CN109759099A - A kind of photochemical catalyst and preparation method thereof, application - Google Patents
A kind of photochemical catalyst and preparation method thereof, application Download PDFInfo
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- CN109759099A CN109759099A CN201910163056.1A CN201910163056A CN109759099A CN 109759099 A CN109759099 A CN 109759099A CN 201910163056 A CN201910163056 A CN 201910163056A CN 109759099 A CN109759099 A CN 109759099A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of photochemical catalyst and preparation method thereof, application, belong to field of functional materials.Preparation method includes: offer composite granule；Again by heat treatment composite granule, the parkerizing process of heterogeneous nucleation participation is carried out.Wherein, composite granule includes the dried object of maceration extract；Maceration extract includes the nickel and cobalt for existing in the form of ionic compound respectively and mixing in the solution with the powder with photocatalytic activity.Have many advantages, such as that raw material is inexpensive, simple process by the above production method, structure-controllable, and prepared photochemical catalyst has certain universality and very high application prospect and practical value.
Description
Technical field
This application involves field of functional materials, in particular to a kind of photochemical catalyst and preparation method thereof, application.
Background technique
Energy and environment problem is always that people pay close attention to a big emphasis.As new energy, solar energy is unique excellent with its
Gesture shows huge application prospect.In field of solar energy utilization, to be turned by the solar battery of photoelectric conversion and photochemistry
The Photocatalyzed Hydrogen Production changed is representative.
Catalysis material is that one kind can convert optical energy into electric energy or chemical energy and itself not changed partly leads
Body material.Catalysis material crosses the conduction band that forbidden band reaches material by absorbing luminous energy, excitation electronics.Conduction band electron has reduction
Property water can be restored to obtain hydrogen with the water molecules of adsorption, therefore photolysis water hydrogen can become most " dry
Only energy preparation method ".
For most photochemical catalysts, it is both needed to that co-catalyst is added during producing hydrogen.Currently, platinum (Pt) is because of tool
There is good set electron ability and is widely used as producing hydrogen co-catalyst without producing hydrogen overpotential.But due to Pt reserves it is low with
And it is expensive, the cost of photocatalysis Decomposition aquatic products hydrogen is greatly improved, therefore develop base metal base and produce hydrogen co-catalyst just
Aobvious is particularly important.
The information disclosed in the background technology section is intended only to deepen the understanding to the general background technology of the application, and
It is not construed as recognizing or implying in any form that the information constitutes the prior art known to those skilled in the art.
Summary of the invention
Based on the deficiencies of the prior art, this application provides a kind of photochemical catalyst and preparation method thereof, application, with part or
Fully improve, even solve the problems, such as noble metal platinum can only be used as photochemical catalyst.
The application is achieved in that
In a first aspect, the example of the application provides a kind of preparation method of photochemical catalyst.
Preparation method includes:
There is provided composite granule, wherein composite granule includes the dried object of maceration extract, and maceration extract includes respectively with ion combination
The nickel and cobalt that the form of object exists and mixes in the solution with the powder with photocatalytic activity；
Heat treatment composite granule simultaneously carries out parkerizing process, grows double-metal phosphide by way of heterogeneous nucleation and attached
In the surface of powder.
It is different from hydro-thermal method production photochemical catalyst, uses binary phosphide as catalyst aid in the embodiment of the present application, leads to
Cross the side for making binary phosphide be uniformly distributed and grow by heterogeneous nucleation on catalyst active component surface in liquid system
Formula adjusts the growth size of binary phosphide, and making it, sufficiently uniformly Dispersed precipitate is in catalyst active component surface, thus real
Now with the photochemical catalyst of desired catalytic effect.
With reference to first aspect, in some optional examples of the first possible embodiment of the first aspect of the application
In, the ionic compound of nickel and the ionic compound of cobalt are water soluble salt.
Optionally, water soluble salt is nitrate.
Optionally, maceration extract includes cobalt nitrate aqueous solution, nickel nitrate aqueous solution and the powder with photocatalytic activity.
Optionally, maceration extract is made by the following method:
By cobalt nitrate aqueous solution, nickel nitrate aqueous solution and powder with photocatalytic activity in a manner of vibrating dipping into
Row mixing；
Optionally, oscillation dip operation is carried out in eddy mixer.
Optionally, the time for vibrating dipping is 10~40 minutes.
Cobalt and nickel are provided and are used in the form of water soluble salt, so that preparation process can be in reaction condition
Mildly, the low technique of ingredient requirement requires lower implementation, so as to reduce the cost of manufacture and process complexity of photochemical catalyst, into
And the price of photochemical catalyst can also be reduced, it is conducive to large-scale use.
The possible embodiment of with reference to first aspect the first, in second of possible reality of the first aspect of the application
It applies in some optional examples of mode, in maceration extract, the molar ratio of nickel and cobalt is 1~4:2；
Optionally, the molar ratio of nickel and cobalt is 1~3:2；
Optionally, the molar ratio of nickel and cobalt is 2~3:2；
Optionally, the molar ratio of nickel and cobalt is 2~4:2.
By the molar ratio of control nickel, cobalt, to realize the increment for adjusting double-metal phosphide in photochemical catalyst.
With reference to first aspect or second of possible embodiment of first aspect, in the third of the first aspect of the application
In some optional examples of the possible embodiment of kind, the moles total number of nickel and cobalt and activity in the powder with photocatalytic activity
The molar ratio of ingredient is 1~4:200.
Optionally, the molar ratio of the moles total number and active constituent of nickel and cobalt is 1~3:200.
Optionally, the molar ratio of the moles total number and active constituent of nickel and cobalt is 2~3:200.
Optionally, the molar ratio of the moles total number and active constituent of nickel and cobalt is 2~4:200.
The double-metal phosphide (binary phosphide) that nickel and cobalt are formed partly or entirely substitutes platinum as co-catalyst, and
And regulate and control its relative amount between the active constituent with catalytic activity, it may be implemented to binary phosphide in active constituent
Load, distributing homogeneity and size adjusting, in favor of playing preferably synergistic effect between each component.
The third possible embodiment with reference to first aspect, in the 4th kind of possible reality of the first aspect of the application
It applies in some optional examples of mode, active constituent includes titanium dioxide and/or carbonitride.
Reasonably selecting active constituent in the powder with photocatalytic activity can make it more preferable with aforementioned double-metal phosphide
Ground cooperation cooperates with to obtain ideal catalytic effect, while can also control the cost of material of catalyst production.
With reference to first aspect, in some optional examples of the 5th kind of possible embodiment of the first aspect of the application
In, the dried object of maceration extract is obtained and by maceration extract freeze-day with constant temperature；
Optionally, the temperature of freeze-day with constant temperature maceration extract is 60~90 DEG C.
Optionally, the temperature of freeze-day with constant temperature maceration extract is 65~85 DEG C.
Optionally, the temperature of freeze-day with constant temperature maceration extract is 70~80 DEG C.
Optionally, the temperature of freeze-day with constant temperature maceration extract is 75~86 DEG C.
It is dry by heating since nickel and cobalt mix in solution system with active constituent in the powder with photocatalytic activity
Dry removal dispersing agent, so as to avoid it from being mutually disengaged so that nickel, cobalt can stably and securely be attached to active constituent, benefit
In the progress of subsequent parkerizing process.
With reference to first aspect, in some optional examples of the 6th kind of possible embodiment of the first aspect of the application
In, the method for being heat-treated composite granule includes the first heating stepses, the second heating stepses carried out after the first heating stepses；
Wherein, the first heating stepses include: that composite granule is heated the first preset time in the first temperature；
Wherein, the second heating stepses include: by composite granule and to provide the phosphorus of phosphorus source under second temperature, inert atmosphere
Change reagent and contact and heat the second preset time, second temperature is higher than the first temperature；
Optionally, the first temperature is 180~240 DEG C or 185~230 DEG C or 190~220 DEG C or 200~210 DEG C.
Optionally, second temperature is 280~340 DEG C or 290~330 DEG C or 300~310 DEG C or 305~320 DEG C.
By heating step by step, cobalt, nickel can be enable by activity and there is better reactivity, to be easier to
In in subsequent and phosphorus progress reaction bonded.
The 6th kind of possible embodiment with reference to first aspect, in the 7th kind of possible reality of the first aspect of the application
It applies in some optional examples of mode, inert atmosphere is provided by one of helium, nitrogen, argon gas or a variety of inert gases.
Optionally, phosphorization reagent is contacted as carrier by conveying with composite granule using inert gas.
Optionally, phosphorization reagent includes sodium dihydric hypophosphite.
Optionally, the mass ratio of composite granule and sodium dihydric hypophosphite is 1~4:20.
Or, the mass ratio of composite granule and sodium dihydric hypophosphite is 1~3:20.
Or, the mass ratio of composite granule and sodium dihydric hypophosphite is 2~3:20.
Or, the mass ratio of composite granule and sodium dihydric hypophosphite is 2~4:20.
In inert environments, unexpected oxidation reaction can occur to avoid nickel and cobalt, and to complete phosphatization with phosphorus reaction
Process.Meanwhile considering the selection of the process and the amount to finished product of reaction, reasonably adjust the proportion of nickel, cobalt and phosphorus.
In second aspect, the example of the application provides a kind of photochemical catalyst.
The preparation method of photochemical catalyst photochemical catalyst above-mentioned is prepared.
Photochemical catalyst includes phosphatization cobalt nickel (double-metal phosphide/binary phosphide) and the powder with photocatalytic activity
(as the aforementioned titanium dioxide, carbonitride), and phosphatization cobalt nickel in the form of granules disperse modification in the powder with photocatalytic activity
Active constituent in end.
The photochemical catalyst provided in example, as co-catalyst, is reducing the same of the cost of catalyst using base metal
When, the effect made with a simpler process is also achieved, and also improve the catalytic effect of catalyst to a certain extent.
In the third aspect, the example of the application provides the above-mentioned photochemical catalyst of one kind in photocatalysis Decomposition aquatic products hydrogen
Using.
During implementation above, the production method of photochemical catalyst provided by the embodiments of the present application is used in liquid system
Mixing has the active constituent of catalytic activity, co-catalyst component, then both makes to combine by dry, then by heat treatment and
Parkerizing process realizes and makes double-metal phosphide by way of heterogeneous nucleation, and ensure its uniformly, be stably adhered to before
The active ingredient stated.Thus obtained photochemical catalyst all has ideal performance in terms of cost of manufacture and catalytic performance,
And production method is also easy and easy to implement.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the transmission electron microscope photo (TEM figure) and elemental analysis figure (EDX figure) of the NCPCN-2 prepared in embodiment 3；
Fig. 2 is the x-ray photoelectron spectroscopy figure (XPS figure) of the NCPCN-2 prepared in embodiment 3；
Fig. 3 is the NCPCN-2 hydrogen-producing speed figure and stability test figure prepared in embodiment 3；
Fig. 4 is the catalyst hydrogen-producing speed figure in embodiment 3 and comparative example 1,2.
Specific embodiment
It is described in detail below in conjunction with embodiment of the embodiment to the application, but those skilled in the art will
Understand, the following example is merely to illustrate the application, and is not construed as limitation scope of the present application.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
A kind of photochemical catalyst below for the embodiment of the present application and preparation method thereof, using being specifically described:
Photochemical catalyst has in terms of field of solar energy utilization to be quite widely applied.Therefore, a kind of ideal light is found
Catalyst is the big important topic of the worker of related fields.
In practice, inventor's acquistion: the catalytic performance of catalyst can be made to be changed using platinum (Pt) as co-catalyst
It is kind.
However, as it is well known that platinum is a kind of noble metal.The cost that it is utilized is very high, so that being based at present
Under the considerations of use cost, it can not be used extensively and in large quantities.
In view of this, find it is a kind of substitute platinum material be it is necessary to and it is imperative.Metal is thought in inventor's research
Phosphide is a kind of co-catalyst with great potential, such as is imitated to the co-catalysis that the catalyst of photocatalysis aquatic products hydrogen has had
Fruit.Particularly, for some binary phosphides, especially double-metal phosphide, its co-catalysis effect is more obvious.Therefore, such as
Double-metal phosphide can be combined both to make to cooperate with catalyst and will be expected to realize better catalytic effect by fruit.Meanwhile
It is apparent that double-metal phosphide can be to avoid the use of noble metal, so as to replace partially or completely by selection appropriate
For the use of platinum.
Under study for action, inventor attempts using hydro-thermal method or directly grows double-metal phosphide in photocatalyst surface.
However, practice have shown that: the method is one in the process that catalysis material surface is grown there are unavoidable defect, i.e. phosphide
The process of a homogeneous nucleation, will lead to surface be unevenly distributed and phosphide reunite the problems such as.
The problem of based on finding in research, inventor propose a kind of new photochemical catalyst and preparation method thereof.The production side
Method is used as base metal co-catalyst using phosphatization cobalt nickel (CoNiP), and replaces Pt class precious metal catalytic agent with it.
Wherein, phosphatization cobalt nickel is grown by way of heterogeneous nucleation and is incorporated in catalyst.And during life, due to that
Around here steric hindrance effect, can effectively regulate and control the growth size of phosphide, make CoNiP particle photocatalyst surface more
Deposition is dissipated, there is good monodispersity, realizes efficient monatomic catalysis.
As a result, in the application example, a kind of photochemical catalyst is suggested, and is that a kind of novel CoNiP particle dispersion is repaired
The photochemical catalyst of decorations.
The photochemical catalyst includes phosphatization cobalt nickel and the powder with photocatalytic activity, and phosphatization cobalt nickel is in the form of granules more
Dissipate active constituent of the modification in the powder with photocatalytic activity.
It should be noted that above indicating phosphatization cobalt nickel CoNiP, be not intended to limit cobalt in phosphatization cobalt nickel chemical formula,
Nickel, phosphorus are combined in the way of 1:1:1.Its specific chemistry is to constitute to have different appropriate ratios generally according to its raw material
Example.In some examples, the chemical formula of phosphatization cobalt nickel can be referred to by following formula: CoxNi2-xPy, such as Co0.08Ni1.92P2.00。
A kind of such photochemical catalyst can be used for through photocatalysis Decomposition aquatic products hydrogen.Certainly, which answers
It is not limited to photochemical catalyzing with field, can according to need and be used for various catalytic applications.
In example, preparation method includes:
Step S101: composite granule is provided.
Wherein, composite granule includes the dried object of maceration extract, and maceration extract includes existing in the form of ionic compound respectively
And the nickel and cobalt mixed in the solution with the powder with photocatalytic activity.
In other words, composite granule, which can be, is produced in advance and directly makes when making the photochemical catalyst mentioned in example
With.Alternatively, composite granule is also in situ configuration during making the photochemical catalyst mentioned in example and to use.
As previously mentioned, be in preparation method by contacting catalyst active component with cobalt, nickel,
Until mixing, combination.In example, liquid system be can be by nickel, cobalt offer.In such an example, nickel and cobalt can be by
Solution form is provided and is used；Alternatively, one such provided using solution form and be used to provide liquid system.Or
Person, liquid system can be to be provided by absolute version.
In order to have nickel and cobalt in the form of an ion, nickel and cobalt can be selected as nickel ionic compound and cobalt from
Sub- compound.Correspondingly, liquid system can be the liquid system that can make nickel and cobalt ions.That is nickel, cobalt can be with liquid
The compatible form appropriate of body is provided.For example, the ionic compound of nickel and the ionic compound of cobalt are water solubility in example
Salt.
It corresponds, in alternative example, water soluble salt is nitrate.Wherein, cobalt is mentioned with cobalt nitrate aqueous solution
For；Nickel is provided with nickel nitrate aqueous solution.Therefore, maceration extract includes cobalt nitrate aqueous solution, nickel nitrate aqueous solution and urges with light
Change active powder.Based on this, as an example, maceration extract is made by the following method: cobalt nitrate aqueous solution, nickel nitrate is water-soluble
Liquid and powder with photocatalytic activity are mixed in a manner of vibrating dipping.
Oscillation dip operation, which for example can be, to be carried out in eddy mixer.Certainly, the application is also not excluded for using it
He carries out oscillation dip operation at equipment.As a kind of optional example, the time for vibrating dipping is 10~40 minutes.Oscillation dipping
Time can be the amount according to nickel, cobalt and the powder with catalytic activity usually come selection.It is clear that ground, oscillation leaching
The time of stain is unsuitable too long, is also not appropriate for too short.Vibrate dipping time it is too long will increase fabrication cycle, it is too short, be unfavorable for
Adequately mixing.
In addition, can be controlled the dosage of nickel and cobalt to regulate and control the amount of subsequent phosphatization cobalt nickel.For example, impregnating
In liquid, the molar ratio of nickel and cobalt is 1~4:2.Optionally, the molar ratio of nickel and cobalt is 1~3:2.Optionally, mole of nickel and cobalt
Than for 2~3:2.Optionally, the molar ratio of nickel and cobalt is 2~4:2.
Further, with aforementioned similar reason, the dosage of the powder with photocatalytic activity can be controlled.Example
In, it is controlled by the relative usage number to nickel and cobalt and the powder with photocatalytic activity.For example, mole of nickel and cobalt
Total amount and the molar ratio of active constituent in the powder with photocatalytic activity are 1-4:200.Optionally, the moles total number of nickel and cobalt
Molar ratio with active constituent is 1~3:200.Optionally, the molar ratio of the moles total number and active constituent of nickel and cobalt is 2~3:
200.Optionally, the molar ratio of the moles total number and active constituent of nickel and cobalt is 2~4:200.Wherein, it is mentioned with water-soluble nitrate
Cobalt and the nickel (Co (NO of confession3)2Solution and Ni (NO3)2Solution) the total amount of addition can be as 0.5~1.5mL.
Based on co-catalyst phosphatization cobalt nickel selected above, the powder with photocatalytic activity can have multiple choices.
It is apparent that the powder with photocatalytic activity cannot mutually repel with co-catalyst phosphatization cobalt nickel.I.e. the two, which is mutually promoted, improves end
The catalytic performance of product is ideal and beneficial selection factor.It, can also be according to tool but except the compatibility for considering the two
It body usage scenario and is considered using nucleation.In example, the active constituent in the powder with photocatalytic activity includes titanium dioxide
And/or carbonitride.In other words, the powder of photocatalytic activity can be titania powder, such as titanic oxide nano powder.One
In a little examples, the titanium dioxide of Detitanium-ore-type has better catalytic activity.
After the maceration extract for obtaining said components, by way of removing liquid with solid powder substance is provided and
It obtains.That is, the dried object of aforementioned impregnation liquid is by obtaining the liquid removal in maceration extract.In example, pass through freeze-day with constant temperature
It is removed liquid.As a kind of nonessential limitation, the temperature of freeze-day with constant temperature maceration extract is 60~90 DEG C.Optionally, constant temperature
The temperature of dry maceration extract is 65~85 DEG C.Optionally, the temperature of freeze-day with constant temperature maceration extract is 70~80 DEG C.Optionally, constant temperature
The temperature of dry maceration extract is 75~86 DEG C.The temperature of freeze-day with constant temperature can according to the liquid component in above-mentioned liquid system come
Selection is not limitation with temperature above-mentioned.
Dry mode can be direct heat source heating, such as with the resistance wire of energization heat production.Alternatively, passing through microwave heating
Etc..Specific heating method can be selected according to heating equipment.Although aforementioned propose is added by constant temperature at a certain temperature
The mode of heat is dried, and still, this is not intended to restriction must heated at constant temperature.In other words, dry maceration extract is also possible to
Certain temperature range carries out alternating temperature, such as gradient increased temperature.
Step S102: heat treatment composite granule simultaneously carries out parkerizing process, makes shape of the double-metal phosphide by heterogeneous nucleation
Formula grows and is attached to the surface of powder.
Wherein, parkerizing process is the process of nickel, cobalt in conjunction with phosphorus reaction.The process is under conditions of thermal energy provides energy
Occur and carries out.
As a kind of alternative scheme, in example, it is heat-treated composite granule and the method that carries out parkerizing process includes the
One heating stepses, the second heating stepses carried out after the first heating stepses.
Wherein, the first heating stepses include: that composite granule is heated the first preset time in the first temperature.First temperature can
To be selected as 180~240 DEG C or 185~230 DEG C or 190~220 DEG C or 200~210 DEG C.
Wherein, the second heating stepses include: by composite granule and to provide the phosphorus of phosphorus source under second temperature, inert atmosphere
Change reagent to contact and heat the second preset time.Second temperature can be selected as 280~340 DEG C or 290~330 DEG C, or
300~310 DEG C or 305~320 DEG C.
Since the presence of, nickel, the oxidised form of cobalt can generate certain influence, therefore, example to the activity of photochemical catalyst
In, it is expected that nickel, cobalt are reacted in the environment that non-oxygen participates in phosphorus.A kind of such environment, it is advantageously ensured that nickel, cobalt with
The abundant association reaction of phosphorus three, while reducing the waste of raw material (nickel oxide, cobalt oxide are usually the reaction of unexpected generation
By-product).In example, parkerizing process carries out under an inert atmosphere；Alternatively, can also be in the environment of non-oxygen, such as vacuum.Inertia
Atmosphere can be by one of helium, nitrogen, argon gas or the offer of a variety of inert gases.
In addition, since nickel, cobalt are provided in the form of composite granule.Therefore, it is reacted with it for the ease of phosphorus, it is usually uncommon
Phosphorus is hoped also to provide in the form of particulate matter.Correspondingly, it can be conveyed by carrier gas with the phosphorus that particulate matter provides, in order to composite powder
Body contact.The phosphorus source therein for providing phosphorus can be used with phosphorization reagent.I.e. composite granule be reacted with phosphorization reagent into
Row parkerizing process.For example, phosphorization reagent is made using inert gas (can also other non-oxygen or non-oxidizing gas)
It is contacted by conveying with composite granule for carrier.
Wherein, phosphorization reagent can be sodium dihydric hypophosphite (NaH2PO2).Based on control phosphorization reagent and composite granule
The mass ratio of the needs of amount ratio, composite granule and sodium dihydric hypophosphite can be 1~4:20；Or, composite granule and hypophosphorous acid
The mass ratio of sodium dihydrogen is 1~3:20；Or, the mass ratio of composite granule and sodium dihydric hypophosphite is 2~3:20；Or, composite powder
The mass ratio of body and sodium dihydric hypophosphite is 2~4:20.
According to above production method, in example, the source Ni and the source Co are formulated into solution, are added dropwise in photochemical catalyst thereafter
In powder, then pass through oscillation dipping.During oscillation, Ni and Co ion can form uniform point in photocatalyst surface
Cloth, dry nucleation, while effectively control component relative amount.
With the heat treatment and parkerizing process in later period, the growth of phosphide is carried out in the form of heterogeneous nucleation.Steric hindrance
Effect can make CoNiP particle in photochemical catalyst (such as nanometer titanium dioxide with Effective Regulation phosphide (double-metal phosphide) size
Titanium) surface dispersion deposition, so that the photochemical catalyst referred to has good monodispersity, the efficient monatomic catalysis of realization.
With reference to embodiments to photochemical catalyst of the application and preparation method thereof, using being described in further detail.
Embodiment 1
Firstly, Co (the NO that concentration is 0.5mol L-1 is respectively configured3)2Ni (the NO of solution and 1mol L-13)2Solution takes
TiO2Photocatalyst powder 80mg is put into centrifuge tube, takes 0.5mL Co (NO respectively3)2Solution and 0.75mL Ni (NO3)2Solution
It is added in centrifuge tube, is mixed 30 minutes on eddy mixer, freeze-day with constant temperature is then carried out at 80 DEG C.By the mixing after drying
First under an argon atmosphere 200 DEG C of powder carry out heat treatment 2h, and 1g NaH is taken after heat treatment2PO2As phosphorus source, nitrogen is as load
Gas, 300 DEG C of progress phosphorating treatment 2h modify photochemical catalyst after cooling up to New Co NiP particle dispersion, are denoted as NCPTO-1, can
It is used for the experiment of photocatalysis Decomposition aquatic products hydrogen.
Embodiment 2
Co (the NO that concentration is 1.33mol L-1 is respectively configured first3)2Ni (the NO of solution and 2.66mol L-13)2It is molten
Liquid takes C3N4Photocatalyst powder 92mg is put into centrifuge tube, takes 0.25mL Co (NO respectively3)2Solution and 0.25mL Ni
(NO3)2Solution is added in centrifuge tube, mixes 10 minutes on eddy mixer, freeze-day with constant temperature is then carried out at 60 DEG C.It will do
First under an argon atmosphere 180 DEG C of mixed-powder after dry carry out heat treatment 1h, and 0.5g NaH is taken after heat treatment2PO2As phosphorus
Source, nitrogen modify photochemical catalyst after cooling as carrier gas, 280 DEG C of progress phosphorating treatment 1h up to New Co NiP particle dispersion,
It is denoted as NCPCN-1, the experiment of photocatalysis Decomposition aquatic products hydrogen can be used for.
Embodiment 3
Co (the NO that concentration is 1mol L-1 is respectively configured first3)2Ni (the NO of solution and 1mol L-13)2Solution takes C3N4
Photocatalyst powder 92mg is put into centrifuge tube, takes 0.5mL Co (NO respectively3)2Solution and 0.5mL Ni (NO3)2Solution is added
In centrifuge tube, is mixed 40 minutes on eddy mixer, freeze-day with constant temperature is then carried out at 80 DEG C.By the mixed-powder after drying
First under an argon atmosphere 220 DEG C carry out heat treatment 3h, and 1.2g NaH is taken after heat treatment2PO2As phosphorus source, nitrogen as carrier gas,
300 DEG C of progress phosphorating treatment 2h modify photochemical catalyst after cooling down up to New Co NiP particle dispersion, are denoted as NCPCN-2, can incite somebody to action
It is used for the experiment of photocatalysis Decomposition aquatic products hydrogen.
Embodiment 4
Co (the NO that concentration is 0.88mol L-1 is respectively configured first3)2Ni (the NO of solution and 0.44mol L-13)2It is molten
Liquid takes C3N4Photocatalyst powder 92mg is put into centrifuge tube, takes 0.75mL Co (NO respectively3)2Solution and 0.75mL Ni
(NO3)2Solution is added in centrifuge tube, mixes 40 minutes on eddy mixer, freeze-day with constant temperature is then carried out at 90 DEG C.It will do
First under an argon atmosphere 240 DEG C of mixed-powder after dry carry out heat treatment 4h, and 1.8g NaH is taken after heat treatment2PO2As phosphorus
Source, nitrogen modify photochemical catalyst after cooling as carrier gas, 340 DEG C of progress phosphorating treatment 4h up to New Co NiP particle dispersion,
It is denoted as NCPCN-3, the experiment of photocatalysis Decomposition aquatic products hydrogen can be used for.
The NCPCN-2 prepared in embodiment 3 is detected.Testing result is as shown in Figure 1 to Figure 3.
As seen from the figure, the TEM photo in Fig. 1 shows the Dispersed precipitate of particle, and soilless sticking phenomenon occurs, and passes through element point
Analysis figure can be seen that tri- kinds of elements of Co, Ni and P exist, to confirm CoNiP clustered particles depositing in photocatalyst surface
?.
The electron binding energy of different elements corresponds to combination energy of the atom in CoNiP in XPS map in Fig. 2, prints again
The presence of CoNiP particle is demonstrate,proved.
Fig. 3 produces hydrogen experiment and uses the xenon lamp of 300W as light source, and uses ultraviolet filter, by 50mg composite catalyst powder
End is added in 90mL deionized water, and the triethanolamine of reaction solution addition 10% is as sacrifice agent.It can be seen that phase from hydrogen figure is produced
Co-catalyst can be played than the CoNiP in the hydrogen for being based only on the trace that catalyst electrolysis water can be generated, the application
Effect make material have higher H2-producing capacity.Stability test can illustrate that CoNiP particle has in photocatalyst surface
Excellent stability makes material have excellent stable H2-producing capacity.
Comparative example 1
Configuration concentration is 1molL first-1Co (NO3)2Solution takes C3N4Photocatalyst powder 92mg is put into centrifuge tube
In, take 1mL Co (NO3)2Solution is added in centrifuge tube, mixes 40 minutes, then carries out at 80 DEG C permanent on eddy mixer
Temperature is dry.Mixed-powder after drying is subjected to heat treatment 3h for first under an argon atmosphere 220 DEG C, takes 1.2g after heat treatment
NaH2PO2As phosphorus source, nitrogen is urged as carrier gas, 300 DEG C of progress phosphorating treatment 2h after cooling up to CoP particle dispersion modification light
Agent is denoted as CPCN, can be used for the experiment of photocatalysis Decomposition aquatic products hydrogen.
Comparative example 2
First configuration concentration be 1mol L-1 Ni (NO3)2Solution takes C3N4Photocatalyst powder 92mg is put into centrifuge tube
In, take 1mL Ni (NO3)2Solution is added in centrifuge tube, mixes 40 minutes, then carries out at 80 DEG C permanent on eddy mixer
Temperature is dry.Mixed-powder after drying is subjected to heat treatment 3h for first under an argon atmosphere 220 DEG C, takes 1.2g after heat treatment
NaH2PO2As phosphorus source, nitrogen is urged as carrier gas, 300 DEG C of progress phosphorating treatment 2h after cooling up to NiP particle dispersion modification light
Agent is denoted as NPCN, can be used for the experiment of photocatalysis Decomposition aquatic products hydrogen.
At identical conditions, in the same way using the catalyst in comparative example 1,2 and embodiment 3, it uses
The xenon lamp of 300W uses ultraviolet filter as light source, 50mg composite catalyst powder is added in 90mL deionized water, instead
It answers the triethanolamine of solution addition 10% as sacrifice agent, carries out the experiment of photocatalysis Decomposition aquatic products hydrogen, catalytic structure such as Fig. 4 institute
Show.
Although illustrate and describing the application with specific embodiment, it will be appreciated that without departing substantially from the application's
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications within the scope of the application.
Claims (10)
1. a kind of preparation method of photochemical catalyst, which is characterized in that the preparation method includes:
Composite granule is provided, the composite granule includes the dried object of maceration extract, wherein the maceration extract includes respectively with ion
The nickel and cobalt that the form of compound exists and mixes in the solution with the powder with photocatalytic activity；
It is heat-treated the composite granule and carries out parkerizing process, grow double-metal phosphide by way of heterogeneous nucleation and attached
In the surface of the powder.
2. the preparation method of photochemical catalyst according to claim 1, which is characterized in that the ionic compound of nickel and cobalt from
Sub- compound is water soluble salt；
Preferably, the water soluble salt is nitrate；
Preferably, the maceration extract includes cobalt nitrate aqueous solution, nickel nitrate aqueous solution and the powder with photocatalytic activity
End；
Preferably, the maceration extract is made by the following method:
By cobalt nitrate aqueous solution, nickel nitrate aqueous solution and the powder with photocatalytic activity in a manner of vibrating dipping into
Row mixing；
It is highly preferred that the oscillation dip operation is carried out in eddy mixer；
It is further preferred that the time of the oscillation dipping is 10~40 minutes.
3. the preparation method of photochemical catalyst according to claim 2, which is characterized in that in the maceration extract, nickel and cobalt
Molar ratio be 1~4:2；
Preferably, the molar ratio of nickel and cobalt is 1~3:2；
It is highly preferred that the molar ratio of nickel and cobalt is 2~3:2；
It is further preferred that the molar ratio of nickel and cobalt is 2~4:2.
4. the preparation method of photochemical catalyst according to claim 1 or 3, which is characterized in that the moles total number of nickel and cobalt with
The molar ratio of active constituent is 1~4:200 in the powder with photocatalytic activity；
Preferably, the moles total number of nickel and cobalt and the molar ratio of the active constituent are 1~3:200；
It is highly preferred that the moles total number of nickel and cobalt and the molar ratio of the active constituent are 2~3:200；
It is further preferred that the moles total number of nickel and cobalt and the molar ratio of the active constituent are 2~4:200.
5. the preparation method of photochemical catalyst according to claim 4, which is characterized in that the active constituent includes titanium dioxide
Titanium and/or carbonitride.
6. the preparation method of photochemical catalyst according to claim 1, which is characterized in that the dried object of the maceration extract is logical
It crosses the maceration extract freeze-day with constant temperature and obtains；
Preferably, the temperature of maceration extract described in freeze-day with constant temperature is 60~90 DEG C；
It is highly preferred that the temperature of maceration extract described in freeze-day with constant temperature is 65~85 DEG C；
It is further preferred that the temperature of maceration extract described in freeze-day with constant temperature is 70~80 DEG C；
It is further preferred that the temperature of maceration extract described in freeze-day with constant temperature is 75~86 DEG C.
7. the preparation method of photochemical catalyst according to claim 1, which is characterized in that be heat-treated the composite granule and go forward side by side
The second heating stepses that the method for row parkerizing process includes the first heating stepses, is carried out after first heating stepses；
Wherein, the first heating stepses include: that the composite granule is heated the first preset time in the first temperature；
Wherein, the second heating stepses include: by the composite granule and to provide the phosphorus of phosphorus source under second temperature, inert atmosphere
Change reagent and contact and heat the second preset time, the second temperature is higher than first temperature；
Preferably, first temperature is 180~240 DEG C or 185~230 DEG C or 190~220 DEG C or 200~210 DEG C；
It is highly preferred that the second temperature is 280~340 DEG C or 290~330 DEG C or 300~310 DEG C or 305~320 DEG C.
8. the preparation method of photochemical catalyst according to claim 7, which is characterized in that the inert atmosphere be by helium,
One of nitrogen, argon gas or a variety of inert gases provide；
Preferably, the phosphorization reagent is contacted as carrier by conveying with the composite granule using inert gas；
It is highly preferred that the phosphorization reagent includes sodium dihydric hypophosphite；
It is further preferred that the mass ratio of the composite granule and sodium dihydric hypophosphite is 1~4:20；
Or, the mass ratio of the composite granule and sodium dihydric hypophosphite is 1~3:20；
Or, the mass ratio of the composite granule and sodium dihydric hypophosphite is 2~3:20；
Or, the mass ratio of the composite granule and sodium dihydric hypophosphite is 2~4:20.
9. a kind of photochemical catalyst, which is characterized in that the photochemical catalyst is according to as described in any one of claim 1~8
The preparation method of photochemical catalyst is prepared, and the photochemical catalyst includes phosphatization cobalt nickel and the powder with photocatalytic activity, and
The active constituent in the powder with photocatalytic activity is modified in disperse to the phosphatization cobalt nickel in the form of granules.
10. a kind of application of photochemical catalyst as claimed in claim 9 in photocatalysis Decomposition aquatic products hydrogen.
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| CN113856711A (en) * | 2020-06-30 | 2021-12-31 | 湖南师范大学 | Design synthesis and electrolytic water hydrogen evolution research of high-efficiency nickel-cobalt phosphide heterojunction catalyst |
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