CN108380231A - A method of preparing boron-nitrogen-carbon ternary material from carbonitride - Google Patents
A method of preparing boron-nitrogen-carbon ternary material from carbonitride Download PDFInfo
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- CN108380231A CN108380231A CN201810139249.9A CN201810139249A CN108380231A CN 108380231 A CN108380231 A CN 108380231A CN 201810139249 A CN201810139249 A CN 201810139249A CN 108380231 A CN108380231 A CN 108380231A
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- boron
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- carbonitride
- carbon ternary
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- 239000000463 material Substances 0.000 title claims abstract description 53
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 13
- 238000006479 redox reaction Methods 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 43
- 238000010792 warming Methods 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000428 dust Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000337 buffer salt Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- -1 nitrogenous small molecule Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NQZKZGHOYUYCHU-UHFFFAOYSA-N boron;tetraethylazanium Chemical compound [B].CC[N+](CC)(CC)CC NQZKZGHOYUYCHU-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention is milled with nitridation carbon dust using boron hydride and is mixed, and under inert gas protection, pyroreaction is prepared for boron nitrogen carbon ternary material.It is added under conditions of activator, further carries out high temperature stripping, be prepared for the boron nitrogen carbon ternary nano material of high-specific surface area.These obtained nitrogen boron carbon ternary materials are used as elctro-catalyst, can be with electro-catalysis redox reactions and hydrogen evolution reaction.
Description
Technical field
The present invention relates to the preparation of boron-nitrogen-carbon ternary material, stripping and its applications in terms of electrochemical catalysis.
Background technology
Climate warming at present, fossil fuel supply increasingly failure, and the mankind is forced to research and develop various clean energy resource conversions and storage
Device.Such as：The various clean energy resource transformation technologies such as fuel cell, electrolysis water, metal-air battery become various countries' basic research and
The hot spot of application study.The core of these Energy Conversion Technologies is a series of electrochemical process, including redox reactions
(ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER).Redox reactions are the core of fuel cell, hydrogen analysis
It is the key that water decomposition hydrogen manufacturing to go out reaction, therefore explores high performance elctro-catalyst and have great importance.In general, with expensive
Material based on metal, if platinum based catalyst is the elctro-catalyst of most effective redox reactions and hydrogen evolution reaction.
However, due to of high cost and scarcity of resources, its business application is limited.At present non-precious metal catalyst (such as：Cobalt/iron/nickel/
Mn catalyst) it is still prohibitively expensive for large size application, and stability and resistance to acid and alkali are poor.And the hetero atom without metal is mixed
Miscellaneous carbon material overcomes these disadvantages.Carbon material stable chemical performance without metal can be that reaction medium, electronics etc. provide
More reaction channels, to greatly improve catalytic efficiency.Such as, the pyridine N structure in nitrogen-doped carbon material generally believes have
High catalytic activity.And boron atom is introduced in nitrogen-doped carbon material, due to the synergistic effect between two kinds of boron, nitrogen elements, it is expected to
Significantly more improve its chemical property.
Carbonitride (C3N4) it is a kind of new carbon that last decade is paid much attention to by scientific circles, unique chemical constitution
Once caused the strong repercussion of whole world scientific circles and engineering technological and huge vibrations with excellent photocatalytic activity.But from
It is always a sciences problems that carbonitride, which further aggregates into greater area of highly conductive class grapheme material,.This is because nitrogen
Change carbon is more than 700 degrees Celsius in normal pressure and can decompose completely, and the planar structure of bigger is aggregated into without being to continue with.Section of China in 2015
A kind of special pressure apparatus of scholar Gu Lindeng groups, it was demonstrated that carbonitride (C3N4) it is that nitridation graphite can be generated with direct carbonization
(the ACS Appl.Mater.Interfaces 2015,7,19626-19634) of alkene.However this method is difficult to realize largely make
It is standby, and special device is needed, yield is very low.If can have a kind of substance that carbonitride can be allowed to continue to aggregate into the plane of bigger
Structure can prepare the New Two Dimensional material of unique structure.We have screened various drugs based on this problem, it is last I
Find using boron hydride (such as：Sodium borohydride, potassium borohydride, tetrabutyl ammonium borohydride, tetramethyl ammonium borohydride etc.) it can be with
Play the role of this.We have found that the material of obtained this lamellar structure, by similar activator (e.g., potassium hydroxide, hydrogen-oxygen
Change sodium, zinc chloride) etching method can further remove into more thinner lamellar structure.These materials can be with very
High electric conductivity and electro-catalysis ability are still maintained under the constituent content of high N and B.On the other hand, carbonitride itself has had
There is larger conjugation two-dimensional structure, use it as nitrogen and the reactant of carbon source, is conducive to ultimately form the knot with high conjugacy
Structure.
Invention content
The present invention is milled with nitridation carbon dust using boron hydride and is mixed, and under inert gas protection, prepared by pyroreaction
Boron-nitrogen-carbon ternary material.The complete decomposition of carbonitride at high temperature is prevented after boron hydride is added, high yield can be obtained
Amount and the ternary material with satisfactory electrical conductivity.Its significance lies in that provide one kind directly preparing boron-nitrogen-carbon ternary from carbonitride
The method of two-dimensional material.Above-mentioned ternary material is carried out high temperature stripping by the present invention, is further prepared for the boron-of high-specific surface area
Nitrogen-carbon ternary nano material, and used as a kind of catalyst of no metal, it can with electro-catalysis redox reactions (ORR)
And electrolysis water evolving hydrogen reaction (HER).
Preparation process mainly includes the following steps that：
(1) first use nitrogenous small organic molecule (including：Melamine, urea, cyanamide, dicyandiamide etc.) 400~600
DEG C polymerization prepares carbonitride；
(2) carbonitride for obtaining the step (1) and boron hydride (including：Sodium borohydride, potassium borohydride, the tetrabutyl
Ammonium borohydride, tetramethyl ammonium borohydride) it mixes and mills to obtain a kind of hydroborated carbonitride；
(3) product that the step (2) obtains is subjected to pyroreaction under inert gas protection and obtains boron-nitrogen-carbon three
First material；
(4) boron-nitrogen-carbon ternary material for obtaining the step (3) high temperature in the presence of KOH (or NaOH, ZnCl etc.)
Stripping obtains boron-nitrogen-carbon ternary nano material of high-specific surface area.
The present invention is characterized in that：
1, the technique for providing a set of preparation high yield nitrogen-boron-carbon ternary material；
2, the technique includes that use carbonitride be nitrogen, the source of carbon, using boron hydride as boron source, inert gas (such as：
Argon gas, nitrogen, hydrogen and its mixed gas) protection (800~1300 DEG C) of lower high temperature reaction 0.5~5 hour, synthesize boron-nitrogen-carbon
Ternary material；Further high ratio is prepared using activator is added and etches the method for stripping under high temperature (700~1000 DEG C)
Boron-nitrogen of surface area-carbon ternary nano material, and be precipitated instead for electro-catalysis redox reactions and hydrogen as catalyst
It answers.
3, wherein, used carbonitride can be by nitrogenous small molecule (such as：Melamine, urea, cyanamide, double cyanogen
Amine etc.) high-temperature roasting obtains；In carbonitride and boron hydride mixing mill processes, the quality of the two is than scope control foundation：
Weight ratio between carbonitride and boron hydrogen radical (referring to the BH4- contained in boron hydride) is 1：0.1~1：
Between 1.2；Used boron hydride includes：Sodium borohydride, potassium borohydride, tetrabutyl ammonium borohydride, tetramethyl
Ammonium borohydride；
4, wherein, the method for high temperature etching stripping is after the boron-nitrogen-carbon ternary material that will be synthesized is mixed with activator lazy
Property gas shield under, in 700~1000 DEG C etching stripping 1~5 hour.Activator therein can be potassium hydroxide, hydroxide
Sodium or zinc chloride.The weight of activator is to be etched 0.5~3 times of material weight.
5, the boron-nitrogen-carbon ternary material and its ternary nano material obtained may be used as elctro-catalyst and carry out catalytic oxygen
Reduction reaction and hydrogen evolution reaction.
The present invention has the following advantages：
1, the boron-nitrogen-carbon ternary material for preparing high boron, nitrogen content is realized；
2, boron-nitrogen-carbon ternary new material of the high boron, nitrogen content that prepare has two-dimensional slice structure；
3, using boron hydride as boron element source, solve that carbonitride decomposes completely under more than 700 DEG C high temperature asks
Topic；
4, use the carbonitride with big planar structure for reactant, promote to obtain planar conjugate structure account for it is leading
Product；
5, this material can be with electro-catalysis redox reactions and hydrogen evolution reaction as catalyst；
6, the three-element catalytic material prepared by the method for the present invention, the activity and stability in catalytic oxygen reduction reaction are excellent
It is different, it can match in excellence or beauty with commercialized Pt/C (containing 10%Pt) catalyst；
7, the three-element catalytic material prepared by the method for the present invention, can be hydrogen catalyzed in acid, neutral, alkaline aqueous solution
Evolution reaction.
Description of the drawings：
Fig. 1 is scanning electron microscope (SEM) photo of typical boron-nitrogen-carbon ternary nano piece.
Fig. 2 is transmission electron microscope (TEM) photo of typical boron-nitrogen-carbon ternary nano piece.
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates of typical boron-nitrogen-carbon ternary material.Wherein, dotted line is not etched
The XRD diffracted rays of boron-nitrogen-carbon ternary material of processing, solid line are the boron-nitrogen-carbon ternary nano piece etched after lift-off processing
XRD diffracted rays.
Fig. 4 is the x-ray photoelectron spectroscopy figure (XPS) of typical boron-nitrogen-carbon ternary material.
Fig. 5 is typical boron-nitrogen-carbon three-way catalyst and business Pt/C, in 0.1M KOH solutions, redox reactions
Cyclic voltammetry curve compare figure.Wherein, dotted line is the curve of business Pt/C, solid line is boron-nitrogen-carbon ternary nano piece catalyst
Curve.
Fig. 6 be typical boron-nitrogen-carbon three-way catalyst in 0.1M KOH solutions, the linear scan of redox reactions
Curve graph.
Fig. 7 be typical boron-nitrogen-carbon three-way catalyst in 1M potassium hydroxide (KOH) solution, the line of hydrogen evolution reaction
Property scanning curve.
Fig. 8 is typical boron-nitrogen-carbon three-way catalyst in 0.5M sulfuric acid (H2SO4) in solution, the line of hydrogen evolution reaction
Property scanning curve.
Fig. 9 is that in the slow buffer salt of phosphoric acid of 1M, (1M PBS, pH are adjusted to 7.0) solution to typical boron-nitrogen-carbon three-way catalyst
In, the linear scan curve of hydrogen evolution reaction.
Note：Redox reactions test carries out in three-electrode system.Weigh the addition of 3mg boron-nitrogen-carbon three-way catalysts
950 μ L and 50 μ L Nafion (Dupont, 5wt%) solution are ultrasonically treated 15min, take conduct in 10 μ L drop coatings to glass-carbon electrode
Working electrode, platinum electrode are used as to electrode, and for Ag/AgCl electrodes as reference electrode, electrolyte is 0.1M KOH solutions.To oxygen
The electro catalytic activity evaluation of gas reduction is tested using cyclic voltammetry, sweep speed 10mV/s.As shown in figure 5, being to be passed through
Oxygen reaches the test result in the 0.1M KOH solutions after being saturated.Prove that boron-nitrogen-carbon three-way catalyst has good oxygen
Reducing property, under the conditions of static test, oxygen reduction performance is better than Pt/C.The test of dynamic oxygen reducing property uses
Linear sweep voltammetry (LSV) is tested at 1600 rpm with rotating disk electrode (r.d.e).As shown in fig. 6, being in sweep speed
10mV/s。
Hydrogen evolution reaction carries out the test of linear scan curve in three-electrode system.3mg 1-1-NBC are weighed to be added
950 μ L and 50 μ L Nafion (Dupont, 5wt%) solution are ultrasonically treated 15min, 27.5 μ L are taken to be coated onto on L-type glass-carbon electrode
As working electrode, platinum electrode is used as to electrode, and Ag/AgCl electrodes are as reference electrode.Respectively in alkaline electrolyte (1M
KOH solution), acidic electrolysis bath 0.5M H2SO4, tested in neutral electrolyte the phosphoric acid of 1M (delay buffer salt) electrolyte.Its
In, the preparation of neutral electrolyte is：The disodium phosphate soln of the sodium dihydrogen phosphate of the 1M of 390ml and the 1M of 610ml mix, and obtain
It is adjusted to pH=7.0 to 1000ml phosphate buffers, then with 3M KOH solutions.
Specific implementation mode
Technical scheme of the present invention is described further with reference to example.
Embodiment 1
Steps are as follows for the preparation method of boron-nitrogen-carbon ternary material of this example for illustrating the present invention：
Melamine is placed in crucible, crucible external application masking foil package, be placed in Muffle furnace, heating rate be 5 DEG C/
Min is warming up to 600 DEG C of holding 2h, to which carbonitride be prepared.Carbonitride 2g, sodium borohydride 2g is taken to be placed in mortar and grind
30min；Mixture is placed in tube furnace, in the case where argon gas/hydrogen (95/5) is mixed gas protected, heating rate is 5 DEG C/min,
After being warming up to 1000 DEG C of isothermal reaction 2h, Temperature fall.For obtained black powder after washing, centrifuging repeatedly, drying obtains boron-
Nitrogen-carbon ternary material.It is 1.72 grams (yield is up to 43%) to finally obtain boron-nitrogen-carbon ternary material, measures wherein each element
Molar content is boron 36.25%, nitrogen 33.04%, carbon 12.21%, oxygen 18.50%.
Embodiment 2
Steps are as follows for the etching stripping means of boron-nitrogen-carbon ternary material of this example for illustrating the present invention：
Boron-nitrogen-carbon the ternary material obtained in 1g embodiments 1 is taken to be dissolved in 30ml deionized waters with 1.5g potassium hydroxide
In, after ultrasonic or stirring 30min, increases temperature and steam the water in mixture, obtain mixed-powder；The powder is placed on nickel earthenware
It in crucible, and is put into tube furnace, in the case where argon gas/hydrogen (95/5) is mixed gas protected, is warming up to the heating rate of 5 DEG C/min
800 DEG C of etching stripping reaction 2h, Temperature fall.Obtained product is cleaned repeatedly with water, is centrifuged, until the close neutrality of pH value；It dries
Boron-nitrogen-carbon ternary nano the sheet material removed after dry.The molar content for measuring wherein each element is boron
33.69%, nitrogen 34.75%, carbon 25.52%, oxygen 6.04%.
Embodiment 3
Steps are as follows for the preparation method of boron-nitrogen-carbon ternary material of this example for illustrating the present invention：
Melamine is placed in crucible, crucible external application masking foil package is placed in Muffle furnace, is warming up to 600 DEG C of holdings
2h, heating rate is 5 DEG C/min, to prepare carbonitride.Step carbonitride 2g, tetrabutyl ammonium borohydride 14g is taken to be placed in mortar
Middle grinding 30min；Mixture is placed in tube furnace, in the case where argon gas/hydrogen (95/5) is mixed gas protected, heating rate 5
DEG C/min, and after being warming up to 1000 DEG C of isothermal reaction 2h, Temperature fall.Obtained black powder after washing, centrifuging repeatedly, drying
Obtain boron-nitrogen-carbon ternary material.
Embodiment 4
Steps are as follows for the preparation method of boron-nitrogen-carbon ternary nano sheet material of this example for illustrating the present invention：
Boron-nitrogen-carbon the ternary material obtained in 1g embodiments 3 is taken to be dissolved in 30ml deionized waters with 2g potassium hydroxide,
After ultrasonic or stirring 30min, increases temperature and steam the water in mixture to obtain mixed-powder；It places it in nickel crucible, and
It is placed in tube furnace, under nitrogen (99.999%) gas shielded, 900 DEG C of reaction 2h is warming up to the heating rate of 5 DEG C/min, from
So cooling.Obtained product is cleaned repeatedly with water, is centrifuged, until the close neutrality of pH value；Boron-the nitrogen-removed after drying
Carbon ternary nano sheet material.
Embodiment 5
This example is used to illustrate the boron-nitrogen-carbon ternary material and preparation method of the present invention.
Melamine is placed in crucible, crucible external application masking foil package is placed in Muffle furnace, is warming up to 600 DEG C of holdings
2h, heating rate are 5 DEG C/min, prepare carbonitride.Take the carbonitride 1g that step obtains, then take tetramethyl ammonium borohydride 3.5g,
Sodium borohydride 0.5g, which is placed in mortar, grinds 30min；Mixture is placed in tube furnace, in argon gas/hydrogen (95/5) gaseous mixture
Under body protection, heating rate is 5 DEG C/min, after being warming up to 1000 DEG C of isothermal reaction 2h, Temperature fall.Obtained black powder warp
It washes repeatedly, after centrifugation, drying obtains boron-nitrogen-carbon ternary material.
Take 1g boron-nitrogen-carbon ternary materials obtained above and 3g potassium hydroxide to be dissolved in 30ml deionized waters, ultrasound or
After stirring 30min, increases temperature and steam the water in mixture to obtain mixed-powder；It places it in nickel crucible in argon gas/hydrogen
Under gas (95/5) is mixed gas protected, 1000 DEG C of reaction 2h, Temperature fall are warming up to the heating rate of 5 DEG C/min.It will obtain
Product cleaned, centrifuged repeatedly with water, until pH value close to neutrality；Boron-the nitrogen removed after drying-carbon ternary nano sheet material
Material.
Embodiment 6
This example is used to illustrate the boron-nitrogen-carbon ternary material and preparation method of the present invention.
Urea is placed in crucible, crucible external application masking foil package is placed in Muffle furnace, is warming up to 600 DEG C of holding 2h, is risen
Warm rate is 5 DEG C/min, prepares carbonitride.Carbonitride 1g is taken, then tetraethyl ammonium borohydride 4.5g, potassium borohydride 0.5g is taken to be placed in
30min is ground in mortar；Mixture is placed in tube furnace, in the case where argon gas/hydrogen (95/5) is mixed gas protected, heating rate
For 5 DEG C/min, after being warming up to 1000 DEG C of isothermal reaction 2h, Temperature fall.Obtained black powder after washing, centrifuging repeatedly,
Drying obtains boron-nitrogen-carbon ternary material.
Take 1g boron-nitrogen-carbon ternary materials obtained above and 3g potassium hydroxide to be dissolved in 30ml deionized waters, ultrasound or
After stirring 30min, increases temperature and steam the water in mixture to obtain mixed-powder；It places it in nickel crucible in argon gas/hydrogen
Under gas (95/5) is mixed gas protected, 1000 DEG C of reaction 2h, Temperature fall are warming up to the heating rate of 5 DEG C/min.It will obtain
Product cleaned repeatedly with water, centrifuge to pH value close to neutrality；Boron-the nitrogen removed after drying-carbon ternary nano sheet material
Material.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. a kind of preparation method of boron-nitrogen-carbon ternary material, key step include：
(a) carbonitride is first prepared using itrogenous organic substance；
(b) carbonitride is mixed again with boron hydride and is milled；
(c) and then by obtained mixture 800~1300 DEG C of pyroreactions under inert gas protection, are warming up to, are dropped naturally afterwards
Temperature；
(d) through washing, centrifuging repeatedly, boron-nitrogen-carbon ternary material is obtained after dry.
2. boron-nitrogen-carbon the ternary material obtained according to the method in claim 1 and activator (including potassium hydroxide, hydroxide
Sodium, zinc chloride) after mixing, it is warming up to 700~1000 DEG C under inert gas shielding, isothermal reaction 1~5 hour, Temperature fall, then
By washing, centrifuging repeatedly, boron-nitrogen-carbon ternary nano material after etching stripping is obtained after dry.
3. according to the method in claim 1, the carbonitride wherein in step (a) is (to refer to trimerization using itrogenous organic substance
Cyanamide, urea, cyanamide or dicyandiamide) at 400~600 DEG C reaction be prepared.
4. according to the method in claim 1, the boron hydride wherein in step (b) includes sodium borohydride, potassium borohydride, four fourths
The mixture of one or more of base ammonium borohydride, tetramethyl ammonium borohydride.
5. according to the method in claim 1, the dosage of the boron hydride wherein in step (b) is controlled in carbonitride and boron hydrogen radical
(refer to the BH contained in boron hydride4 -) between weight ratio be 1：0.1~1：Between 1.2.
6. according to the product that the method for method of claim 1 or claim 2 is prepared, electro-catalysis is used for as catalyst
Redox reactions and hydrogen evolution reaction.
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