CN106960965B - A kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide - Google Patents
A kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide Download PDFInfo
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- CN106960965B CN106960965B CN201710131707.XA CN201710131707A CN106960965B CN 106960965 B CN106960965 B CN 106960965B CN 201710131707 A CN201710131707 A CN 201710131707A CN 106960965 B CN106960965 B CN 106960965B
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Abstract
The present invention provides a kind of preparation methods of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide; include the steps for preparing the different structural material processed of black phosphorus titanium dioxide: after black phosphorus nanoscale twins material and titanium dioxide nanoplate layer material are carried out ball milling under protection of argon gas; it is washed respectively with ethyl alcohol and water; suction filtration obtains the different structural material processed of black phosphorus titanium dioxide, and vacuum drying is collected；It again disperses the different structural material processed of black phosphorus titanium dioxide in ethyl alcohol, stabilizer and metal precursor, continual ultrasonic stirring is added after ultrasonic treatment, adjusting pH is 9-11, reducing agent is added, it is lasting to stir, up to the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide after vacuum drying.The combination of the different structural material carrier processed of black phosphorus titanium dioxide and noble metal is more preferable in the present invention, effectively raises the electro-chemical activity and stability of fuel-cell catalyst, and preparation process is easy to operate, is suitble to large-scale production.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of fuel battery anode catalyst material, specifically a kind of black
The preparation method of the different structural material material load noble metal nano particles processed of phosphorus titanium dioxide.
Background technique
Since the increasingly depleted and problem of environmental pollution of global fossil energy resources increasingly sharpens, it is badly in need of people and looks for
Cleaning, the efficient novel environment friendly energy.Wherein, fuel cell is since with energy density, high, fuel source is applied extensively
In every field, the key of fuel cell power conversion efficiency is catalyst.Direct alcohol fuel cell elctro-catalyst is with your gold
Based on category, but the reserves of noble metal in nature are limited and expensive, vulnerable to poisoning for intermediate product.So expensive
Metal needs will carry out compound with other materials, wherein the different structural material processed of black phosphorus titanium dioxide has biggish specific surface area, conjunction
Suitable band gap, good thermal stability and chemical stability etc., the different structural material processed of black phosphorus titanium dioxide can change black phosphorus
The structure of material increases the chemical active sites of material surface, and therefore, the different structural material processed of black phosphorus titanium dioxide has
Preferable development prospect.
Summary of the invention
For above-mentioned technical problem existing for catalyst in the prior art, the present invention provides a kind of black phosphorus titanium dioxide is different
The preparation method of structural material supported precious metal nano-particle processed, this new different structural material processed of black phosphorus titanium dioxide are negative
The preparation method of supported noble metal nanoparticle will solve the catalytic activity of direct alcohol fuel cell catalyst in the prior art not
High, expensive technical problem.
The present invention provides a kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide,
Include the following steps:
1) prepare black phosphorus titanium dioxide different structural material processed the step of, by black phosphorus nanoscale twins material and titanium dioxide
Nanoscale twins material mechanical ball mill 24-48h under protection of argon gas, obtained precursor ethyl alcohol and deionized water are centrifuged respectively
Washing 2 ~ 6 times carries out collected by suction, then will obtain the different structural wood processed of black phosphorus titanium dioxide after above-mentioned product vacuum drying
Material；
2) prepare black phosphorus titanium dioxide different structural material supported precious metal nano-particle processed the step of, by black phosphorus dioxy
Change the different structural material processed of titanium to be scattered in ethyl alcohol, stabilizer and metal precursor, the black phosphorus dioxy are added after ultrasonic treatment
The mass ratio for changing the different structural material processed of titanium and stabilizer is 1:1 ~ 10, and the metal in the metal precursor is platinum, palladium, Jin Huo
Silver, persistently stirs 8-12h, and adjusting pH is 9-11, adds reducing agent, the reducing agent be potassium borohydride, sodium borohydride or
The mass ratio of hydrazine hydrate, metal precursor and reducing agent is 1:1 ~ 100, and the quality of the metal in the metal precursor is black
The 10 ~ 30% of the sum of the different structural material processed of phosphorus titanium dioxide and metal quality, persistently stir 1-5h, obtain after vacuum drying black
The different structural material supported precious metal nano-particle processed of phosphorus titanium dioxide.
Further, the stabilizer is CTAB.
Further, in step 1), the mass ratio of black phosphorus and titanium dioxide is 1:2.
Further, in the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide, noble metal
Content be 1-90wt%.
Further, based on red phosphorus, mechanical ball mill obtains the black phosphorus material under protection of argon gas.
Further, the titanic oxide material is prepared based on butyl titanate hydro-thermal method.
Further, its different structure processed is mechanical by applying external force in the different structural material processed of the black phosphorus titanium dioxide
What ball milling black phosphorus and titanium dioxide obtained.
After black phosphorus nanoscale twins material and titanium dioxide nanoplate layer material are carried out ball milling under protection of argon gas by the present invention,
It is washed respectively with ethyl alcohol and water, finally filters and obtain the different structural material processed of black phosphorus titanium dioxide, vacuum drying is collected；Again by black phosphorus
The different structural material processed of titanium dioxide is scattered in ethyl alcohol, and stabilizer and metal precursor, the metal are added after ultrasonic treatment
Metal in presoma is platinum, palladium, gold or silver, and continual ultrasonic stirring, adjusting pH is 9-11, adds reducing agent, persistently stirs
It mixes, up to the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide after vacuum drying.
It is obtained by testing characterization, black phosphorus and titanium dioxide effectively form different structure processed, and realize a variety of members
The co-doped of element, the present invention combines the electronic structure between different structure carrier processed and noble metal to influence, so that its catalyst exists
There is preferable electro catalytic activity and electrochemical stability in alkaline alcohols.
Compared with prior art, the present invention its technological progress is significant.The present invention is formed with black phosphorus and titanium dioxide
The combination of different structure processed, the different structural material carrier processed of black phosphorus titanium dioxide and noble metal is more preferable, shape characteristic at sheet, platinum,
Palladium, gold or Nano silver grain are evenly distributed and have good electro catalytic activity in alkaline alcohols.The present invention effectively mentions
The electro-chemical activity and stability of high fuel-cell catalyst, and preparation process is simple and clear, is suitble to large-scale production, has one
Fixed use value.
Detailed description of the invention
Fig. 1 is the XRD diagram of the different structural load Pd nano particle material processed of the resulting black phosphorus titanium dioxide of embodiment 1.
Fig. 2 is the TEM figure and EDS-mapping figure of the 1 different structural material processed of resulting black phosphorus titanium dioxide of embodiment.
Fig. 3 is that the XPS of the different structural load Pd nano particle material processed of the resulting black phosphorus titanium dioxide of embodiment 1 schemes.
Fig. 4 is the different structural load Pd nano particle material processed of the resulting black phosphorus titanium dioxide of embodiment 1 in 1M NaOH+1M
CH3CH2Cyclic voltammogram in OH.
Fig. 5 is the different structural load Pd nano particle material processed of the resulting black phosphorus titanium dioxide of embodiment 1 in 1M NaOH+1M
CH3CH2Time current curve in OH.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method of the different structural load noble metal nano particles material processed of black phosphorus titanium dioxide, specifically includes following
Step:
(1) preparation of the different structural material processed of black phosphorus titanium dioxide
1. the preparation of black phosphorus: taking 2g red phosphorus and 15mL ultrapure water to be added in the water heating kettle of 25mL together at room temperature, 200
Heat steams 12h at DEG C, for removing the oxide layer on red phosphorus surface.After then taking out and drying, 0.5-1h is ground with agate mortar, so
By multilayer black phosphorus presoma, argon filling gas shielded carries out mechanical ball mill, ball milling 24-48h at normal temperatures and pressures afterwards, and revolving speed is maintained at
500r/min.Black phosphorus is obtained after the completion of mechanical ball mill.
2. the preparation of titanium dioxide: being added to 50 dry mL using the tetra-n-butyl titanate that liquid-transfering gun measures 10 mL
In reaction kettle liner, 3.0 mL of hydrofluoric acid is measured with the liquid-transfering gun that specification is 1 mL while magnetic agitation and is slowly dropped to
In tetra-n-butyl titanate, persistently stirs 10 min and obtain uniform mixed liquor.Reaction kettle sealing is fitted into baking oven, at 200 DEG C
24 h of lower reaction, then allow reaction kettle cooled to room temperature.Sample obtained is centrifuged using deionized water and dehydrated alcohol
Then sample is put in 70 DEG C of baking oven dry 12 h by cleaning, final to obtain dry titanic oxide nano powder.
3. the preparation of the different structural material processed of black phosphorus titanium dioxide: by black phosphorus nanoscale twins material and titanium dioxide nanoplate
Layer material under protection of argon gas, by 500r/min mechanical ball mill 24-48h, the precursor ethyl alcohol and deionized water that will be obtained
Centrifuge washing three times, then carries out collected by suction respectively, then will be above-mentioned 40 DEG C of product vacuum drying after obtain black phosphorus titanium dioxide
The different structural material processed of titanium.
(2) preparation of the different structural load noble metal nano particles material processed of black phosphorus titanium dioxide
It disperses the different structural material processed of black phosphorus titanium dioxide in ethyl alcohol, stabilizer and metal front is added after ultrasonic treatment
The ratio of body, the different structural material processed of the black phosphorus titanium dioxide and stabilizer is 1:1 ~ 10, the gold in the metal precursor
Belonging to is platinum, palladium, gold or silver, persistently stirs 8-12h.Adjusting pH is 9-11, adds reducing agent, and the reducing agent is boron hydrogen
The mass ratio of change potassium, sodium borohydride or hydrazine hydrate, metal precursor and reducing agent is 1:1 ~ 100, and the quality of the metal is
The 10 ~ 30% of the hollow carbon balls of Heteroatom doping and the sum of metal quality, persistently stir 1-5h, and black phosphorus is obtained after vacuum drying
The different structural load noble metal nano particles processed of titanium dioxide.
The XRD diagram of the different structural load noble metal nano particles material processed of black phosphorus titanium dioxide obtained above, such as Fig. 1 institute
Show.(020), (040) of black phosphorus, (060) three peak as seen from the figure, (101) (002) (200) of metal Ti in titanium dioxide
(102) (111) of (110) five characteristic peaks and metal Pd, (200), (220), (311) four characteristic diffraction peaks, it was confirmed that
The different structural load precious metal palladium nanoparticle processed of black phosphorus titanium dioxide.
The TEM of the above-mentioned different structural material processed of resulting black phosphorus titanium dioxide schemes and EDS-mapping figure, as shown in Figure 2.From
As can be seen that there are tri- kinds of elements of P, Ti, O in figure, and it is evenly distributed.
By the above-mentioned resulting different structural load noble metal nano particles material processed of black phosphorus titanium dioxide, member is carried out using XPS
Element analysis, as a result as shown in figure 3, as can be seen from the figure BP-TiO2After loading Pd nanoparticle, the peak 3d of Pd exists, by
This is proved, successfully loads Pd nano particle.
Fig. 4 corresponding is the different structural load noble metal nano particles material processed of black phosphorus titanium dioxide in 1M NaOH+1M
CH3CH2Cyclic voltammogram in OH.It can be seen from the figure that the starting of the different structural load Pd nano particle processed of black phosphorus titanium dioxide
Oxidizing potential is apparently higher than activated carbon-carried palladium；The oxidation for just sweeping ethyl alcohol of the different structural load Pd nano particle processed of black phosphorus titanium dioxide
Current density is 2091mA mg-1Compared to the 697 mA mg of oxidate current for just sweeping ethyl alcohol of activated carbon-carried palladium-1, it is it
3 times, thus prove the different structural load Pd nano particle material processed of black phosphorus titanium dioxide to ethyl alcohol have higher oxidation activity.
Fig. 5 corresponding is time electricity of the different structural load Pd nano particle material processed of black phosphorus titanium dioxide in ethanol solution
Flow curve is higher.After 3600s, the electric current of the different structural load Pd nano particle material processed of black phosphorus titanium dioxide remains 347
mA mg-1, compared to 29.5 mA mg of activated carbon-carried palladium-1It is higher by 10 times.To demonstrate the different structure processed of black phosphorus titanium dioxide
Supported palladium nanometer particle material has better electrochemical stability in ethanol.
Claims (7)
1. a kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide, it is characterised in that including
Following steps:
1) prepare black phosphorus titanium dioxide different structural material processed the step of, by black phosphorus nanoscale twins material and nano titania
Obtained precursor ethyl alcohol and deionized water are distinguished centrifuge washing by sheet layer material mechanical ball mill 24-48h under protection of argon gas
2~6 times, collected by suction is carried out, then will obtain the different structural material processed of black phosphorus titanium dioxide after above-mentioned product vacuum drying；
2) prepare black phosphorus titanium dioxide different structural material supported precious metal nano-particle processed the step of, by black phosphorus titanium dioxide
Different structural material processed is scattered in ethyl alcohol, and stabilizer and metal precursor, the black phosphorus titanium dioxide are added after ultrasonic treatment
The mass ratio of different structural material processed and stabilizer is 1:1~10, and the metal in the metal precursor is platinum, palladium, gold or silver,
8-12h is persistently stirred, adjusting pH is 9-11, adds reducing agent, and the reducing agent is potassium borohydride, sodium borohydride or hydration
The mass ratio of hydrazine, metal precursor and reducing agent is 1:1~100, and the quality of metal is black phosphorus two in the metal precursor
The 10~30% of the sum of the different structural material processed of titanium oxide and metal quality, persistently stir 1-5h, and black phosphorus is obtained after vacuum drying
The different structural material supported precious metal nano-particle processed of titanium dioxide.
2. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: the stabilizer is CTAB.
3. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: in step 1), the mass ratio of black phosphorus nanoscale twins material and titanium dioxide nanoplate layer material is 1:2.
4. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: in the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide, noble metal is received
The content of rice corpuscles is 1-90wt%.
5. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: mechanical ball mill obtains the black phosphorus nanoscale twins material under protection of argon gas based on red phosphorus.
6. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: the titanium dioxide nanoplate layer material is prepared based on butyl titanate hydro-thermal method.
7. a kind of preparation of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide according to claim 1
Method, it is characterised in that: its different structure processed is mechanical by applying external force in the different structural material processed of the black phosphorus titanium dioxide
What ball milling black phosphorus nanoscale twins material and titanium dioxide nanoplate layer material obtained.
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| CN107376957B (en) * | 2017-06-27 | 2020-01-24 | 青岛鲁润能源环境有限公司 | Preparation method and application of red phosphorus-coated titanium dioxide nanofiber photocatalytic material |
| CN108586227B (en) * | 2018-04-24 | 2020-10-20 | 鹏辰新材料科技股份有限公司 | Preparation method of pyromellitic acid based on porous black phosphorus catalyst |
| CN108483416A (en) * | 2018-05-08 | 2018-09-04 | 戚明海 | A kind of black phosphorus and preparation method thereof of boride modification |
| CN109301209B (en) * | 2018-09-27 | 2022-03-18 | 三峡大学 | Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material |
| CN110327952A (en) * | 2019-08-16 | 2019-10-15 | 济南大学 | Self-water absorption type two dimension P/MoS2The preparation method of base composite photocatalyst |
| CN111029594B (en) * | 2019-12-31 | 2022-05-17 | 南通大学 | Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell |
| CN111129509B (en) * | 2019-12-31 | 2022-05-17 | 南通大学 | Direct methanol fuel cell anode catalyst and preparation method thereof |
| CN111509241B (en) * | 2020-05-29 | 2021-07-13 | 贵州大学 | Black phosphorus @ titanium dioxide supported noble metal composite material and preparation method thereof |
| CN113336206B (en) * | 2021-07-20 | 2022-05-17 | 哈尔滨工程大学 | Method for synthesizing porous black phosphorus nanosheet for negative electrode material of ion battery |
| CN114000174B (en) * | 2021-11-26 | 2022-07-19 | 武汉工程大学 | Preparation method of black phosphorus/cobaltosic oxide composite oxygen evolution electrocatalyst |
| CN114937768A (en) * | 2022-06-10 | 2022-08-23 | 浙江大学 | Titanium dioxide/red phosphorus composite material, preparation method thereof and sodium ion half cell |
| CN115155626A (en) * | 2022-08-02 | 2022-10-11 | 陕西科技大学 | BPQDs/TiO 2 Binary heterostructure composite photocatalytic material and preparation method and application thereof |
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| CN106366121A (en) * | 2015-12-18 | 2017-02-01 | 中国科学院深圳先进技术研究院 | Titanium ligand modified black phosphorus, and preparation method and application thereof |
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| DK109330C (en) * | 1958-07-07 | 1968-04-16 | Bayer Ag | Process for the preparation of organic phosphorus halides. |
| CN106366121A (en) * | 2015-12-18 | 2017-02-01 | 中国科学院深圳先进技术研究院 | Titanium ligand modified black phosphorus, and preparation method and application thereof |
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