CN106975510A - 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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- CN106975510A CN106975510A CN201710267741.XA CN201710267741A CN106975510A CN 106975510 A CN106975510 A CN 106975510A CN 201710267741 A CN201710267741 A CN 201710267741A CN 106975510 A CN106975510 A CN 106975510A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 34
- 239000010439 graphite Substances 0.000 title claims abstract description 34
- 230000000694 effects Effects 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 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 21
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 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
- -1 carbon nitrides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000001354 calcination Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 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 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 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
- 238000012360 testing 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
- 238000002329 infrared spectrum Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000243 solution 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 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
- 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
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 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
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 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
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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
- 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
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- 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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the preparing technical field of new material, a kind of high activity graphite phase carbon nitride and its application in visible light catalytic hydrogen production by water decomposition are specifically disclosed.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 having expanded the visible light-responded scope of carbonitride, Photocatalyzed Hydrogen Production performance is significantly improved.This method technique is simple, raw materials used single to be easy to get, it is easy to mass industrialized production, has broad application prospects.
Description
Technical field
The present invention relates to the preparing technical field of new material, and in particular to a kind of high activity graphite phase carbon nitride and its can
The application seen in photocatalytic hydrogen production by water decomposition.
Background technology
Graphite phase carbon nitride has the lamellar structure of class graphite-like, because it has preferable heat endurance, 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. field 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. it is obtained (J.Phys.Chem.C, 2015,119,
14938-14946).But, obtained carbonitride, its low yield in this way, it is seen that photoresponse narrow range, and photocatalysis lives
Property is poor.It is generally believed that widening the raising that visible light-responded scope is conducive to graphite phase carbon nitride photocatalysis performance.But widen
The visible light-responded scope of carbonitride often needs other materials such as introducing hetero-atoms (Appl.Catal.B:Environ.2017,205,
319-32) or secondary clacining (Adv.Mater.2016,28,6471-6477) is needed, preparation procedure is cumbersome.Therefore, one is developed
Simple and high-efficiency environment friendly is planted, while having the preparation method of the graphite phase carbon nitride photochemical catalyst of high yield and high activity concurrently, very
It is necessary.
The content of the invention
In view of the deficienciess of the prior art, a kind of the present invention is intended to provide simple (without additive) preparation technology of raw material
Simplicity, yield is high, it is seen that light abstraction width is wide, and the high yield carbonitride preparation method with excellent photocatalysis performance.We
Research is found, carries out high-pressure sealed thermal polymerization by the way that raw material dicyanodiamine is placed in into autoclave, it is possible to high activity is 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, its preparation method comprises the following steps：
(1) dicyanodiamine is placed in alumina crucible, is capped, crucible is placed in stainless steel cauldron；
(2) after reactor is sealed, it is positioned in Muffle furnace, carries out high pressure heat polymerization；
(3) question response kettle naturally cools to room temperature after reacting, by the sample grind into powder of gained, produces high visible work
The graphite phase carbon nitride photochemical catalyst of property.
Further, the actual conditions of above-mentioned high pressure heat polymerization is：It is warming up to insulation reaction 2- after 525-600 DEG C
6h；
It is preferred that, the actual conditions of the high pressure heat polymerization is：It is warming up to insulation reaction 4h after 560 DEG C；
Further, reactor volume and the mass ratio of dicyanodiamine are 100ml in step 1：(1-10)g；
Most preferably, reactor volume and the mass ratio of dicyanodiamine are 50ml in step 1：3g；
Further, the heating rate of the Muffle furnace is 5 DEG C of min-1.Graphite-phase nitridation prepared by the inventive method
Carbon, the test of its characterizing method and application performance is：
(1) XRD tests are carried out to sample using Germany's Bruker-D8 types 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 tests are carried out to sample using U.S. NEXUIS-470 types infrared spectrometer.
(3) ultraviolet-visible solid is carried out to sample using Japanese Shimadzu UV-2550 types ultraviolet-visible spectrophotometer to overflow
Reflectance spectrum is tested.(using barium sulfate as standard reflection reference in test, scanning wavelength is 200-800nm).
(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 is nitrogenized
The experiment of carbon photochemical catalyzing, is carried out in a volume is 100mL flat three-necked flask.Weigh 0.05g graphite-phase nitrogen
Change C catalyst in flat three-necked flask, then add the aqueous solution (70mL water and the ethanol of 10mL tri- of 80mL triethanolamines
Amine).Under magnetic stirring, 150 μ L chloroplatinic acids are added.Solution is carried out into ultrasound to handle within 5 minutes, then 350W Xenon light shinings
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 filters off the light that wavelength is below 420nm as light source, and with 420nm filter plate, and visible ray is carried out under magnetic stirring
Hydrogen production by water decomposition reacts.React after 1h, extract the gaseous sample in closed container, hydrogen output is surveyed with gas chromatograph
Examination.
Compared with prior art, the advantages of the present invention are as follows：
The technique that the present invention prepares graphite phase carbon nitride is simple, 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.
Brief description of the drawings
Fig. 1-embodiment 1-5 high pressure system (stainless steel cauldron) and comparative example 1-5 normal pressure system (reactionless kettle)
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 compares made from Fig. 6-embodiment 1-5 and comparative example 1-5.
Embodiment
Applicant will be described in detail with reference to specific case study on implementation to technical scheme below, so as to ability
The technical staff in domain is further understood by the present invention, but following case study on implementation is not construed to the present invention in any way
The limitation of protection domain.
Embodiment 1：
3.0g dicyanodiamines are taken in 10mL alumina crucibles, after capping, 50 milliliters of stainless steel cauldron are placed on
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,
Powder is ground into, gained sample is labeled as S1 samples.
As shown in a1 in Fig. 2, the sample S1 of gained is faint yellow, obtains product 2.18g (yield is 73%).Powder X-ray is penetrated
Line diffraction spectrogram result shows (Fig. 3 A) that sample S1 is the not high graphite phase carbon nitride (a lines) of crystallinity, and this may be with its hot polymerization
Close the not high oligomeric degree for causing product of temperature more relevant than relatively low.Sample S1 FTIR spectrum as shown in a lines in Fig. 4 A,
1242cm-1、1319cm-1、1398cm-1、1412cm-1Typical CN heterocycle vibration peaks in correspondence carbonitride, and 809cm-1Correspondence
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 result shows that sample S1 average hydrogen-producing speed 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, except without 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 is faint yellow, obtains powder in product 1.65g (yield is 55%), Fig. 3 B
X-ray diffraction spectrogram result shows that sample M1 is graphite phase carbon nitride (a lines).Sample M1 FTIR spectrum in Fig. 4 B
As shown in a lines, 1242cm-1、1319cm-1、1398cm-1、1412cm-1、1574cm-1、1635cm-1It is typical in correspondence carbonitride
CN heterocycle vibration peaks, and 809cm-1The typical triazine ring vibration peak of correspondence, XRD spectrum and infared spectrum all show that M1 is nitridation
Carbon.Sample M1 ultraviolet-visible solids diffusing reflection spectrum (absorbs band edge 456nm) as shown in Figure 5 B.Photocatalyzed Hydrogen Production result shows,
Sample M1 average hydrogen-producing speed is 0.7 μm of olh-1(Fig. 6), its is active suitable with high-pressure sealed system, but relative to identical
The yield of sample M1, S1 under polymeric reaction temperature (500 DEG C) add 18%.
Embodiment 2：
In order to examine influence of the calcining heat to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcining heat is adjusted into 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 is faint yellow, obtains powder X-ray in product 1.8g (yield is 60%), Fig. 3 A
X ray diffraction spectrogram result shows that sample S2 is the higher graphite phase carbon nitride (b lines) of crystallinity.In Fig. 4 A in sample S2 Fu
Leaf infrared spectrum is as shown in b lines, and dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
It is highly crystalline carbonitride all to show S2 with infared spectrum.Sample S2 ultraviolet-visible solid diffusing reflection spectrum (is inhaled as shown in Figure 5A
Take-up side 438nm).Photocatalyzed Hydrogen Production result shows that sample S2 average hydrogen-producing speed 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 into 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 is faint yellow, obtains product 1.47g (yield is 49%), Fig. 3 B powder X-rays
X ray diffraction spectrogram result shows that sample M2 is graphite phase carbon nitride (b lines).Sample M2 FTIR spectrum is such as in Fig. 4 B
Shown in b lines, dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum are all
It is carbonitride to show M2.Sample M2 ultraviolet-visible solids diffusing reflection spectrum as shown in Figure 5 B, relative to comparative example 1, its visible ray
Response slightly enhancing (absorbing band edge 459nm).Photocatalyzed Hydrogen Production result shows that sample M2 average hydrogen-producing speed is 1.4 μ
mol·h-1(Fig. 6).
Relative to M2 samples under same polymeric reaction temperature (525 DEG C), the increased activity 664% of S2 samples, yield increase
11%.
Embodiment 3：
In order to examine influence of the calcining heat to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcining heat is adjusted into 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, obtains product 1.53g (yield is 51%), Fig. 3 A powder X-rays
X ray diffraction spectrogram result shows that sample S3 is the higher graphite phase carbon nitride (c lines) of crystallinity.In Fig. 4 A in sample S3 Fu
Leaf infrared spectrum is as shown in c lines, and dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
It is highly crystalline carbonitride all to show S3 with infared spectrum.As shown in Figure 5A, it can for sample S3 ultraviolet-visible solids diffusing reflection spectrum
See that photoresponse is remarkably reinforced and (absorbs band edge 473nm).Photocatalyzed Hydrogen Production result shows that sample S3 average hydrogen-producing speed 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 into 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, obtains product 1.26g (yield is 42%), Fig. 3 B powder X-rays are penetrated
Line diffraction spectrogram result shows that sample M3 is graphite phase carbon nitride (c lines).Sample M3 FTIR spectrum such as c in Fig. 4 B
Shown in line, dotted line institute's target peak is identical with 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 solids 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 samples under same polymeric reaction temperature (560 DEG C), the increased activity 704% of S3 samples, yield increase
9%, and absorptions of the S3 in 450-580nm visible-ranges be remarkably reinforced, and embodies the superiority of high-pressure sealed system.
Embodiment 4：
In order to examine influence of the calcining heat to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).In addition to calcining heat is adjusted into 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, obtains product 1.56g (yield is 52%), Fig. 3 A powder X-rays
X ray diffraction spectrogram result shows that sample S4 is the higher graphite phase carbon nitride (d lines) of crystallinity.In Fig. 4 A in sample S4 Fu
Leaf infrared spectrum is as shown in d lines, and dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
It is highly crystalline carbonitride all to show S4 with infared spectrum.Sample S4 ultraviolet-visible solids diffusing reflection spectrum as shown in Figure 5A, relatively
In embodiment 3, its is visible light-responded to be further remarkably reinforced and (absorbs band edge 645nm).Photocatalyzed Hydrogen Production result shows, 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 into normal pressure system, other reaction conditions and operation are identical with embodiment 4, gained
Sample is labeled as M4.
As shown in d2 in Fig. 2, gained sample M4 is yellow, obtains product 1.05g (yield is 35%), Fig. 3 B powder X-rays are penetrated
Line diffraction spectrogram result shows that sample M4 is graphite phase carbon nitride (d lines).Sample M4 FTIR spectrum such as e in Fig. 4 B
Shown in line, dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum all tables
Bright M4 is carbonitride.As shown in Figure 5 B, relative to comparative example 3, its visible ray rings sample M4 ultraviolet-visible solids diffusing reflection spectrum
It should have no and be remarkably reinforced and (absorb band edge 468nm), Photocatalyzed Hydrogen Production result is shown, sample M4 average hydrogen-producing speed is 4.4 μ
mol·h-1(Fig. 6).
Relative to M4 samples under same polymeric reaction temperature (580 DEG C), the increased activity 166% of S4 samples, yield increase
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 calcining heat to gained carbon nitride catalyst photocatalysis performance, it is real that we carry out temperature control
Test (high-pressure sealed system).Except calcining heat is adjusted into 600 DEG C, other reaction conditions and operation are identical with embodiment 1, institute
Obtain sample and be labeled as S5.
As shown in e1 in Fig. 2, gained sample S5 is crocus, obtains product 1.41g (yield is 47%), Fig. 3 A powder X-rays
X ray diffraction spectrogram result shows that sample S5 is the higher graphite phase carbon nitride (e lines) of crystallinity.In Fig. 4 A in sample S5 Fu
Leaf infrared spectrum is as shown in e lines, and dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum
It is highly crystalline carbonitride all to show S5 with infared spectrum.Sample S5 ultraviolet-visible solids diffusing reflection spectrum (absorbs as shown in Figure 5A
Band edge 480nm).Photocatalyzed Hydrogen Production result shows that sample S5 average hydrogen-producing speed 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 into 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 is faint yellow, obtains product 0.6g (yield is 20%), Fig. 3 B powder X-rays are penetrated
Line diffraction spectrogram result shows that sample M5 is graphite phase carbon nitride (e lines).Sample M5 FTIR spectrum such as e in Fig. 4 B
Shown in line, dotted line institute's target peak is identical with comparative example 1 in figure, is all the characteristic peak of carbonitride, XRD spectrum and infared spectrum all tables
Bright M5 is carbonitride.As shown in Figure 5 B, relative to comparative example 4, its visible ray rings sample M5 ultraviolet-visible solids diffusing reflection spectrum
Should be without significant change (absorbing band edge 468nm), sample M5 average hydrogen-producing speed is 6.3 μm of olh-1(Fig. 6).
Relative to M5 samples under same polymeric reaction temperature (600 DEG C), the increased activity 49% of S5 samples, yield increase
27%, and S5 absorbs band edge red shift 12nm, embodies the superiority of high-pressure sealed system.
By above experiment case study, it will be seen that with the graphite phase carbon nitride obtained by high-pressure sealed system thermal polymerization
Catalyst, its color is gradually deepened and (is changed into crocus from faint yellow), with more excellent visible light-responded performance and stronger
Visible ray H2-producing capacity, by comparing X-ray diffraction spectrogram, the high-pressure sealed system institute when calcining heat is in 525 DEG C and the above
Obtaining carbonitride has higher crystallinity.Especially, when calcining heat is 560 DEG C, its visible light catalytic decomposes aquatic products hydrogen and lived
Property highest, is 18.1 μm of olh-1, it is catalyst production hydrogen activity (2.25 μm of olh made from synthermal lower normal pressure system-1)
8 times, while catalyst production obtained by high-pressure sealed system is also relatively higher, illustrate that high-pressure sealed system prepares graphite phase carbon nitride
Catalyst has obvious advantage.
Claims (7)
1. a kind of high activity graphite phase carbon nitride, it is characterised in that：Its preparation method comprises the following steps：
（1）Dicyanodiamine is placed in alumina crucible, is capped, crucible is placed in stainless steel cauldron；
（2）After reactor is sealed, it is positioned in Muffle furnace, carries out high pressure heat polymerization；
（3）Question response kettle naturally cools to room temperature after reaction, by the sample grind into powder of gained.
2. 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：It is warming up to insulation reaction 2-6h after 525-600 DEG C.
3. high activity graphite phase carbon nitride according to claim 2, it is characterised in that：Reactor volume in the step 1
Mass ratio with dicyanodiamine is 100ml：（1-10）g.
4. the high activity graphite phase carbon nitride according to Claims 2 or 3, it is characterised in that：The heating speed of the Muffle furnace
Rate is 5 DEG C of min-1。
5. high activity graphite phase carbon nitride according to claim 2, it is characterised in that：The tool of the high pressure heat polymerization
Concrete conditions in the establishment of a specific crime is：It is warming up to insulation reaction 4h after 560 DEG C.
6. a kind of any described high activity graphite phase carbon nitrides of claim 1-4 answering in visible light catalytic decomposes aquatic products hydrogen
With.
7. application of the high activity graphite phase carbon nitride in visible light catalytic decomposes aquatic products hydrogen described in a kind of claim 5.
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