CN101619466A - Load type multi-element oxygen-separating catalyst and preparation method thereof - Google Patents
Load type multi-element oxygen-separating catalyst and preparation method thereof Download PDFInfo
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- CN101619466A CN101619466A CN200910088962A CN200910088962A CN101619466A CN 101619466 A CN101619466 A CN 101619466A CN 200910088962 A CN200910088962 A CN 200910088962A CN 200910088962 A CN200910088962 A CN 200910088962A CN 101619466 A CN101619466 A CN 101619466A
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Abstract
The invention provides a multi-element load type oxygen-separating electric catalyst and relates to a water electrolytic anode catalyst of a proton exchange membrane and a preparation thereof. The invention provides a multi-element load type catalyst Ir[1-x]Ru[x]O2/TiC (x is larger than 0 and smaller than 1), or Ir[1-z]Ta[z]O2/TiC (z is larger than 0 and smaller than 1), or Ir[1-x-y]Ru[x]Ta[y]O2/TiC (x is larger than 0 and smaller than 1, y is larger than 0 and smaller than 0.4, and the sum of x and y is smaller than 1) which takes a TiC powder body with both electric conductivity and erosion resistance as a carrier, takes a mixed organic solution of H2IrCl6 and RuCl3 or TaCl5 as a precursor body and is prepared and obtained by adopting the methods of ultrasonic dispersion and heating decomposition. The adopted preparation method of the invention has simple procedure and high activity of the catalyst, can greatly lower the use quantity of noble metal and is an effective means for lowering the water electrolytic cost of the proton exchange membrane, and the oxygen-separating performance of the multi-element load type oxygen-separating electric catalyst is obviously superior to that of a no-load type catalyst.
Description
Technical field
What the present invention relates to is that a kind of polynary loading type is analysed the oxygen anodes Catalysts and its preparation method, belongs to proton exchange membrane (PEM) brine electrolysis technical field.
Background technology
PEM water electrolysis technology be the seventies in 20th century by the researchdevelopment of AM General company get up based on the electrolytic technology of pure water, still be in development at present, use proton exchange membrane to have excellent mechanical intensity and chemical stability as ionogen, high proton-conducting, good advantages such as gas delivery; Higher proton-conducting, the PEM electrolyzer can be operated under the higher electric current, thereby has increased electrolytic efficiency; And because proton exchange membrane is thinner, reduced ohmic loss, also improved the efficient of system.Adopt the pure water electrolysis, avoided the corrosion of electrolytic solution cell body.It is a kind of safe water electrolysis technology.
The core of water electrolysis technology is the PEM membrane electrode, it is the place of water electrolysis electrochemical reaction, wherein selection of catalysts optimization, membrane electrode optimization of preparation and structure Design are the keys of brine electrolysis technology, it is to reducing the electrode cost, improve the utilization ratio of catalyzer, reduce electrolysis energy consumption and play important effect.Negative electrode and hydrogen-precipitating electrode generally adopt the black or carbon of Pt to carry Pt black to wait the platinum group precious metal be catalyzer, it is 1.229V that anode is analysed the oxygen standard potential, the current potential that reaction takes place is higher, and because the generation of active oxygen atom, it is very serious to make that anodic corrodes.Under certain electrolytic condition, the complexity of oxygen evolution reaction depends primarily on the quality of analysing oxygen electro catalytic activity and stability thereof of anode material (catalyzer).
Trasatti, S..Electrocatalysis:understanding the success of DSA.Electrochim.Acta, 2000,45,2377-2385 report, IrO
2With RuO
2Deng the platinum group metal oxide containing precious metals is good oxygen-separating catalyst, yet the platinum metals resource-constrained costs an arm and a leg, and makes that the technology cost of water electrolysis hydrogen producing is very high, is difficult to realize industrialization.In order to reduce the amount of platinum metals, reduce the industrial cost of brine electrolysis, mainly, reduce the noble metal dosage aspect and set about from improving the utilization ratio of precious metal.
Summary of the invention
The present invention proposes to improve the noble metal catalyst utilization ratio for solving, reduce the problem of noble metal dosage, the TiC nano-powder that proposition has concurrently with electroconductibility and solidity to corrosion is as carrier, preparation loading type binary or ternary loaded catalyst, make oxide catalyst be coated on the TiC nano grain surface, can increase effective electro catalytic activity surface-area, reduce the consumption of precious metal greatly, effectively reduce the water electrolysis hydrogen producing cost.
The polynary loaded catalyst of the present invention is Ir
1-xRu
xO
2/ TiC, wherein 0＜x＜1; Or Ir
1-zTa
zO
2/ TiC, wherein 0＜z＜1; Or Ir
1-x-yRu
xTa
yO
2/ TiC, wherein 0＜x＜1,0＜y＜0.4 and x+y＜1.
Preparation process of the present invention may further comprise the steps:
1) organic solvent of configuration dehydrated alcohol and Virahol, wherein the ratio of dehydrated alcohol and Virahol is 1: between the 2--2:1, and with the organic solvent that prepared configuration complex catalyst precursor liquid solution, the metallics total concn of precursor solution remains between the 0.005mol/L--0.2mol/L.
2) a certain amount of nano titanium carbide is placed crucible, get made organic solvent in a certain amount of step 1), splash in the crucible, make just submergence TiC powder of solvent, form suspension liquid, then, take out standby this suspension liquid ice ultrasonic 0.5--1h in territory.
3) catalyst precursor solution made in the step 1) is splashed in the crucible that is loaded with the TiC powder, TiC is fully immersed wherein, take out in 80 ℃ behind the ice ultrasonic 10--15min in territory--100 ℃ of oven dry 20--40min.
4) powder after will drying is in 390 ℃--and heat 10--20min in 490 ℃ the tube furnace, take out air cooling to room temperature.
5) repeat above step 3)-4 after the catalyzer that will be attached to sidewall of crucible scrapes grinding) 6--10 time until the catalyst loading amount to predetermined value, this is worth between 20%80%, makes polynary loaded catalyst Ir
1-xRu
xO
2(0＜x＜1) or Ir
1-zTa
zO
2(0＜z＜1) or Ir
1-x-yRu
xTa
yO
2/ TiC (0＜x＜1,0＜y＜0.4 and x+y＜1).
Described precursor solution is H
2IrCl
6With RuCl
3Organic mixing solutions, or H
2IrCl
6With TaCl
5Organic mixing solutions, or H
2IrCl
6, RuCl
3With TaCl
5Organic mixing solutions.
TaCl in the described mixing solutions
5Ta ionic weight≤total concentration of metal ions 40%.
The prepared oxygen-separating catalyst of the present invention is polynary loaded catalyst, carrier is TiC, adopt preparation method of the present invention can make prepared catalyst pack be overlying on the TiC particle surface, increased the activity of such catalysts specific surface area, thereby improved the utilization ratio of catalyzer.When loading was 50%, the cyclic voltammetric performance of loaded catalyst has improved 3-4 than the powder catalyzer of no-load build, and doubly (loading of catalyzer was 5mg/cm
2).Comparing with non-loaded type catalyzer, greatly reduce noble metal dosage, is the effective means that reduces proton exchange membrane water electrolysis cost.
Description of drawings
Fig. 1 is embodiment 1Ir
0.7Ta
0.3O
2/ TiC catalyst recirculation volt-ampere test curve figure.
Fig. 2 is embodiment 2Ir
0.6Ru
0.4O
2/ TiC catalyst recirculation volt-ampere test curve figure.
Fig. 3 is embodiment 3Ir
0.5Ru
0.2Ta
0.3O
2/ TiC catalyst recirculation volt-ampere test curve figure.
Embodiment
Will be prepared fine catalyst get a certain amount of and n-propyl alcohol after grinding, Nafion solution mixes to drip to be applied on the titanium plate behind the ice ultrasonic 0.5-1h in territory makes working electrode after the drying, drips that to be coated with area be 1cm
2, the carrying capacity of loaded catalyst is 1-10mg, for the data that electro-chemical test is obtained have comparability, following examples are all carried out the cyclic voltammetric test in VMP electrochemical test (U.S. Ametek).Test condition is all as follows: test soln is the sulphuric acid soln of 0.1mol/L; Counter electrode is the Pt plate electrode; With the saturated calomel electrode is reference electrode, adopts the Repone K salt bridge.
Embodiment 1
1) configuration dehydrated alcohol and Virahol ratio is 1: 1 organic solvent, and is the H of 0.1mol/L with its configuration metallics concentration
2IrCl
6+ TaCl
5Solution (metal ion Ir: Ta=7: 3) 0.5mL; Get and configure precursor solution, preparing the catalyst loading amount according to above said preparation process is 50% TiC loaded catalyst.
2) get 11mgTiC and place crucible, getting the organic solvent that configures splashes in the crucible, make just submergence TiC powder of organic solvent, form suspension liquid, then splash in the crucible that is loaded with the TiC powder getting the catalyst precursor solution that configures behind the ultrasonic 0.5h of this suspension liquid, TiC is fully immersed wherein, take out behind the ice ultrasonic 10min in territory, in 80 ℃ of oven dry 20min.
3) powder after the oven dry heats 20min in 440 ℃ tube furnace, takes out air cooling to room temperature.
4) repeat above step 2 after the catalyzer that will be attached to sidewall of crucible scrapes grinding)-3) promptly make binary loaded catalyst Ir for 6 times
0.7Ta
0.3O
2/ TiC, catalyst I r
0.7Ta
0.3O
2Loading is 50wt%.
Get 5mg Ir
0.7Ta
0.3O
2/ TiC catalyzer, with the 0.5mL n-propyl alcohol, the Nafion solution of 50 μ L5% drips behind the ice ultrasonic 0.5h in territory and is applied on the Ti matrix and (drips that to be coated with area be 1cm
2).The cyclic voltammetric test result as shown in Figure 1.As can be seen from Figure 1, TiC loading type Ir
0.7Ta
0.3O
2The electrochemical window broad of catalyzer shows that electro catalytic activity is higher, and the oxygen current density of analysing during 1.26V is the catalyzer apparently higher than non-loaded type.
1) configuration dehydrated alcohol and Virahol ratio is 2: 1 organic solvent, and is the H of 0.1mol/L with its configuration metallics concentration
2IrCl
6+ RuCl
3Solution (metal ion Ir: Ru=6: 4) 0.5mL; Get and configure precursor solution, preparing the catalyst loading amount according to above said preparation process is 80% TiC loaded catalyst.
2) get 2.0mgTiC and place crucible, getting the organic solvent that configures splashes in the crucible, make just submergence TiC powder of solvent, form suspension liquid, then splash in the crucible that is loaded with the TiC powder getting the catalyst precursor solution that configures behind the ultrasonic 0.75h of this suspension liquid, TiC is fully immersed wherein, take out behind the ice ultrasonic 12min in territory, in 90 ℃ of oven dry 25min.
3) powder after the oven dry heats 15min in 460 ℃ tube furnace, takes out air cooling to room temperature.
4) repeat above step 2 after the catalyzer that will be attached to sidewall of crucible scrapes grinding)-3) promptly make binary loaded catalyst Ir for 10 times
0.6Ru
0.4O
2/ TiC, catalyst I r
0.6Ru
0.4O
2Carrying capacity is 80wt%.
Get 5mg Ir
0.6Ru
0.4O
2/ TiC catalyzer, with the 0.5mL n-propyl alcohol, the Nafion solution of 50 μ L5% drips behind the ice ultrasonic 0.5h in territory and is applied on the Ti matrix and (drips that to be coated with area be 1cm
2).The cyclic voltammetric test result as shown in Figure 2, as can be seen, the electrochemical window broad shows that electro catalytic activity is better from the figure, when current potential was 1.26V (vs.SCE), analysing the oxygen peak current density was 3.8mAcm
-2
Embodiment 3
1) configuration dehydrated alcohol and Virahol ratio is 1: 2 organic solvent, and is the H of 0.1mol/L with its configuration metallics concentration
2IrCl
6+ RuCl
3+ TaCl
5Solution (metal ion Ir: Ru: Ta=5: 2: 3) 0.5mL; Get and configure precursor solution, preparing the catalyst loading amount according to above said preparation process is 40% TiC loaded catalyst.
2) get 12.8mgTiC and place crucible, getting the organic solvent that configures splashes in the crucible, make just submergence TiC powder of solvent, form suspension liquid, then splash in the crucible that is loaded with the TiC powder getting the catalyst precursor solution that configures behind the ultrasonic 0.75h of this suspension liquid, TiC is fully immersed wherein, take out behind the ice ultrasonic 15min in territory in 100 ℃ of oven dry 10min.
3) powder after the oven dry heats 10min in 490 ℃ tube furnace, takes out air cooling to room temperature.
4) repeat above step 2 after the catalyzer that will be attached to sidewall of crucible scrapes grinding)-3) promptly make binary loaded catalyst Ir for 8 times
0.5Ru
0.2Ta
0.3O
2/ TiC, catalyst I r
0.5Ru
0.2Ta
0.3O
2Loading is 40wt%.
Get 5mg Ir
0.5Ru
0.2Ta
0.3O
2/ TiC catalyzer, with the 0.5mL n-propyl alcohol, the Nafion solution of 50 μ L5% drips behind the ice ultrasonic 0.5h in territory and is applied on the Ti matrix and (drips that to be coated with area be 1cm
2).The cyclic voltammetric test result as shown in Figure 3, the electrochemistry integral area is bigger, shows that electro catalytic activity is better, when current potential 1.26V (vs.SCE), analysing the oxygen peak current density is 12.5mAcm
-2, as seen, the performance of ternary loaded catalyst is particularly excellent.
Claims (4)
1, a kind of polynary loading type is analysed the oxygen anodes Catalysts and its preparation method, it is characterized in that, this kind catalyzer is Ir
1-xRu
xO
2/ TiC, wherein 0＜x＜1; Or Ir
1-zTa
zO
2/ TiC, wherein 0＜z＜1; Or Ir
1-x-yRu
xTa
yO
2/ TiC, wherein 0＜x＜1,0＜y＜0.4 and x+y＜1.
2, polynary loading type is analysed oxygen anodes Preparation of catalysts method, it is characterized in that preparation process is as follows:
1) organic solvent of configuration dehydrated alcohol and Virahol, wherein the ratio of dehydrated alcohol and Virahol is 1: 2-2: between 1, and with the mixture that has prepared as solvent configuration complex catalyst precursor liquid solution, the metallics concentration of precursor solution remains between the 0.005mol/L-0.2mol/L;
2) titanium carbide is placed crucible, get the made organic solvent of a certain amount of step 1) and splash in the crucible, make just submergence TiC powder of solvent, form suspension liquid,, take out standby then with the ultrasonic 0.5-1h of this suspension liquid;
3) catalyst precursor solution made in the step 1) is splashed in the crucible that is loaded with the TiC powder, TiC is fully immersed wherein, take out in 80 ℃ behind the ice ultrasonic 10--15min in territory--100 ℃ of oven dry 20--40min;
4) powder after will drying is in 390 ℃--and heat 10--20min in 490 ℃ the tube furnace, take out air cooling to room temperature;
5) repeat above step 3)-4 after the catalyzer that will be attached to sidewall of crucible scrapes grinding) 6--10 time until the catalyst loading amount between 20%-80%, make polynary loaded catalyst.
As claims 2 described preparation methods, it is characterized in that 3, described precursor solution is H
2IrCl
6With RuCl
3Organic mixing solutions, or H
2IrCl
6With TaCl
5Organic mixing solutions, or H
2IrCl
6, RuCl
3With TaCl
5Organic mixing solutions.
4, as claims 3 described preparation methods, it is characterized in that TaCl in the described mixing solutions
5Ta ionic weight≤total concentration of metal ions 40%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220993A (en) * | 2016-12-09 | 2018-06-29 | 广州华秦机械设备有限公司 | A kind of water electrolysis antioxidant activity anode plate prescription and preparation method thereof |
| CN109569594A (en) * | 2018-11-29 | 2019-04-05 | 全球能源互联网研究院有限公司 | A kind of titanate supports noble metal base analysis oxygen elctro-catalyst and preparation method thereof |
| CN113277573A (en) * | 2021-06-29 | 2021-08-20 | 成都天芮科技有限公司 | PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof |
-
2009
- 2009-07-15 CN CN200910088962A patent/CN101619466A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220993A (en) * | 2016-12-09 | 2018-06-29 | 广州华秦机械设备有限公司 | A kind of water electrolysis antioxidant activity anode plate prescription and preparation method thereof |
| CN109569594A (en) * | 2018-11-29 | 2019-04-05 | 全球能源互联网研究院有限公司 | A kind of titanate supports noble metal base analysis oxygen elctro-catalyst and preparation method thereof |
| CN109569594B (en) * | 2018-11-29 | 2021-06-22 | 全球能源互联网研究院有限公司 | Titanate-supported noble metal-based oxygen evolution electrocatalyst and preparation method thereof |
| CN113277573A (en) * | 2021-06-29 | 2021-08-20 | 成都天芮科技有限公司 | PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof |
| CN113277573B (en) * | 2021-06-29 | 2022-06-17 | 成都天芮科技有限公司 | PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof |
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Open date: 20100106 |