CN106975510B - A kind of high visible-light activity graphite phase carbon nitride and its application - Google Patents
A kind of high visible-light activity graphite phase carbon nitride and its application Download PDFInfo
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- CN106975510B CN106975510B CN201710267741.XA CN201710267741A CN106975510B CN 106975510 B CN106975510 B CN 106975510B CN 201710267741 A CN201710267741 A CN 201710267741A CN 106975510 B CN106975510 B CN 106975510B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000001354 calcination Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000012719 thermal polymerization Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 22
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 235000004237 Crocus Nutrition 0.000 description 4
- 241000596148 Crocus Species 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
-
- 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
-
- 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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Abstract
The invention belongs to the preparation technical fields of new material, specifically disclose a kind of high activity graphite phase carbon nitride and its application in visible light catalytic hydrogen production by water decomposition.The preparation of the graphite phase carbon nitride prepares carbonitride using common rich nitrogen material dicyanodiamine as raw material, using autoclave enclosed system thermal polymerization one-step calcination method.Compared with common normal pressure heat polymerization, the high pressure thermal polymerization used in the present invention not only increases the yield of catalyst, while also greatly expanding the visible light-responded range of carbonitride, and Photocatalyzed Hydrogen Production performance is significantly improved.This method simple process, it is raw materials used it is single be easy to get, be easy to large-scale industrial production, have broad application prospects.
Description
Technical field
The present invention relates to the preparation technical fields of new material, and in particular to a kind of high activity graphite phase carbon nitride and its can
See the application in photocatalytic hydrogen production by water decomposition.
Background technique
Graphite phase carbon nitride has the lamellar structure of class graphite-like, because it is with preferable thermal stability, chemical stability,
And good photocatalysis performance, in recent years photocatalytic hydrogen production by water decomposition (J.Am.Chem.Soc., 2009,131,1680-
1681), dye wastewater treatment (J.Am.Chem.Soc., 2013,135,7118-7121), POPs are administered
(Environ.Sci.Technol., 2016,50,12938-12948) and electro-catalysis (ACS
Appl.Mater.Interfaces, 2016,8,28678-28688) etc. fields widely studied.
According to the literature, the common preparation method of graphite phase carbon nitride is normal pressure thermal polymerization, that is, is 500-600 DEG C
Under, dinectly bruning richness nitrogen raw material such as urea, melamine and dicyanodiamine etc. be made (J.Phys.Chem.C, 2015,119,
14938-14946).But carbonitride obtained in this way, low yield, it is seen that optical response range is narrow, and photocatalysis is living
Property is poor.It is generally believed that widening the raising that visible light-responded range is conducive to graphite phase carbon nitride photocatalysis performance.But it widens
The visible light-responded range of carbonitride often need other substances such as introducing hetero-atoms (Appl.Catal.B:Environ.2017,205,
319-32) it or needs secondary clacining (Adv.Mater.2016,28,6471-6477), preparation procedure is cumbersome.Therefore, one is developed
Simple and high-efficiency environment friendly is planted, while having both the preparation method of the graphite phase carbon nitride photochemical catalyst of high yield and high activity, very
It is necessary.
Summary of the invention
In view of the deficienciess of the prior art, the present invention is intended to provide a kind of simple (the being not necessarily to additive) preparation process of raw material
Simplicity, yield are high, it is seen that light abstraction width is wide, and the high yield carbonitride preparation method with excellent photocatalysis performance.We
The study found that carrying out high-pressure sealed thermal polymerization by the way that raw material dicyanodiamine is placed in autoclave, so that it may high activity be made
Graphite phase carbon nitride photochemical catalyst.
Realize that the object of the invention is adopted the technical scheme that:
A kind of high activity graphite phase carbon nitride, preparation method include the following steps:
(1) dicyanodiamine is placed in alumina crucible, covers, crucible is placed in stainless steel cauldron；
(2) it after sealing reaction kettle, is placed in Muffle furnace, carries out high pressure heat polymerization；
(3) to reaction kettle cooled to room temperature after reacting, resulting sample grind into powder is living to get high visible
The graphite phase carbon nitride photochemical catalyst of property.
Further, the actual conditions of above-mentioned high pressure heat polymerization are: insulation reaction 2- after being warming up to 525-600 DEG C
6h；
Preferably, the actual conditions of the high pressure heat polymerization are: insulation reaction 4h after being warming up to 560 DEG C；
Further, reactor volume and the mass ratio of dicyanodiamine are 100ml:(1-10 in step 1) g；
Most preferably, reactor volume and the mass ratio of dicyanodiamine are 50ml:3g in step 1；
Further, the heating rate of the Muffle furnace is 5 DEG C of min-1.The nitridation of graphite-phase prepared by the method for the present invention
The test of carbon, characterizing method and application performance are as follows:
(1) XRD test is carried out to sample using Germany's Bruker-D8 type X-ray diffractometer (Cu K α, λ=0.154nm)
(step-length of the X-ray diffractometer is 0.02 ° of s-1, operating voltage and operating current are respectively 15kV and 30mA).
(2) FT-IR test is carried out to sample using U.S. NEXUIS-470 type infrared spectrometer.
(3) ultraviolet-visible solid is carried out to sample using Japanese Shimadzu UV-2550 type ultraviolet-visible spectrophotometer to overflow
Reflectance spectrum test.(using barium sulfate as standard reflection reference, scanning wavelength 200-800nm) in test.
(4) the photocatalysis performance test of graphite phase carbon nitride photochemical catalyst:
Photolytic activity reacts to be evaluated by visible light catalytic hydrogen production by water decomposition.Experimentation is as follows: graphite-phase nitridation
The experiment of carbon photochemical catalyzing carries out in the flat three-necked flask that a volume is 100mL.Weigh 0.05g graphite-phase nitrogen
Change C catalyst in flat three-necked flask, aqueous solution (70mL water and tri- ethyl alcohol of 10mL of 80mL triethanolamine is then added
Amine).Under magnetic stirring, 150 μ L chloroplatinic acids are added.Solution handle within ultrasound 5 minutes, then 350W Xenon light shining
20min completes light deposition platinum plating.Lead to N toward the solution after the completion of platinum plating2, to exclude dissolved oxygen.Then container is sealed, with 350W
Xenon lamp is as light source, and filtering off wavelength with the filter plate of 420nm is 420nm light below, carries out visible light under magnetic stirring
Hydrogen production by water decomposition reaction.After reacting 1h, the gaseous sample in closed container is extracted, hydrogen output is surveyed with gas chromatograph
Examination.
Compared with prior art, the advantages of the present invention are as follows:
The present invention prepares the simple process of graphite phase carbon nitride, and yield is high, and the graphite phase carbon nitride activity of preparation is high, it is seen that
Photoresponse is stronger, and photocatalysis performance is superior, has broad application prospects.
Detailed description of the invention
The normal pressure system (reactionless kettle) of Fig. 1-embodiment 1-5 high pressure system (stainless steel cauldron) and comparative example 1-5
Reaction unit compares；
The optical digital photo of catalyst made from Fig. 2-embodiment 1-5 and comparative example 1-5；
Fig. 3 A, Fig. 3 B are respectively the X-ray diffractogram of catalyst made from embodiment 1-5 and comparative example 1-5；
Fig. 4 A, Fig. 4 B are respectively the fourier transform infrared spectroscopy of catalyst made from embodiment 1-5 and comparative example 1-5
Figure；
Fig. 5 A, Fig. 5 B are respectively the UV-vis DRS spectrum of catalyst made from embodiment 1-5 and comparative example 1-5
Figure；
The production hydrogen activity of catalyst made from Fig. 6-embodiment 1-5 and comparative example 1-5 compares.
Specific embodiment
Applicant will be described in detail technical solution of the present invention in conjunction with specific case study on implementation below, so as to ability
The technical staff in domain is further understood the present invention, but following case study on implementation is not construed in any way to the present invention
The limitation of protection scope.
Embodiment 1:
It takes 3.0g dicyanodiamine in 10mL alumina crucible, after capping, places it in 50 milliliters of stainless steel cauldron
In, then closed stainless steel cauldron is put into Muffle furnace, with 5 DEG C of min in air atmosphere-1500 DEG C are warming up to,
Heat polymerization 4h (high pressure system, as shown in Figure 1a) at this temperature.After it is cooled to room temperature, the catalyst of generation is taken out,
It is ground into powder, gained sample is labeled as S1 sample.
As shown in a1 in Fig. 2, resulting sample S1 be it is faint yellow, obtain product 2.18g (yield 73%).Powder X-ray is penetrated
For line diffraction spectrogram the result shows that (Fig. 3 A), sample S1 are the not high graphite phase carbon nitride (a line) of crystallinity, this may be with its hot polymerization
It is relatively low related to close the not high oligomeric degree for leading to product of temperature.The FTIR spectrum of sample S1 as shown in a line in Fig. 4 A,
1242cm-1、1319cm-1、1398cm-1、1412cm-1Typical CN heterocycle vibration peak in corresponding carbonitride, and 809cm-1It is corresponding
Typical triazine ring vibration peak, XRD spectrum and infared spectrum all show that S1 is carbonitride.Its ultraviolet-visible solid diffuses
Spectrum (absorbs band edge 437nm) as shown in Figure 5A.
Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample S1 is 0.6 μm of olh-1(Fig. 6).
Comparative example 1:
In order to illustrate the superiority of high-pressure sealed system, we have equally carried out the normal pressure system of carbonitride at 500 DEG C
Prepare control experiment.Normal pressure system is prepared shown in device such as Fig. 1 (b) of control experiment reaction, in addition to not having to stainless steel cauldron
Outside, other reaction conditions and operation are identical with embodiment 1, and gained sample is labeled as M1.
As shown in a2 in Fig. 2, gained sample M1 be it is faint yellow, obtain product 1.65g (yield 55%), powder in Fig. 3 B
X-ray diffraction spectrogram the result shows that, sample M1 be graphite phase carbon nitride (a line).The FTIR spectrum of sample M1 in Fig. 4 B
As shown in a line, 1242cm-1、1319cm-1、1398cm-1、1412cm-1、1574cm-1、1635cm-1It is typical in corresponding carbonitride
CN heterocycle vibration peak, and 809cm-1Corresponding typical triazine ring vibration peak, XRD spectrum and infared spectrum all show that M1 is nitridation
Carbon.Sample M1 ultraviolet-visible solid diffusing reflection spectrum (absorbs band edge 456nm) as shown in Figure 5 B.Photocatalyzed Hydrogen Production the results show that
The average hydrogen-producing speed of sample M1 is 0.7 μm of olh-1(Fig. 6), activity is suitable with high-pressure sealed system, but relative to identical
The yield of sample M1, S1 under polymeric reaction temperature (500 DEG C) increase 18%.
Embodiment 2:
In order to examine influence of the calcination temperature to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcination temperature is adjusted to 525 DEG C, other reaction conditions and operation are identical with embodiment 1,
Gained sample is labeled as S2.
As shown in b1 in Fig. 2, gained sample S2 be it is faint yellow, obtain product 1.8g (yield 60%), powder X-ray in Fig. 3 A
X ray diffraction spectrogram the result shows that, sample S2 be the higher graphite phase carbon nitride of crystallinity (b line).In Fig. 4 A in Fu of sample S2
Leaf infrared spectroscopy is as shown in b line, and dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
All show that S2 is highly crystalline carbonitride with infared spectrum.The ultraviolet-visible solid diffusing reflection spectrum of sample S2 (is inhaled as shown in Figure 5A
Take-up side 438nm).Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample S2 is 10.7 μm of olh-1(Fig. 6).
Comparative example 2:
In order to illustrate the superiority of high-pressure sealed system, we have carried out the conventional preparation of carbonitride equally at 525 DEG C
Control experiment.In addition to enclosed system is changed to conventional atmospheric system, other reaction conditions and operation are identical with embodiment 2,
Gained sample is labeled as M2.
As shown in b2 in Fig. 2, gained sample M2 be it is faint yellow, obtain product 1.47g (yield 49%), Fig. 3 B powder X-ray
X ray diffraction spectrogram the result shows that, sample M2 be graphite phase carbon nitride (b line).The FTIR spectrum of sample M2 is such as in Fig. 4 B
Shown in b line, dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum are all
Show that M2 is carbonitride.Sample M2 ultraviolet-visible solid diffusing reflection spectrum is as shown in Figure 5 B, relative to comparative example 1, visible light
Response slightly enhancing (absorbing band edge 459nm).Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample M2 is 1.4 μ
mol·h-1(Fig. 6).
Relative to M2 sample under same polymeric reaction temperature (525 DEG C), the increased activity 664% of S2 sample, yield increases
11%.
Embodiment 3:
In order to examine influence of the calcination temperature to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcination temperature is adjusted to 560 DEG C, other reaction conditions and operation are identical with embodiment 1,
Gained sample is labeled as S3.
As shown in c1 in Fig. 2, gained sample S3 is crocus, is obtained product 1.53g (yield 51%), Fig. 3 A powder X-ray
X ray diffraction spectrogram the result shows that, sample S3 be the higher graphite phase carbon nitride of crystallinity (c line).In Fig. 4 A in Fu of sample S3
Leaf infrared spectroscopy is as shown in c line, and dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
All show that S3 is highly crystalline carbonitride with infared spectrum.Sample S3 ultraviolet-visible solid diffusing reflection spectrum is as shown in Figure 5A, can
Light-exposed response is remarkably reinforced and (absorbs band edge 473nm).Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample S3 is 18.1
μmol·h-1(Fig. 6).
Comparative example 3:
In order to illustrate the superiority of high-pressure sealed system, we have carried out the conventional preparation of carbonitride equally at 560 DEG C
Control experiment.In addition to high-pressure sealed system is changed to normal pressure system, other reaction conditions and operation are identical with embodiment 3,
Gained sample is labeled as M3.
As shown in c2 in Fig. 2, gained sample M3 is yellow, is obtained product 1.26g (yield 42%), Fig. 3 B powder X-ray is penetrated
Line diffraction spectrogram the result shows that, sample M3 be graphite phase carbon nitride (c line).The FTIR spectrum of sample M3 such as c in Fig. 4 B
Shown in line, dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum all tables
Bright M3 is carbonitride.Sample M3 ultraviolet-visible solid diffusing reflection spectrum (absorbs band edge 460nm) as shown in Figure 5 B, sample M3's
Average hydrogen-producing speed is 2.25 μm of olh-1(Fig. 6).
Relative to M3 sample under same polymeric reaction temperature (560 DEG C), the increased activity 704% of S3 sample, yield increases
9%, and absorption of the S3 in 450-580nm visible-range is remarkably reinforced, and embodies the superiority of high-pressure sealed system.
Embodiment 4:
In order to examine influence of the calcination temperature to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcination temperature is adjusted to 580 DEG C, other reaction conditions and operation are identical with embodiment 1,
Gained sample is labeled as S4.
As shown in d1 in Fig. 2, gained sample S4 is crocus, is obtained product 1.56g (yield 52%), Fig. 3 A powder X-ray
X ray diffraction spectrogram the result shows that, sample S4 be the higher graphite phase carbon nitride of crystallinity (d line).In Fig. 4 A in Fu of sample S4
Leaf infrared spectroscopy is as shown in d line, and dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
All show that S4 is highly crystalline carbonitride with infared spectrum.Sample S4 ultraviolet-visible solid diffusing reflection spectrum is as shown in Figure 5A, relatively
It is visible light-responded to be further remarkably reinforced and (absorb band edge 645nm) in embodiment 3.Photocatalyzed Hydrogen Production is the results show that sample S4
Average hydrogen-producing speed be 11.7 μm of olh-1(Fig. 6).
Comparative example 4:
In order to illustrate the superiority of high-pressure sealed system, we have carried out the conventional preparation of carbonitride equally at 580 DEG C
Control experiment.In addition to enclosed system is changed to normal pressure system, other reaction conditions and operation, gained identical with embodiment 4
Sample is labeled as M4.
As shown in d2 in Fig. 2, gained sample M4 is yellow, is obtained product 1.05g (yield 35%), Fig. 3 B powder X-ray is penetrated
Line diffraction spectrogram the result shows that, sample M4 be graphite phase carbon nitride (d line).The FTIR spectrum of sample M4 such as e in Fig. 4 B
Shown in line, dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum all tables
Bright M4 is carbonitride.Sample M4 ultraviolet-visible solid diffusing reflection spectrum is as shown in Figure 5 B, and relative to comparative example 3, visible light is rung
It should have no and be remarkably reinforced and (absorb band edge 468nm), Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample M4 is 4.4 μ
mol·h-1(Fig. 6).
Relative to M4 sample under same polymeric reaction temperature (580 DEG C), the increased activity 166% of S4 sample, yield increases
17%, and S4 absorbs band edge red shift 177nm, embodies the superiority of high-pressure sealed system.
Embodiment 5:
In order to examine influence of the calcination temperature to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).Except calcination temperature is adjusted to 600 DEG C, other reaction conditions and, institute identical with embodiment 1 is operated
It obtains sample and is labeled as S5.
As shown in e1 in Fig. 2, gained sample S5 is crocus, is obtained product 1.41g (yield 47%), Fig. 3 A powder X-ray
X ray diffraction spectrogram the result shows that, sample S5 be the higher graphite phase carbon nitride of crystallinity (e line).In Fig. 4 A in Fu of sample S5
Leaf infrared spectroscopy is as shown in e line, and dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
All show that S5 is highly crystalline carbonitride with infared spectrum.Sample S5 ultraviolet-visible solid diffusing reflection spectrum (absorbs as shown in Figure 5A
Band edge 480nm).Photocatalyzed Hydrogen Production is the results show that the average hydrogen-producing speed of sample S5 is 9.4 μm of olh-1(Fig. 6).
Comparative example 5:
In order to illustrate the superiority of high-pressure sealed system, we have carried out the conventional preparation of carbonitride equally at 600 DEG C
Control experiment.In addition to high-pressure sealed system is changed to normal pressure system, other reaction conditions and operation are identical with embodiment 5,
Gained sample is labeled as M5.
As shown in e2 in Fig. 2, gained sample M5 be it is faint yellow, obtain product 0.6g (yield 20%), Fig. 3 B powder X-ray is penetrated
Line diffraction spectrogram the result shows that, sample M5 be graphite phase carbon nitride (e line).The FTIR spectrum of sample M5 such as e in Fig. 4 B
Shown in line, dotted line institute's target peak is identical as comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum all tables
Bright M5 is carbonitride.Sample M5 ultraviolet-visible solid diffusing reflection spectrum is as shown in Figure 5 B, and relative to comparative example 4, visible light is rung
It should be 6.3 μm of olh without significant change (absorbing band edge 468nm), the average hydrogen-producing speed of sample M5-1(Fig. 6).
Relative to M5 sample under same polymeric reaction temperature (600 DEG C), the increased activity 49% of S5 sample, yield increases
27%, and S5 absorbs band edge red shift 12nm, embodies the superiority of high-pressure sealed system.
By the above experiment case study, it will be seen that with the high-pressure sealed resulting graphite phase carbon nitride of system thermal polymerization
Catalyst, color gradually deepen and (become crocus from faint yellow), have superior visible light-responded performance and stronger
Visible light H2-producing capacity, by comparing X-ray diffraction spectrogram, the high-pressure sealed system institute when calcination temperature is at 525 DEG C or more
Obtaining carbonitride has higher crystallinity.Particularly, when calcination temperature is 560 DEG C, it is living that visible light catalytic decomposes aquatic products hydrogen
Property highest, be 18.1 μm of olh-1, it is that catalyst made from synthermal lower normal pressure system produces hydrogen activity (2.25 μm of olh-1)
8 times, while catalyst production obtained by high-pressure sealed system is also relatively higher, illustrates high-pressure sealed system preparation graphite phase carbon nitride
Catalyst has apparent advantage.
Claims (5)
1. a kind of high activity graphite phase carbon nitride, it is characterised in that: preparation method includes the following steps:
(1) dicyanodiamine is placed in alumina crucible, covers, crucible is placed in stainless steel cauldron；The reaction kettle holds
The long-pending mass ratio with dicyanodiamine is 100ml:(1-10) g；
(2) it after sealing reaction kettle, is placed in Muffle furnace, carries out high pressure heat polymerization；
The actual conditions of the high pressure heat polymerization are: insulation reaction 2-6h after being warming up to 525-600 DEG C；
(3) to reaction kettle cooled to room temperature after reacting, by resulting sample grind into powder.
2. high activity graphite phase carbon nitride according to claim 1, it is characterised in that: the heating rate of the Muffle furnace is
5℃·min-1。
3. high activity graphite phase carbon nitride according to claim 1, it is characterised in that: the tool of the high pressure heat polymerization
Concrete conditions in the establishment of a specific crime is: insulation reaction 4h after being warming up to 560 DEG C.
4. a kind of high activity graphite phase carbon nitride of any of claims 1 or 2 decomposes the application in aquatic products hydrogen in visible light catalytic.
5. a kind of high activity graphite phase carbon nitride as claimed in claim 3 decomposes the application in aquatic products hydrogen in visible light catalytic.
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