CN107597110A - A kind of template prepares TiO2The method of@Au core shell structures - Google Patents
A kind of template prepares TiO2The method of@Au core shell structures Download PDFInfo
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- CN107597110A CN107597110A CN201710985663.7A CN201710985663A CN107597110A CN 107597110 A CN107597110 A CN 107597110A CN 201710985663 A CN201710985663 A CN 201710985663A CN 107597110 A CN107597110 A CN 107597110A
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Abstract
The invention discloses a kind of template to prepare TiO2The method of@Au core shell structures, comprises the following steps：Template prepares PS@Au, and TiO is obtained in PS@Au one layer of unbodied titanium dioxide of outer cladding2@PS@Au, by TiO2@PS@Au calcine to obtain TiO2@Au.The use of PS is template, Au is coated on TiO2In, uniform and stable TiO can be obtained after firing2@Au core shell structures, there is good dispersiveness.This core shell structure is hollow structure, light weight, can there is larger surface area under equal quality.Nanogold can be combined with a variety of large biological molecules, and not influence its bioactivity, available for living things catalysis, bio-sensing aspect, the TiO that the present invention obtains2@Au can be used as a kind of enzyme reactor, compared to simple using titanium dioxide as carrier, nanogold can be avoided to be come off in subsequent reactions, can play the advantage of titanium dioxide semiconductor, improve overall catalytic efficiency.
Description
Technical field
The present invention relates to a kind of template to prepare TiO2The method of@Au core shell structures, synthesized by PS and homogeneous be used as template
Prepare a kind of TiO of size uniformity2@Au core shell structures.
Background technology
Titanium dioxide has been widely used for photocatalysis field as a kind of semi-conducting material at present, but because it has
Wider energy gap and the probability of electron-hole recombinations are higher, cause it not have very big carry on photocatalysis performance
It is high.Therefore, doped precious metal and raising high-energy surface, which prepare ratio, turns into more popular raising optically catalytic TiO 2 performance
Method.Gold is entrained in inside titanium dioxide, one, which can improve it, absorbs the region of ultraviolet light, and two can make its electronics empty
Cave is efficiently separated；And improve high-energy surface ratio mainly can make its produced when receiving illumination more electronics and
Hole puies forward high performance purpose so as to reach.Therefore the method that we select to prepare TiO2@Au core shell structures carrys out doped precious metal.
Au has good suction-operated to biology, can be used for living things catalysis, as a kind of enzyme reactor, the titanium dioxide of Au outsides cladding
Titanium can play a protective role.
TiO2@Au belong to inorganic-inorganic core shell structure.Inorganic-inorganic core shell structure mainly has two kinds of preparation methods：Seed
Sedimentation and hydro-thermal method.The center of seed deposition method is the inorganic nuclear material of embedding inside shell, can be selected to the pre- place of nuclear material
Reason does not process, and is dissolved in the solution containing shell material, precipitates shell material using certain method.And solution
It is middle the physical actions such as stirring, absorption, surface-active, lattice defect to be present, precipitation is deposited on core surface, grow, most
Whole shell material growth globulate completes the embedding to nuclear material.The preparation of core-shell nano material, simple, side are carried out using sedimentation
Just, cost is low, but also has significant deficiency.If using the method without strict theoretical foundation or formation mechenism, such as bonding action,
Cohesion, electrostatic interaction etc., can prepare that cladding is complete, the preferable core shell nanoparticles of pattern can not be affirmed.Therefore,
This method is simultaneously immature.Hydro-thermal method prepares the mechanism of inorganic nanoparticles, is typically considered to high temperature, height in enclosed high pressure kettle
In pressure ring border, using water as reaction medium, dissolve usual indissoluble or insoluble predecessor, so that its reaction and crystallization.
But hydro-thermal method length reaction time, course of reaction carry out in the system of closing, course of reaction can not be observed directly.This reality
Test and use bath oiling, improve container heat transfer performance, be heated evenly vessel in heating material, and can observe at any time and
Sampling.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of high treating effect
Template prepares TiO2The method of@Au core shell structures, the TiO with core shell structure can be synthesized using the present invention2@Au are different
The use of polystyrene is template using hydro-thermal method in the preparation method of traditional titanium dioxide composite noble metal, polyvinyl pyrrole
Alkanone can synthesize TiO as bridging agent by the relative amount for adjusting each reactant in reaction2Can after@PS@Au, burning-off PS
Obtain the TiO with core shell structure2@Au.The TiO prepared2@Au are in the photocatalysis performance field of titanium dioxide composite noble metal
Play an important role, the sample gone out compared to general self assembly, TiO prepared by the present invention2@Au size uniformities, its single dispersing
Property is also fine.
In order to solve the above-mentioned technical problem, the present invention provides a kind of template and prepares TiO2The method of@Au core shell structures, its
It is characterised by, comprises the following steps：Template prepares PS@Au, is obtained in PS@Au one layer of unbodied titanium dioxide of outer cladding
TiO2@PS@Au, by TiO2@PS@Au calcine to obtain TiO2@Au。
As the preferred of above-mentioned technical proposal, template provided by the invention prepares TiO2The method of@Au core shell structures is entered
One step includes the part or all of of following technical characteristic：
As the improvement of above-mentioned technical proposal, the template preparation PS@Au steps are as follows, and water and alcohol are pressed into 1:2-1：
4 volume ratio mixing, obtains solution A, potassium sulfate and SSS is added in solution A, the potassium sulfate, styrene sulphur
The ratio of sour sodium and solution A is 0.5g-2g：0.06g-1.50g：100ml-120ml, stir to obtain at 60-80 DEG C
Potassium peroxydisulfate-SSS mixed solution, is designated as solution B；Styrene and divinylbenzene, stirring are added in solution B
Add aurosol after 2-4 minutes, the solution B, styrene, the ratio of divinylbenzene and aurosol are 100ml-120ml：
0.99-2ml：0.01-0.05ml：20-40ml, the stirring reaction 4-6h at 60-80 DEG C, obtain purple has Tyndall effect
PS@Au beads, obtain sample A
It is described to obtain TiO in one layer of unbodied titanium dioxide of sample A outer claddings as the improvement of above-mentioned technical proposal2@
The step of PS@Au, is as follows, will be dried after sample A centrifuge washings, pulverizes, be dispersed in 90%-99% alcohol, obtain dense
The PS@Au bead alcoholic solutions for 0.01-0.03g/ml are spent, are designated as solution C；Polyvinylpyrrolidone is dispersed in water and ethanol
Mixed solution in, be designated as solution D, solution C added in solution D, obtain solution E, allow solution E that 1-2h is stirred at room temperature,
Isopropyl titanate stirring 45-60min is added, obtains TiO2@PS@Au spherical structure；The polyvinylpyrrolidone, water,
The ratio of ethanol, solution C and isopropyl titanate is 0.20g-0.30g：0.5-2ml：30-35ml：5-10mL：0.3-0.7mL.
It is described by TiO as the improvement of above-mentioned technical proposal2@PS@Au calcine to obtain TiO2The step of@Au, is as follows, will
TiO2@PS@Au calcine 4-6h under the conditions of 400-500 DEG C, obtain the TiO of core shell structure2@Au。
As the improvement of above-mentioned technical proposal, the PS@Au are a kind of regular shapes, the core shell structure of size uniformity, its
Average grain diameter is 300-350nm.
As the improvement of above-mentioned technical proposal, all vessel needed to use are both needed to be soaked and cleaned with chloroazotic acid, so with
To consumptive material be both needed to clean up.
As the improvement of above-mentioned technical proposal, the aurosol is by HAuCl that ultra-pure water and mass fraction are 1%4It is mixed
Merge stirring 1-2min, add citric acid three sodium solution afterwards, NaBH is added after being stirred for 1-2min4With the mixing of trisodium citrate
Liquid, stir the aurosol that the claret solution obtained after 5-8min is 3-8nm gold nano grain；The ultra-pure water, quality
Fraction is 1% HAuCl4, citric acid three sodium solution, NaBH4Volume ratio with the mixed liquor of trisodium citrate is 90：1：2：2-
100：1：2：2, the citric acid three sodium solution is 0.224g：20ml trisodium citrate and the mixed liquor of water.
Template of the present invention prepares TiO2The preparation method of@Au core shell structures, by using NaBH4For reducing agent
5nm or so Au nano particles (aurosol) are made；By using potassium peroxydisulfate it is initiator under the conditions of oil bath, is different from biography
System method is not added with the condition of stabilizer, and it is stabilizer that the present invention, which adds divinylbenzene and SSS, can prevent from receiving
Rice gold grain is assembled during the course of the reaction, gold is entered in PS early growth periods, and the good PS@Au structures of monodispersity are made；
It is dispersed in after obtained PS@Au are centrifuged inside alcohol, then using polyvinylpyrrolidone as bridging agent, isopropyl titanate is titanium source
TiO is made2@PS@Au；450 degree of lower calcination obtain TiO2@Au。
Compared with prior art, technical scheme has the advantages that：The synthesis side of traditional PS templates
Method is one-step method, then carries gold using PS as carrier, and the particle combination effect so obtained is unsatisfactory, with reference to loosely, molten
Coming off for gold easily occurs in liquid.Using the obtained PS Au of the present invention, nanogold particle is coated on to the inside of PS templates, can be with
Coming off for gold is effectively prevented from, improves the stability of gold nano grain.And in this building-up process, PS Au are one-step synthesis
, it is necessary to strictly control the time of reaction, the overlong time of reaction, PS grows up to complete bead then can not be by nanogold bag
Enter；Reaction time is too short, then golden scattered inequality, and gold can not be made to be wrapped by completely.This patent is suitable by testing regulation
Reaction time, the PS@Au size uniforms obtained by this method, and it is simple to operate, can quickly it obtain.Pass through in this patent
The content for regulating and controlling titanium source obtains a kind of more uniform TiO of cladding ratio2@PS@Au structures.
The use of PS is template, Au is coated on TiO2In, uniform and stable TiO can be obtained after firing2@Au nucleocapsid knots
Structure, there is good dispersiveness.This core shell structure is hollow structure, light weight, can there is larger surface under equal quality
Product.Nanogold can be combined with a variety of large biological molecules, and not influence its bioactivity, available for living things catalysis, bio-sensing side
Face, the TiO that the present invention obtains2@Au can be used as a kind of enzyme reactor, can be with compared to simple using titanium dioxide as carrier
Avoid nanogold from being come off in subsequent reactions, the advantage of titanium dioxide semiconductor can be played, improve overall catalytic efficiency.
PS technology of preparing is highly stable at present, but is directly still deposited Au particles coats inside PS with one-step method
In certain difficulty.Compared with existing PS carries golden method, gold is coated on inside titanium dioxide, gold can be avoided follow-up anti-
Coming off in answering, makes it more stably react.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the present invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the accompanying drawing of embodiment will be simply situated between below
Continue.
The SEM figures that Fig. 1 is sample P S@Au prepared by embodiment 1；
Fig. 2 is sample TiO prepared by embodiment 12@PS@Au1# SEM figures；
Fig. 3 is sample TiO prepared by embodiment 22@PS@Au2# SEM figures；
Fig. 4 is sample TiO prepared by embodiment 32@PS@Au3# SEM figures；
Fig. 5 is sample TiO prepared by embodiment 12@Au1# SEM figures；
Fig. 6 is sample TiO prepared by embodiment 22@Au2# SEM figures；
Fig. 7 is sample TiO prepared by embodiment 32@Au3# SEM figures.
Embodiment
The following detailed description of the present invention embodiment, its as part of this specification, by embodiment come
Illustrate the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Preparation：All vessel needed to use are both needed to be soaked and cleaned with chloroazotic acid, so the consumptive material used is both needed to clearly
Wash clean.
The preparation of aurosol：
90ml ultra-pure waters are taken, adds in flask and stirs, add the HAuCl that 1ml mass fractions are 1%4(gold chloride) simultaneously
Allow it to stir 1min, add 2ml citric acid three sodium solutions after 1min, 1mlNaBH is added after being stirred for 1min4With 1ml citric acids
The mixed liquor of trisodium, stir the gold nano grain (NaBH that the claret solution obtained after 5min is 5nm or so4Solution is prepared
Method：0.025g NaBH4It is dissolved in 20ml water and obtains the NaBH that concentration is 1.25mg/ml4Solution；Citric acid three sodium solution preparation side
Method：0.224g trisodium citrates are dissolved in 20ml water)
Embodiment 1：
1.PS@Au preparation method, is comprised the steps of：
(1) 0.5g potassium peroxydisulfates and 0.06g SSSs are dissolved in 45ml water and 165ml alcohol, are placed on oil bath
70 degree are heated in pot, potassium peroxydisulfate and SSS is fully dissolved.
(2) dose volume ratio is 99:1 styrene (1.98ml) and the mixing liquid of divinylbenzene (0.02ml), will
It is added to the mixing liquid in (1), starts simultaneously at timing, the aurosol that 30ml is prepared is added after 2min.
(3) reaction solution allowed in (2) reacts 4h at 70 DEG C, then stops reaction, obtain purple has dindar
The PS@Au beads of effect.
Mark sample is PS@Au, if Fig. 1 is its SEM figures.
2.TiO2@PS@Au preparation method, is comprised the steps of：
(1) obtained PS@Au beads in embodiment 1 are centrifuged and are dispersed in absolute ethyl alcohol, make 0.01g/ml's
PS@Au solution.
(2) 0.1g polyvinylpyrrolidones (PVP) are dispersed in the mixed solution of 0.8ml water and 33ml ethanol, then
The PS@Au of 0.01g/ml in 5ml (1) are added, allow it that 1.5h is stirred at room temperature, add the stirring of 0.3ml isopropyl titanates
45min, obtain TiO2@PS@Au spherical structure.
Mark sample is TiO2@PS@Au1#, if Fig. 2 is its SEM figures.
3. core-shell type TiO2@Au preparation method, is comprised the steps of：
(1) by obtained TiO in embodiment 22The sample of@PS@Au spherical structure is put into 450 DEG C of Muffle furnace calcination
4h, PS templates are burnt up, obtain the TiO of core shell structure2@Au。
Mark sample is TiO2@Au1#, if Fig. 5 is its SEM figures.
Embodiment 2：
1.PS@Au preparation method, is comprised the steps of：
(1) 0.5g potassium peroxydisulfates and 0.06g SSSs are dissolved in 45ml water and 165ml alcohol, are placed on oil bath
70 degree are heated in pot, potassium peroxydisulfate and SSS is fully dissolved.
(2) dose volume ratio is 99:1 styrene (1.98ml) and the mixing liquid of divinylbenzene (0.02ml), will
It is added to the mixing liquid in (1), starts simultaneously at timing, the aurosol that 30ml is prepared is added after 2min.
(3) reaction solution allowed in (2) reacts 4h at 70 DEG C, then stops reaction, obtain purple has dindar
The PS@Au beads of effect.
2.TiO2@PS@Au preparation method, is comprised the steps of：
(1) obtained PS@Au beads in embodiment 1 are centrifuged and are dispersed in absolute ethyl alcohol, make 0.01g/ml's
PS@Au solution.
(2) 0.1g polyvinylpyrrolidones (PVP) are dispersed in the mixed solution of 0.8ml water and 33ml ethanol, then
The PS@Au of 0.01g/ml in 5ml (1) are added, allow it that 1.5h is stirred at room temperature, add the stirring of 0.25ml isopropyl titanates
45min, obtain TiO2@PS@Au spherical structure.
Mark sample is TiO2@PS@Au2#, if Fig. 3 is its SEM figures.
3. core-shell type TiO2@Au preparation method, is comprised the steps of：
(1) by obtained TiO in embodiment 22The sample of@PS@Au spherical structure is put into 450 DEG C of Muffle furnace calcination
4h, PS templates are burnt up, obtain the TiO of core shell structure2@Au。
Mark sample is TiO2@Au2#, if Fig. 6 is its SEM figures.
Embodiment 3
1.PS@Au preparation method, is comprised the steps of：
(1) 0.5g potassium peroxydisulfates and 0.06g SSSs are dissolved in 45ml water and 165ml alcohol, are placed on oil bath
70 degree are heated in pot, potassium peroxydisulfate and SSS is fully dissolved.
(2) dose volume ratio is 99:1 styrene (1.98ml) and the mixing liquid of divinylbenzene (0.02ml), will
It is added to the mixing liquid in (1), starts simultaneously at timing, the aurosol that 30ml is prepared is added after 2min.
(3) reaction solution allowed in (2) reacts 4h at 70 DEG C, then stops reaction, obtain purple has dindar
The PS@Au beads of effect.
2.TiO2@PS@Au preparation method, is comprised the steps of：
(1) obtained PS@Au beads in embodiment 1 are centrifuged and are dispersed in absolute ethyl alcohol, make 0.01g/ml's
PS@Au solution.
(2) 0.1g polyvinylpyrrolidones (PVP) are dispersed in the mixed solution of 0.8ml water and 33ml ethanol, then
The PS@Au of 0.01g/ml in 5ml (1) are added, allow it that 1.5h is stirred at room temperature, add the stirring of 0.1ml isopropyl titanates
45min, obtain TiO2@PS@Au spherical structure.
Mark sample is TiO2@PS@Au3#, if Fig. 4 is its SEM figures.
3. core-shell type TiO2@Au preparation method, is comprised the steps of：
(1) by obtained TiO in embodiment 22The sample of@PS@Au spherical structure is put into 450 DEG C of Muffle furnace calcination
4h, PS templates are burnt up, obtain the TiO of core shell structure2@Au。
Mark sample is TiO2@Au3#, if Fig. 7 is its SEM figures.
By three above examples of implementation, we can therefrom find optimal titanium dioxide addition.In an experiment can
It is enough to find, when titanium dioxide addition very little when, it is impossible to PS is coated completely, do not reach expected effect；But titanium dioxide
When excessive, then accumulation of the unnecessary raw material on the bead coated can be caused, make size heterogeneity, and may be to performance
Cause necessarily to influence.From Fig. 1 SEM figures can from homogeneous spherical PS@Au are presented, its size is 250-300nm.From Fig. 2-
The TiO synthesized after 4 addition titanium dioxide2@PS@Au substantially become big, and add the more experimental group of titanium source, obtained TiO2@
PS@Au sizes are larger.By Fig. 5-7 in accompanying drawing it was found that adding less one group of titanium source, the TiO obtained after burning2@Au cores
Shell structure is more easy to cave in.Comprehensive consideration, the titanium source addition in embodiment 2 are the most suitable.
Described above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly
Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also
To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.
Claims (7)
1. a kind of template prepares TiO2The method of@Au core shell structures, it is characterised in that comprise the following steps：It is prepared by template
PS@Au, TiO is obtained in PS@Au one layer of unbodied titanium dioxide of outer cladding2@PS@Au, by TiO2@PS@Au calcine to obtain
TiO2@Au。
2. template as claimed in claim 1 prepares TiO2The method of@Au core shell structures, it is characterised in that：The template legal system
Standby PS@Au steps are as follows, and water and alcohol are pressed into 1:2-1：4 volume ratio mixing, obtains solution A, by potassium sulfate and styrene sulphur
Sour sodium is added in solution A, and the ratio of the potassium sulfate, SSS and solution A is 0.5g-2g：0.06g-1.50g：
100ml-120ml, stir to obtain potassium peroxydisulfate-SSS mixed solution at 60-80 DEG C, be designated as solution B；
Styrene and divinylbenzene are added in solution B, aurosol, the solution B, styrene, diethyl are added after stirring 2-4 minutes
The ratio of alkenyl benzene and aurosol is 100ml-120ml：0.99-2ml：0.01-0.05ml：20-40ml, stirred at 60-80 DEG C
Reaction 4-6h is mixed, the PS@Au beads with Tyndall effect of purple is obtained, obtains sample A.
3. template as claimed in claim 1 prepares TiO2The method of@Au core shell structures, it is characterised in that：It is described in sample A
One layer of unbodied titanium dioxide of outer cladding obtains TiO2The step of@PS@Au, is as follows, will be dried after sample A centrifuge washings, grinding
Cheng Fen, it is dispersed in 90%-99% alcohol, obtains the PS Au bead alcoholic solutions that concentration is 0.01-0.03g/ml, be designated as
Solution C；Polyvinylpyrrolidone is dispersed in the mixed solution of water and ethanol, is designated as solution D, solution is added in solution D
C, solution E is obtained, allow solution E that 1-2h is stirred at room temperature, added isopropyl titanate stirring 45-60min, obtain TiO2@PS@
Au spherical structure；The polyvinylpyrrolidone, water, ethanol, the ratio of solution C and isopropyl titanate are 0.20g-0.30g：
0.5-2ml：30-35ml：5-10mL：0.3-0.7mL.
4. template as claimed in claim 1 prepares TiO2The method of@Au core shell structures, it is characterised in that：It is described by TiO2@
PS@Au calcine to obtain TiO2The step of@Au, is as follows, by TiO2@PS@Au calcine 4-6h under the conditions of 400-500 DEG C, obtain nucleocapsid
The TiO of structure2@Au。
5. template as claimed in claim 1 prepares TiO2The method of@Au core shell structures, it is characterised in that：The PS@Au are
A kind of regular shape, the core shell structure of size uniformity, its average grain diameter are 300-350nm.
6. the template as described in claim 1-5 prepares TiO2The method of@Au core shell structures, it is characterised in that：Institute is in need to be made
Vessel are both needed to be soaked and cleaned with chloroazotic acid, so the consumptive material used is both needed to clean up.
7. template as claimed in claim 2 prepares TiO2The method of@Au core shell structures, it is characterised in that：The aurosol is
By the HAuCl that ultra-pure water and mass fraction are 1%41-2min is mixed and stirred for, adds citric acid three sodium solution afterwards, is stirred for 1-
NaBH is added after 2min4With the mixed liquor of trisodium citrate, the gold that the claret solution obtained after 5-8min is 3-8nm is stirred
The aurosol of nano particle；The ultra-pure water, the HAuCl that mass fraction is 1%4, citric acid three sodium solution, NaBH4And citric acid
The volume ratio of the mixed liquor of trisodium is 90：1：2：2-100：1：2：2, the citric acid three sodium solution is 0.224g：20ml lemon
The mixed liquor of lemon acid trisodium and water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108906038A (en) * | 2018-07-10 | 2018-11-30 | 东北大学 | A kind of Au-TiO2Egg yolk structure nanocomposite and preparation method thereof |
| CN110918095A (en) * | 2019-11-12 | 2020-03-27 | 华南师范大学 | Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof |
| CN114068960A (en) * | 2021-10-25 | 2022-02-18 | 黑龙江大学 | 3D porous spherical carbon shell-supported transition metal monatomic catalyst and preparation method and application thereof |
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| CN102267719A (en) * | 2010-06-04 | 2011-12-07 | 中国科学院化学研究所 | Simple method for preparing titanium dioxide multi-shell hollow spheres and sphere-in-sphere structure |
| CN103803643A (en) * | 2014-03-03 | 2014-05-21 | 福州大学 | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof |
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| CN102267719A (en) * | 2010-06-04 | 2011-12-07 | 中国科学院化学研究所 | Simple method for preparing titanium dioxide multi-shell hollow spheres and sphere-in-sphere structure |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906038A (en) * | 2018-07-10 | 2018-11-30 | 东北大学 | A kind of Au-TiO2Egg yolk structure nanocomposite and preparation method thereof |
| CN108906038B (en) * | 2018-07-10 | 2020-08-21 | 东北大学 | Au-TiO2Yolk structure nano composite material and preparation method thereof |
| CN110918095A (en) * | 2019-11-12 | 2020-03-27 | 华南师范大学 | Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof |
| CN114068960A (en) * | 2021-10-25 | 2022-02-18 | 黑龙江大学 | 3D porous spherical carbon shell-supported transition metal monatomic catalyst and preparation method and application thereof |
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