CN110170332A - A kind of carbonitride and preparation method thereof can be used for photocatalysis seawater liberation of hydrogen - Google Patents
A kind of carbonitride and preparation method thereof can be used for photocatalysis seawater liberation of hydrogen Download PDFInfo
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- CN110170332A CN110170332A CN201910537381.XA CN201910537381A CN110170332A CN 110170332 A CN110170332 A CN 110170332A CN 201910537381 A CN201910537381 A CN 201910537381A CN 110170332 A CN110170332 A CN 110170332A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 239000013535 sea water Substances 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- -1 alkali metal salt Chemical class 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 abstract description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Inorganic materials [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Inorganic materials [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 abstract 1
- 239000012298 atmosphere Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
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- 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 content of present invention is selected with a series of alkali metal salt (KI, RbI, CsI, CsBr, CsCl), body phase g-C3N4It is raw material with micro deionized water, certain time is calcined under 550 DEG C of nitrogen atmospheres, carbonitride is modified.Modified carbonitride is able to observe that lattice structure, and the introducing of water makes its surface contain more polyhydroxy, improves the hydrophilicity of material.Alkali metal cation is coordinated on carbonitride in modifying process, the distribution of charges of nitridation carbon surface is further influenced, to realize the separation in its light induced electron and hole.Finally it is applied to photocatalysis seawater liberation of hydrogen, compared to the effect of body phase carbon nitride in deionized water, modified carbonitride is up to 257.7 times in the liberation of hydrogen effect promoting of seawater.Meanwhile the stability of liberation of hydrogen is also obviously improved.Attached drawing: the transmission electron microscope picture (TEM) of CsI modified carbonitride.
Description
Technical field
The present invention relates to a kind of carbonitrides and preparation method thereof that can be used for photocatalysis seawater liberation of hydrogen, belong to nitridation carbon technique
Field.
Background technique
Graphite phase carbon nitride (g-C3N4), as a kind of organic semiconductor catalyst, stablized with its excellent physical chemistry
Property, moderate band gap (about 2.7eV) and extensive photocatalytic applications, the favor by numerous researchers.However, exactly nitrogenizing
The excellent physical and chemical stability of carbon makes it difficult to be modified by surface to enhance its photocatalysis performance.Alkali metal haloid
Halide anion is easy to seize the amino of nitridation carbon surface, makes it have the potentiality modified to nitridation carbon surface.Herein, I
By being modified under the conditions of alkali metal haloid to carbonitride, on the one hand adjust carbonitride lattice structure, make its shape
Promote electronics transfer at the high material of degree of crystallization, on the other hand under the conditions of not melting, alkali metal salt can as template
To improve the specific surface area of modified carbonitride.In addition, partial alkaline-metal salts can utilize coordination introducing portion with carbonitride
Alkali metal ion changes the Cloud Distribution of carbonitride, optimizes the directional migration of charge.It is final to improve g-C3N4Photocatalytic
Energy.
Summary of the invention
1. the present invention is to design a kind of carbonitride that can be used for photocatalysis seawater liberation of hydrogen, using dicyandiamide as precursor preparation body
Phase carbon nitride, alkali metal haloid are modified it, are made by hot polymerization reaction, ultrasonic agitation, centrifuge washing and drying,
It is characterized in that the selection and preparation process of raw material:
(1) weighs a certain amount of dicyandiamide, is laid in quartz boat after being fully ground in mortar, is then put into
In tubular heater；
(2) under nitrogen atmosphere, is warming up to 550 DEG C with the heating rate of 2.3 DEG C/min and keeps 4h, after natural cooling
Flaxen body phase g-C can be obtained3N4.It is collected after these blocks of solid are fully ground spare.It is named as CN；
(3) 500mg CN is placed in mortar by, and total 0.2mL deionized water is added dropwise in process of lapping several times, is fully ground
After add 1000mg alkali metal haloid and be fully ground again, be finally stacked in corundum boat, be placed in tubular type
In furnace；
(4) is heated to 550 DEG C in nitrogen atmosphere with the heating rate of 5 DEG C/min and keeps 2h；
(5) it after the sample cooled to room temperature that is obtained, is stirred by ultrasonic and is scattered in deionized water, use deionization
Water centrifuge washing 3 times；
(6) drying overnight in 60 DEG C of baking oven obtains the modified carbonitride of alkali metal salt, and collection is spare, according to addition
Alkali metal haloid difference be respectively designated as KI-CN, RbI-CN, CsI-CN, CsBr-CN and CsCl-CN.
Based on the outstanding photochemical properties of the modified carbonitride of alkali metal haloid, we apply it to photocatalysis
On seawater liberation of hydrogen.To each sample in pure water, simulated seawater (the NaCl aqueous solution of 3.5wt.%), Huanghai Seawater and South China Sea
The comparison of photocatalysis Hydrogen Evolution Performance is done, the photocatalysis Hydrogen Evolution Performance of each sample in the seawater increases.Wherein, CsI-CN is being adopted
When with Huanghai Seawater, the hydrogen-separating quantity of 4h has reached 46.38 μm of ol, is 5.9 of the sample in deionized water (7.89 μm of ol)
Times, it is 113.1 times in Huanghai Seawater (0.41 μm of ol), 257.7 times in deionized water (0.18 μm of ol) of CN.This is sufficiently
Illustrate that the modified carbonitride of alkali metal haloid is more suitable resource seawater liberation of hydrogen more abundant.
Detailed description of the invention
The transmission electron microscope picture (TEM) of Fig. 1: CsI modified carbonitride (CsI-CN)；
The scanning electron microscope (SEM) photograph (SEM) of Fig. 2: CsI modified carbonitride (CsI-CN)；
Fig. 3: the Solid fluorescene spectrum that each sample is excited in 380nm, it can be seen that the modified nitridation of alkali metal haloid
The fluorescence intensity of carbon is decreased obviously compared with CN, this illustrates that these materials have the separation of more preferably light induced electron and hole
Ability；
Fig. 4: the uv-visible absorption spectra of each sample；
Fig. 5: the X ray diffracting spectrum (XRD) of each sample, it can be seen that carry out two only by simple and a small amount of water
On the crystalline structure of carbonitride and crystallinity, almost without what influence, the sample that alkali metal haloid obtains is added in secondary calcining
XRD occurs significantly to change；It is similar to it can be seen that KI-CN, RbI-CN, CsI-CN, CsBr-CN and CsCl-CN all have
The crystal phase of PHI；
Fig. 6: the Fourier transform infrared spectroscopy (FT-IR) of each sample, it can be seen that all samples all have carbonitride
Characteristic peak, in 2400-3650cm-1Broad absorption band show material surface there are hydroxyls, the water and terminal amino group of absorption；
Table 1: by the constituent content of the obtained each sample of XPS, it can be seen that the modified carbonitride table of alkali metal haloid
Cation is contained in face, and is practically free of anion；
Fig. 7: each sample reacts the photocatalysis liberation of hydrogen yield of 4h in deionized water, simulated seawater, the Huanghai Sea and South China Sea
Histogram, it can be found that hydrogen output of all samples in real sea water all gets a promotion, the modified nitrogen of alkali metal haloid
It is more obvious to change the yield that carbon is promoted.
Fig. 8: CsI-CN under the conditions of deionized water photocatalysis liberation of hydrogen cyclical stability test chart (left side) CsI-CN in Huang
The cyclical stability test chart (right side) of photocatalysis liberation of hydrogen under extra large sea conditions.
Specific embodiment
Carry out enumeration technical characterstic of the invention below in conjunction with specific embodiment.
Embodiment 1
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.After being fully ground again
1000mg KI is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace, in nitrogen gas
550 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere and keep 2h.After obtained sample cooled to room temperature, surpassed
Sound is dispersed with stirring in deionized water.Finally, with deionized water centrifuge washing 3 times, the drying overnight in 60 DEG C of baking oven.It will dry
Dry sample is collected spare after being fully ground.Sample is named as KI-CN.It is used respectively according to identical reaction condition in embodiment 1
In photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity is respectively 11.73,13.5,
26.27、28.23μmol。
Embodiment 2
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.After being fully ground again
1000mg RbI is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace, in nitrogen gas
550 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere and keep 2h.After obtained sample cooled to room temperature, surpassed
Sound is dispersed with stirring in deionized water.Finally, with deionized water centrifuge washing 3 times, the drying overnight in 60 DEG C of baking oven.It will dry
Dry sample is collected spare after being fully ground.Sample is named as RbI-CN.It is used respectively according to identical reaction condition in embodiment 1
In photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity is respectively 12.84,20.27,
34.91、34.02μmol。
Embodiment 3
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.After being fully ground again
1000mg CsI is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace, in nitrogen gas
550 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere and keep 2h.After obtained sample cooled to room temperature, surpassed
Sound is dispersed with stirring in deionized water.Finally, with deionized water centrifuge washing 3 times, the drying overnight in 60 DEG C of baking oven.It will dry
Dry sample is collected spare after being fully ground.Sample is named as CsI-CN.It is used respectively according to identical reaction condition in embodiment 1
In photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity is respectively 7.9,33.62,46.38,
43.21μmol。
Embodiment 4
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.After being fully ground again
1000mg CsBr is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace, in nitrogen
550 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere and keep 2h.After obtained sample cooled to room temperature, by it
Ultrasonic agitation is scattered in deionized water.Finally, with deionized water centrifuge washing 3 times, the drying overnight in 60 DEG C of baking oven.It will
The sample of drying is collected spare after being fully ground.Sample is named as CsBr-CN.According to identical reaction condition in embodiment 1 point
Not Yong Yu photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity is respectively 12.16,37.91,
52.84、48.61μmol。
Embodiment 5
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.After being fully ground again
1000mg CsCl is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace, in nitrogen
550 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere and keep 2h.After obtained sample cooled to room temperature, by it
Ultrasonic agitation is scattered in deionized water.Finally, with deionized water centrifuge washing 3 times, the drying overnight in 60 DEG C of baking oven.It will
The sample of drying is collected spare after being fully ground.Sample is named as CsCl-CN.According to identical reaction condition in embodiment 1 point
Not Yong Yu photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity is respectively 10.96,28.65,
39.88、35.72μmol。
Comparative example 1
10g dicyandiamide is laid in quartz boat after being fully ground in mortar, after quartz boat is wrapped up with aluminium-foil paper
It is placed in tube furnace.Under nitrogen atmosphere, 550 DEG C are warming up to the heating rate of 2.3 DEG C/min and keep 4h, natural cooling
After flaxen body phase g-C can be obtained3N4.It is collected after these blocks of solid are fully ground spare.It is named as CN.According to implementation
Identical reaction condition is respectively used to photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h analysis in example 1
Hydrogen amount is respectively 0.18,0.27,0.41,0.35 μm of ol.
Comparative example 2
500mg CN is placed in mortar, total 0.2mL deionized water is added dropwise in process of lapping several times.It will after being fully ground
It is stacked in corundum boat, is then placed in tube furnace, is heated in nitrogen atmosphere with the heating rate of 5 DEG C/min
550 DEG C and keep 2h.It is collected after obtained sample cooled to room temperature spare.It is named as CN-2h.According to phase in embodiment 1
Same reaction condition is respectively used to photocatalysis deionized water, simulated seawater, the Huanghai Sea and South China Sea liberation of hydrogen, 4h hydrogen-separating quantity difference
For 1.11,1.37,1.89,1.85 μm of ol.
Invention effect
1. liberation of hydrogen effect of the CsI-CN in deionized water, simulated seawater, the Huanghai Sea and South China Sea is observed, wherein using
When Huanghai Seawater, the hydrogen-separating quantity of 4h reaches 46.38 μm of ol, is 5.9 times of the sample in deionized water (7.89 μm of ol), is
113.1 times, 257.7 times in deionized water (0.18 μm of ol) in Huanghai Seawater (0.41 μm of ol) of CN.
2. further test NaI-CN, KI-CN, RbI-CN, CsBr-CN and CsCl-CN sample is in the Huanghai Sea and South China Sea
In liberation of hydrogen effect, it is found that hydrogen output of all samples in real sea water all gets a promotion, alkali metal haloid is modified
The yield that carbonitride is promoted is more obvious.
3. steady using CsI-CN as photocatalysis liberation of hydrogen of the modified carbonitride of comparison in deionized water and seawater is represented
Qualitative, CsI-CN gets a promotion on the liberation of hydrogen under sea conditions not only yield, and stability is also obviously improved.
This absolutely proves that the modified carbonitride of alkali metal haloid is more suitable resource seawater liberation of hydrogen more abundant.
Claims (6)
1. a kind of carbonitride and preparation method thereof that can be used for photocatalysis seawater liberation of hydrogen, using dicyandiamide as precursor preparation body phase nitrogen
Change carbon, alkali metal haloid is modified it, is made by hot polymerization reaction, ultrasonic agitation, centrifuge washing and drying, feature
It is the selection and preparation process of raw material:
(1) weighs a certain amount of dicyandiamide, is laid in quartz boat after being fully ground in mortar, is then put into tubular type
In heating furnace；
(2) under nitrogen atmosphere, is warming up to 550 DEG C with the heating rate of 2.3 DEG C/min and keeps 4h, can obtain after natural cooling
To flaxen body phase g-C3N4.It collects spare after these blocks of solid are fully ground, is named as CN；
(3) 500mg CN is placed in mortar by, total 0.2mL deionized water is added dropwise in process of lapping several times, after being fully ground again
1000mg alkali metal haloid is added and is fully ground again, is finally stacked in corundum boat, is placed in tube furnace；
(4) is heated to 550 DEG C in nitrogen atmosphere with the heating rate of 5 DEG C/min and keeps 2h；
(5) after the sample cooled to room temperature that is obtained, be stirred by ultrasonic and be scattered in deionized water, with deionized water from
The heart washs 3 times；
(6) drying overnight in 60 DEG C of baking oven obtains the modified carbonitride of alkali metal salt, and collection is spare, according to the alkali of addition
The difference of metal halogen salt is respectively designated as KI-CN, RbI-CN, CsI-CN, CsBr-CN and CsCl-CN.
2. a kind of carbonitride and preparation method thereof that can be used for photocatalysis seawater liberation of hydrogen according to claim 1, feature
It is: using carbonitride as presoma, carbonitride is modified with alkali metal haloid and prepares a kind of alkali metal haloid modification
Carbonitride.
3. a kind of carbonitride that can be used for photocatalysis seawater liberation of hydrogen according to claim 1 and its preparation, it is characterised in that:
The calcining sample in nitrogen atmosphere is needed, so that sample is completely cut off air, prevents from being oxidized.
4. a kind of carbonitride that can be used for photocatalysis seawater liberation of hydrogen according to claim 1 and its preparation, it is characterised in that:
Need to be added dropwise deionized water during grinding CN, the additional amount of water is strict controlled in 500mg graphite phase carbon nitride corresponding 0.1
~0.2mL deionized water, and can be amplified with equal proportion.
5. a kind of carbonitride that can be used for photocatalysis seawater liberation of hydrogen according to claim 1 and its preparation, it is characterised in that:
The ratio that CN and alkali metal haloid is added is 1:1~1:4.
6. a kind of carbonitride that can be used for photocatalysis seawater liberation of hydrogen according to claim 1 and its preparation, it is characterised in that:
Heating rate control is heated to 550 DEG C in 2.3~10 DEG C/min in reaction process, keeps 1~2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN113680373A (en) * | 2021-09-28 | 2021-11-23 | 中化学朗正环保科技有限公司 | Graphite phase carbon nitride photocatalyst for sewage treatment and preparation method and application thereof |
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