CN105772738A - Carbon nitride composite, preparation method and application thereof - Google Patents
Carbon nitride composite, preparation method and application thereof Download PDFInfo
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- CN105772738A CN105772738A CN201510837162.5A CN201510837162A CN105772738A CN 105772738 A CN105772738 A CN 105772738A CN 201510837162 A CN201510837162 A CN 201510837162A CN 105772738 A CN105772738 A CN 105772738A
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 51
- 239000010439 graphite Substances 0.000 claims abstract description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000005588 protonation Effects 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000009466 transformation Effects 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract 3
- 239000002243 precursor Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000002372 labelling Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
Abstract
The invention provides a carbon nitride composite, a preparation method and application thereof. The method comprises the steps of 1) heating and calcining precursor dicyandiamide through a program to synthesize a graphite phase carbon nitride material; 2) treating the graphite phase carbon nitride material with hydrochloric acid of different concentrations for certain time, and carrying out centrifugation, water washing, alcohol washing and drying to obtain protonated graphite phase carbon nitride material; and 3) putting the obtained protonated graphite phase carbon nitride material into a flask, adding water for dispersion, adding a certain amount of chloroplatinic acid, stirring to ensure that the Ion exchange becomes balanced, carrying out centrifugation and water washing, adding water again for dispersion, adding a proper amount of a sodium borohydride solution, reacting for certain time, and carrying out centrifugation, water washing, alcohol washing and drying on an obtained product to obtain platinum nanoparticles-loaded graphite phase carbon nitride material. According to the preparation method, the carbon nitride composite is prepared through adopting an ion exchange method, so that the electrical conductivity is good, the platinum particles are uniformly dispersed, and the photocurrent signal strength can reach 2.8 times as much as that of bulk phase graphite phase carbon nitride material.
Description
Technical field
The present invention relates to one with graphite phase carbon nitride for raw material, protonated by hydrochloric acid, utilize ion-exchange reactions to introduce platiniferous anion, then through the graphite phase carbon nitride material of reduction synthesis Pt nanoparticle load and the application in photoelectric signal transformation thereof.
Background technology
In recent years, day by day exhausted at the energy, when environment runs down, luminous energy is as clean energy resource, and its research and utilization also begins to cause concern, and photoelectric conversion material, as the material that solar energy can convert electric energy, causes and pays close attention to widely.Being found from nitrogen carbide material in 2008 under visible light illumination can since photolysis water hydrogen, and nitrogen carbide potentiality in opto-electronic conversion are mined out gradually.Nitrogen carbide is a kind of high polymer, the degraded etc. of photocatalytic water and organic pollution it is mainly used in visible light catalytic reaction, its heat stability and chemical stability are stronger, there is relatively low band gap (2.7eV), but as inorganic polymer, the electric conductivity of simple graphite phase carbon nitride is too weak again, and the recombination rate of the electron hole pair produced under the irradiation of light is high so that its photoelectric conversion and catalytic efficiency are relatively low.Therefore, the electricity conversion of carbon nitride material to be improved, it is necessary to improve its electric conductivity.Have been reported that the electric conductivity showing that doped with metal elements and protonation can be effectively improved nitrogen carbide material, improve photoelectron transfer speed.
All the time, liquid deposition reducing process is by the people's a kind of method as general synthesis platinum element doping material, owing to the deposition principle of this method is mainly physical absorption, therefore its deposition effect is difficult to control to, and the nanoparticle of load is easily reunited, unstable, uneven, after causing load, material property promotes less, and the uniform exchange site that the carbon nitride material protonated possesses can provide precise positioning for platinum load, and the load effect obtained is more stable.Therefore, the graphite phase carbon nitride material of Pt nanoparticle load prepared by the present invention, as a kind of photoelectric material, its morphology controllable, good conductivity, there is in opto-electronic conversion good prospect.
Summary of the invention
Technical problem: it is an object of the invention to provide a kind of carbonitride composite and its preparation method and application, improve body phase graphite phase carbon nitride poorly conductive, debt weak effect, the problem that photoelectric signal transformation is inefficient.
Technical scheme: a kind of carbonitride composite, graphite phase carbon nitride material is protonated by hydrochloric acid, then carry out ion-exchange reactions again with chloroplatinic acid and introduce platiniferous anion, finally adopt sodium borohydride liquid deposition reduction to obtain the graphite phase carbon nitride material of Pt nanoparticle load.
The preparation method of described carbonitride composite, step is:
The first step, prepared by protonation graphite phase carbon nitride material: by centrifugal, the washing after HCl treatment of graphite phase carbon nitride material, alcohol wash, vacuum drying, prepare and protonate graphite phase carbon nitride material；
Second step, ion exchange prepares the graphite phase carbon nitride material of platinum load: is placed in by the protonation graphite phase carbon nitride material obtained in water and disperses, and adds chloroplatinic acid, stirring, makes ion exchange reach balance, the product obtained is centrifuged, is washed；
3rd step, liquid phase deposition prepares platinum load phase graphite phase carbon nitride material: the product obtained by second step adds water dispersion again, add sodium borohydride solution reaction, the product obtained is centrifuged, washes, alcohol wash, vacuum drying obtain the graphite phase carbon nitride material of platinum load.
Described graphite phase carbon nitride material is to be obtained by dicyandiamide heating and calcining.
In the first step, hydrochloric acid mass percent concentration used is 18.5%～37%, and the materials of graphite-phase nitrogen carbide and hydrochloric acid are than for 1g:10mL.
The lower reaction of stirring in the first step, reaction temperature is room temperature.
In second step, nano platinum particle theoretical addition amount is 3wt.%.
In 3rd step, the sodium borohydride solution concentration of addition is 1mol/L, and the response time is 3h.
The application in photoelectric signal transformation material of the described carbonitride composite.
Beneficial effect: carbonitride composite prepared by the present invention, as photoelectric conversion material, has feature with low cost, excellent performance, stable in properties, is the high-performance semiconductor material for photoelectric conversion.On the basis of protonation, using ion exchange as core methed, so that platinum grain has higher adhesion and binding site evenly when load with carbonitride.The carbonitride composite of the present invention, good conductivity, platinum grain is uniformly dispersed, and its photo-signal intensity can reach 4 times of the graphite phase carbon nitride material of body phase.
Accompanying drawing explanation
Fig. 1 is synthetic graphite phase carbon nitride and scanning electron microscope (SEM) figure of ion exchange reducing process method Supported Pt Nanoparticles graphite phase carbon nitride after 27.75% hydrochloric acid protonation processes,
Fig. 2 is transmission electron microscope (TEM) figure that platinum load protonates the graphite phase carbon nitride after material and platinum load variable concentrations hydrochloric acid protonation process mutually,
The photosignal test figure of the graphite phase carbon nitride of platinum load difference protonation when Fig. 3 is constant potential-0.2V.As seen from the figure, when applied voltage is-0.2V, the photo-current intensity of material is stable at certain value.Along with the increase of material protonation, the photo-current intensity of material first increases, and reduces afterwards, if these families have and protonation and what platinum load density together decided on.Material TEM in conjunction with accompanying drawing 2 schemes, by contrasting it can be seen that relative to platinum load phase graphite phase carbon nitride, in the graphite phase carbon nitride of protonation, the nano platinum particle load effect of load is best, reuniting less, photoelectric current promotes clearly relative to body phase material GPPCN.Wherein the photoelectric current of PtGPPCN-H-27.75 promotes the most notable, reach 2.8 times of body phase GPPCN, this can be moderate owing to the protonation of PtGPPCN-H-27.75, structural deterioration degree after protonation, lifting and the light absorption equilibrium of material conductivity reach optimum, and now Pt nanoparticle is best for the transfer effect of light induced electron.
Detailed description of the invention
The preparation method of a kind of carbonitride composite, comprises the following steps:
1) presoma dicyandiamide is calcined synthetic graphite phase carbon nitride material through programmed heating；
2) by the HCl treatment regular hour of graphite phase carbon nitride material variable concentrations, then it is centrifuged, washes, alcohol wash, vacuum drying, prepare protonation graphite phase carbon nitride material；
3) being placed in flask by the protonation graphite phase carbon nitride material obtained, add water dispersion, adds a certain amount of chloroplatinic acid, stirring, makes ion exchange reach balance, the product obtained is centrifuged, is washed；
4) by step 3) product that obtains again adds water dispersion, adds appropriate sodium borohydride solution, react a period of time, and the product obtained is centrifuged, washes, alcohol wash, vacuum drying obtain the graphite phase carbon nitride material of platinum load.
Step 1) described in the graphite phase carbon nitride material of synthesis specifically include following steps:
1) dicyandiamide solid is placed in the crucible of clean dried, covers crucible cover.
2) being placed in Muffle furnace by crucible, arranging heating ramp rate is 2.3 DEG C/min, and target temperature is 550 DEG C, and is incubated 4h, is cooled to after room temperature obtains yellow solid powder until temperature is graphite phase carbon nitride.
Step 2) in, used salt acid concentration respectively 18.5%, 27.75%, 37%, the materials of graphite-phase nitrogen carbide and hydrochloric acid are than for 1g:10mL.
Step 2) in, respectively the hydrochloric acid that concentration is 37% being diluted to 27.75%, 18.5% with redistilled water respectively, the hydrochloric acid solution respectively taking tri-kinds of variable concentrations of 10mL adds in each flask equipped with 1g graphite phase carbon nitride, and after stirring 3h, reaction temperature is room temperature.
Step 2) in, time centrifugal, rotating speed is 12000rpm, and the time is 15min, and chilling temperature is 10 DEG C, and second distillation water washing is neutral to the centrifugal supernatant, and for several times, vacuum drying temperature is 50 DEG C to washing with alcohol, and drying time is 12h.
Step 3) in, reaction mixing time is 24h.
Step 3) in, time centrifugal, rotating speed is 12000rpm, and the time is 15min, and chilling temperature is 10 DEG C, and second distillation water washing is neutral to the centrifugal supernatant；
Step 4) in, by step 3) in the centrifugal product of gained again dissipate with bis-moisture of 10mL, add the sodium borohydride solution of 15mL1mol/L, the response time is 3h.
Step 4) in, centrifugal rotational speed is 12000rpm, and the time is 15min, and chilling temperature is 10 DEG C, and second distillation water washing is neutral to the centrifugal supernatant, and washing with alcohol 3 times, vacuum drying temperature is 50 DEG C, and drying time is 12h.
The graphite phase carbon nitride materials application of Pt nanoparticle load prepared by described method is in prepared by photoelectric signal transformation material.
Further illustrate the present invention below by instantiation and prepare the concrete grammar of carbonitride composite.
Embodiment 1
(1) synthesis of graphite phase carbon nitride
Take 10g dicyandiamide (DCDA) and be placed in the crucible of clean dried, cover crucible cover.Being placed in Muffle furnace by crucible, arranging ramped heating rate is 2.3 DEG C/min, is heated to 550 DEG C, is incubated 4h.Being cooled to after room temperature until temperature to take out, obtain yellow solid, be graphite phase carbon nitride, grind to form relatively fine powder, bottling labeling is standby.
(2) synthesis of graphite phase carbon nitride is protonated
Take 1g graphite phase carbon nitride (g-C respectively3N4) pressed powder be placed in the beaker of clean dried, respectively in beaker add 10mL18.5%, 27.75%, 37% hydrochloric acid solution, under room temperature stir 3h.With the centrifugal 15min of 12000rpm at 10 DEG C, and it is neutral with secondary water washing to supernatant liquid, then by washing with alcohol 3 times.It is placed in the vacuum desiccator of 50 DEG C and dries 12h, obtain light yellow solid powder, grind and labeling of bottling is standby.
(3) (4) ion exchange prepares the body phase graphite phase carbon nitride material of platinum load
Take the above-mentioned prepared graphite phase carbon nitride 50mg protonated in various degree in the round-bottomed flask of clean dried, be added thereto to the platinum acid chloride solution of 3.905mL12.5mmoL, when lucifuge, stir 24h.With the centrifugal 15min of 12000rpm at 10 DEG C, and it is neutral with secondary water washing to supernatant liquid.Again after being dissipated with bis-moisture of 10mL respectively by solid, the sodium borohydride solution of 15mL1mol/L it is separately added into from big to small by the volume of the chloroplatinic acid added, lucifuge stirring 3h.With the centrifugal 15min of 12000rpm at 10 DEG C, and it is neutral with secondary water washing to supernatant liquid, then by washing with alcohol 3 times.It is placed in the vacuum desiccator of 50 DEG C and dries 12h, obtain yellow solid, grind bottling labeling standby.
Comparative example: liquid phase deposition prepares platinum load graphite-phase nitrogen carbide material
Step (1) (2) is identical with embodiment 1, and in step (3), graphite phase carbon nitride is aprotic.Take above-mentioned prepared graphite phase carbon nitride 50mg in the round-bottomed flask of clean dried, be added thereto to the platinum acid chloride solution of 3.905mL12.5mmoL, when lucifuge, stir 24h.With the centrifugal 15min of 12000rpm at 10 DEG C, and it is neutral with secondary water washing to supernatant liquid.Again after being dissipated with bis-moisture of 10mL respectively by solid, it is separately added into the sodium borohydride solution of 15mL1mol/L, lucifuge stirring 3h.With the centrifugal 15min of 12000rpm at 10 DEG C, and it is neutral with secondary water washing to supernatant liquid, then by washing with alcohol 3 times.It is placed in the vacuum desiccator of 50 DEG C and dries 12h, obtain yellow solid, grind bottling labeling standby.The material electromicroscopic photograph and the photosignal test figure that obtain are shown in accompanying drawing 3.
Claims (8)
1. a carbonitride composite, it is characterized in that, graphite phase carbon nitride material is protonated by hydrochloric acid, then carries out ion-exchange reactions again with chloroplatinic acid and introduces platiniferous anion, finally adopts sodium borohydride liquid deposition reduction to obtain the graphite phase carbon nitride material of Pt nanoparticle load.
2. the preparation method of the carbonitride composite described in claim 1, it is characterised in that step is:
The first step, prepared by protonation graphite phase carbon nitride material: by centrifugal, the washing after HCl treatment of graphite phase carbon nitride material, alcohol wash, vacuum drying, prepare and protonate graphite phase carbon nitride material；
Second step, ion exchange prepares the graphite phase carbon nitride material of platinum load: is placed in by the protonation graphite phase carbon nitride material obtained in water and disperses, and adds chloroplatinic acid, stirring, makes ion exchange reach balance, the product obtained is centrifuged, is washed；
3rd step, liquid phase deposition prepares platinum load phase graphite phase carbon nitride material: the product obtained by second step adds water dispersion again, add sodium borohydride solution reaction, the product obtained is centrifuged, washes, alcohol wash, vacuum drying obtain the graphite phase carbon nitride material of platinum load.
3. the preparation method of carbonitride composite as claimed in claim 2, it is characterised in that: described graphite phase carbon nitride material is to be obtained by dicyandiamide heating and calcining.
4. the preparation method of carbonitride composite as claimed in claim 2, it is characterised in that: in the first step, hydrochloric acid mass percent concentration used is 18.5% ~ 37%, and the materials of graphite-phase nitrogen carbide and hydrochloric acid ratio is for 1g:10mL.
5. the preparation method of carbonitride composite as claimed in claim 2, it is characterised in that: the lower reaction of stirring in the first step, reaction temperature is room temperature.
6. the preparation method of carbonitride composite as claimed in claim 2, it is characterised in that: in second step, nano platinum particle theoretical addition amount is 3wt.%.
7. the preparation method of carbonitride composite as claimed in claim 1, it is characterised in that: in the 3rd step, the sodium borohydride solution concentration of addition is 1mol/L, and the response time is 3h.
8. the application in photoelectric signal transformation material of the carbonitride composite described in claim 1.
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Cited By (7)
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| CN107649167A (en) * | 2017-10-26 | 2018-02-02 | 金华职业技术学院 | CO oxidation catalysts and preparation method thereof under a kind of steam and carbon dioxide atmosphere |
| CN107827091A (en) * | 2017-11-17 | 2018-03-23 | 中南大学 | A kind of protonation is modified class graphitic nitralloy carbon material and its preparation and the application in lithium ion battery negative material |
| CN109755640A (en) * | 2019-03-13 | 2019-05-14 | 西安交通大学 | A kind of preparation method of composite solid polymer electrolyte |
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| CN107649167A (en) * | 2017-10-26 | 2018-02-02 | 金华职业技术学院 | CO oxidation catalysts and preparation method thereof under a kind of steam and carbon dioxide atmosphere |
| CN107827091A (en) * | 2017-11-17 | 2018-03-23 | 中南大学 | A kind of protonation is modified class graphitic nitralloy carbon material and its preparation and the application in lithium ion battery negative material |
| CN109755640A (en) * | 2019-03-13 | 2019-05-14 | 西安交通大学 | A kind of preparation method of composite solid polymer electrolyte |
| CN110143648A (en) * | 2019-05-28 | 2019-08-20 | 江苏智诚达环保科技有限公司 | A kind of preparation method of pt atom modification azotized carbon nano stick photoelectrocatalysielectrode electrode |
| CN110346420A (en) * | 2019-06-09 | 2019-10-18 | 重庆工商大学融智学院 | A kind of space-time data intelligence polymerization |
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| CN112295582A (en) * | 2019-08-02 | 2021-02-02 | 南京理工大学 | g-C3N4/C2N nano composite visible light catalytic material and preparation method thereof |
| CN112295582B (en) * | 2019-08-02 | 2022-09-13 | 南京理工大学 | g-C 3 N 4 /C 2 N nano composite visible light catalytic material and preparation method thereof |
| CN112121836A (en) * | 2020-09-22 | 2020-12-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of palladium-cobalt/carbon nitride composite material, product and application thereof |
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