CN115818622A - Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof - Google Patents
Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN115818622A CN115818622A CN202211556683.XA CN202211556683A CN115818622A CN 115818622 A CN115818622 A CN 115818622A CN 202211556683 A CN202211556683 A CN 202211556683A CN 115818622 A CN115818622 A CN 115818622A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- nanosphere
- template
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002077 nanosphere Substances 0.000 title claims abstract description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- 239000011807 nanoball Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- -1 secondary battery Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 229960000502 poloxamer Drugs 0.000 claims description 6
- 229920001983 poloxamer Polymers 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 24
- 238000011065 in-situ storage Methods 0.000 abstract description 19
- 230000001105 regulatory effect Effects 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The application belongs to the technical field of materials, and particularly relates to a hollow nitrogen-doped carbon nanosphere and a preparation method and application thereof. The method comprises the following steps: preparing a nano-sphere template; preparing an organic carbon source coating layer and an organic nitrogen source coating layer on the surface of the nanosphere template to obtain composite nanospheres; calcining the composite nanospheres to obtain carbonized composite nanospheres; and etching and removing the nano-sphere template in the carbonized composite nano-sphere by adopting a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere. The nano template is removed by etching with the aqueous solution of lithium fluoride and hydrochloric acid, so that the direct contact with strong corrosive hydrofluoric acid is avoided, the safety of the experiment is improved, and the limitation of controlled reagents is overcome. The size of the prepared hollow nitrogen-doped carbon nanosphere can be flexibly regulated and controlled by regulating and controlling the size of the nanosphere template. The hollow nitrogen-doped carbon nanospheres generated in situ have the advantages of good structural stability, high specific surface area, uniform surface aperture and high porosity, and are suitable for various application fields.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a hollow nitrogen-doped carbon nanosphere and a preparation method and application thereof.
Background
The preparation and observation of hollow microspheres was first reported in the middle of the last century, and the precise and controlled synthesis of nanohollow materials and a thorough understanding of the structure-property correlations were not realized until the last two decades. The commercialization of the characterization device and the maturation of the nano-synthesis. Today, various synthetic schemes have been developed to prepare hollow nanomaterials with various structural features (e.g., yolk shell, multishell, porous, etc.), from organic/inorganic compounds to hybrid or layered materials. These synthetic methods have been systematically outlined by a number of outstanding reviews and can be generally divided into four types depending on the shape-directing agent: soft template methods, hard template methods, self-templated methods, template-free methods, and the like. In addition to the template-free approach based on Ostwald ripening, voids are typically fabricated by post-processing procedures, including thermal treatment, chemical etching, the kirkendall effect, electrical displacement, and the like.
Hollow nanomaterials have attracted extensive interest in multidisciplinary research due to their unique structure and excellent properties. Due to the fact that the hollow nanostructure has a high specific surface area, definite active sites, separated void spaces and an adjustable mass transfer rate, the hollow nanostructure has excellent performance in various emerging research fields, such as the fields of catalysis, lithium Ion Batteries (LIB), supercapacitors, proton Exchange Membrane Fuel Cells (PEMFCs), chemical sensors, biomedicine and the like. In addition, researchers have focused on purposeful functionalization of hollow nanomaterials for catalytic mechanism studies and complex catalytic reactions based on the most advanced synthetic methods and characterization techniques.
At present, silicon dioxide is often used as a template in a method for preparing hollow carbon spheres, then the silicon dioxide template is etched to obtain the hollow carbon spheres, in the prior art, hydrofluoric acid solution is mostly directly used for etching, but hydrofluoric acid is strong in corrosivity, dangerous to use and extremely high in operation safety requirement.
Disclosure of Invention
The application aims to provide a hollow nitrogen-doped carbon nanosphere and a preparation method thereof, and application of the hollow nitrogen-doped carbon nanosphere, and aims to solve the problems of low safety coefficient and high difficulty of the existing preparation method of the hollow carbon nanosphere to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a hollow nitrogen-doped carbon nanosphere, comprising the following steps:
preparing a nano-sphere template;
preparing an organic carbon source coating layer and an organic nitrogen source coating layer on the surface of the nanosphere template to obtain composite nanospheres;
calcining the composite nanospheres to obtain carbonized composite nanospheres;
and etching and removing the nano-sphere template in the carbonized composite nano-sphere by adopting a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere.
In a second aspect, the present application provides a hollow nitrogen-doped carbon nanoball manufactured by the above-mentioned method.
In a third aspect, the present application provides an application of the hollow nitrogen-doped carbon nanosphere in catalysts, secondary batteries, capacitors, sensors, and biomedicine.
According to the preparation method of the hollow nitrogen-doped carbon nanosphere, after the nanosphere template is prepared, the organic carbon source coating layer and the organic nitrogen source coating layer are prepared on the surface of the template, the organic carbon source and the organic nitrogen source are carbonized through calcination treatment, the carbon material is converted into the nanosphere template in situ on the surface of the nanosphere template, and nitrogen elements are doped into the carbon material in situ. And then removing the nano-sphere template in the carbonized composite nano-sphere by etching with a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere. On one hand, the nano template is removed by etching hydrofluoric acid with a certain concentration generated by in-situ lithium fluoride and hydrochloric acid aqueous solution, and the concentration of the generated hydrofluoric acid can be adjusted by adjusting the ratio of the lithium fluoride to the hydrochloric acid, so that the direct contact with the hydrofluoric acid with strong corrosivity is avoided, the safety of an experiment is improved, and the limitation of a control reagent is overcome. On the other hand, the size of the prepared hollow nitrogen-doped carbon nanosphere can be flexibly regulated and controlled by regulating and controlling the size of the nanosphere template. On the other hand, the hollow nitrogen-doped carbon nanospheres generated in situ have good structural stability, high specific surface area, uniform surface aperture and high porosity, and are suitable for various application fields.
The hollow nitrogen-doped carbon nanospheres provided by the second aspect of the present application are prepared by the above method, have good structural stability, high uniformity of particle size, high specific surface area, uniform surface pore size and high porosity, and are suitable for various application fields.
The hollow nitrogen-doped carbon nanospheres provided by the third aspect of the application have the characteristics of good structural stability, high granularity uniformity, high specific surface area, uniform surface aperture, high porosity and the like, and can be widely applied to the fields of catalysts, secondary batteries, capacitors, sensors, biomedicine and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing hollow nitrogen-doped carbon nanospheres according to embodiments of the present application;
FIG. 2 is a Transmission Electron Microscope (TEM) morphology of the hollow N-doped carbon nanospheres provided in example 1 of the present application;
fig. 3 is an XPS diagram of a hollow nitrogen-doped carbon nanoball provided in example 1 of the present application;
fig. 4 is a graph of adsorption isotherms of the hollow nitrogen-doped carbon nanospheres provided in example 1 of the present application;
fig. 5 is a pore size distribution diagram of the hollow nitrogen-doped carbon nanoball provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the examples of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components according to the examples of the present application is scaled up or down within the scope disclosed in the examples of the present application. Specifically, the mass described in the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a hollow nitrogen-doped carbon nanosphere, comprising the following steps:
s10, preparing a nano-sphere template;
s20, preparing an organic carbon source coating layer and an organic nitrogen source coating layer on the surface of the nanosphere template to obtain composite nanospheres;
s30, calcining the composite nanospheres to obtain carbonized composite nanospheres;
and S40, removing the nano-sphere template in the carbonized composite nano-sphere by etching with a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere.
According to the preparation method of the hollow nitrogen-doped carbon nanosphere, after the nanosphere template is prepared, the organic carbon source coating layer and the organic nitrogen source coating layer are prepared on the surface of the template, the organic carbon source and the organic nitrogen source are carbonized through calcination treatment, the carbon material is converted in situ on the surface of the nanosphere template, and nitrogen elements are doped in the carbon material in situ. And then removing the nano-sphere template in the carbonized composite nano-sphere by etching with a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere. On one hand, the nano template is removed by etching hydrofluoric acid with a certain concentration generated by in-situ lithium fluoride and hydrochloric acid aqueous solution, and the concentration of the generated hydrofluoric acid can be adjusted by adjusting the ratio of the lithium fluoride to the hydrochloric acid, so that the direct contact with the hydrofluoric acid with strong corrosivity is avoided, the safety of an experiment is improved, and the limitation of a control reagent is overcome. On the other hand, the size of the prepared hollow nitrogen-doped carbon nanosphere can be flexibly regulated and controlled by regulating and controlling the size of the nanosphere template. On the other hand, the hollow nitrogen-doped carbon nanospheres generated in situ have good structural stability, high specific surface area, uniform surface aperture and high porosity, and are suitable for various application fields.
In some embodiments, in the step S10, the step of preparing the nanoparticle template includes: and mixing the silicon dioxide precursor with a basic catalyst, an alcohol solvent and water to prepare colloid, thus obtaining the nanosphere template. The colloid ball is formed by polymerization in a mixed solution of an alcohol solvent and a basic catalyst. Emulsion droplets are first formed by hydrogen bonding of water, alcohol, resorcinol and formaldehyde, and phenolic polymerization takes place from the interior of the droplets by ammonia catalysis, producing uniform nanospheres, i.e., nanosphere templates.
In some embodiments, the volume ratio of the basic catalyst, the alcohol solvent and water is (0.1 to 1): (1-5): 1.
in some embodiments, the basic catalyst comprises at least one of ammonia, ethylene diamine.
In some embodiments, the alcoholic solvent comprises at least one of methanol, ethanol.
In some embodiments, the silica precursor is selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, Y- (2, 3-epoxypropoxy) propyltrimethoxysilane, Y- (methacryloyloxy) propyltrimethoxysilane, Y-mercaptopropyltrimethoxysilane; these silica precursors can each react with a solution of a basic catalyst, an alcohol solvent, and water to produce a silica nanosphere template.
In some embodiments, by adjusting the concentration of the silica precursor, a silica nanosphere template with controllable size can be formed.
In some embodiments, the basic catalyst, the alcohol solvent and the deionized water are mixed according to the volume ratio of (0.1-1): (1-5): 1, mixing and stirring at room temperature, dropwise adding at least one silicon dioxide precursor of tetramethyl orthosilicate, tetraethyl orthosilicate, Y- (2, 3-epoxypropoxy) propyl trimethoxy silane, Y- (methacryloyloxy) propyl trimethoxy silane and Y-mercaptopropyl trimethoxy silane while stirring, and changing the solution from transparent to milky colloid to obtain the nanosphere template.
In some embodiments, in step S20, the step of preparing the organic carbon source coating layer and the organic nitrogen source coating layer on the surface of the nanosphere template comprises: and mixing the nano-sphere template with a surfactant and an organic carbon source, adding an organic nitrogen source for mixing treatment, and carrying out hydrothermal reaction to obtain the composite nano-sphere. In order to prevent agglomeration of the nanosphere template, a surfactant is added into a system, so that an organic carbon source can be uniformly and stably attached to the surface of the nanosphere template to form a coating layer, an organic nitrogen source is added for mixing treatment so that the organic nitrogen source continues to form the coating layer, and the stable-coated organic carbon source coating layer and the organic nitrogen source coating layer are formed on the surface of the nanosphere template through hydrothermal reaction. In some embodiments, after the hydrothermal reaction, the reaction product is separated and washed, and then dried to obtain the composite nanosphere.
In some embodiments, the surfactant comprises a poloxamer ， The surfactant can prevent the nano-sphere template in a reaction system from being agglomerated into large particles, is favorable for independently coating the nano-sphere template with a subsequent organic nitrogen source and an organic carbon source to form an organic carbon layer and an organic nitrogen layer, and improves the structural stability and the granularity uniformity of the composite nano-sphere.
In some embodiments, the organic carbon source comprises resorcinol and formaldehyde. In the embodiment of the application, an organic carbon source containing resorcinol and formaldehyde is mixed with the nanosphere template, and an organic carbon source reaction product generated by in-situ condensation of resorcinol and formaldehyde is tightly coated on the surface of the nanosphere template in the subsequent reaction process to form an organic carbon source coating layer.
In some embodiments, the molar ratio of resorcinol to formaldehyde is (0.1 to 0.5): 1; the molar ratio fully ensures the in-situ condensation reaction of the resorcinol and the formaldehyde, and is beneficial to the in-situ generation of the organic carbon source coating layer on the surface of the nanosphere template. In some embodiments, the molar ratio of the resorcinol to the formaldehyde includes, but is not limited to, 0.1.
In some embodiments, the organic nitrogen source comprises formaldehyde and at least one of urea, hexamethylenetetramine, dicyanodiamine, melamine. After the organic nitrogen source comprising the nitrogen source and the formaldehyde is added into the reaction system, the organic nitrogen source reaction product generated by in-situ condensation of the nitrogen source and the formaldehyde is tightly coated on the surface of the organic carbon source coating layer in the subsequent reaction process to form the organic nitrogen coating layer. In some embodiments, the nitrogen source is preferably melamine.
In some embodiments, the molar ratio of the nitrogen source to the formaldehyde is (0.1-0.4): 1. The molar ratio fully ensures the in-situ condensation reaction of the nitrogen source and the formaldehyde, and is beneficial to generating the organic nitrogen source coating layer in situ. In some embodiments, the molar ratio of the nitrogen source to the formaldehyde includes, but is not limited to, 0.1.
In some embodiments, after mixing the nanosphere template with a surfactant and an organic carbon source, adding an organic nitrogen source for mixing treatment, and then performing hydrothermal reaction at a temperature of 90-110 ℃; the reaction temperature can fully ensure that the organic carbon source and the organic nitrogen source respectively carry out in-situ polymerization reaction, and a stable organic carbon source coating layer and the organic nitrogen source coating layer are formed in situ on the surface of the nanosphere template. In some embodiments, the temperature of the hydrothermal reaction includes, but is not limited to, 90 to 95 ℃, 95 to 100 ℃,100 to 105 ℃, 105 to 110 ℃, and the like, with 100 ℃ being particularly preferred.
In some specific embodiments, after mixing and stirring the nanosphere template with the surfactant and the organic carbon source for 10 to 60 minutes, adding the organic nitrogen source, continuing stirring at room temperature for 12 to 36 hours, transferring to a reaction kettle, performing hydrothermal reaction at 90 to 110 ℃ for 12 to 36 hours, finally centrifuging, washing with an alcohol solvent such as ethanol and deionized water for three times, and drying overnight to obtain the composite nanosphere. In some embodiments, the centrifugation speed is 6000 to 12000rpm, preferably 10000rpm.
In some embodiments, in the step S30, the conditions for performing the calcination treatment on the composite nanospheres include: in inert atmosphere, the temperature is raised to 600-1000 ℃ at the temperature raising rate of 1-10 ℃/min, and the calcination is carried out for 1-3 hours. The calcination condition can carbonize the organic carbon source in the composite nano material, form a carbon material coating layer in situ, convert the organic nitrogen source into nitrogen element, and dope the nitrogen element in situ in the organic carbon material coating layer.
In some embodiments, the inert atmosphere includes, but is not limited to, at least one of nitrogen, argon, helium, and further preferably argon.
In some embodiments, the temperature ramp rate of the calcination process includes, but is not limited to, 1-2 deg.C/min, 2-3 deg.C/min, 3-4 deg.C/min, 4-5 deg.C/min, 5-6 deg.C/min, 6-7 deg.C/min, 7-8 deg.C/min, 8-9 deg.C/min, 9-10 deg.C/min, and the like; the temperature includes, but is not limited to, 600-700 ℃, 700-800 ℃, 800-900 ℃, 900-1000 ℃, and the like, and the specific preference is 750 ℃; calcination times include, but are not limited to, 1, 2,3 hours, and the like.
In some embodiments, in step S40, the nanoparticle template in the carbonized composite nanosphere is removed by etching with a mixed solution of lithium fluoride and hydrochloric acid, wherein in the mixed solution of lithium fluoride and hydrochloric acid, the concentration of lithium fluoride is 1 to 2.5mol/L, and the concentration of hydrochloric acid is 2 to 10mol/L, and the mixed solution of lithium fluoride and hydrochloric acid with the concentration ratio can react well to generate hydrofluoric acid to remove the nanoparticle template by etching, so as to obtain the hollow nitrogen-doped carbon nanosphere. The concentration of the generated hydrofluoric acid can be adjusted by adjusting the ratio of the lithium fluoride to the hydrochloric acid, the hydrofluoric acid with strong corrosivity is prevented from being directly contacted, the safety of an experiment is improved, and the limitation of a control reagent is overcome. In some embodiments, the concentration of lithium fluoride in the mixed solution of lithium fluoride and hydrochloric acid includes, but is not limited to, 1 to 1.5mol/L, 1.5 to 2mol/L, 2 to 2.5mol/L, etc., and the concentration of hydrochloric acid includes, but is not limited to, 2 to 3mol/L, 3 to 4mol/L, 4 to 5mol/L, 5 to 6mol/L, 6 to 7mol/L, 7 to 8mol/L, 8 to 9mol/L, 9 to 10mol/L, etc.
In some embodiments, the hollow nitrogen-doped carbon nanospheres have a particle size of 150 to 400nm. The size of the prepared hollow nitrogen-doped carbon nanosphere can be flexibly regulated and controlled by regulating and controlling the size of the nanosphere template, so that the requirement of the application field on the particle size is not met, the particle size range of 150-400 nm is wide, and the application range is wide and wide. In some embodiments, the particle size of the hollow nitrogen-doped carbon nanosphere includes, but is not limited to, 150-200 nm, 200-300 nm, 300-400 nm, 400-500 nm, and the like.
In some embodiments, the surface pore size of the hollow nitrogen-doped carbon nanosphere is 40-100 nm.
A second aspect of the embodiments of the present application provides a hollow nitrogen-doped carbon nanoball manufactured by the above-described method.
The hollow nitrogen-doped carbon nanospheres provided in the second aspect of the embodiments of the present application are manufactured by the above method, have good structural stability, high uniformity of particle size, high specific surface area, uniform surface pore size, and high porosity, and are suitable for various application fields.
In some embodiments, the hollow nitrogen-doped carbon nanosphere has a particle size of 150 to 400nm; the surface aperture of the hollow nitrogen-doped carbon nanosphere is 40-100 nm.
In a third aspect of the embodiments of the present application, there is provided an application of the hollow nitrogen-doped carbon nanosphere in catalysts, secondary batteries, capacitors, sensors, and biomedicine.
The hollow nitrogen-doped carbon nanospheres provided by the third aspect of the embodiment of the application have the characteristics of good structural stability, high granularity uniformity, high specific surface area, uniform surface pore diameter, high porosity and the like, and can be widely applied to the fields of catalysts, secondary batteries, capacitors, sensors, biomedicine and the like.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art and to make the progress of the hollow nitrogen-doped carbon nanospheres and the preparation method thereof obviously apparent, the above technical solutions are illustrated by a plurality of examples.
Example 1
A hollow nitrogen-doped carbon nanosphere, which is prepared by the following steps:
1. 60mL of ethanol and 20mL of deionized water are sequentially measured by a measuring cylinder and poured into a beaker, 2.5mL of ammonia water is added, the mixture is mixed and stirred for 30 minutes at room temperature, 2.8mL of tetraethyl orthosilicate (TEOS) is slowly dropped, and the solution is changed into milky colloid from transparent to obtain the silicon dioxide nanosphere template.
2. Poloxamer (0.3 g) as a surfactant, poloxamer (F127), resorcinol (0.4 g) and formaldehyde (0.5 mL) were added and stirring was continued at room temperature for 30 minutes. A further 0.315g of melamine and 0.42mL of formaldehyde are added and stirring is continued at room temperature for 24 hours. Then, the solution is transferred into a 100mL reaction kettle and put into an oven to react for 24 hours at 100 ℃, centrifuged for 10 minutes at 10000rpm, repeatedly washed for 3 times by deionized water and ethanol, and put into an oven at 80 ℃ to be dried for 12 hours, thus obtaining the composite nanosphere.
3. And (3) putting the composite nanospheres under the argon condition, calcining for 2 hours at the temperature rising rate of 2 ℃/minute to 700 ℃, and obtaining a black powder sample after calcining, namely the carbonized composite nanospheres.
4. Then 1.93M lithium fluoride and 6M hydrochloric acid solution are prepared, calcined black powder (carbonized composite nanospheres) is added, stirring is carried out for 24 hours at room temperature, silicon dioxide nanosphere templates are removed by etching, finally deionized water and ethanol are used for repeatedly cleaning, and drying is carried out in an oven at 80 ℃ for 12 hours, so that the hollow nitrogen-doped nanospheres are obtained.
Example 2
A hollow carbon nanoball, which is prepared by the steps of:
1. 60mL of ethanol and 20mL of deionized water are measured by a measuring cylinder in sequence and poured into a beaker, 2.5mL of ammonia water is added, the mixture is mixed and stirred for 30 minutes at room temperature, 2.8mL of tetraethyl orthosilicate (TEOS) is slowly dropped, and the solution is changed into milky colloid from transparent to obtain the silicon dioxide nanosphere template.
2. Poloxamer (0.3 g) surfactant poloxamer (F127), resorcinol (0.4 g) and formaldehyde (0.5 mL) were added and stirred at room temperature for 24 hours. Then, the solution is transferred into a 100mL reaction kettle and put into an oven to react for 24 hours at 100 ℃, centrifuged for 10 minutes at 10000rpm, repeatedly washed for 3 times by deionized water and ethanol, and put into an oven at 80 ℃ to be dried for 12 hours, thus obtaining the composite nanosphere.
3. And (3) putting the composite nanospheres under the argon condition, calcining for 2 hours at the temperature rising rate of 2 ℃/minute to 700 ℃, and obtaining a black powder sample after calcining, namely the carbonized composite nanospheres.
4. Then 1.93M lithium fluoride and 6M hydrochloric acid solution are prepared, calcined black powder (carbonized composite nanospheres) is added, the mixture is stirred for 24 hours at room temperature, a silicon dioxide nanosphere template is removed by etching, finally, the mixture is repeatedly washed by deionized water and ethanol, and the mixture is dried in an oven at 80 ℃ for 12 hours to obtain the hollow carbon nanospheres.
Example 3
A hollow nitrogen-doped carbon nanoball which is different from example 1 in that: TEOS was added in an amount of 3.5mL, and the other steps were the same.
Example 4
A hollow nitrogen-doped carbon nanoball which is different from example 2 in that: TEOS was added in an amount of 3.5mL, and the other steps were the same.
Comparative example 1
A hollow nitrogen-doped carbon nanoball which is different from example 1 in that: step 2 was carried out without the "addition of 0.315g of melamine and 0.42mL of formaldehyde, stirring was continued for 24 hours at room temperature", and the other steps were the same.
Further, in order to verify the advancement of the examples of the present application, the following performance tests were performed on the examples and comparative examples:
1. the morphology of the hollow nitrogen-doped carbon nanospheres prepared in example 1 was observed by transmission electron microscopy, and the test chart is shown in fig. 2, which shows that the prepared hollow nitrogen-doped carbon nanospheres have high sphericity, complete structure and uniform size.
2. The hollow nitrogen-doped carbon nanoball obtained in example 1 was subjected to the X-ray diffraction test, and the XPS chart is shown in fig. 3, from which it can be seen that the carbon nanoball obtained has very little residual si and stable nitrogen doping.
3. The hollow nitrogen-doped carbon nanoball prepared in example 1 was subjected to an adsorption isothermal curve test, and the test chart is shown in fig. 4, from which it can be seen that the prepared hollow nitrogen-doped carbon nanoball has high adsorption performance and a large specific surface area.
4. The surface pore diameter distribution diagram of the hollow nitrogen-doped carbon nanosphere prepared in example 1 is shown in fig. 5, and it can be known from the test chart that the surface of the prepared hollow nitrogen-doped carbon nanosphere has a microporous structure with a pore diameter of 40-100 nm, and the pore diameter distribution is relatively uniform.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of hollow nitrogen-doped carbon nanospheres is characterized by comprising the following steps:
preparing a nano-sphere template;
preparing an organic carbon source coating layer and an organic nitrogen source coating layer on the surface of the nanosphere template to obtain composite nanospheres;
calcining the composite nanospheres to obtain carbonized composite nanospheres;
and etching and removing the nano-sphere template in the carbonized composite nano-sphere by adopting a mixed solution of lithium fluoride and hydrochloric acid to obtain the hollow nitrogen-doped carbon nano-sphere.
2. The method for preparing the hollow nitrogen-doped carbon nanosphere of claim 1, wherein the concentration of the lithium fluoride in the mixed solution of lithium fluoride and hydrochloric acid is 1-2.5 mol/L, and the concentration of the hydrochloric acid is 2-10 mol/L.
3. The method of fabricating the hollow nitrogen-doped carbon nanoball of claim 2, wherein the step of fabricating the template of the nanoball comprises: mixing a silicon dioxide precursor with a basic catalyst, an alcohol solvent and water to prepare a colloid, thereby obtaining the nanosphere template;
and/or the step of preparing the organic carbon source coating layer and the organic nitrogen source coating layer on the surface of the nanosphere template comprises the following steps: mixing the nano-sphere template with a surfactant and an organic carbon source, adding an organic nitrogen source for mixing treatment, and carrying out hydrothermal reaction to obtain the composite nano-sphere;
and/or the conditions of the calcination treatment include: in inert atmosphere, the temperature is raised to 600-1000 ℃ at the temperature raising rate of 1-10 ℃/min, and the calcination is carried out for 1-3 hours.
4. The method of preparing the hollow nitrogen-doped carbon nanoball of claim 3, wherein the volume ratio of the basic catalyst, the alcohol solvent and the water is (0.1-1): (1-5): 1;
and/or the basic catalyst comprises at least one of ammonia water and ethylenediamine;
and/or the alcohol solvent comprises at least one of methanol and ethanol;
and/or the silicon dioxide precursor is selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, Y- (2, 3-epoxypropoxy) propyl trimethoxy silane, Y- (methacryloyloxy) propyl trimethoxy silane and Y-mercaptopropyl trimethoxy silane.
5. The method of making hollow nitrogen-doped carbon nanospheres of claim 3, wherein the surfactant comprises a poloxamer;
and/or, the organic carbon source comprises resorcinol and formaldehyde;
and/or the organic nitrogen source comprises at least one nitrogen source of urea, hexamethylenetetramine, dicyandiamide and melamine and formaldehyde;
and/or the temperature of the hydrothermal reaction is 90-110 ℃, and the duration is 12-36 hours.
6. The method for preparing the hollow nitrogen-doped carbon nanosphere according to claim 5, wherein the molar ratio of the resorcinol to the formaldehyde is (0.1-0.5): 1;
and/or the molar ratio of the nitrogen source to the formaldehyde is (0.1-0.4): 1.
7. The method of manufacturing the hollow nitrogen-doped carbon nanoball of claims 1 to 6, wherein the hollow nitrogen-doped carbon nanoball has a particle size of 150 to 400nm;
and/or the surface aperture of the hollow nitrogen-doped carbon nanosphere is 40-100 nm.
8. A hollow nitrogen-doped carbon nanoball manufactured by the method of any one of claims 1 to 7.
9. The hollow nitrogen-doped carbon nanoball of claim 8, wherein the particle size of the hollow nitrogen-doped carbon nanoball is 150-400 nm; the surface aperture of the hollow nitrogen-doped carbon nanosphere is 40-100 nm.
10. Use of the hollow nitrogen-doped carbon nanoball of any one of claims 8 to 9 in catalyst, secondary battery, capacitor, sensor, biomedicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211556683.XA CN115818622A (en) | 2022-12-06 | 2022-12-06 | Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211556683.XA CN115818622A (en) | 2022-12-06 | 2022-12-06 | Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115818622A true CN115818622A (en) | 2023-03-21 |
Family
ID=85544225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211556683.XA Pending CN115818622A (en) | 2022-12-06 | 2022-12-06 | Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115818622A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032321A (en) * | 2017-06-14 | 2017-08-11 | 山东科技大学 | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application |
| CN108557822A (en) * | 2018-08-02 | 2018-09-21 | 合肥学院 | Preparation method of surface organic modified titanium carbide nanosheet |
| CN110252378A (en) * | 2019-07-04 | 2019-09-20 | 福州大学 | A kind of monatomic double activity center Co base ammonia synthetic catalyst and preparation method thereof |
| KR20210087674A (en) * | 2020-01-03 | 2021-07-13 | 경북대학교 산학협력단 | Absorbent having MXene beads coated with prussian blue and cesium removal method using the same |
| CN114797936A (en) * | 2022-04-19 | 2022-07-29 | 东莞理工学院 | Novel CO 2 Reduction catalyst, application and preparation method thereof |
-
2022
- 2022-12-06 CN CN202211556683.XA patent/CN115818622A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032321A (en) * | 2017-06-14 | 2017-08-11 | 山东科技大学 | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application |
| CN108557822A (en) * | 2018-08-02 | 2018-09-21 | 合肥学院 | Preparation method of surface organic modified titanium carbide nanosheet |
| CN110252378A (en) * | 2019-07-04 | 2019-09-20 | 福州大学 | A kind of monatomic double activity center Co base ammonia synthetic catalyst and preparation method thereof |
| KR20210087674A (en) * | 2020-01-03 | 2021-07-13 | 경북대학교 산학협력단 | Absorbent having MXene beads coated with prussian blue and cesium removal method using the same |
| CN114797936A (en) * | 2022-04-19 | 2022-07-29 | 东莞理工学院 | Novel CO 2 Reduction catalyst, application and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨颖 等: "碳纳米管的结构、性能、合成及其应用", 31 May 2018, 电子科技大学出版社, pages: 22 - 23 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | A multiple coating route to hollow carbon spheres with foam-like shells and their applications in supercapacitor and confined catalysis | |
| US9126840B2 (en) | Thioether-bridged organic/inorganic composite and method for preparing hollow or porous carbon structures and silica structures using the same | |
| EP3828133A1 (en) | Mesoporous carbon and manufacturing method of the same, and polymer electrolyte fuel cell | |
| US20150352522A1 (en) | Carbon material for catalyst support use | |
| CN107481827B (en) | The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs | |
| EP2626131A1 (en) | Highly sinter-stable metal nanoparticles supported on mesoporous graphitic particles and their use | |
| US20140183415A1 (en) | Graphene-Based Composite and Method of Preparing the Same | |
| KR20130097640A (en) | Method for producing two-dimensional sandwich nanomaterials based on graphene | |
| CN109174155A (en) | A kind of preparation method and applications of loose porous coated with silica Co-N-C hollow Nano tube material | |
| JP2007220414A (en) | Catalyst layer and polymer electrolyte fuel cell | |
| KR20220062552A (en) | Electroactive materials for use in metal-ion batteries | |
| CN111892039A (en) | MXene and carbon nanotube composite hollow nanosphere and autocatalytic preparation method and application thereof | |
| Zhu et al. | A one-step ultrasonic spray pyrolysis approach to large-scale synthesis of silica microspheres | |
| CN115818622A (en) | Hollow nitrogen-doped carbon nanosphere and preparation method and application thereof | |
| WO2023282036A1 (en) | C/sic composite particles and their manufacturing method, electrode catalyst and polymer electrolyte fuel cell comprising the c/sic composite particles | |
| JP2019169317A (en) | Monodispersed spherical carbon porous body and polymer electrolyte fuel cell | |
| RU2530124C2 (en) | Carbon material and method for production thereof | |
| KR20220072301A (en) | Porous carbon body containing heterogeneous pores and manufacturing method for the same | |
| JP7284776B2 (en) | Mesoporous carbon, electrode catalyst and catalyst layer for fuel cell | |
| US20230299308A1 (en) | Mesoporous carbon, electrode catalyst for fuel cell, and catalyst layer | |
| CN111333059B (en) | Silver-doped sea urchin-shaped copper oxide/multilayer graphene composite material, preparation method and glucose sensor | |
| US20240006619A1 (en) | Catalyst for fuel cell | |
| Umegaki et al. | Role of Interparticle Space in Hollow Spheres of Silica-Based Solid Acids on Their Acidic Properties and Activity for Hydrolytic Dehydrogenation of Ammonia Borane | |
| CN116550358A (en) | N-carbon@Ag-void@SiO 2 Preparation method and application of nano catalyst with yolk-eggshell structure | |
| CN115679359A (en) | Highly graphitized mesoporous carbon microsphere material, preparation method thereof and application thereof in electrocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |