CN101455971A - Preparation method of borohydride hydrolytic hydrogen production catalyst - Google Patents
Preparation method of borohydride hydrolytic hydrogen production catalyst Download PDFInfo
- Publication number
- CN101455971A CN101455971A CNA2009100760691A CN200910076069A CN101455971A CN 101455971 A CN101455971 A CN 101455971A CN A2009100760691 A CNA2009100760691 A CN A2009100760691A CN 200910076069 A CN200910076069 A CN 200910076069A CN 101455971 A CN101455971 A CN 101455971A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- group metal
- platinum group
- preparation
- platinum
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a method for preparing a catalyst for the hydrolysis hydrogen production of borohydride, which relates to a hydrogen supply system of hydrogen-oxygen fuel cells. The method comprises the following steps: foamed nickel is taken as a carrier; the cleaned foamed nickel is put into a palladium salt solution to be preplated for a period; palladium is taken as a transition layer of the carrier and the catalyst and then is put into a platinum-group metal salt solution with a certain concentration and a certain pH value; after a period of redox reaction, a platinum-group metallic element is uniformly deposited on the surface of the foamed nickel carrier; and the supported catalyst is washed and dried to form the catalyst taking palladium as the transition layer, namely the needed catalyst. The catalyst is used for the hydrolysis hydrogen production of borohydride, and has good catalytic activity and long life span. The catalyst is a platinum-group metal, has the advantages of simple preparation method and high catalytic activity, and can be repeatedly recycled.
Description
Technical field
The present invention relates to borohydride hydrolytic hydrogen production system field, can be used for the hydrogen-oxygen fuel cell hydrogen-feeding system.
Background technology
Hydrogen Energy is one of following most promising energy, and is optimal electrochmical power source with hydrogen as the hydrogen-oxygen fuel cell of raw material.Hydrogen-oxygen fuel cell has distinguishing features such as high-energy-density, pollution-free, life-span be long, is referred to as by people by " green generator ", and the electric automobile that drives with hydrogen-oxygen fuel cell is called as " zero pollutes automobile ".The hydrogen-oxygen fuel cell technology being is all is being researched and developed energetically in countries in the world at present, in the hope of realizing the purpose of extensive use.Yet the one of the main reasons that hinders its extensive use is exactly to lack a kind of efficient and rational hydrogen source.Though the hydrogen storage technology and the means of existing at present multiple maturation, for example liquid storage hydrogen, high-pressure hydrogen storing etc., because the container that uses is heavy and it is high that material is required, shortcoming such as energy density is low is not suitable as the hydrogen source of portable fuel battery.Borohydride hydrolytic hydrogen production is a kind of advantages of simplicity and high efficiency hydrogen producing technology and since the boron hydride catalytic hydrogen supply have can be quick, reliable, controlled on demand advantages such as output hydrogen, be subjected to people's generally favor.In this hydrogen-feeding system, catalyst is its important critical material, and the catalyst of developing high catalytic efficiency, high stability becomes one of catalytic hydrogen supply Study on Technology emphasis.In the past by NaBH
4Hydrogen manufacturing mainly adopts anion exchange resin supported ruthenium (Ru), platinum noble metals such as (Pt) to make catalyst.Compare with the amberlite lipid, nickel foam has good structural strength, and the mechanical performance of catalyst also will promote thereupon.Patent 03118847 discloses a kind of Catalysts and its preparation method and purposes, though the price of this catalyst is comparatively cheap, is convenient to extensive use, and the base metal catalytic performance is lower than noble metal catalyst, is difficult to satisfy the use than high power fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is used for the effective catalyst of borohydride hydrolytic hydrogen production.This catalyst preparation process is simple, and catalytic performance is good, and long service life can be applicable to the boron hydride hydrogen-feeding system of various hydrogen-oxygen fuel cells.
Technical scheme provided by the invention is: prepare by carrier nickel foam and platinum group metal salts generation redox reaction, it is 0.5% palladium salting liquid preplating 2min to 30min that the metal foam nickel that cleans up is put into mass concentration, with Pd as the transition zone between carrier and catalyst, be used to improve the adhesion between carrier and catalyst, reduce coming off of catalyst, thereby strengthen the service life of catalyst.Insert the pH value afterwards and be 2 to 7 and concentration be in the platinum group metal salting liquid between the 0.02mol/L to 0.03mol/L, the mass ratio of nickel foam quality and platinum group metal salting liquid remains between the 1:50 to 1:100, flooded 20 to 40 hours or flooded to the platinum group metal salting liquid and occur precipitating, during this period, platinum group metal salts and nickel foam generation redox reaction, the platinum group metal uniform deposition obtains required catalyst on the nickel foam surface with post-depositional catalyst detergent drying.
The platinum group metal salts of above-mentioned catalyst is selected a kind of or wherein multiple mixing of platinum, ruthenium, rhodium, iridium salt, and the metal that correspondence obtains is the metal simple-substance of platinum, ruthenium, rhodium, iridium.Platinum group metal salts is chloride, nitrate, sulfate or phosphatic a kind of or wherein multiple mixture of platinum group metal.
In the above-mentioned catalyst mass ratio of nickel foam quality and platinum group metal solution between the 1:50 to 1:100 and dip time can change according to the change in concentration of different platinums group metal solution.
The above-mentioned loading that obtains required catalyst is 10%-40%.
The catalyst for preparing is put into borohydride alkaline dry solution, and catalyst contacts with solution can produce hydrogen.
Catalyst used in the present invention is a platinum metal catalysts, the preparation method is simple, the catalytic activity height, adopt the transition zone of palladium, strengthened the adhesive force of catalyst on carrier, reduced catalyst coming off in use as carrier and catalyst, thereby make prolong service life, do not compare as the catalyst of transition zone with adopting palladium, can be enhanced about more than once service life, and repeatedly utilization capable of circulation.Can be applicable to the boron hydride hydrogen-feeding system of various hydrogen-oxygen fuel cells, application prospect is extensive.
Description of drawings
Fig. 1 is the time of catalyst hydrogen manufacturing among the embodiment 1 and the graph of a relation of hydrogen output.
Fig. 2 is the pattern (electromicroscopic photograph) of the catalyst of preparation among the embodiment 1.
Fig. 3 is the time of catalyst hydrogen manufacturing among the embodiment 2 and the graph of a relation of hydrogen output.
Fig. 4 uses back pattern (electromicroscopic photograph) for the catalyst that embodiment 3 does not add Pd.
Fig. 5 is the catalyst use back pattern (electromicroscopic photograph) that embodiment 3 adds Pd.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1: nickel foam is put into absolute ethyl alcohol ultrasonic cleaning 15min, and the hydrochloric acid solution of putting into concentration after cleaning and be 0.01mol/L floods 30min, cleans up the back drying and is weighed as 0.1728g, puts it into mass concentration and be 0.5% PdCl
2Flood 10min in the solution, vertically insert 15ml pH value after the taking-up and be 6, molar concentration is the RuCl of 0.025mol/L
3Dipping took out after 35 hours in the solution, and washing is dry, promptly gets catalyst required for the present invention, and the gained catalyst quality is 0.1816g, and loading is about 38%.Its reaction equation is as follows:
3Ni+2RuCl
3＝2Ru+3NiCl
2
Platinum group metal salts in the foregoing description, boron hydride replaces with other platinum group metal salts of the present invention, boron hydride, can obtain similar catalyst.
With the catalyst 0.1728g for preparing, put into 20ml concentration and be 15% sodium borohydride alkaline solution testing catalytic effect, catalyst produces hydrogen with after sodium borohydride solution contacts, and produces 1090ml hydrogen behind the 2min, and hydrogen-producing speed is 545ml/min.As shown in Figure 1.The stereoscan photograph of this catalyst as shown in Figure 2.
Embodiment 2: nickel foam is put into absolute ethyl alcohol ultrasonic cleaning 15min, and the hydrochloric acid solution of putting into concentration after cleaning and be 0.01mol/L floods 30min, cleans clean back drying and is weighed as 0.1606g, puts it into the 20ml mass concentration and be 0.5% PdCl
2Flood 5min in the solution, vertically insert 10ml pH value after the taking-up and be 5, molar concentration is the RuCl of 0.02mol/L
3Flood in the solution to the solution post precipitation, washing is dry, promptly gets catalyst required for the present invention, and the gained catalyst quality is 0.1676g, and loading is about 29.2%.
With the catalyst for preparing, putting into concentration is that 15% sodium borohydride alkaline solution is tested for 20ml concentration, and catalyst produces hydrogen with after sodium borohydride solution contacts, and produces 900ml hydrogen behind the reaction 2min, and hydrogen-producing speed is 450ml/min.As shown in Figure 3.
Embodiment 3: get the two nickel foam A and the B that clean up, the A quality is 0.2712g, and the RuCl3 solution that without the Pd salt solution impregnation, directly put into 20ml pH value and be 5, molar concentration is 0.02mol/L floods to the solution post precipitation, and washing is dry.The B quality is 0.2624g, is 0.5% PdCl with mass concentration
2Flood 5min in the solution, vertically insert 20ml pH value after the taking-up and be 5, molar concentration is the RuCl of 0.02mol/L
3Flood in the solution to the solution post precipitation, washing is dry.A and B are put into 50mlNaBH respectively
4React completely in the solution and loop test, behind the A circular response 4 times, activity has reduced by 85%, actively afterwards keeps stable, and after the B reaction 8 times, activity has reduced by 50%, actively afterwards keeps stable.The catalyst of the B situation that comes off is compared with A, and it is less to come off.Fig. 4 and Fig. 5 are the stereoscan photograph after A and B catalyst use.As seen from the figure, after using repeatedly, the catalyst that adheres on the carrier surface among the A comes off substantially, has adhered to a large amount of catalyst and still can observe on the carrier surface among the B, will be longer than the catalyst A of not adding Pd so added the catalytic life of the catalyst B of Pd.
Claims (6)
1, a kind of Preparation of catalysts method that is used for borohydride hydrolytic hydrogen production, it is characterized in that, concrete implementation step is: it is 0.5% palladium salting liquid preplating 2min to 30min that the carrier nickel foam that cleans up is put into mass concentration, with Pd as the transition zone between carrier and catalyst, to insert the pH value afterwards be in 2 to 7 scopes and concentration is in the platinum group metal salting liquid between the 0.02mol/L to 0.03mol/L, the mass ratio of nickel foam quality and platinum group metal salting liquid remains between the 1:50 to 1:100, flooded 20 to 40 hours or flooded to the platinum group metal salting liquid and occur precipitating, during this period, platinum group metal salts and nickel foam generation redox reaction, the platinum group metal uniform deposition obtains required catalyst on the nickel foam surface with post-depositional catalyst detergent drying.
2, preparation method according to claim 1 is characterized in that, described platinum group metal salts is selected a kind of or wherein multiple mixing of platinum, ruthenium, rhodium, iridium salt, and the metal that correspondence obtains is the metal simple-substance of platinum, ruthenium, rhodium, iridium.
3, preparation method according to claim 1 and 2 is characterized in that, described platinum group metal salts is chloride, nitrate, sulfate or phosphatic a kind of or wherein multiple mixture of platinum group metal.
4, preparation method according to claim 1 is characterized in that, the mass ratio of nickel foam quality and platinum group metal solution is between 1:50 to 1:100 in the above-mentioned catalyst.
5, preparation method according to claim 1 is characterized in that, the described loading that obtains required catalyst is 10%-40%.
6, preparation method according to claim 1 is characterized in that, the catalyst for preparing is put into borohydride alkaline dry solution, and catalyst contacts with solution can produce hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100760691A CN101455971A (en) | 2009-01-06 | 2009-01-06 | Preparation method of borohydride hydrolytic hydrogen production catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100760691A CN101455971A (en) | 2009-01-06 | 2009-01-06 | Preparation method of borohydride hydrolytic hydrogen production catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101455971A true CN101455971A (en) | 2009-06-17 |
Family
ID=40767260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100760691A Pending CN101455971A (en) | 2009-01-06 | 2009-01-06 | Preparation method of borohydride hydrolytic hydrogen production catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101455971A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949272A (en) * | 2014-05-21 | 2014-07-30 | 江西师范大学 | NiPt@RGO composite nano catalyst for producing hydrogen by using hydrazine borane and preparation method thereof |
| CN108435165A (en) * | 2018-02-12 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of rothenio-palladium, store method and its application |
| CN113774217A (en) * | 2021-08-19 | 2021-12-10 | 南方科技大学 | Method for synchronously recovering multiple metal ions in electronic product leaching solution |
-
2009
- 2009-01-06 CN CNA2009100760691A patent/CN101455971A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949272A (en) * | 2014-05-21 | 2014-07-30 | 江西师范大学 | NiPt@RGO composite nano catalyst for producing hydrogen by using hydrazine borane and preparation method thereof |
| CN108435165A (en) * | 2018-02-12 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of rothenio-palladium, store method and its application |
| CN108435165B (en) * | 2018-02-12 | 2021-03-26 | 浙江工业大学 | Preparation method, preservation method and application of rhodium-palladium alloy |
| CN113774217A (en) * | 2021-08-19 | 2021-12-10 | 南方科技大学 | Method for synchronously recovering multiple metal ions in electronic product leaching solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wei et al. | Highly efficient and reactivated electrocatalyst of ruthenium electrodeposited on nickel foam for hydrogen evolution from NaBH4 alkaline solution | |
| CN101728541B (en) | Method for preparing carbon nano tube loaded cobalt-platinum alloy catalyst | |
| CN110438528A (en) | A kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof | |
| CN105845954A (en) | Silk-derived nitrogen-doped graphene fibers | |
| CN106334561A (en) | Non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride and preparation method of non-noble metal catalyst for alcoholysis hydrogen production of sodium borohydride | |
| CN107159227B (en) | High-efficiency and long-life CoWB/NF catalyst for hydrogen production by sodium borohydride hydrolysis and preparation method thereof | |
| CN110512228A (en) | A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material | |
| CN109055972A (en) | Mn adulterates Ni3S2Nano-array liberation of hydrogen catalyst and its preparation method and application | |
| CN100411740C (en) | Carried catalyst chemical plating method for hydrolyzing hydroborates to produce hydrogen | |
| CN106058277A (en) | PdAu electrocatalyst for fuel cell and preparation method thereof | |
| CN113652707A (en) | Nickel telluride hydrogen evolution catalyst and preparation method and application thereof | |
| CN109055975A (en) | One kind preparing porous Ni based on two-dimensional metallic organic backbone template2The method of P/C electrode | |
| CN101455971A (en) | Preparation method of borohydride hydrolytic hydrogen production catalyst | |
| CN102513120A (en) | Hydrogen production catalyst as well as preparation method thereof and catalytic hydrogen production method using same | |
| CN108057446A (en) | Ammonia borane hydrolysis hydrogen manufacturing Co-Mo-B nanocatalysts and preparation method | |
| CN101138721A (en) | Process for preparation of catalysts for catalytic decomposition of hydrogen iodide | |
| CN101580225B (en) | Method for preparing low platinum modified carbon-loaded ruthenium nano particles and application thereof | |
| CN101549297A (en) | Preparation method of fixed bed raney nickel catalyst | |
| CN102403516A (en) | Preparation method of curved surface electrode catalyst layer | |
| CN107159282A (en) | A kind of carbon fiber loaded CoWP catalyst and preparation method | |
| CN107447209B (en) | Method for preparing Pd-Co-P composite membrane by utilizing chemical plating-displacement | |
| CN109225256A (en) | Sodium borohydride alcoholysis catalyst for preparing hydrogen | |
| CN115466979B (en) | Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen | |
| CN108543944B (en) | The preparation method and its resulting materials of a kind of porous dandelion shape Pd nanodendrites and application | |
| CN116062722A (en) | Catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20090617 |