CN112717977A - Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material - Google Patents
Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material Download PDFInfo
- Publication number
- CN112717977A CN112717977A CN202110151202.6A CN202110151202A CN112717977A CN 112717977 A CN112717977 A CN 112717977A CN 202110151202 A CN202110151202 A CN 202110151202A CN 112717977 A CN112717977 A CN 112717977A
- Authority
- CN
- China
- Prior art keywords
- boron
- carbon
- nitrogen
- ammonia
- nitrogen material
- 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
- 239000000463 material Substances 0.000 title claims abstract description 61
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000005416 organic matter Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 239000010431 corundum Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 claims description 14
- 238000006303 photolysis reaction Methods 0.000 claims description 11
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method for synthesizing a boron-carbon-nitrogen material by ammonia-free airflow, which comprises the following specific steps: step S1, uniformly mixing 1 part of carbon source solid organic matter, 3-20 parts of boron source solid raw material and 6-200 parts of nitrogen source solid organic matter in parts by weight; step S2, transferring the uniformly mixed powder to a covered arc-bottom corundum boat, then placing the covered arc-bottom corundum boat in the middle of a high-temperature tube furnace, and carrying out high-temperature thermal polymerization reaction under inert gas to obtain a boron-carbon-nitrogen material; the method for synthesizing the boron-carbon-nitrogen material has the advantages of simple process flow, short time consumption, cheap and easily-obtained raw materials, no need of introducing ammonia gas, no generation of a large amount of ammonia-containing waste gas, capability of photolyzing water to produce hydrogen and the like.
Description
Technical Field
The invention relates to the technical field of preparation of boron-carbon-nitrogen materials, in particular to a preparation method and application of a boron-carbon-nitrogen material synthesized by ammonia-free airflow.
Background
Semiconductor photocatalysis technology can convert low-density solar energy into high-density chemical energy (such as H)2、CH4Etc.) or solar energy to drive degradation, mineralization and pollutants, and is a new technology which is expected to solve the problems of energy shortage, environmental pollution and the like. The core direction of the technology is to develop a photocatalyst which is cheap and easy to obtain, strong in stability and high in solar energy conversion rate. The hexagonal phase boron carbon nitride is a novel non-metal photocatalyst material, and has the advantages of good thermal stability and chemical stability, wide raw material source, low toxicity and the like. In 2015, the Wangxinchen subject group firstly adopted the material for reactions such as hydrogen production by photolysis of water, oxygen production, carbon dioxide reduction and the like (nat. Commun.2015,6,7698; Sci. China mater, 2015,58, 867). After that, researchers also find that the boron carbon nitrogen material can be applied to organic matter redox reactions such as photocatalysis phenol synthesis (Catal. today,324,73), benzyl alcohol oxidation (ACS Catal.2018,8,4928), N-heterocyclic dehydrogenation (CN107353245A, CN108546233A) and the like, and the boron carbon nitrogen material has wide application prospects.
There are many methods for synthesizing boron-carbon-nitrogen materials, such as CVD method, high-temperature and high-pressure method, mechanical grinding method, solvothermal method, high-temperature pyrolysis polymerization method, etc. (ACS appl. Most of the methods have harsh synthesis process, precise equipment and low yield, and are not suitable for large-scale synthesis; in addition, the boron-carbon-nitrogen material synthesized by the method has no report on the photocatalytic activity of a semiconductor, and is only suitable for the fields of semiconductor circuits, gas adsorption, fluorescent display, lithium ion batteries, electrochemistry and the like. The boron-carbon-nitrogen material with photocatalytic performance is usually prepared by adopting a high-temperature solid-phase method, and ammonia gas (CN103787289A, CN106430128A and CN108341404A) with a certain flow rate is continuously introduced in the synthesis process. The ammonia gas is used as a reducing atmosphere to reduce a boron source and a carbon source, is a nitrogen source, and is one of essential raw materials in the synthesis of the boron-carbon-nitrogen material. Therefore, in the conventional method, it is indispensable to introduce ammonia gas into the reaction. However, ammonia gas is a toxic gas with pungent odor, and if ammonia gas is continuously introduced in the whole high-temperature polymerization process, a large amount of ammonia-containing waste gas is generated, and the environment is greatly damaged.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a preparation method for synthesizing a boron-carbon-nitrogen material by using a gas flow without ammonia gas and application thereof, expensive instruments and raw materials are not needed, and the process flow is simple; the boron-carbon-nitrogen material can be synthesized in batch without continuously introducing toxic ammonia gas with serious environmental pollution. Therefore, the invention can better overcome the defects of the prior art displayed by the background part and has wide application prospect. Meanwhile, the boron carbon nitride material prepared by the invention is a semiconductor photocatalytic material, has proper band gap width and energy band structure position, has the semi-reaction performance of hydrogen production by photolysis of water, and is a photocatalyst material with great potential.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a preparation method for synthesizing a boron-carbon-nitrogen material by ammonia-free airflow comprises the following specific steps: step S1, uniformly mixing 1 part of carbon source solid organic matter, 3-20 parts of boron source solid raw material and 6-200 parts of nitrogen source solid organic matter in parts by weight;
and step S2, transferring the uniformly mixed powder to a covered arc-bottom corundum boat, then placing the covered arc-bottom corundum boat in the middle of a high-temperature tube furnace, and carrying out high-temperature thermal polymerization reaction under inert gas to obtain the boron-carbon-nitrogen material.
Further, the reaction conditions of the high-temperature thermal polymerization reaction are as follows: the heating rate is 2-10 ℃/min; the heat preservation time is 2-8 h; the constant temperature is 900-1500 ℃.
Further, the method for uniformly mixing is one of mechanical grinding mixing, water dissolving dispersion and heating and drying mixing or water dissolving dispersion and freezing and drying mixing.
Further, the carbon source solid organic matter is one of glucose, fructose or citric acid.
Further, the boron source solid raw material is one of boron oxide, boric acid or sodium tetraphenylborate.
Further, the nitrogen source solid organic matter is one of biuret, urea and dicyandiamide.
Further, the inert gas is one of nitrogen, argon and helium; the gas flow rate is 50-500 mL/min.
The application of the boron-carbon-nitrogen material synthesized by the gas flow without ammonia gas is characterized in that the boron-carbon-nitrogen material has the half-reaction performance of hydrogen production by photolysis of water and is applied to the field of photolysis of water but not limited thereto.
(III) advantageous effects
The invention has the beneficial effects that: the present invention introduces common nitrogen source solid organics which decompose at elevated temperatures to release nitrogen-containing species such as ammonia and the like. The nitrogen-containing species generated in situ can not only create a good reducing atmosphere to reduce a boron source and a carbon source, but also serve as a nitrogen source to improve the proportion of nitrogen in the product, thereby obtaining the boron-carbon-nitrogen material with semiconductor photocatalytic performance in one step. Therefore, the method for synthesizing the boron-carbon-nitrogen material has the advantages of simple process flow, short time consumption, cheap and easily-obtained raw materials, no need of introducing ammonia gas, no generation of a large amount of ammonia-containing waste gas, capability of photolyzing water to produce hydrogen and the like.
Drawings
FIG. 1 is an XRD pattern of a boron carbon nitride material in accordance with one embodiment of the present invention;
FIG. 2 is an FT-IR plot of a boron carbon nitride material in accordance with one embodiment of the present invention;
FIG. 3 is a DRS map of a boron carbon nitride material in accordance with one embodiment of the present invention;
FIG. 4 is an SEM image of a boron carbon nitride material in accordance with one embodiment of the invention;
FIG. 5 is a graph showing the half-reaction performance of the boron carbon nitride material in hydrogen production by photolysis of water according to an embodiment of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The preparation method for synthesizing the boron-carbon-nitrogen material by the ammonia-free airflow, provided by the embodiment of the invention, comprises the following specific steps of: step S1, uniformly mixing 1 part of carbon source solid organic matter, 3-20 parts of boron source solid raw material and 6-200 parts of nitrogen source solid organic matter in parts by weight;
and step S2, transferring the uniformly mixed powder to a covered arc-bottom corundum boat, then placing the covered arc-bottom corundum boat in the middle of a high-temperature tube furnace, and carrying out high-temperature thermal polymerization reaction under inert gas to obtain the boron-carbon-nitrogen material.
Further, the reaction conditions of the high-temperature thermal polymerization reaction are as follows: the heating rate is 2-10 ℃/min; the heat preservation time is 2-8 h; the constant temperature is 900-1500 ℃.
Further, the method for uniformly mixing is one of mechanical grinding mixing, water dissolving dispersion and heating and drying mixing or water dissolving dispersion and freezing and drying mixing.
Further, the carbon source solid organic matter is one of glucose, fructose or citric acid.
Further, the boron source solid raw material is one of boron oxide, boric acid or sodium tetraphenylborate.
Further, the nitrogen source solid organic matter is one of biuret, urea and dicyandiamide.
Further, the inert gas is one of nitrogen, argon and helium; the gas flow rate is 50-500 mL/min.
The application of the boron-carbon-nitrogen material synthesized by the gas flow without ammonia gas is characterized in that the boron-carbon-nitrogen material has the half-reaction performance of hydrogen production by photolysis of water and is applied to the field of photolysis of water but not limited thereto.
The invention adopts a strategy of high-temperature solid-phase polymerization, reasonably adjusts the input proportion of solid organic matters such as a boron source, a carbon source, a nitrogen source and the like, and carries out thermal polymerization reaction on the mixture under the conditions of inert atmosphere and high temperature. During the heating process, a higher proportion of the nitrogen source can decompose a certain amount of nitrogen-containing species (such as ammonia gas, etc.) in situ. At the moment, the method not only can create a good reducing atmosphere to reduce a boron source and a carbon source, but also can be used as a nitrogen source to improve the proportion of nitrogen in the product, and is beneficial to producing the boron-carbon-nitrogen material with semiconductor photocatalytic performance. In the invention, expensive instruments and raw materials are not needed, and the process flow is simple; the boron-carbon-nitrogen material can be synthesized in batch without continuously introducing toxic ammonia gas with serious environmental pollution; meanwhile, the boron carbon nitride material prepared by the invention is a semiconductor photocatalytic material, has proper band gap width and energy band structure position, has the semi-reaction performance of hydrogen production by photolysis of water, and is a photocatalyst material with great potential.
As shown in fig. 1, the XRD pattern of the boron carbon nitride material shows two diffraction peaks: (002) interlaminar stacking diffraction peaks with a low angle of 26.4 degrees attributed to the graphite phase characteristics; the high angle of 42.3 ° is attributed to the in-plane six-membered ring repeat unit (100) diffraction peak, and the data indicates that the resulting boron carbon nitride material is a hexagonal phase crystal structure.
As shown in FIG. 2, the FT-IR chart of the boron carbon nitride material shows two characteristic infrared absorption peaks: at 1380cm-1The wider peaks correspond to stretching vibrations in the B-N, C-N and C-C bond planes in the transverse direction; at 780cm-1The peak at (a) corresponds to bending vibration out of the B-N-B bonding plane. In addition, a larger infrared absorption is obtained within the range of 3000-3600 cm < -1 >, and the results correspond to the stretching vibration peaks of N-H with unpolymerized tail ends and O-H of adsorbed water, and all the results accord with the chemical structure characteristics of hexagonal repeating units of the boron-carbon-nitrogen material.
As shown in fig. 3, the DRS graph of the boron carbon nitride material indicates that the synthesized boron carbon nitride material can absorb a certain range of visible light and has the semiconductor performance of a multi-level energy band structure.
As shown in FIG. 4, the SEM image of the B-C-N material shows that the synthesized B-C-N material is irregular bulk material with the size of 10-20 μm.
Example 1
The preparation method for synthesizing the boron-carbon-nitrogen material by the ammonia-free airflow, provided by the embodiment of the invention, comprises the following specific steps of: step S1, uniformly mixing 1 part of glucose, 7 parts of boron oxide and 20 parts of urea in parts by weight;
and step S2, transferring the uniformly mixed powder to a covered arc-bottom corundum boat, then placing the covered arc-bottom corundum boat in the middle of a high-temperature tube furnace, and carrying out high-temperature thermal polymerization reaction under inert gas to obtain the boron-carbon-nitrogen material.
Further, the reaction conditions of the high-temperature thermal polymerization reaction are as follows: nitrogen is taken as carrier gas, and the gas flow is 100 mL/min; the heating rate is 5 ℃/min; keeping the temperature for 5 hours; the constant temperature is 1250 ℃.
Further, the method for uniformly mixing is mechanical grinding and mixing. Dispersing 30mg of boron carbon nitrogen material in 100mL of triethanolamine aqueous solution containing 10 vol.% and adding an amount of chloroplatinic acid solution (such that the loading of Pt atoms is 1 wt.% of the mass of the photocatalyst); transferring the mixed solution into an up-illuminated photolysis water reactor, and reacting by using a xenon lamp (300W) as a light source; from fig. 5, it can be seen that the prepared product has certain photolytic water hydrogen production activity under visible light irradiation (the lambda of the filter at the light source is greater than 420nm) and full-band irradiation (no filter is placed).
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. The preparation method for synthesizing the boron-carbon-nitrogen material by using the ammonia-free gas flow is characterized by comprising the following specific steps of: step S1, uniformly mixing 1 part of carbon source solid organic matter, 3-20 parts of boron source solid raw material and 6-200 parts of nitrogen source solid organic matter in parts by weight;
and step S2, transferring the uniformly mixed powder to a covered arc-bottom corundum boat, then placing the covered arc-bottom corundum boat in the middle of a high-temperature tube furnace, and carrying out high-temperature thermal polymerization reaction under inert gas to obtain the boron-carbon-nitrogen material.
2. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the reaction conditions of the high-temperature thermal polymerization reaction are as follows: the heating rate is 2-10 ℃/min; the heat preservation time is 2-8 h; the constant temperature is 900-1500 ℃.
3. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the uniform mixing method is one of mechanical grinding mixing, water dissolving dispersion and heating drying mixing or water dissolving dispersion and freezing drying mixing.
4. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the carbon source solid organic matter is one of glucose, fructose or citric acid.
5. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the boron source solid raw material is one of boron oxide, boric acid or sodium tetraphenylborate.
6. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the nitrogen source solid organic matter is one of biuret, urea and dicyandiamide.
7. The method for preparing the boron-carbon-nitrogen material synthesized by the airflow without ammonia gas as claimed in claim 1, wherein the method comprises the following steps: the inert gas is one of nitrogen, argon and helium; the gas flow rate is 50-500 mL/min.
8. Use of the ammonia-free gas stream synthesized boron carbon nitride material according to any one of claims 1 to 7, characterized in that: the boron carbon nitrogen material has the half-reaction performance of hydrogen production by photolysis of water, and is applied to the field of photolysis of water but not limited thereto.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110151202.6A CN112717977A (en) | 2021-02-03 | 2021-02-03 | Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110151202.6A CN112717977A (en) | 2021-02-03 | 2021-02-03 | Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112717977A true CN112717977A (en) | 2021-04-30 |
Family
ID=75596810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110151202.6A Pending CN112717977A (en) | 2021-02-03 | 2021-02-03 | Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112717977A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113813926A (en) * | 2021-10-19 | 2021-12-21 | 中国科学院江西稀土研究院 | Porous carbon material with B-N Lewis acid-base pair structure and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6287889B1 (en) * | 1999-01-27 | 2001-09-11 | Applied Diamond, Inc. | Diamond thin film or the like, method for forming and modifying the thin film, and method for processing the thin film |
CN103721737A (en) * | 2014-01-07 | 2014-04-16 | 福州大学 | Non-metallic material for driving photocatalytic decomposition of water by using efficient visible light |
CN107082408A (en) * | 2017-06-22 | 2017-08-22 | 山东大学 | A kind of method that utilization freeze-drying process prepares porous boron carbon nitrogen nanometer sheet |
CN108341404A (en) * | 2018-04-11 | 2018-07-31 | 福州大学 | A kind of three-dimensional porous boron-carbon-nitrogen material and its preparation method and application |
CN110498400A (en) * | 2019-09-27 | 2019-11-26 | 福州大学 | A kind of preparation method and its H of the porous BCN of two-dimensional layer2S selective oxidation application |
-
2021
- 2021-02-03 CN CN202110151202.6A patent/CN112717977A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6287889B1 (en) * | 1999-01-27 | 2001-09-11 | Applied Diamond, Inc. | Diamond thin film or the like, method for forming and modifying the thin film, and method for processing the thin film |
CN103721737A (en) * | 2014-01-07 | 2014-04-16 | 福州大学 | Non-metallic material for driving photocatalytic decomposition of water by using efficient visible light |
CN107082408A (en) * | 2017-06-22 | 2017-08-22 | 山东大学 | A kind of method that utilization freeze-drying process prepares porous boron carbon nitrogen nanometer sheet |
CN108341404A (en) * | 2018-04-11 | 2018-07-31 | 福州大学 | A kind of three-dimensional porous boron-carbon-nitrogen material and its preparation method and application |
CN110498400A (en) * | 2019-09-27 | 2019-11-26 | 福州大学 | A kind of preparation method and its H of the porous BCN of two-dimensional layer2S selective oxidation application |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113813926A (en) * | 2021-10-19 | 2021-12-21 | 中国科学院江西稀土研究院 | Porous carbon material with B-N Lewis acid-base pair structure and preparation method and application thereof |
CN113813926B (en) * | 2021-10-19 | 2024-02-20 | 中国科学院江西稀土研究院 | Porous carbon material with B-N Lewis acid-base pair structure and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20200385878A1 (en) | Copper nanocatalyst, method for preparing the same, and application of the same in the synthesis of acetate or ammonia | |
CN107876087B (en) | preparation of methylamine lead iodine-reduced graphene oxide composite photocatalytic material and application of composite photocatalytic material in photocatalytic hydrogen production | |
CN108067281B (en) | Porous g-C3N4Photocatalyst and preparation method and application thereof | |
CN111115649B (en) | Preparation method of BCN nanosheet, BCN nanosheet prepared by preparation method and application of BCN nanosheet | |
CN108993574B (en) | Preparation method of high-performance graphite-phase carbon nitride photocatalytic material | |
CN113457713A (en) | Preparation method of carbon nitride based single-atom catalyst, product and application thereof | |
CN112473698A (en) | Sulfur vacancy Cu-MoS2Process for preparing catalyst | |
CN112473713A (en) | Sulfur-doped crystalline carbon nitride for producing hydrogen by photocatalytic decomposition of water and preparation method and application thereof | |
CN112209815B (en) | Preparation method of liquid oxygen-containing compound mainly containing formic acid | |
CN113101963A (en) | Ultrathin phosphorus-doped carbon nitride nanosheet, preparation method thereof and method for photocatalytic degradation of bisphenol A | |
CN112076738A (en) | Boron-doped defective zinc oxide and preparation method and application thereof | |
CN112871196A (en) | Preparation method of aminated fluorine-doped carbon nitride photocatalyst | |
CN111644192A (en) | g-C3N4@CdxZn1-xSe composite photocatalyst and preparation method and application thereof | |
CN112537783A (en) | W18O49Modified g-C3N4Application of material in photocatalysis nitrogen fixation | |
CN113856730A (en) | Copper monatomic material, preparation method thereof and application thereof in photocatalysis of CO2Application in reduction | |
CN104944391A (en) | Preparing method of hexagonal boron nitride with high specific surface area | |
CN114289036B (en) | Sulfide photocatalyst containing rare earth elements and preparation method and application thereof | |
CN112717977A (en) | Preparation method and application of ammonia-free airflow synthesis boron-carbon-nitrogen material | |
CN112844410B (en) | Preparation method and application of nickel ion modified bismuth oxysulfide photocatalyst | |
CN113522340A (en) | Photocatalyst composite material for reducing carbon dioxide and preparation method and application thereof | |
CN111439732B (en) | C with good visible light response 6 N 7 Carbon nitride material and preparation method and application thereof | |
CN110227533B (en) | Preparation method of graphite-phase carbon nitride photocatalyst | |
CN112844371A (en) | Catalyst for photolysis of water to produce oxygen and preparation method thereof | |
CN111943152A (en) | Photocatalyst and method for synthesizing ammonia by photocatalysis | |
CN109289898B (en) | Graphite-phase carbon nitride foam composite cuprous oxide quantum dot photocatalytic material and preparation method thereof |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |