CN109012725A - The graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification - Google Patents
The graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 31
- 239000010439 graphite Substances 0.000 title claims abstract description 31
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010953 base metal Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000012986 modification Methods 0.000 title claims abstract description 25
- 230000004048 modification Effects 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 239000000725 suspension Substances 0.000 claims description 32
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 24
- 238000002604 ultrasonography Methods 0.000 claims description 17
- 239000012901 Milli-Q water Substances 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 16
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 10
- 239000003426 co-catalyst Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006303 photolysis reaction Methods 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition 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
-
- B01J35/39—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/16—Reducing
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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 graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification, it is related to graphite phase carbon nitride and preparation method thereof, and the present invention is in order to solve graphite phase carbon nitride (i.e. g-C3N4) efficiency of light energy utilization is low, the low problem of photocatalytic water splitting hydrogen production activity, it is by NiBxIt is supported on g-C3N4It is upper obtained；Wherein, NiBxRelative to g-C3N4Mass percentage is 0.5wt%, 2.0wt%, 5.0wt%, 8.0wt% or 10wt%, and the present invention is applied to photochemical catalyst field.
Description
Technical field
The present invention relates to graphite phase carbon nitrides and preparation method thereof.
Background technique
Photocatalytic hydrogen production by water decomposition is a kind of Hydrogen Technology that stability and high efficiency is converted solar energy into using semiconductor material,
The main body of photocatalytic system is made of semiconductor, water and co-catalyst.Wherein co-catalyst plays in photolysis water hydrogen reaction
The effects of reducing liberation of hydrogen overpotential, active site is provided.Suitable co-catalyst is selected to optimize photocatalytic system, light is improved and urges
Changing reaction efficiency is still a current important research content.
Co-catalysis material is broadly divided into two major classes, and it is the precious metal material of representative that one kind, which is with Pt, Pd, Ru etc., restricted
The factors such as, at high price few in resource, precious metal material are restricted in photocatalysis practical application.Therefore another in recent years
A kind of material non-noble metallic materials are explored and are applied extensively in co-catalyst.In non-noble metallic materials nickel-base material by
It is absorbed in extensively in its unique PhotoelectrochemicalProperties Properties.Nickel borides is a kind of novel material, analyses oxygen in electrocatalytic hydrogen evolution
Aspect shows original property.Nickel borides is seldom in the application of photocatalysis field, and Li et al. has studied typical unformed transition
The co-catalysis performance in cadmium sulfide (CdS) system such as metal boride (NiB, FeB, NiCoB), the calculated results show
NiB can effectively adsorb Hydrogen Proton, desorption hydrogen molecule during photolysis water hydrogen, therefore nickel borides shows excellent co-catalysis
Performance.
The visible light-responded photochemical catalyst stable as property, g-C3N4Possess suitable forbidden bandwidth (~2.7eV) with
Suitable position of energy band, to attract the sight of numerous researchers.But g-C3N4Also have the shortcomings that its is fatal, i.e. photoproduction
The features such as electronics is quickly compound with hole, and the efficiency of light energy utilization is low.
Summary of the invention
The purpose of the present invention is to solve graphite phase carbon nitride (i.e. g-C3N4) efficiency of light energy utilization is low, photocatalytic water splitting
The low problem of hydrogen production activity, and provide the graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification.
The graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is in g-C3N4Upper loading NiBx；Its
In, NiBxRelative to g-C3N4Mass percentage is 0.5wt%, 2.0wt%, 5.0wt%, 8.0wt% or 10wt%.
The preparation method of the graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is according to the following steps
It carries out:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:0.7~0.8mL；
NiBxRelative to g-C3N4Mass percentage is 0.5wt%.
The preparation method of the graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is according to the following steps
It carries out:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:2.8~2.9mL；
NiBxRelative to g-C3N4Mass percentage is 2.0wt%.
The preparation method of the graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is according to the following steps
It carries out:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:7.1~7.2mL；
NiBxRelative to g-C3N4Mass percentage is 5.0wt%.
The preparation method of the graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is according to the following steps
It carries out:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:11.5~11.6mL；
NiBxRelative to g-C3N4Mass percentage is 8.0wt%.
The preparation method of the graphite phase carbon nitride of base metal base nickel borides modification of the invention, it is according to the following steps
It carries out:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:14.3~14.4mL；
NiBxRelative to g-C3N4Mass percentage is 10wt%.
The present invention include it is following the utility model has the advantages that
Nickel borides (i.e. NiB of the present inventionx) modification graphite phase carbon nitride (i.e. g-C3N4) photolysis water hydrogen schematic diagram, g-C3N4
Light induced electron is generated by visible light (λ > 400nm) and hole, electronics are excited to conduction band and are then rapidly migrated to NiBxSurface is real
The reduction of existing water.And according to theoretical calculation it is found that NiBxThere is the characteristics of being easy to adsorb hydrogen ion and desorption hydrogen molecule.
Therefore, NiBxModify g-C3N4It can achieve efficient photocatalytic water splitting hydrogen production activity.
In g-C3N4The suitable co-catalyst of area load is a kind of letter with the separative efficiency for improving its light induced electron and hole
Single effective method.In consideration of it, nickel borides is introduced g-C for the first time by us3N4In system, the load of co-catalyst nickel borides is inquired into
Amount and the active relationship of photolysis water hydrogen, and its co-catalysis mechanism is furtherd investigate using photoelectricity means.
Detailed description of the invention
Fig. 1 is different loads amount NiBxThe g-C of modification3N4The figure that Photocatalyzed Hydrogen Production rate compares；
Fig. 2 is the NiB of 5.0wt%xModify g-C3N4The Photocatalyzed Hydrogen Production of composite photo-catalyst recycles figure；
Fig. 3 is the NiB of 5.0wt%xModify g-C3N4The electrochemical impedance map figure of composite photo-catalyst；Wherein, A is not
Through NiBxThe g-C of modification3N4Electrochemical impedance figure；B is the NiB through 5.0wt%xModify g-C3N4The resistance of composite photo-catalyst electrochemistry
Anti- figure；
Fig. 4 is the NiB of 5.0wt%xModify g-C3N4The photocurrent response figure of composite photo-catalyst；
Fig. 5 is NiBxModify g-C3N4Photolysis water hydrogen schematic diagram.
Specific embodiment
Specific embodiment 1: the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified, it be
g-C3N4Upper loading NiBx；Wherein, NiBxRelative to g-C3N4Mass percentage be 0.5wt%, 2.0wt%, 5.0wt%,
8.0wt% or 10wt%.
Specific embodiment 2: the preparation side for the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified
Method, it is followed the steps below:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:0.7~0.8mL；
NiBxRelative to g-C3N4Mass percentage is 0.5wt%.
Specific embodiment 3: present embodiment is unlike specific embodiment two: g-C3N and NiCl2The matter of solution
Amount volume ratio is 0.1g:0.72mL.It is other to be identical with embodiment two.
Specific embodiment 4: the preparation side for the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified
Method, it is followed the steps below:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:2.8~2.9mL；
NiBxRelative to g-C3N4Mass percentage is 2.0wt%.
Specific embodiment 5: present embodiment is unlike specific embodiment four: g-C3N and NiCl2The matter of solution
Amount volume ratio is 0.1g:2.88mL.It is other identical as specific embodiment four.
Specific embodiment 6: the preparation side for the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified
Method, it is followed the steps below:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:7.1~7.2mL；
NiBxRelative to g-C3N4Mass percentage is 5.0wt%.
Specific embodiment 7: present embodiment is unlike specific embodiment six: g-C3N and NiCl2The matter of solution
Amount volume ratio is 0.1g:7.195mL.It is other identical as specific embodiment six.
Specific embodiment 8: the preparation side for the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified
Method, it is followed the steps below:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:11.5~11.6mL；
NiBxRelative to g-C3N4Mass percentage is 8.0wt%.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: g-C3N and NiCl2The matter of solution
Amount volume ratio is 0.1g:11.51mL.It is other identical as specific embodiment eight.
Specific embodiment 10: the preparation side for the graphite phase carbon nitride that the base metal base nickel borides of present embodiment is modified
Method, it is followed the steps below:
One, to g-C30.01MNiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath,
0.5MNaBH is added dropwise while stirring4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum
Dry 12h, obtains NiB in drying boxxThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:14.3~14.4mL；
NiBxRelative to g-C3N4Mass percentage is 10wt%.
Specific embodiment 11: present embodiment is unlike specific embodiment ten: g-C3N and NiCl2Solution
Mass volume ratio is 0.1g:14.385mL.It is other identical as specific embodiment ten.
The content of present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several specific embodiments
The purpose of invention also may be implemented in contract sample.
Beneficial effects of the present invention are verified by following embodiment:
Embodiment 1
The NiB of the present embodimentxThe g-C of modification3N4Composite photo-catalyst the preparation method is as follows:
Respectively by the g-C of 5 parts of 0.2g3N4It is placed in 5 50mL beakers, to each g-C3N4Middle addition 0.01MNiCl2It is molten
Liquid, volume are respectively 1.44mL, 5.76mL, 14.39mL, 23.02mL and 28.77mL；It is separately added into high pure nitrogen saturation again
Suspension vol of the ultrapure water into each beaker is 50mL；
Suspension in each beaker, which is respectively placed in ultrasound 30min, ultrasonic power in numerical control ultrasonic cleaner, is
600W；It then passes in ice bath, quickly stirs, while stirring by 0.5MNaBH4In solution after each ultrasound is added dropwise, make
The NaBH of addition4Substance amount be Ni 3 times of (i.e. molar ratio NaBH4: Ni=3) continue to stir 30min to bubble stopping production
It is raw.Sediment is collected by centrifugation respectively, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains different NiB in casexThe NiB of load percentagex/g-C3N4, NiB is obtained by calculationxRelative to g-C3N4Quality
Than for 0.5wt%, 2.0wt%, 5.0wt%, 8.0wt%, 10wt%.
To the present embodiment difference NiBxThe NiB of load percentagex/g-C3N4The comparative analysis of Photocatalyzed Hydrogen Production rate is carried out, as a result
As shown in Figure 1, as shown in Figure 1, as a small amount of NiBxIt is carried on g-C3N4Its photolysis water hydrogen effect can be significantly improved when surface.It is negative
Photocatalytic water hydrogen production activity highest when carrying capacity is 5.0wt%, rate are 176.90 μm of olh-1g-1；When load capacity continues to increase, light
There is decline instead in solution water hydrogen production activity, this may be because of excessive NiBxIt reduces the efficiency of light energy utilization or becomes light
The load center of raw carrier.
To the NiB of the present embodiment 5.0wt%xThe NiB of load percentagex/g-C3N4Photocatalyzed Hydrogen Production circulation is carried out to compare point
Analysis, as a result as shown in Fig. 2, as shown in Figure 2, NiBxThe g-C of modification3N4Composite photo-catalyst has good cyclical stability,
Hydrogen activity is produced after recycling three times not occur significantly reducing.
To the NiB of the present embodiment 5.0wt%xThe NiB of load percentagex/g-C3N4Carry out electrochemical impedance and photocurrent response
Comparative analysis, as a result as shown in Figures 3 and 4, by Fig. 3 and 4 it is found that semi arch size represents composite material in electrochemical impedance map
Electronics transmission process in the drag size received, resistance is bigger, and transfer ability is weaker.The size of photoelectric current is then electronics in Fig. 4
The intuitive reflection of hole separative efficiency height.Fig. 3 and 4 reflects NiB jointlyxIntroducing be conducive to photo-generated carrier effectively point
From, and then promote g-C3N4The active promotion of photolysis water hydrogen.
Embodiment 2
The present embodiment is comparative example, in addition to not adding g-C3N4Outside, same as Example 1 with operating method.
By Examples 1 and 2 it is found that g-C is not added3N4Sample be co-catalyst, here we be inquire into co-catalyst plus
Enter to photochemical catalyst g-C3N4The improvement of H2-producing capacity, therefore the electrochemical impedance provided and photoelectricity flow data are all based on g-
C3N4With NiBxThe g-C of load3N4Comparison between the two.Illustrate that the latter is a kind of NEW TYPE OF COMPOSITE that photocatalysis performance is excellent with this
Photochemical catalyst.
Claims (10)
1. the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is in g-C3N4Upper loading NiBx；Its
In, NiBxRelative to g-C3N4Mass percentage is 0.5wt%, 2.0wt%, 5.0wt%, 8.0wt% or 10wt%.
2. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is according to the following steps
It carries out:
One, to g-C30.01M NiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath, while stirring
It mixes side and 0.5M NaBH is added dropwise4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains NiB in casexThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:0.7~0.8mL；
NiBxRelative to g-C3N4Mass percentage is 0.5wt%.
3. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification according to claim 2, feature
It is g-C3N and NiCl2The mass volume ratio of solution is 0.1g:0.72mL.
4. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is according to the following steps
It carries out:
One, to g-C30.01M NiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath, while stirring
It mixes side and 0.5M NaBH is added dropwise4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains NiB in casexThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:2.8~2.9mL；
NiBxRelative to g-C3N4Mass percentage is 2.0wt%.
5. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification according to claim 4, feature
It is g-C3N and NiCl2The mass volume ratio of solution is 0.1g:2.88mL.
6. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is according to the following steps
It carries out:
One, to g-C30.01M NiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath, while stirring
It mixes side and 0.5M NaBH is added dropwise4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains NiB in casexThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:7.1~7.2mL；
NiBxRelative to g-C3N4Mass percentage is 5.0wt%.
7. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification according to claim 6, feature
It is g-C3N and NiCl2The mass volume ratio of solution is 0.1g:7.195mL.
8. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is according to the following steps
It carries out:
One, to g-C30.01M NiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath, while stirring
It mixes side and 0.5M NaBH is added dropwise4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains NiB in casexThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:11.5~11.6mL；
NiBxRelative to g-C3N4Mass percentage is 8.0wt%.
9. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification according to claim 8, feature
It is g-C3N and NiCl2The mass volume ratio of solution is 0.1g:11.51mL.
10. the preparation method of the graphite phase carbon nitride of base metal base nickel borides modification, it is characterised in that it is according to following step
Suddenly it carries out:
One, to g-C30.01M NiCl is added in N2Solution；The ultrapure water for adding high pure nitrogen saturation obtains suspension；
Two, by suspension 25~35min of ultrasound of previous step, ultrasonic power is 550~650W；It then passes in ice bath, while stirring
It mixes side and 0.5M NaBH is added dropwise4Solution makes NaBH4: the molar ratio of Ni is 3:1；It then proceedes to stirring and stops generating to bubble；
Three, sediment is collected by centrifugation, and for several times with the milli-Q water of high pure nitrogen saturation, is subsequently placed at 25 DEG C of vacuum drying
Dry 12h, obtains NiB in casexThe NiB of loadx/g-C3N4；
Wherein, g-C3N and NiCl2The mass volume ratio of solution is 0.1g:14.3~14.4mL；
NiBxRelative to g-C3N4Mass percentage is 10wt%.
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