CN108246331A - ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application - Google Patents
ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application Download PDFInfo
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- CN108246331A CN108246331A CN201810037542.4A CN201810037542A CN108246331A CN 108246331 A CN108246331 A CN 108246331A CN 201810037542 A CN201810037542 A CN 201810037542A CN 108246331 A CN108246331 A CN 108246331A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- 230000004048 modification Effects 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 29
- 238000012986 modification Methods 0.000 title claims abstract description 29
- 238000003763 carbonization Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 6
- 238000000502 dialysis Methods 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 54
- 239000001257 hydrogen Substances 0.000 abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 54
- 238000004519 manufacturing process Methods 0.000 abstract description 40
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 73
- 239000002096 quantum dot Substances 0.000 description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052724 xenon Inorganic materials 0.000 description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005549 size reduction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 amino Compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application, belongs to semiconductor composite technical field.This method first prepares ZnS (en)0.5Nanometer sheet；Then amino-compound is added in porcelain boat, is placed on temperature reaction in tube furnace, obtain body phase g C3N4Powder；Finally by ZnS (en)0.5Nanometer sheet and g C3N4Powder is mixed, and carries out hydro-thermal reaction in a kettle, obtains the ZnS micro-composites of graphene carbonization nitrogen quantity point modification.The present invention also provides application of the ZnS micro-composites as photochemical catalyst of above-mentioned graphene carbonization nitrogen quantity point modification.The photochemical catalyst can reach 5600 μm of ol h under visible light‑1g‑1Production hydrogen activity, be 140 times of ZnS under the same terms, and with good photocatalysis stability, catalytic effect not decreased significantly after four cycles.
Description
Technical field
The invention belongs to semiconductor composite technical fields, and in particular to a kind of graphene carbonization nitrogen quantity point modification
ZnS micro-composites and its preparation method and application.
Background technology
Graphene nitrogen carbide (g-C3N4) due to having low toxicity, low consumption, without metal, stability is high, the advantage of abundant raw material
It is had a wide range of applications in photocatalysis field.Compared with other patterns, g-C3N4Quantum dot (QDs) has many advantages.For example,
Good hydrophilic property, active site is more, quantum size effect etc..But existing g-C3N4The preparation method of quantum dot is complicated, and individually
g-C3N4Quantum dot is easily reunited.
It is reunited in order to prevent, can be compound with 3 D semiconductor by quantum dot.This can not only improve point of quantum dot
Property is dissipated, hetero-junctions can also be formed in two kinds of interfaces, so as to promote the separation of carrier, improve photocatalytic activity.
Three-dimensional ZnS has the advantages such as low toxicity, low consumption.But band gap is higher, and sun light utilization efficiency is relatively low.By itself and g-C3N4Amount
Son puts the compound dispersibility that can improve quantum dot, prevents from reuniting；Expand the specific surface area of catalyst, increase reaction active site
Point.In addition, g-C3N4Quantum dot can widen utilization rates of the ZnS to visible ray as photosensitizer.And pass through point for improving carrier
Photocatalytic activity is greatly improved from transmittability.
However, current g-C3N4The preparation of quantum dot is required for the etching of strong acid or prolonged ultrasound mostly, this is not
Only waste time, it is costly, and also yield is relatively low.
Invention content
The purpose of the present invention is to solve existing g-C3N4The problem of quantum dot is easily reunited and preparation method is complicated,
And provide a kind of ZnS micro-composites of graphene carbonization nitrogen quantity point modification and its preparation method and application.
Present invention firstly provides a kind of preparation method of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification,
This method includes：
Step 1：Prepare ZnS (en)0.5Nanometer sheet；
Step 2：Amino-compound is added in porcelain boat, is placed in tube furnace, is heated up under nitrogen atmosphere, 550~
600 DEG C are heated 2~4 hours, obtain body phase g-C3N4Powder；
Step 3：The ZnS (en) that step 1 is obtained0.5The g-C that nanometer sheet and step 2 obtain3N4Powder is mixed,
Then hydro-thermal reaction is carried out in a kettle, is lyophilized through dialysis, and the ZnS microns for obtaining graphene carbonization nitrogen quantity point modification are compound
Material.
Preferably, the step one is specially：Zinc salt and thiocarbamide are added in ethylenediamine, stirred, then 180
~200 DEG C of hydro-thermal reactions 10~for 24 hours, obtain ZnS (en)0.5Nanometer sheet.
Preferably, the zinc salt is zinc chloride, zinc nitrate or zinc acetate.
Preferably, the amino-compound of the step two is melamine, thiocarbamide, urea or semicarbazide hydrochloride.
Preferably, the heating rate of the step two is 2.5~5 DEG C/min.
Preferably, the ZnS (en)0.5Nanometer sheet and g-C3N4The molar ratio of powder is 1.0：(0.5~4.0).
Preferably, the mixing time of the step three is 30~120 minutes.
Preferably, the reaction temperature of the step three in a kettle is 200 DEG C, and the reaction time is 6~12h.
The present invention also provides the ZnS micron composite woods of graphene carbonization nitrogen quantity point modification that above-mentioned preparation method obtains
Material.
ZnS micro-composites the present invention also provides the carbonization nitrogen quantity point modification of above-mentioned graphene are as photochemical catalyst
Using.
Beneficial effects of the present invention
The present invention provides a kind of ZnS micro-composites of graphene carbonization nitrogen quantity point modification and preparation method thereof, should
Method is to prepare ZnS (en) first with solvent-thermal method0.5Nanometer sheet；Then the g-C of body phase is prepared3N4；Finally by different proportion
ZnS(en)0.5The g-C of nanometer sheet and body phase3N4Hydro-thermal reaction, during the reaction, the g-C of body phase occur for mixing3N4Form g-
C3N4Quantum dot finally obtains g-C3N4Three-dimensional (3D) ZnS micro-composites of quantum dot modification.It compares with the prior art,
The present invention is by introducing good water solubility, it is seen that the strong g-C of photoresponse ability3N4ZnS- is formed in QDs and three-dimensional ZnS micrometer structures
g-C3N4(according to ZnS and g-C3N4Rate of charge different definition be ZCNx:X=0.05~4.00) composite material, overcome zinc sulphide
The defects of semiconductor catalyst itself Carrier recombination rate is high, and sun light utilization efficiency is low；Improve g-C simultaneously3N4The dispersibility of QDs,
Its reunion is reduced, so as to improve the specific surface area of catalyst and active site.In addition, the method for a step hydrothermal synthesis promotes g-
C3N4The close contact of QDs and ZnS, and g-C3N4Electronics and g-C on QDs smaller size reductions ZnS conduction bands3N4QDs valencys
The compound of hole is taken, so as to improve the separation of carrier and transmission rate, composite material is finally obtained and is urged with higher light
Change activity.
ZnS micro-composites the present invention also provides the carbonization nitrogen quantity point modification of above-mentioned graphene are as photochemical catalyst
Using due to g-C3N4The quantum size effect of QDs, compared with ZnS, which uses as photochemical catalyst, composite catalyzing
Visible-range has been widened in the absorption of agent, and specific surface area increases, due to foring hetero-junctions between two kinds of interfaces,
So the separation of carrier and transmittability are also obviously improved.The experimental results showed that：The photochemical catalyst under visible light can be with
Reach 5600 μm of ol h-1g-1Photocatalytic activity, be 140 times of ZnS, and with good photocatalysis stability, followed at four times
Catalytic activity not decreased significantly after ring.
Description of the drawings
Fig. 1 is g-C prepared by embodiment 13N4The transmission of QDs, high-resolution photo, Size Distribution and absorption, fluorescence curve；
Fig. 2 is ZnS (en) prepared by embodiment 40.5The stereoscan photograph of nanometer sheet and ZCN-2, ZCN-2 composite materials
Transmission and high-resolution photo；
Fig. 3 is ZnS, bulk-g-C prepared by embodiment 43N4(BCN) and XRD diffraction curves of ZCN-2 composite materials and red
Outer absorption curve；
Fig. 4 is the ultraviolet absorption curve and nitrogen adsorption desorption curve of ZCN-2 composite materials prepared by embodiment 4；
Fig. 5 is the transient photocurrents density of ZCN-2 composite materials and fluorescence lifetime curve prepared by embodiment 4；
Fig. 6 is hydrogen output and hydrogen-producing speed curve of the ZCNx composite materials of the preparation of embodiment 4 in 210min；
Fig. 7 is the production hydrogen activity of ZCN-2 catalyst prepared by embodiment 4 and is catalyzed front and rear XRD curves；
Fig. 8 is ZnS and g-C prepared by embodiment 1-23N4The band gap of QDs and XPS valence band spectrums.
Specific embodiment
Present invention firstly provides a kind of preparation method of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification,
This method includes：
Step 1：Prepare ZnS (en)0.5Nanometer sheet, specially：Zinc salt and thiocarbamide are added in ethylenediamine, stirred, institute
The mixing time stated is preferably 30min, and then in 180~200 DEG C of hydro-thermal reactions 10~for 24 hours, the reaction temperature is preferably
180 DEG C, the reaction time is preferably 18h, after cooling washing and drying, obtains ZnS (en)0.5Nanometer sheet；The zinc salt is preferred
For zinc chloride, zinc nitrate or zinc acetate；The zinc salt and the mass ratio of thiocarbamide are preferably 272.6：304；The washing is excellent
Choosing is respectively to clean reactant 2-3 times with second alcohol and water, and the drying temperature is preferably 60~80 DEG C, and drying time is preferably
10-12h；
Step 2：Amino-compound is added in porcelain boat, is placed in tube furnace, is heated up under nitrogen atmosphere, heating rate
Preferably 2.5~5 DEG C/min is warming up to 550~600 DEG C and heats 2~4 hours, obtains body phase g-C3N4Powder；The amino
Compound is preferably melamine, thiocarbamide, urea or semicarbazide hydrochloride；
Step 3：The ZnS (en) that step 1 is obtained0.5The g-C that nanometer sheet and step 2 obtain3N4Powder is mixed,
The mixing time is preferably 30~120 minutes, then carries out hydro-thermal reaction in a kettle, and the reaction temperature is preferred
It it is 200 DEG C, the reaction time is preferably 6~12h, and reactant is transferred to dialysis in dialysis bag, and the dialysis time is preferably
12-24h, it is freeze-dried, obtain the ZnS micro-composites of graphene carbonization nitrogen quantity point modification.
The present invention is by ZnS (en)0.5The g-C of nanometer sheet and body phase3N4Hydro-thermal reaction occurs for mixing, in hydrothermal reaction process
In, the g-C of body phase3N4Form g-C3N4Quantum dot finally obtains g-C3N4ZnS microns of composite woods of three-dimensional (3D) of quantum dot modification
Material.
The present invention during the reaction, ZnS (en)0.5The g-C of nanometer sheet and body phase3N4Mole when hydrothermal temperature and when
Between all key parameters of the reaction process in order to control, the ZnS (en)0.5Nanometer sheet and g-C3N4The molar ratio of powder is preferably
1.0：(0.5~4.0), more preferably 1：2；As ZnS (en)0.5Nanometer sheet and g-C3N4The molar ratio of powder is more than 1：When 4, it can make
g-C3N4Quantum dot reduces catalytic activity in the excessive reunion in ZnS surfaces, as ZnS (en)0.5Nanometer sheet and g-C3N4Powder
Molar ratio is less than 1：When 0.5, g-C3N4The hetero-junctions that quantum dot and ZnS are formed is further reduced, and is unfavorable for carrying for catalytic activity
It is high；The reaction temperature is preferably 200 DEG C, and the reaction time is preferably 6~12h, will not when reaction temperature is less than 200 DEG C
Obtain the g-C of good dispersion3N4Quantum dot；When reaction temperature is higher than 200 DEG C, g-C can be caused3N4The loss of surface N excess and
Form C points；When being less than 6h between when reacted, body phase g-C3N4It will not be cut into g-C completely3N4Quantum dot；It is higher than between when reacted
It during 12h, can also increase the loss of N, be unfavorable for the raising of catalytic activity.
The present invention is by introducing good water solubility, it is seen that the strong g-C of photoresponse ability3N4QDs is in three-dimensional ZnS micrometer structures
ZCNx composite materials are formed, overcome zinc sulfide semiconductor catalyst itself Carrier recombination rate high, sun light utilization efficiency is low to be lacked
It falls into；Improve g-C simultaneously3N4The dispersibility of QDs reduces its reunion, so as to improve the specific surface area of catalyst and active site.This
Outside, the method for a step hydrothermal synthesis promotes g-C3N4The close contact of QDs and ZnS, and g-C3N4The smaller size reductions of QDs
Electronics and g-C on ZnS conduction bands3N4Hole is compound in QDs valence band, so as to be conducive to improve carrier separation and transmission speed
Rate finally obtains higher photocatalytic activity.
The present invention also provides the ZnS micron composite woods of graphene carbonization nitrogen quantity point modification that above-mentioned preparation method obtains
Material.
ZnS micro-composites the present invention also provides the carbonization nitrogen quantity point modification of above-mentioned graphene are as photochemical catalyst
Using.Specially：By synthesized ZCNx composite materials for the tests such as XRD, XPS, SEM, TEM and Photocatalyzed Hydrogen Production, catalysis
Agent dosage is 20mg, and light source is visible ray (300 watts of xenon lamps, wavelength are more than 420nm).
Due to g-C3N4The quantum size effect of QDs, compared with ZnS, which uses as photochemical catalyst, compound
Visible-range has been widened in the absorption of catalyst, and specific surface area increases, different due to being formd between two kinds of interfaces
Matter knot, so the separation of carrier and transmittability are also obviously improved.
In order to make invention apparent specific, the present invention is described below below, specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
Embodiment 1g-C3N4The preparation of QDs
The melamine of 100mg is added in porcelain boat, is placed in tube furnace, lower 550 DEG C of nitrogen atmosphere heats 4 hours,
Heating rate is per minute for 2.5 degree, obtains body phase g-C3N4Yellow powder, by 100mg g-C3N4Powder is dissolved in 50mL deionizations
60min is stirred in water, is then transferred into 100mL reaction kettles and reacts 6h at 200 DEG C, obtained flaxen g-C3N4QDs is transparent
Solution.
Fig. 1 is g-C prepared by embodiment 13N4Transmission (a), high-resolution photo (b), Size Distribution (c) and the absorption of QDs,
Fluorescence curve (d)；It will be seen from figure 1 that g-C3N4QDs has good dispersibility, and lattice is apparent in high-resolution photo, explanation
Crystallinity is good, mean particle diameter 5.6nm, blue light-emitting, absorbs and fluorescence and body phase g-C3N4Compared to apparent blue shift, explanation
The band gap of quantum dot broadens, that is, leads valence band and move in the opposite direction, shows quantum dot than body phase g-C3N4With higher oxidation
Reducing power.
Embodiment 2
1st, ZnS (en) is prepared0.5
First by 272.6mg ZnCl2It is added in 60mL ethylenediamines with 304mg thiocarbamides, stirs 30min, 180 DEG C of hydro-thermals
18h is reacted, after being cooled to room temperature, is respectively cleaned 2-3 times with second alcohol and water, 60 DEG C of dry 12h.
2nd, body phase g-C is prepared3N4
The melamine of 100mg is added in porcelain boat, is placed in tube furnace, lower 550 DEG C of nitrogen atmosphere heats 4 hours,
Heating rate is per minute for 2.5 degree, obtains body phase g-C3N4Yellow powder.
3rd, the synthesis of ZCN-0.5
Take above-mentioned ZnS (en)0.5Nanometer sheet and g-C3N4Powder, wherein ZnS (en)0.5Nanometer sheet and g-C3N4Powder rubs
You are than being 1.0：0.5, it is mixed 60 minutes, it is small to be then transferred into dialysis 24 in dialysis bag by 200 DEG C of hydro-thermal 6h in reaction kettle
When, products therefrom is lyophilized, obtains ZCN-0.5.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 1280 μm of ol h-1g-1,
As shown in table 1.
Fig. 8 is ZnS and g-C prepared by embodiment 1-23N4The band gap (a) of QDs and XPS valence band spectrums (b)；It can from Fig. 8
Go out, ZnS and g-C3N4The band gap of QDs is respectively 3.42 and 3.21eV, and valence band is 2.21 and 1.20V.Therefore ZnS and CNQDs is led
Band is respectively -1.21 and -2.01V, therefore type II hetero-junctions is formd between two kinds of semiconductors, so as to enhance carrier
Separation and transmission.
Embodiment 3
Step and method parameter are with embodiment 1, and the difference lies in ZnS (en)0.5Nanometer sheet and g-C3N4Mole of powder
Than being 1.0：1.0, obtain ZCN-1.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 2800 μm of ol h-1g-1,
As shown in table 1.
Embodiment 4
Step and method parameter are with embodiment 1, and the difference lies in ZnS (en)0.5Nanometer sheet and g-C3N4Mole of powder
Than being 1.0：2.0, obtain ZCN-2.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 5600 μm of ol h-1g-1,
As shown in table 1.
Fig. 2 is ZnS (en) prepared by embodiment 40.5Stereoscan photograph (b), the ZCN-2 of nanometer sheet (a) and ZCN-2 are multiple
The transmission (c) of condensation material and high-resolution photo (d)；Fig. 2 can be seen that ZnS (en)0.5For nanometer chip architecture, size is about
200nm, and the size of ZCN-2 composite materials is about 2 μm.G-C can be obtained by transmission electron microscope photo3N4QDs is uniformly dispersed in
ZnS surfaces improve the specific surface area of ZnS, contribute to coming into full contact with for catalyst and sunlight and hydrone, increase sunlight
Utilization rate, so as to improve the efficiency of Photocatalyzed Hydrogen Production.
Fig. 3 is the XRD diffraction curves (a) of ZnS, BCN and ZCN-2 composite material prepared by embodiment 4 and infrared absorption song
Line (b)；Fig. 3 can be seen that the mixed phase that ZnS is hexagon and buergerite, due to g-C3N4The size of QDs is smaller, compound
The peak of quantum dot is not detected in XRD.From infrared absorption spectrum as can be seen that in water-heat process, g-C3N4In QDs
Triazine ring be effectively maintained, the peak of C-OH and C-N-H becomes strong, illustrates that there are more hydrophilic radicals on surface.
Fig. 4 is the ultraviolet absorption curve (a) and nitrogen adsorption desorption curve of ZCN-2 composite materials prepared by embodiment 4
(b)；The absorption region that Fig. 4 can be seen that zinc sulphide is narrow (300-550nm), it is impossible to make full use of visible ray, g-C3N4QDs
Introducing widened the absorption region (300-900nm) of zinc sulphide significantly, the photocatalytic activity higher for composite material is established
Basis.Nitrogen adsorption desorption curve shows g-C3N4The introducing of QDs substantially increases the specific surface area of ZnS, it ensure that catalyst
Higher reactivity site.
Fig. 5 is the transient photocurrents density (a) of ZCN-2 composite materials prepared by embodiment 4 and fluorescence lifetime curve (b)；
Fig. 5 can be seen that g-C3N4The introducing of QDs improves the photoelectric current of ZnS, and reduce charge transfer resistance.It is it follows that multiple
The transmission rate and separating effect of the electrons and holes of condensation material improve, and imply its increased photocatalytic activity.
Fig. 6 is hydrogen output (a) and hydrogen-producing speed curve (b) of the ZCNx composite materials of the preparation of embodiment 4 in 210min；
As can be seen from Figure 6, the production hydrogen activity of ZnS, ZCN-1, ZCN-2 and ZCN-3 are respectively 40,2800,5600 and 3550 μm of ol h-1g-1,
Illustrate g-C3N4The introducing of QDs substantially increases the photocatalytic activity of ZnS really.
Fig. 7 is the production hydrogen activity (a) of ZCN-2 catalyst prepared by embodiment 4 and is catalyzed front and rear XRD curves (b)；From figure
7 find out, which has higher stability, not decreased significantly in four circulation experiment behind efficiencies.
Embodiment 5
Step and method parameter are with embodiment 1, and the difference lies in ZnS (en)0.5Nanometer sheet and g-C3N4Mole of powder
Than being 1.0：3.0, obtain ZCN-3.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 3550 μm of ol h-1g-1,
As shown in table 1.
Embodiment 6
Step and method parameter are with embodiment 1, and the difference lies in ZnS (en)0.5Nanometer sheet and g-C3N4Mole of powder
Than being 1.0：4.0, obtain ZCN-4.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 2560 μm of ol h-1g-1,
As shown in table 1.
Embodiment 7
Step and method parameter obtain ZCN-2 with embodiment 3.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.35M) and sodium sulfite (0.25M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 3860 μm of ol h-1g-1,
As shown in table 1.
Embodiment 8
Step and method parameter obtain ZCN-2 with embodiment 3.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise triethanolamine.After photocatalytic water evaluation system is evacuated with vacuum pump, 300W xenon lamps are opened, are filtered with visible filter
Fall ultraviolet portion, detected the peak area of production hydrogen by on-line chromatograph every 30 minutes, the object of production hydrogen is calculated by standard curve
The amount of matter.The hydrogen-producing speed for measuring catalyst is 1658 μm of ol h-1g-1, as shown in table 1.
Embodiment 9
Step and method parameter are with embodiment 3, and the difference lies in ZnS (en)0.5Nanometer sheet and body phase g-C3N4Powder exists
Reaction time in reaction kettle is 12h, obtains ZCN-2.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 4368 μm of ol h-1g-1,
As shown in table 1.
Embodiment 10
With embodiment 3, the difference lies in reactant, the dialysis time is 12h in dialysis bag, is obtained for step and method parameter
To ZCN-2.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 3980 μm of ol h-1g-1,
As shown in table 1.
Embodiment 11
Step and method parameter are with embodiment 3, and the difference lies in ZnS (en)0.5Nanometer sheet and body phase g-C3N4Powder mixes
It is 120 minutes to close mixing time, obtains ZCN-2.
Photocatalyzed Hydrogen Production is tested
Suspension (15 milliliters, about 20 milligrams of powder) obtained by dialysis is added in quartz reaction pond, then adds in 45 millis
Rise the mixed solution of vulcanized sodium (0.25M) and sodium sulfite (0.35M).Photocatalytic water evaluation system is evacuated with vacuum pump
Afterwards, 300W xenon lamps are opened, ultraviolet portion is filtered out with visible filter, production hydrogen is detected by on-line chromatograph every 30 minutes
Peak area, pass through standard curve calculate production hydrogen substance amount.The hydrogen-producing speed for measuring catalyst is 5216 μm of ol h-1g-1,
As shown in table 1.
Table 1：ZnS and body phase g-C3N4Ratio and sacrifice agent type to the shadow of the Photocatalyzed Hydrogen Production activity of composite material
It rings
As can be drawn from Table 1, ZnS and body phase g-C in embodiment 43N4Ingredient proportion be 1.0:2.0, sacrifice agent is
Na2S (0.25M) and Na2SO3During the mixed solution of (0.35M), catalysis production hydrogen effect highest, in the feelings without any co-catalyst
5600 μm of ol h can be reached under condition-1g-1。
In conclusion the present invention has obtained g-C by a kind of simple hydro-thermal method3N4The three-dimensional ZnS of quantum dot modification is compound
Material.g-C3N4The quantum confined effect of quantum dot has widened the visible light-responded range of catalyst, increases specific surface area.This
G-C is improved after outer two kinds of semiconductors couplings3N4The dispersibility of quantum dot greatly reduces its reunion.And quantum dot is in ZnS tables
The growth in situ in face causes two kinds of semiconductors to be in close contact, so as to promote the separation of carrier and efficiency of transmission so that compound
Catalyst has efficient Photocatalyzed Hydrogen Production activity, and with good catalytic stability.The preparation process of composite material is simple,
Less toxic low consumption is suitble to Routine Test Lab research, has broad application prospects in the field of Photocatalyzed Hydrogen Production.
Claims (10)
- A kind of 1. preparation method of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification, which is characterized in that this method Including：Step 1：Prepare ZnS (en)0.5Nanometer sheet；Step 2：Amino-compound is added in porcelain boat, is placed in tube furnace, is heated up under nitrogen atmosphere, at 550~600 DEG C Heating 2~4 hours, obtains body phase g-C3N4Powder；Step 3：The ZnS (en) that step 1 is obtained0.5The g-C that nanometer sheet and step 2 obtain3N4Powder is mixed, then Hydro-thermal reaction is carried out in a kettle, is lyophilized through dialysis, obtains the ZnS micron composite woods of graphene carbonization nitrogen quantity point modification Material.
- 2. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the step one is specially：Zinc salt and thiocarbamide are added in ethylenediamine, stirred, then 180~ 200 DEG C of hydro-thermal reactions 10~for 24 hours, obtain ZnS (en)0.5Nanometer sheet.
- 3. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the zinc salt is zinc chloride, zinc nitrate or zinc acetate.
- 4. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the amino-compound of the step two is melamine, thiocarbamide, urea or semicarbazide hydrochloride.
- 5. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the heating rate of the step two is 2.5~5 DEG C/min.
- 6. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the ZnS (en)0.5Nanometer sheet and g-C3N4The molar ratio of powder is 1.0：(0.5~4.0).
- 7. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the mixing time of the step three is 30~120 minutes.
- 8. a kind of preparation side of the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 1 Method, which is characterized in that the reaction temperature of the step three in a kettle is 200 DEG C, and the reaction time is 6~12h.
- 9. the ZnS of graphene carbonization nitrogen quantity point modification that the preparation method according to claim 1-8 any one obtains Micro-composites.
- 10. the ZnS micro-composites of graphene carbonization nitrogen quantity point modification according to claim 9 are as photochemical catalyst Application.
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