CN110240189A - A kind of preparation method and applications of poly-metal deoxide nano material - Google Patents

A kind of preparation method and applications of poly-metal deoxide nano material Download PDF

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CN110240189A
CN110240189A CN201910543219.9A CN201910543219A CN110240189A CN 110240189 A CN110240189 A CN 110240189A CN 201910543219 A CN201910543219 A CN 201910543219A CN 110240189 A CN110240189 A CN 110240189A
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source metal
solution
fecl
metal
poly
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俞书宏
段玉
张楚天
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University of Science and Technology of China USTC
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Abstract

The present invention provides a kind of preparation methods of poly-metal deoxide nano material, comprising the following steps: A) the first source metal is mixed with water, obtain uniform first solution；Second source metal is mixed with water, obtains uniform second solution；B first solution is mixed with second solution), obtains homogeneous precipitation；C) precipitating is freeze-dried, obtains poly-metal deoxide nano material.Method provided by the present application is prepared for a kind of poly-metal deoxide nano material, which shows porous structure, is made of small nano particle；And excellent OER catalytic performance and stability are shown under alkaline condition.

Description

A kind of preparation method and applications of poly-metal deoxide nano material
Technical field
The present invention relates to technical field of nano material more particularly to a kind of preparation methods of poly-metal deoxide nano material And its application.
Background technique
With environmental pollution and lack of energy, cleaning, the utilization of renewable energy become a project being concerned.Hydrogen The energy is a kind of new energy being concerned, and generally prepares hydrogen energy source using electrolysis water, however prepares hydrogen energy source in electrolysis water During, anodic oxygen is precipitated the slow kinetics of (OER) method and consumes great overpotential, causes energy wave Take.
During anodic oxygen is precipitated, the noble metals such as existing frequently-used Ru/Ir are the efficient OER catalyst of comparison, but It is that high cost limits its large-scale application.Researcher passes through continuous effort, has prepared many nano materials to open up Reveal good OER catalytic performance.However, the often synthesis condition of these efficient non-noble metal nano catalyst requirement complexity And step, artificial and equipment cost is increased, large scale preparation is unfavorable for；Organic solvent used simultaneously etc. can cause environment Harm, is unfavorable for green syt；On the other hand, the output of raw material feeds intake smaller, is unfavorable for maximally utilizing for substance.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of poly-metal deoxide nano material, this method Unformed poly-metal deoxide nano material can be prepared, is applied to OER and has excellent catalytic properties and stability.
In view of this, this application provides a kind of preparation methods of poly-metal deoxide nano material, comprising the following steps:
A the first source metal is mixed with water), obtains uniform first solution；
Second source metal is mixed with water, obtains uniform second solution；
The concentration of first solution is 1~3mol/L, and the concentration of second solution is 1~3mol/L；
B first solution is mixed with second solution), obtains homogeneous precipitation；
C) precipitating is freeze-dried, obtains poly-metal deoxide nano material；
First source metal is selected from one or more source metals soluble easily in water, and second source metal is selected from and is soluble in One or more source metals of water.
Preferably, the concentration of first solution is 1mol/L, and the concentration of second solution is 1mol/L.
Preferably, first source metal is selected from NiCl2·2H2O、FeCl3、CoCl2·6H2O、MnCl2·4H2O、 CuCl2·2H2O、ZnCl2、VCl3And CrCl3One of or it is a variety of, second source metal be selected from Na2MoO4·2H2O、 Na2WO4·2H2O、Na2CO3·1H2O and Na3PO4·12H2One of O etc. or a variety of.
Preferably, first source metal is selected from NiCl2·2H2O and FeCl3, second source metal is selected from Na2MoO4· 2H2O；Or first source metal is selected from CoCl2·6H2O and FeCl3, second source metal is selected from Na2MoO4·2H2O；Or First source metal is selected from MnCl2And FeCl3, second source metal is selected from Na2MoO4·2H2O；Or first source metal be selected from CuCl2·2H2O and FeCl3, second source metal is selected from Na2MoO4·2H2O；Or first source metal is selected from NiCl2· 2H2O and FeCl3, second source metal is selected from Na2WO4·2H2O。
Preferably, first source metal is selected from NiCl2·2H2O and FeCl3When, the NiCl2·2H2O and FeCl3's Molar ratio is (0.1~6): 1；First source metal is selected from CoCl2·6H2O and FeCl3When, CoCl2·6H2O and FeCl3's Molar ratio is (0.1~6): 1；First source metal is selected from MnCl2And FeCl3When, the MnCl2And FeCl3Molar ratio be (0.1 ~6): 1；First source metal is selected from CuCl2·2H2O and FeCl3When, the CuCl2·2H2O and FeCl3Molar ratio is (0.1~6): 1.
Preferably, during obtaining the first solution, the mixing is carried out by the way of ultrasonic agitation；It is molten to obtain second During liquid, the mixing is carried out by the way of ultrasonic agitation.
Preferably, during obtaining the first solution, the temperature of the ultrasonic agitation is 20~40 DEG C, the ultrasonic agitation Time be 1~10min；During obtaining the second solution, the temperature of the ultrasonic agitation is 20~40 DEG C, and the ultrasound is stirred The time mixed is 1~10min.
Preferably, the freeze-drying is first freezed in liquid nitrogen and is lyophilized in freeze dryer again；The time of the freezing is 10 ~30min, the time of the freeze-drying are 1~4 day.
Present invention also provides a kind of method for being electrolysed aquatic products oxygen, poly-metal deoxide nano material described in above scheme It is carried on electrode as working electrode.
This application provides a kind of preparation methods of poly-metal deoxide nano material, first by the first source metal and water Mixing, has obtained uniform first solution, while the second source metal being mixed with water, obtains the second solution, then by the first solution It is mixed with the second solution, obtains uniform second solution, then two kinds of solution are mixed, obtain homogeneous precipitation, will finally precipitate cold It is lyophilized dry to get to poly-metal deoxide nano material；It is molten using the first solution of high concentration and second in above-mentioned preparation process Liquid realizes various metals cation in solution while precipitating, avoids the separation of metal and phase, has finally obtained without lattice Structure, that is, unformed, the poly-metal deoxide nano material of uniform Elemental redistribution are applied in OER, have excellent urge Change performance and stability.
Detailed description of the invention
Fig. 1 is the scanning electron microscope of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 1 Photo；
Fig. 2 is the scanning electron microscope of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 2 Photo；
Fig. 3 is the transmission electron microscope of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 2 Photo；
Fig. 4 is that the high-resolution of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 2 is saturating Penetrate photo and selective electron diffraction figure；
Fig. 5 is the XRD diagram of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 2；
Fig. 6 is the transmission electron microscope of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 3 Photo；
Fig. 7 is the transmission electron microscope of unformed CoFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 6 Photo；
Fig. 8 is the transmission electron microscope of unformed MnFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 6 Photo；
Fig. 9 is the transmission electron microscope of unformed CuFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 6 Photo；
Figure 10 is the transmission electron microscope of unformed NiFeW poly-metal deoxide nano material prepared by the embodiment of the present invention 7 Photo；
Figure 11 is the electrolysis aquatic products of unformed NiFeMo poly-metal deoxide nano material prepared by the embodiment of the present invention 2 The polarization curve of oxygen.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.
For studying a question for OER catalyst, this application provides one kind can be prepared on a large scale poly-metal deoxide nanometer The preparation method of material, by the quick mixing of high concentration source metal solution, precipitating while realizing various metals ion, Thus it is prepared for a kind of poly metal oxide nano material, which shows porous structure, it is made of small nano particle, Excellent OER catalytic performance and stability are shown under alkaline condition.Specifically, the embodiment of the invention discloses a kind of more metals The preparation method of oxide-based nanomaterial, comprising the following steps:
A the first source metal is mixed with water), obtains uniform first solution；
Second source metal is mixed with water, obtains uniform second solution；
The concentration of first solution is 1~3mol/L, and the concentration of second solution is 1~mol/L；
B first solution is mixed with second solution), obtains homogeneous precipitation；
C) precipitating is freeze-dried, obtains poly-metal deoxide nano material；
First source metal is selected from one or more source metals soluble easily in water, and second source metal is selected from and is soluble in One or more source metals of water.
In above-mentioned preparation process, the application first mixes the first source metal and water, obtains the first solution, while by the Two source metals are mixed with water, obtain the second solution, wherein the first source metal and the second source metal are source metal soluble easily in water, To guarantee that the first source metal and the second source metal are dissolved in after water respectively and are capable of forming uniform solution.The application is for the first metal Source and the second source metal are not particularly limited, as long as source metal is capable of forming uniform solution after being dissolved in water；Specifically, First source metal is selected from NiCl2·2H2O、FeCl3、CoCl2·6H2O、MnCl2·4H2O、CuCl2·2H2O、ZnCl2、 VCl3And CrCl3One of or it is a variety of, second source metal be selected from Na2MoO4·2H2O、Na2WO4·2H2O、Na2CO3· 1H2O and Na3PO4·12H2One of O etc. or a variety of.In specific preparation process, the first source metal and the second source metal are not Together.First source metal can be one kind, and the second source metal can be one kind, and equally, the first source metal can be two kinds, the second gold medal Category source can be one kind, same first source metal can be it is a variety of, the second source metal can be it is a variety of, to this application without spy Other limitation.In a particular embodiment, first source metal is selected from NiCl2·2H2O and FeCl3, the second source metal choosing From Na2MoO4·2H2O, the NiCl2·2H2O and FeCl3Molar ratio be (0.1~6): 1, it is in a particular embodiment, described NiCl2·2H2O and FeCl3Molar ratio be (1~3): 1.In a particular embodiment, first source metal is selected from CoCl2· 6H2O and FeCl3, second source metal is selected from Na2MoO4·2H2O；Or first source metal is selected from MnCl2And FeCl3, institute It states the second source metal and is selected from Na2MoO4·2H2O；Or first source metal be selected from CuCl2·2H2O and FeCl3, second source metal Selected from Na2MoO4·2H2O；Or first source metal is selected from NiCl2·2H2O and FeCl3, second source metal is selected from Na2WO4·2H2O；First source metal is selected from CoCl2·6H2O and FeCl3When, CoCl2·6H2O and FeCl3Molar ratio be (0.1~6): 1, in a particular embodiment, CoCl2·6H2O and FeCl3Molar ratio be (1~3): 1；First source metal is selected from MnCl2And FeCl3When, the MnCl2And FeCl3Molar ratio be (0.1~6): 1, in a particular embodiment, the MnCl2With FeCl3Molar ratio be (1~3): 1；First source metal is selected from CuCl2·2H2O and FeCl3When, the CuCl2·2H2O And FeCl3Molar ratio is (0.1~6): 1, in a particular embodiment, the CuCl2·2H2O and FeCl3Molar ratio is (1~3): 1。
The concentration of first solution is 1~3mol/L, and the concentration of second solution is 1~3mol/L, specific real It applies in example, the concentration of first solution is 1mol/L, and the concentration of second solution is 1mol/L；First solution and institute The excessive product density that will lead to of concentration for stating the second solution is excessive, and intergranular space reduces, and specific surface area decline is unfavorable for exposing More active sites, it is too small and to will lead to precipitating uneven.
It is above-mentioned obtain the first solution and the second solution during, the mixed mode is all made of the side of ultrasonic agitation Formula, to guarantee to obtain uniform solution；During obtaining the first solution, the temperature of the ultrasonic agitation is 20~40 DEG C, the time of the ultrasonic agitation is 1~10min；During obtaining the second solution, the temperature of the ultrasonic agitation is 20~ 40 DEG C, the time of the ultrasonic agitation is 1~10min.
Then the application mixes the first solution and the second solution, obtain homogeneous precipitation, realizes the metal in the first solution Ion precipitates simultaneously with the metal ion in the second solution.
Precipitating is finally freeze-dried to get poly-metal deoxide nano material is arrived by the application；Above-mentioned various metals Cation precipitates simultaneously, avoids the separation of metallic element and phase, advantageously forms using freeze-drying unformed mostly golden Belong to oxide-based nanomaterial.The freeze-drying is first freezed in liquid nitrogen and is lyophilized in freeze dryer again；The time of the freezing is 10~30min, the time of the freeze-drying are 1~4 day.
It is to receive the poly-metal deoxide of above scheme preparation present invention also provides a kind of method for being electrolysed aquatic products oxygen Rice material load on electrode be used as working electrode.
The method of above-mentioned electrolysis aquatic products oxygen is OER method, and difference is only that on working electrode that load has poly-metal deoxide to receive Rice material, other and prior art indistinction.
For a further understanding of the present invention, below with reference to embodiment to poly-metal deoxide nano material provided by the invention Preparation method and applications be described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) preparation of unformed NiFeMo poly-metal deoxide nano material slurries: by 0.5mmol NiCl2·6H2O With 0.5mmol FeCl3It is added in 1ml deionized water, ultrasound 20 minutes forms homogeneous solution；
By 1mmol Na2MoO4·2H2O is added in 1ml deionized water, and same ultrasound 20 minutes forms homogeneous solution；
Under the conditions of ultrasonic agitation/shaking, the latter is poured into former solution rapidly, ultrasonic agitation/shaking 2 minutes, shape At precipitating；
(2) described be deposited in liquid nitrogen is freezed 20 minutes, is then transferred into freeze dryer and is lyophilized 2 days.
Ni prepared by the embodiment of the present invention 10.5Fe0.5Mo poly-metal deoxide nano material carries out transmission electron microscope detection, Result is examined as shown in Figure 1, as shown in Figure 1, Ni0.5Fe0.5Mo poly-metal deoxide appearance of nano material is nano particle.
Embodiment 2
Embodiment 1 is repeated, difference is: adjusting the ratio of Ni:Fe in cationic solution, be added in 1ml deionized water 0.75mmol NiCl2·6H2O and 0.25mmol FeCl3。
Ni prepared by the embodiment of the present invention 20.75Fe0.25Mo poly-metal deoxide nano material is scanned Electronic Speculum detection, Testing result is as shown in Fig. 2, as shown in Figure 2, Ni0.75Fe0.25The pattern of Mo poly-metal deoxide nano material is nano particle.
Ni prepared by the embodiment of the present invention 20.75Fe0.25Mo poly-metal deoxide nano material carries out transmission electron microscope detection, Testing result is as shown in figure 3, from the figure 3, it may be seen that Ni0.75Fe0.25The pattern of Mo poly-metal deoxide nano material is nano particle, Partial size is 60nm or so.
Ni prepared by the embodiment of the present invention 20.75Fe0.25Mo poly-metal deoxide nano material carries out high-resolution and selection Electron diffraction analysis, testing result is as shown in figure 4, as shown in Figure 4, the Ni that the embodiment of the present invention 2 is prepared0.75Fe0.25Mo is more Metal oxide nano-material high-resolution does not have ordered lattice presence, does not have independent diffraction spot to exist in selective electron diffraction, Show undefined structure feature.
Ni prepared by the embodiment of the present invention 20.75Fe0.25Mo poly-metal deoxide nano material carries out the detection of XRD diffraction, Testing result is as shown in figure 5, as shown in Figure 5, Ni0.75Fe0.25The XRD peak broadening of Mo poly-metal deoxide nano material, without generation The sharp peak of table crystal type exists.
Polarization curve is tested using three traditional electrode test methods, the Ni prepared to the embodiment of the present invention 20.75Fe0.25Mo Poly-metal deoxide nano material carries out the detection of alkaline water oxidation susceptibility, is loaded on glass-carbon electrode as work electricity Pole, load capacity 0.25mg/cm2, it is to electrode with platinized platinum, using Ag/AgCl as reference electrode, electrolyte is oxygen saturation The KOH aqueous solution of 0.1mol/L.
Testing result is as shown in figure 11, as shown in Figure 11, reaches 10mA/cm-2When overpotential be only 280mV, have it is excellent Water oxygen electrocatalysis characteristic.
Embodiment 3
Embodiment 1 is repeated, difference is: adjusting the ratio of Ni:Fe in cationic solution, be added in 1ml deionized water 0.25mmol NiCl2·6H2O and 0.75mmol FeCl3。
Ni prepared by the embodiment of the present invention 30.25Fe0.75Mo poly-metal deoxide nano material carries out transmission electron microscope detection, Result is examined as shown in fig. 6, it will be appreciated from fig. 6 that Ni0.25Fe0.75Mo poly-metal deoxide appearance of nano material is nano particle.
Embodiment 4
Embodiment 1 is repeated, difference is: adjusting the ratio of Ni:Fe in cationic solution, be added in 1ml deionized water 1mmol NiCl2·6H2O。
Embodiment 5
Embodiment 1 is repeated, difference is: adjusting the ratio of Ni:Fe in cationic solution, be added in 1ml deionized water 1mmol FeCl3。
Embodiment 6
It repeats to implement 2, difference is: adjustment cation type, by 0.75mmol NiCl2·6H2O is changed to equally respectively MM amount CoCl2·6H2O、MnCl2·4H2O、CuCl2·2H2O。
Co prepared by the embodiment of the present invention 60.75Fe0.25Mo、Mn0.75Fe0.25Mo and Cu0.75Co0.25Mo multi-metal oxygen Object nano material carries out transmission electron microscope detection, and inspection result is as Figure 7-9, by Fig. 7-9 it is found that Co0.75Fe0.25Mo、 Mn0.75Fe0.25Mo and Cu0.75Co0.25Mo poly-metal deoxide nano material successfully synthesizes, and pattern is nano particle.
Embodiment 7
It repeats to implement 2, difference is: adjustment anion species, by 1mmol Na2MoO4·2H2O is changed to same mmoles The Na of your amount2WO4·2H2O。
Ni prepared by the embodiment of the present invention 70.75Fe0.25W poly-metal deoxide nano material carries out transmission electron microscope detection, The results are shown in Figure 10 for inspection, as shown in Figure 10, Ni0.75Fe0.25W poly-metal deoxide nano material successfully synthesizes, and pattern is nanometer Particle.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (9)

1. a kind of preparation method of poly-metal deoxide nano material, comprising the following steps:
A the first source metal is mixed with water), obtains uniform first solution；
Second source metal is mixed with water, obtains uniform second solution；
The concentration of first solution is 1~3mol/L, and the concentration of second solution is 1~3mol/L；
B first solution is mixed with second solution), obtains homogeneous precipitation；
C) precipitating is freeze-dried, obtains poly-metal deoxide nano material；
First source metal is selected from one or more source metals soluble easily in water, and second source metal is selected from soluble easily in water One or more source metals.
2. preparation method according to claim 1, which is characterized in that the concentration of first solution is 1mol/L, described The concentration of second solution is 1mol/L.
3. preparation method according to claim 1, which is characterized in that first source metal is selected from NiCl2·2H2O、 FeCl3、CoCl2·6H2O、MnCl2·4H2O、CuCl2·2H2O、ZnCl2、VCl3And CrCl3One of or it is a variety of, described Two source metals are selected from Na2MoO4·2H2O、Na2WO4·2H2O、Na2CO3·1H2O and Na3PO4·12H2One of O etc. or more Kind.
4. preparation method according to claim 1 or 3, which is characterized in that first source metal is selected from NiCl2·2H2O And FeCl3, second source metal is selected from Na2MoO4·2H2O；Or first source metal is selected from CoCl2·6H2O and FeCl3, Second source metal is selected from Na2MoO4·2H2O；Or first source metal is selected from MnCl2And FeCl3, second source metal Selected from Na2MoO4·2H2O；Or first source metal be selected from CuCl2·2H2O and FeCl3, second source metal is selected from Na2MoO4· 2H2O；Or first source metal is selected from NiCl2·2H2O and FeCl3, second source metal is selected from Na2WO4·2H2O。
5. the preparation method according to claim 4, which is characterized in that first source metal is selected from NiCl2·2H2O and FeCl3When, the NiCl2·2H2O and FeCl3Molar ratio be (0.1~6): 1；First source metal is selected from CoCl2· 6H2O and FeCl3When, CoCl2·6H2O and FeCl3Molar ratio be (0.1~6): 1；First source metal is selected from MnCl2And FeCl3 When, the MnCl2And FeCl3Molar ratio be (0.1~6): 1；First source metal is selected from CuCl2·2H2O and FeCl3When, The CuCl2·2H2O and FeCl3Molar ratio is (0.1~6): 1.
6. preparation method according to claim 1, which is characterized in that during obtaining the first solution, the mixing is adopted It is carried out with the mode of ultrasonic agitation；During obtaining the second solution, the mixing is carried out by the way of ultrasonic agitation.
7. preparation method according to claim 6, which is characterized in that during obtaining the first solution, the ultrasound is stirred The temperature mixed is 20~40 DEG C, and the time of the ultrasonic agitation is 1~10min；During obtaining the second solution, the ultrasound The temperature of stirring is 20~40 DEG C, and the time of the ultrasonic agitation is 1~10min.
8. preparation method according to claim 1, which is characterized in that the freeze-drying first freezes in liquid nitrogen is freezing again It is lyophilized in dry machine；The time of the freezing is 10~30min, and the time of the freeze-drying is 1~4 day.
9. a kind of method for being electrolysed aquatic products oxygen, which is characterized in that poly-metal deoxide according to any one of claims 1 to 8 is received Rice material load on electrode be used as working electrode.
CN201910543219.9A 2019-06-21 2019-06-21 A kind of preparation method and applications of poly-metal deoxide nano material Pending CN110240189A (en)

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