CN108714432A - A kind of photocatalysis hydrogen production catalyst and preparation method thereof - Google Patents
A kind of photocatalysis hydrogen production catalyst and preparation method thereof Download PDFInfo
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- CN108714432A CN108714432A CN201810586881.8A CN201810586881A CN108714432A CN 108714432 A CN108714432 A CN 108714432A CN 201810586881 A CN201810586881 A CN 201810586881A CN 108714432 A CN108714432 A CN 108714432A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 64
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004327 boric acid Substances 0.000 claims abstract description 29
- 239000004202 carbamide Substances 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract 2
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 2
- 238000000227 grinding Methods 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 229910052571 earthenware Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 34
- 239000000203 mixture Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 229910052582 BN Inorganic materials 0.000 description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
-
- 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
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
A kind of photocatalysis hydrogen production catalyst and preparation method thereof, catalyst are h-BN (x, t), and 1/6≤x≤1/48,30min≤t≤50min, wherein x are the ratios of boric acid and urea, and t is microwave heating time.Preparation method is：Boric acid and urea are fully dissolved with deionized water, then dried in an oven, sample is evaporated and is transferred in mortar and grind 3；It is then transferred in 25 milliliters of alumina crucible, it is integrally put into 50 milliliters of alumina crucible again and is covered with alumina silicate, it is finally put into 200 milliliters of alumina crucible and is covered with copper oxide by them, be then transferred to heat 30~50 minutes in micro-wave oven and obtain finished product.The catalyst has good photocatalytic hydrogen production activity, has preferable actual application prospect.
Description
Technical field
The present invention relates to photocatalysis hydrogen production field of material technology, more particularly to a kind of photocatalysis hydrogen production catalyst and its preparation
Method.
Background technology
The energy is the important substance basis that human society is depended on for existence and development.Currently, the energy that the mankind use is mainly
Non-regeneration energy based on fossil fuel, the fossil energy based on oil, natural gas, coal will be in the year two thousand fifty by inference
SO preceding with nothing left, while being generated when fossil energy use2、CO2It is a series of that equal pernicious gases have caused acid rain and greenhouse effects etc.
Environmental problem, energy problem have become the huge obstruction of social sustainable development.Therefore, in order to realize society sustainable development
Exhibition, cleaning, efficient, reproducible new energy development is extremely urgent.
Hydrogen energy source is because it is with high heating value, product cleaning, a kind of protium rich reserves on earth, it is considered to be ideal
Secondary energy sources.Currently, the production of hydrogen energy source is main or reformation by coal and natural gas, this improvement for energy resource structure
There is no practical significance.Photocatalysis technology absorbs sunlight by photochemical catalyst, and catalyst is made to inspire hole and electronics, hollow
Cave is consumed by the sacrifice agent in reaction system and hydrogen is made in electronics and water reaction, and entire light hydrogen production process green non-pollution is
Obtain one of optimal approach of hydrogen energy source.
Hexagonal phase boron nitride (h-BN) is a kind of III-V important compounds of group, have with layer structure as graphite-like,
Show many excellent physics and chemical property.It has high-fire resistance, high-termal conductivity, anti-oxidant, coefficient of thermal expansion is low, rub
Wipe the features such as coefficient is low, and processability is good, and through performance is good.In addition, h-BN chemical stabilities are high, there is extraordinary anti-corruption
Corrosion energy has huge application prospect in high temperature, high frequency, high-power, photoelectron and radioresistance etc..In recent years, people
It was found that h-BN can be used as hole trapping agents to promote the separation of photo-generated carrier, also there is good performance in photocatalysis field.
Such as Song etc. modifies Ag using h-BN3PO4, it is effective improve material light catalysis degradation of dye performance (RSC Adv, 2014,4:
56853)；Jiang etc. is prepared for h-BN/g-C3N4The introducing of composite catalyst, h-BN makes the activity of catalyst degradation tetracycline carry
2.3 times high (Appl Catal B, 2018,221:715), Nasr etc. then improves Ag/TiO with h-BN modifications2Catalyst can
Light-exposed sterilization ability (New J Chem, 2018,42:1250).Or but the h-BN employed in these researchs is quotient
The h-BN of product, that is, pass through B2O3And NH4High temperature congruent melting is made Cl under an inert atmosphere；Or using boric acid and urea as raw material,
Nitrogen or the lower 900 DEG C of roastings of nitrogen and hydrogen mixture atmosphere obtain for 5 hours.In addition, also there is the preparation of other h-BN to be seen in report, such as electric arc
Electric discharge, laser heating, chemical vapour deposition technique etc..But all these methods are almost required for complicated and expensive set
Standby or harsh preparation condition.
Invention content
The technical problem to be solved in the present invention is to provide a kind of photocatalysis hydrogen productions with high efficiency photocatalysis hydrogen manufacturing performance to urge
Agent and preparation method thereof.
To solve the technical problem, the technical solution adopted by the present invention is：A kind of photocatalysis hydrogen production catalyst, feature exist
In：The catalyst is h-BN (x, t), 1/6≤x≤1/48；30min≤t≤50min, wherein x are the ratio of boric acid and urea, t
It is microwave heating time.
The optimal proportion of x is 1:24；Best heating time t is 35min.
The preparation method of the catalyst includes the following steps:
(1) BN is produced
A) boric acid and urea for weighing certain mol proportion example, are poured into the beaker equipped with 40 ml deionized waters,
Being stirred 30 minutes on magnetic stirring apparatus makes it fully dissolve.
B) mixed liquor is moved on in baking oven 65 DEG C to dry 24 hours, is evaporated sample and is transferred in mortar and grinds 30 minutes.
C) sample is transferred in 25 milliliters of alumina crucible after grinding, then it is integrally put into 50 milliliters of aluminium oxide earthenware
It covers in crucible and with alumina silicate, be finally put into 200 milliliters of alumina crucible and covered with copper oxide by them,
This crucible suit, which is transferred to heating different time in micro-wave oven, can obtain target product h-BN.
The present invention substitutes traditional high temperature process furnances using microwave method and produces target product hexagonal phase boron nitride, this method letter
Folk prescription just, can produce hexagonal phase boron nitride, greatly shorten the sample preparation time in a short time.Pass through the optimization of experiment condition, hair
Now best microwave heating time is 35 minutes；The optimal proportion of boric acid and urea is 1:24.The h-BN tools prepared under the conditions of this
There is best photocatalysis hydrogen production performance.
This catalyst has the characteristics that：1. the preparation process of nitridation B catalyst prepared by the present invention is mainly common
Micro-wave oven in complete, quick heating, cooling is also fast, and the time of sample preparation is short, and preparation method is easy；2. boron nitride prepared by the present invention
Hydrogen producing rate of the catalyst under full spectrum light photograph can reach 355.98 μm of olh-1·g-1, have good light and urge
Change hydrogen production activity.In summary feature, nitridation B catalyst prepared by microwave method have preferable actual application prospect.The present invention
Provide a kind of method of extremely simple preparation hexagonal phase boron nitride.The method had not both needed the instrument and equipment of complex and expensive,
Harsh preparation condition is not needed, it is only necessary to which common microwave stove can synthesize hexagonal phase nitridation as microwave generating apparatus yet
Boron, experiment condition are also very simple, it is only necessary to which preparation can be completed in dozens of minutes, and experimental period is short.Pass through party's legal system
The hexagonal phase boron nitride obtained also has good photocatalytic hydrogen production activity.According to above description, the present invention and other six sides
The preparation method of phase boron nitride compares with obviously advantage.
Description of the drawings
Fig. 1 is three crucible suit figures.
Fig. 2 is the photocatalytic hydrogen production activity figure of embodiment 1-5.
Fig. 3 is the photocatalytic hydrogen production activity figure of embodiment 6-9.
Fig. 4 is the photocatalytic hydrogen production activity figure of embodiment 2 and Comparative Examples 1 and 2.
Fig. 5 is the XRD characterization collection of illustrative plates of embodiment 2 and Comparative Examples 1 and 2.
Specific implementation mode
Using embodiment below, the present invention is furture elucidated, but the present invention is not limited to following embodiment.
Embodiment 1
By 8.64g urea and 0.370g boric acid (nBoric acid:nUrea=1:24) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirring apparatus is stirred for making it dissolve for 30 minutes, then by the mixture after stirring be put into 65 DEG C of baking ovens dry it is 24 small
When, then gained mixture is moved in mortar and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible
In, then it is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally by 50 milliliters of aluminium oxide
Crucible is put into 200 milliliters of alumina crucible and is covered with copper oxide by them, and three crucible suits are shown in Fig. 1, then
Can be obtained within 30 minutes x with microwave stove heat is 1:24, t be 30 minutes hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 2 is
165.74μmol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 2
By 8.64g urea and 0.370g boric acid (nBoric acid:nUrea=1:24) 40 milliliters are added to go, from water, to use magnetic at room temperature
Power blender is stirred 30 minutes and is made it dissolve, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, then
Gained mixture is moved in mortar and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, is finally put into 50 milliliters of alumina crucible
It is covered in 200 milliliters of alumina crucible and with copper oxide by them, three crucible suits are shown in Fig. 1, then use micro-wave oven
It is 1 that heating, which can be obtained x for 35 minutes,:24, t be 35 minutes hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 2 is 355.98 μm of ol
h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.XRD characterization collection of illustrative plates is shown in Fig. 5, passes through
With the comparison of the XRD spectrum of comparative example 1 and comparative example 2, determine that gained sample is target product hexagonal phase boron nitride.
Embodiment 3
By 8.64g urea and 0.370g boric acid (nBoric acid:nUrea=1:24) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 1 that stove heat, which can be obtained x for 40 minutes,:24, t be 40 minutes hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 2 is 292.27 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 4
By 8.64g urea and 0.370g boric acid (nBoric acid:nUrea=1:24) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 1 that stove heat, which can be obtained x for 45 minutes,:24, t be 45 minutes hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 2 is 36.38 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 5
By 8.64g urea and 0.370g boric acid (nBoric acid:nUrea=1:24) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 1 that stove heat, which can be obtained x for 50 minutes,:24, t be 50 minutes hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 2 is 35.78 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 6
By 8.64g urea and 1.482g boric acid (nBoric acid:nUrea=1:6) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 35 minutes that stove heat, which can be obtained t for 35 minutes, x 1:6 hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 3 is 10.50 μm of ol
h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is dominant.
Embodiment 7
By 8.64g urea and 0.741g boric acid (nBoric acid:nUrea=1:12) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 35 minutes that stove heat, which can be obtained t for 35 minutes, x 1:12 hexagonal phase boron nitride；Hydrogen production activity is shown in that Fig. 3 is 43.59 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 8
By 8.64g urea and 0.247g boric acid (nBoric acid:nUrea=1:36) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 35 minutes that stove heat, which can be obtained t for 35 minutes, x 1:36 hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 3 is 268.42 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Embodiment 9
By 8.64g urea and 0.185g boric acid (nBoric acid:nUrea=1:48) it is added in 40 ml deionized waters, uses at room temperature
Magnetic stirrer makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, so
Gained mixture is moved in mortar afterwards and is ground 30 minutes, the mixture after grinding is put into 25 milliliters of alumina crucible, then
It is integrally put into 50 milliliters of alumina crucible and is covered with alumina silicate, finally puts 50 milliliters of alumina crucible
They are covered in 200 milliliters of alumina crucibles and with copper oxide, three crucible suits are shown in Fig. 1, then use microwave
It is 35 minutes that stove heat, which can be obtained t for 35 minutes, x 1:48 hexagonal phase boron nitride.Hydrogen production activity is shown in that Fig. 3 is 129.92 μ
mol·h-1·g-1, in Fig. 4 comparative example 1 and comparative example 2 compared with, hydrogen production activity is obviously dominant.
Comparative example 1
8.64g urea and 0.370g boric acid are mixed, is added in 40 ml deionized waters, uses magnetic stirring apparatus at room temperature
Stirring makes it dissolve for 30 minutes, then the mixture after stirring is put into 24 hours of drying in 65 DEG C of baking ovens, and gained mixture moves
It grinds 30 minutes, and is transferred in aluminium oxide ship shape crucible in mortar, is put into high temperature process furnances under nitrogen atmosphere with 10
DEG C/min be warming up to 900 DEG C roast 5 hours.Hexagonal phase boron nitride is obtained after natural cooling.Hydrogen production activity is shown in Fig. 4 .XRD characterizations
Collection of illustrative plates is shown in Fig. 5.
Comparative example 2
The finished product hexagonal phase boron nitride of purchase；Hydrogen production activity is shown in that Fig. 4 .XRD characterization collection of illustrative plates is shown in Fig. 5.
Labsolar III-(AG) the type hydrogen manufacturing of the photocatalytic hydrogen production activity of catalyst in Beijing Bo Feilai Science and Technology Ltd.s
It is carried out in system, Beijing bodyguard is that the GC-7806 type gas chromatographs of Pu Xin Analytical Instrument Co., Ltd carry out the inspection of hydrogen product
It surveys.Light source uses the PLS-SXE300UV light sources (illuminator power 300W) of Beijing Bo Feilai Science and Technology Ltd.s.Photocatalysis system
Hydrogen reaction solution used is 100ml methanol solutions (20ml methanol+80ml water), catalyst amount 0.1g.1mL concentration is added simultaneously
It is the chloroplatinic acid of 1g/L to promote Photocatalyzed Hydrogen Production performance.Photocatalytic activity tests total duration 1.5h, and per 15min, sampling is primary.
The household that the microwave heating equipment used when catalyst preparation produces for Guangdong Glanz microwave living electric apparatus Manufacturing Co., Ltd
Micro-wave oven, specifications and models P70D20TL-D4, power 700W, heating use high fire screen.
Fig. 1 is that three crucibles are set with；The photocatalytic hydrogen production activity of above example 1~9 and comparative example 1~2 see Fig. 2,
Fig. 3 and Fig. 4, Fig. 2 are certain for the molar ratio of urea and boric acid, and the hydrogen manufacturing of the hexagonal phase boron nitride under different roasting times is lived
Property；Fig. 3 is that roasting time is certain, the hydrogen production activity of ratio (molar ratio of urea and boric acid) different hexagonal phase boron nitride.
By evaluation result it is found that the photocatalytic activity of example 1~2 and Examples 1 to 9, embodiment 2 have best photocatalysis by comparing
Activity, photocatalysis hydrogen production efficiency have reached 355.98 μm of olh-1·g-1, and the hydrogen production activity of hexagonal phase boron nitride is commercialized
Only 0.7 μm of olh-1·g-1, the superiority of the hexagonal phase boron nitride through more further embodying microwave method roasting above
(not only preparation method is easy, but also has excellent hydrogen production activity)；Fig. 5 is the XRD tables of comparative example 1, comparative example 2, embodiment 2
Sign figure can determine that obtained sample is exactly target product hexagonal phase boron nitride by XRD characterization.
Claims (3)
1. a kind of photocatalysis hydrogen production catalyst, it is characterised in that：The catalyst is h-BN (x, t), 1/6≤x≤1/48,30min
≤ t≤50min, wherein x are the ratios of boric acid and urea, and t is microwave heating time.
2. photocatalysis hydrogen production catalyst according to claim 1, it is characterised in that：X is 1:24；T is 35min.
3. the preparation method of catalyst described in claims 1 or 2, it is characterised in that：The preparation method of the catalyst includes following
Step：
A) boric acid and urea are weighed, is poured into the beaker equipped with deionized water, being stirred 30 minutes on magnetic stirring apparatus makes
It is fully dissolved；
B) mixed liquor is moved on in baking oven 65 DEG C to dry 24 hours, is evaporated sample and is transferred in mortar and grinds 30 minutes；
C) sample is transferred in 25 milliliters of alumina crucible after grinding, then it is integrally put into 50 milliliters of alumina crucible
It is used in combination alumina silicate to cover, is finally put into 200 milliliters of alumina crucible and is covered with copper oxide by them, this earthenware
Crucible suit, which is transferred to heat 30~50 minutes in micro-wave oven, can obtain target product h-BN.
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| CN115445642B (en) * | 2022-09-19 | 2023-10-03 | 佛山科学技术学院 | Coated bifunctional catalyst and preparation method and application thereof |
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