CN104046967A - Preparation method of Co-P nano catalytic material - Google Patents
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Abstract
A preparation method of a Co-P nano catalytic material is provided. The preparation method takes a metal substrate as a carrier, adopts a chemical plating method to deposit a metal Co and a non-metal P for preparing the Co-P nano catalytic material, and comprises the following specific implementation steps: after successively carrying out hot alkali solution soaking, copper corrosion solution soaking, sensitizing solution soaking and activating solution soaking treatment on a substrate substance, dipping into a chemical plating solution, carrying out chemical plating, washing, and drying to obtain the Co-P nano catalytic material. The prepared catalyst material has higher catalytic activity, can accelerate the reaction rate of hydrogen release of sodium borohydride hydrolysis, reduces the activation energy of the hydrogen release reaction, has the advantages of better cyclic utilization performance, safety and high efficiency, and has wide application prospects in an aspect of vehicle-mounted hydrogen storage.
Description
Technical field
She of the present invention is Ji the preparation method of ー kind Co-P nano catalytic material belongs to field of inorganic nano material.
Background technology
Along with the fast development of global economy, the fossil energy in Nonrenewable energy resources, the i.e. continuous consumption of coal, oil and natural gas etc., and the problem of using these fossil oils to bring: as Global warming, climatic anomaly, acid rain and pollution etc.; To the growing to even greater heights of the cry that taps a new source of energy, Hydrogen Energy is paid close attention to by increasing researcher in the world.The features such as Hydrogen Energy is abundant with its source, and combustion heat value is high, environmentally friendly, zero pollution, become one of main new forms of energy of 21 century.In various potential storage hydrogen modes, solid-state hydrogen storage material is obviously better than high pressure vessel storage hydrogen and low temperature liquid storage hydrogen at aspects such as energy density, processing safeties.Be regarded as for a long time storage hydrogen mode most with prospects always.Existing solid-state hydrogen storage material mainly comprises metal (as Rare Earth, titanium system and magnesium base etc.) and the large class of nonmetal (as carbon nanotube and metal organic frame etc.) hydrogen storage material two.Yet though most solid-state hydrogen storage material has high volume hydrogen-storage density, the virtual mass hydrogen storage capability under mild conditions is many lower than 3wt%, is difficult to meet the demand of portable hydrogen source homenergic conversion.The coordinate hydride hydrogen-storing material being comprised of protium, as lithium borohydride (LiBH
4), sodium borohydride (NaBH
4) and ammonia borine (NH
3bH
3) etc. hydroborate because thering is high hydrogen storage capability, become one of emphasis material of current storage hydrogen research field.
Sodium borohydride (NaBH
4) because thering is higher quality hydrogen storage capability 19.6wt%, and can pass through the mode hydrogen manufacturing of catalytic hydrolysis, and become one of more potential hydrogen storage material.At present, about the research of preparing hydrogen by sodium borohydride hydrolysis catalyzer, mostly be Pt catalyst based (Brown H C, Brown C A.J.Am.Chem.Soc., 1962,84 (8): 1493-1494; Guella G, Patton B, Miotello A.The Journal of Physical Chemistry C, 2007,111 (50): 18744-18750) and Ru catalyst based (Zahmakiran M,
s.Langmuir, 2008,24 (14): 7065-7067), they all can effectively improve hydrogen discharging rate to a certain extent, but high cost is not suitable for industrial production and living needs, hinders its widespread use.In order to reduce material cost when improving catalyst speed, researchist is precious metal and base metal combination, the catalyzer of this combination can utilize the synergy between each element, effectively regulate responsiveness (the Wang X of each element to reaction, Sun S and Huang Z, et al.Int.J.Hydrogen Energy, 2014,39 (2): 905-916).The catalytic performance of the alloy material that contains base metal element is outstanding, and the single precious metal of cost ratio has obvious reduction.But precious metal composition certainly will increase catalyzer cost, thereby cause hydrogen manufacturing cost to improve.So, want fundamentally to solve hydrogen manufacturing Cost Problems, only have and use non-precious metal catalyst could really realize Hydrogen Energy widespread use completely, this becomes affects the key issue that can sodium borohydride hydrogen manufacturing apply.
Domestic investigator Li etc. points out that base metal simple substance nano Co film has higher catalytic activity (Li H, Liao J Y, Zhang X B, et al.J.Power Sources, 2013.239:277-283) for catalysis preparing hydrogen by sodium borohydride hydrolysis.Binary non-precious metal catalyst also can effectively improve catalytic efficiency, strengthen the stability of catalyzer, such as Co-B, Co-P, Ni-B and Fe-B alloy have all been obtained good catalytic effect in succession, and the catalytic performance of binary non-precious metal catalyst will significantly be better than its simple substance (Cho K W, Kwon H S.Catal.Today, 2007,120 (34): 298-304).Binary base metal is put the effective application in hydrogen in the hydrolysis of catalysis sodium borohydride as can be seen here.Wherein, binary base metal Co-P catalystic material receives much concern because having good catalytic activity.
The character of Co-P material and the acquisition of purposes are not only relevant with its chemical constitution, purity, and relevant with indexs such as the pattern of Co-P, size-grade distribution, size of particles, this just has higher requirement to the preparation process of Co-P material, people are being grasped on the basis of controlling Co-P granule technology, and the research of the particulate form of Co-P is controlled in the attention of having to.Particle shape is not so good as ion size and is easy to like that control, and this is because grain form is subject to the impact of the factors such as thermodynamics and kinetics simultaneously.
At present, in numerous methods of the Co-P particle of preparation, ubiquitous problem is: the pattern of synthetic Co-P particle is more single, mostly is ball-type (Eom, K., K.Cho, and H.Kwon, J.Power Sources, 2008.180 (1): 484-490).Adopt the Co-P catalystic material of the synthetic different-shape of electroless plating multistep processes have not been reported.
Summary of the invention
The present invention be take and addressed the above problem as object, and object of the present invention aims to provide a kind of preparation method of Co-P nano catalytic material.
For achieving the above object, the present invention adopts following technical proposals:
A kind of preparation method of Co-P nano catalytic material, this preparation method be take metal base as carrier, adopt electroless plating method to deposit metal Co and nonmetal P, produce Co-P nano catalytic material, specific implementation step is as follows: substrate is soaked after 3-5min, the immersion of copper etchant, sensitizing solution immersion and activation solution immersion treatment with hot alkaline solution successively, invade in chemical plating fluid and carry out electroless plating, through washing, dry, obtain Co-P nano catalytic material;
Described substrate is 3-5min in the soak time of hot alkaline solution, and the soak time of copper etchant is 3-6min, and the soak time of sensitizing solution is 1-3min, and the soak time of activation solution is 2-4min, and the time of invading chemical plating fluid is 2-20min.
Described substrate is Ni paper tinsel, Cu paper tinsel, foam Ni or Cu;
Described hot alkaline solution is the NaOH solution of 70 ℃ of 3mol/L; Copper etchant is that massfraction is 85% phosphoric acid 30-60mL, the mixed solution of the nitric acid 5-20mL that the acetic acid 30-50mL that massfraction is 36% and massfraction are 69%; The preparation steps of described sensitizing solution: take 1g stannous chloride dihydrate, in the hydrochloric acid that ultrasonic dissolution is 37% at 5mL massfraction, adding distil water is settled to 1L and is made into sensitizing solution; The preparation steps of described activation solution: take 0.1g Palladous chloride, in the hydrochloric acid that ultrasonic dissolution is 37% at 1mL massfraction, adding distil water is settled to 1L and is made into activation solution.
The preparation concrete steps of described chemical plating fluid are: (1) is dissolved in the divalent cobalt of solid that in distilled water, to be made into concentration be 0.05～1.0mol/L cobalt salt solution; (2) 2-8g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6-1:10; (3) tensio-active agent that is 0.1～1% by weight percent concentration joins in above-mentioned settled solution and obtains mixing solutions; (4) add 2-12g reductive agent sodium hypophosphite in above-mentioned mixing solutions; (5) mixing solutions of step (4) is put into after the water bath with thermostatic control constant temperature 5min of 70～100 ℃, between ammoniacal liquor or sodium hydrate solid regulation system pH to 10-13.
Described tensio-active agent adopts a kind of in polyvinyl alcohol in cetyl trimethylammonium bromide, Aerosol OT or the nonionic surface active agent in ionogenic surfactant, polyoxyethylene nonylphenol ether, polyoxyethylene sorbitan ester.
The pattern of described Co-P catalytic material comprises needle-like, the acicular structure that spins bulk and have ball-type to inlay, and described pattern is all piled up and is formed by nano level spherical granules.
The invention has the beneficial effects as follows:
Catalytic material prepared by the present invention is not containing precious metal, cost is low, the advantage that this catalyzer is applied to preparing hydrogen by sodium borohydride hydrolysis system is to have higher catalytic activity, can realize and under lesser temps, put fast hydrogen, effectively improved the dynamic performance of preparing hydrogen by sodium borohydride hydrolysis, the activation energy of reduction system, and there is good recycle performance.
By the interpolation of different sorts tensio-active agent, realized the controlled preparation of pattern of Co-P catalytic material, and the electroless plating method adopting is easy and simple to handle, safe and efficient.The pattern of Co-P catalytic material provided by the invention comprises needle-like, the acicular structure that spins bulk and have ball-type to inlay, and described pattern is all piled up and is formed by nano level spherical granules, this has increased the specific surface area of material to a certain extent, therefore there is higher catalytic activity, can accelerate the speed of reaction that hydrogen is put in sodium borohydride hydrolysis, reduce the activation energy of its hydrogen discharge reaction, and there is good recycle performance, safe and efficient, aspect vehicle-mounted Chu Qing, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of the catalytic material CP-A sample of the embodiment of the present invention 1 preparation;
Fig. 2 is high resolution scanning Electronic Speculum (HRSEM) figure of the catalytic material CP-A sample of the embodiment of the present invention 1 preparation;
Fig. 3 is scanning electron microscope (SEM) figure of the catalytic material CP-B sample of the embodiment of the present invention 2 preparations;
Fig. 4 is scanning electron microscope (SEM) figure of the catalytic material CP-D sample of the embodiment of the present invention 4 preparations;
Fig. 5 is the cycle performance test curve of the catalytic material CP-G catalysis preparing hydrogen by sodium borohydride hydrolysis of the embodiment of the present invention 7 preparations.
Embodiment
Below in conjunction with embodiment, further the present invention is described in detail.
Embodiment 1
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant: measure 50mL phosphoric acid, 35mL acetic acid, 15mL nitric acid and mix the copper etchant that is made into 100mL;
(2) preparation sensitizing solution: take 1g stannous chloride dihydrate ultrasonic dissolution in 5mL hydrochloric acid, adding distil water is settled to 1L, is made into sensitizing solution;
(3) preparation activation solution: take 0.1g Palladous chloride ultrasonic dissolution in 1mL hydrochloric acid, adding distil water is settled to 1L, is made into activation solution;
(4) preparation chemical plating fluid: 1. 2.379g cobalt chloride hexahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.5g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the tensio-active agent cetyl trimethylammonium bromide that is 0.1% by weight percent concentration joins in above-mentioned settled solution and obtains mixing solutions; 4. add 4.240g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 70 ℃, is 12.5 with sodium hydrate solid regulation system pH.
(5) prepare Co-P catalytic material: by area, be 4 * 4cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, the hot alkaline solution of 70 ℃ soaks 3min, above-mentioned copper etchant soaks 3min, sensitizing solution immersion 1min and activation solution soaks after 2min processing, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 2min.Gained catalytic material is designated as CP-A.Scanning electron microscope (SEM) figure that Fig. 1 is the catalytic material of preparation, visible, this catalytic material is needle-like the pattern that is inlaid with spherical granules.Fig. 2 is high resolution scanning Electronic Speculum (HRSEM) figure of this catalytic material, visible, and the spherical granules of inlaying is to be piled up and formed by countless less nano particles, and these short grained sizes are about 2-10nm.
Embodiment 2
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant, sensitizing solution and activation solution are respectively with the step in embodiment 1 (1), step (2), step (3);
(2) preparation chemical plating fluid: 1. 2.812g Cobalt monosulfate heptahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.503g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the surface active agent polyvinyl alcohol that is 0.1% by weight percent concentration (PVA-124) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 6.359g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 70 ℃, is 12 with ammoniacal liquor regulation system pH;
(3) prepare Co-P catalytic material: by area, be 4 * 4cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 4min, copper etchant and soaks 5min, sensitizing solution and soak 2min and activation solution and soak 3min and process, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 2min.Gained catalytic material is designated as CP-B.Scanning electron microscope (SEM) figure that Fig. 3 is the catalytic material of preparation, visible, this catalytic material is more uniform nanometer needle-like pattern.
Embodiment 3
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant, sensitizing solution and activation solution are respectively with the step in embodiment 1 (1), step (2), step (3);
(2) preparation chemical plating fluid: 1. 2.812g Cobalt monosulfate heptahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.503g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the surface active agent polyvinyl alcohol that is 0.1% by weight percent concentration (PVA-124) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 6.359g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 70 ℃, is 13 with ammoniacal liquor regulation system pH;
(3) prepare Co-P catalytic material: by area, be 4 * 4cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 5min, copper etchant and soaks 4min, sensitizing solution and soak 2min and activation solution and soak 3min and process, invade in above-mentioned chemical plating fluid and carry out electroless plating, plating time is 4min.Gained catalytic material is designated as CP-C.
Embodiment 4
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant: measure 48mL phosphoric acid, 37mL acetic acid, 15mL nitric acid and mix the copper etchant that is made into 100mL;
(2) preparation sensitizing solution and activation solution are with the step in embodiment 1 (2) and step (3);
(3) preparation chemical plating fluid: 1. 2.379g cobalt chloride hexahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.503g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the tensio-active agent Aerosol OT that is 0.1% by weight percent concentration (A-OT) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 8.479g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 70 ℃, is 11 with ammoniacal liquor regulation system pH.
(4) prepare Co-P catalytic material: by area, be 4 * 4cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 5min, copper etchant and soaks 6min, sensitizing solution and soak 3min and activation solution and soak 4min and process, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 2min.Gained catalytic material is designated as CP-D.Scanning electron microscope (SEM) figure that Fig. 4 is the catalytic material of preparation, visible, this catalytic material is the group's of the spinning pattern being overmolding to by needle-like, this group's of spinning diameter is about 600nm left and right.
Embodiment 5
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant, sensitizing solution and activation solution are respectively with the step in embodiment 1 (1), step (2), step (3).
(2) preparation chemical plating fluid: 1. 2.910g Cobaltous nitrate hexahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 6.004g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:8; 3. the surface active agent polyvinyl alcohol that is 0.1% by weight percent concentration (PVA-124) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 6.359g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 75 ℃, is 13 with ammoniacal liquor regulation system pH.
(3) prepare Co-P catalytic material: by area, be 2 * 3cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 3min, copper etchant and soaks 4min, sensitizing solution and soak 3min and activation solution and soak 4min and process, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 5min.Gained catalytic material is designated as CP-E.
Embodiment 6
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant, sensitizing solution and activation solution are respectively with the step in embodiment 1 (1), step (2), step (3).
(2) preparation chemical plating fluid: 1. 2.812g Cobalt monosulfate heptahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.503g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the tensio-active agent polyoxyethylene nonylphenol ether that is 0.1% by weight percent concentration (NP-10) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 6.359g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 75 ℃, is 10 with sodium hydrate solid regulation system pH.
(3) prepare Co-P catalytic material: by area, be 2 * 2cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 5min, copper etchant and soaks 6min, sensitizing solution and soak 1min and activation solution and soak 4min and process, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 6min.Gained catalytic material is designated as CP-F.
Embodiment 7
A preparation method for Co-P nano catalytic material, realizes by following concrete steps:
(1) preparation copper etchant, sensitizing solution and activation solution are respectively with the step in embodiment 1 (1), step (2), step (3).
(2) preparation chemical plating fluid: 1. 2.379g cobalt chloride hexahydrate is dissolved in and is made into the cobalt salt solution that concentration is 0.1mol/L in 100mL distilled water; 2. 4.503g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6; 3. the surfactant polyoxyethylene sorbitan fatty acid ester that is 0.1% by weight percent concentration (TWEEN-80) joins in above-mentioned settled solution and obtains mixing solutions; 4. add 8.479g reductive agent inferior sodium phosphate in above-mentioned mixing solutions; 5. step mixing solutions 4. being put into after the water bath with thermostatic control constant temperature 5min of 70 ℃, is 12.5 with sodium hydrate solid regulation system pH.
(3) prepare Co-P catalytic material: by area, be 4 * 4cm
2substrate Cu paper tinsel use successively 3mol/LNaOH, after the hot alkaline solution of 70 ℃ soaks 3min, copper etchant and soaks 3min, sensitizing solution and soak 2min and activation solution and soak 4min and process, invade in the above-mentioned chemical plating fluid preparing and carry out electroless plating, plating time is 2min.Gained catalytic material is designated as CP-G.
Embodiment 8
The catalytic material CP-G of preparation in embodiment 7 is joined in alkaline sodium borohydride solution, put hydrogen circulation dynamics performance test experiment, concrete steps are:
(1) taking 0.4g solid sodium hydroxide is dissolved in and in 10mL distilled water, is made into the settled solution that concentration is 1mol/L;
(2) add 0.05g sodium borohydride in above-mentioned settled solution, stir and make, after its dissolving, to be transferred in 10mL single port bottle, add immediately the catalytic material CP-G of preparation, timing starts, and probe temperature is 30 ℃.Repeat aforesaid operations 11 times, the cycle performance curve recording as shown in Figure 5.Can find out: the hydrogen discharging rate of catalyzer CP-G catalysis preparing hydrogen by sodium borohydride hydrolysis be take the consumption of unit mass catalyzer and calculated: be 1647.9mLmin for the first time
-1g
-1, the tenth is once 1011.8mLmin
-1g
-1, that is to say, after ten recycles, its catalytic efficiency still remains on primary 61%.
Tensio-active agent described in embodiment 1-7 can adopt a kind of in polyvinyl alcohol (PVA-124) in cetyl trimethylammonium bromide (CTAB), Aerosol OT A-OT or the nonionic surface active agent in ionogenic surfactant, polyoxyethylene nonylphenol ether (NP-10), polyoxyethylene sorbitan ester (TWEEN-80).
The pattern of the Co-P catalytic material in the present invention comprises needle-like, the acicular structure that spins bulk and have ball-type to inlay, and described pattern is all piled up and is formed by nano level spherical granules.
Claims (9)
1. the preparation method of ー kind Co-P nano catalytic material, it is characterized in that: this preparation method be take metal base as carrier, adopt electroless plating method to deposit metal Co and nonmetal P, produce Co-P nano catalytic material, specific implementation step is as follows: by substrate successively with hot alkaline solution soak, copper etchant soaks, sensitizing solution soaks and activation solution immersion treatment after, invade in chemical plating fluid and carry out electroless plating, through washing, dry, obtain Co-P nano catalytic material.
2. the preparation method of a kind of Co-P nano catalytic material as claimed in claim 1, it is characterized in that: described substrate is 3-5min in the soak time of hot alkaline solution, the soak time of copper etchant is 3-6min, the soak time of sensitizing solution is 1-3min, the soak time of activation solution is 2-4min, and the time of invading chemical plating fluid is 2-20min.
3. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: described substrate is Ni paper tinsel, Cu paper tinsel, foam Ni or Cu.
4. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: described hot alkaline solution is the NaOH solution of 70 ℃ of 3mol/L; Copper etchant is that massfraction is 85% phosphoric acid 30-60mL, the mixed solution of the nitric acid 5-20mL that the acetic acid 30-50mL that massfraction is 36% and massfraction are 69%.
5. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: the preparation steps of described sensitizing solution is for taking 1g stannous chloride dihydrate, in the hydrochloric acid that ultrasonic dissolution is 37% at 5mL massfraction, adding distil water is settled to 1L and is made into sensitizing solution.
6. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: the preparation steps of described activation solution is for taking 0.1g Palladous chloride, and in the hydrochloric acid that ultrasonic dissolution is 37% at 1mL massfraction, adding distil water is settled to 1L and is made into activation solution.
7. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: the preparation concrete steps of described chemical plating fluid are: a, the divalent cobalt of solid is dissolved in in distilled water, to be made into concentration be 0.05～1.0mol/L cobalt salt solution; B, 2-8g glycine is joined in above-mentioned cobalt salt solution, cobalt salt is evenly mixed with glycine, be made into Co
2+: the settled solution that glycine mol ratio is 1:6-1:10; C, the tensio-active agent that is 0.1～1% by weight percent concentration join in above-mentioned settled solution and obtain mixing solutions; D, add 2-12g reductive agent sodium hypophosphite in above-mentioned mixing solutions; E, the mixing solutions of steps d is put into after the water bath with thermostatic control constant temperature 5min of 70～100 ℃, between ammoniacal liquor or sodium hydrate solid regulation system pH to 10-13.
8. as the preparation method of claim 7 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: described tensio-active agent adopts a kind of in polyvinyl alcohol in cetyl trimethylammonium bromide, Aerosol OT or the nonionic surface active agent in ionogenic surfactant, polyoxyethylene nonylphenol ether, polyoxyethylene sorbitan ester.
9. as the preparation method of claim 1 Suo Shu ー kind Co-P nano catalytic material, it is characterized in that: the pattern of described Co-P catalytic material comprises needle-like, the acicular structure that spins bulk and have ball-type to inlay, and described pattern is all piled up and is formed by nano level spherical granules.
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| JP2018510833A (en) * | 2015-03-05 | 2018-04-19 | テラジェニック リミテッド | Method for catalyst-induced hydrolysis and recycling of metal borohydride solutions |
| US10919763B2 (en) | 2015-03-05 | 2021-02-16 | Electriq-Global Energy Solutions Ltd | Method for catalytically induced hydrolysis and recycling of metal borohydride solutions |
| CN109072458A (en) * | 2016-04-18 | 2018-12-21 | 沙特基础工业全球技术公司 | The analysis oxygen elctro-catalyst of cobalt (II, III) oxide skin(coating) containing carbon coating |
| CN106906458A (en) * | 2017-01-10 | 2017-06-30 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of Novel magnetic nip electroless cobalt plating P magnetic films plating solution, method and gained magnetic head using its electroless cobalt plating P magnetic films |
| CN107983379A (en) * | 2017-11-28 | 2018-05-04 | 沈阳师范大学 | A kind of ZnO/CoP compound nanometer photocatalysts and preparation method thereof |
| CN108091889A (en) * | 2017-12-14 | 2018-05-29 | 沈阳师范大学 | Preparing hydrogen by sodium borohydride hydrolysis Co-Ni-P nanocatalysts and preparation method |
| CN108993573A (en) * | 2018-08-09 | 2018-12-14 | 沈阳师范大学 | Compound nanometer photocatalyst and preparation method |
| CN111495370A (en) * | 2020-05-08 | 2020-08-07 | 沈阳师范大学 | Twisted nano banded Co-Fe-B catalyst, preparation method and application thereof |
| CN114682279A (en) * | 2022-04-14 | 2022-07-01 | 辽宁大学 | MXene loaded Co-Ni-P catalyst, preparation method thereof and application thereof in hydrogen production by hydrolysis of sodium borohydride |
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