 2021-10-22 | 中国科学院海洋研究所 | Cobalt-based catalyst electrode and preparation method thereof |
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