CN105964305A - ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst and preparation method thereof - Google Patents
ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- -1 2-amino p-phthalic acid Chemical compound 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 abstract 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 abstract 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 239000013147 Cu3(BTC)2 Substances 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a novel ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst and belongs to the technical field of photocatalysis. The novel ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst is characterized in that ZnIn2S4 is nanosheet-shaped and is uniformly distributed on the surface of lumpy NH2-MIL-125(Ti), and the mass percent of the NH2-MIL-125(Ti) is 20.0% to 6.0%. A preparation method comprises the steps: (1) dissolving a certain amount of tetrabutyl titanate and 2-amino terephthalic acid in a mixture solution of N,N-dimethylformamide and methanol, and carrying out a crystallizing reaction for 48 hours in an autoclave at the temperature of 150 DEG C, so as to obtain the NH2-MIL-125(Ti); (2) dispersing the synthesized NH2-MIL-125(Ti) into a certain volume of ethanol in an ultrasonic dispersion manner, then, sequentially adding a certain amount of propanetriol, indium chloride, zinc chloride and thioacetamide into the dispersion while carrying out stirring, carrying out a crystallizing reaction for 10 hours in an autoclave at the temperature of 180 DEG C to 200 DEG C so as to obtain a solid product, and subjecting the obtained solid product to filtrating, washing and drying, thereby obtaining the ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst. The preparation method of the composite visible-light catalyst is environmentally-friendly and is simple in process. The prepared composite catalyst has very high visible-light catalytic activity and has a potential application value in photocatalytic hydrogen production using solar energy.
Description
Technical field
The present invention relates to a kind of ZnIn2S4/NH2-MIL-125 (Ti) composite visible light catalyst and preparation method thereof, belongs to
Photocatalysis technology field.
Background technology
The mankind are increasing to the demand of the energy, find new forms of energy extremely urgent.Hydrogen Energy is owing to having high-energy, cleaning etc.
Feature and become the future type clean energy resource of substitute fossil fuels.TiO is used from Fujishima in 1972 etc.2Single Crystalline Electrodes is real
Since existing photochemical catalyzing (A. Fujishima and K. Honda,Nature, 1972,238:37-38), light is urged
Change the hydrogen production by water decomposition extensive concern by various countries.But TiO2The ultraviolet light accounting for sunlight total amount 3%-5% can only be absorbed, its sun
Energy utilization rate is low, it is difficult to industrial applications.Owing to visible ray accounts for the 45% of sunlight total amount, therefore, develop visible light-responded
, high efficiency photocatalyst become the study hotspot of recent photocatalysis research field.
Ternary metal sulfide ZnIn2S4Because there is layer structure, the suitable energy gap of uniqueness, having in visible region
The series of advantages such as stronger absorption, cause the great interest of photocatalysis field researcher in recent years.Research shows, ZnIn2S4?
The photocatalytic degradation aspect of photocatalysis hydrolytic hydrogen production and organic pollution presents higher catalysis activity, and golden with binary
Belong to testing sulphide ratio, there is more preferable photochemical stability.But single ZnIn2S4Photogenerated charge be easily combined, quantum efficiency
Low.At present by metal ion mixing, noble metal loading and with the method such as semiconductors coupling to ZnIn2S4It is modified, one
Determine in degree, to improve its photocatalysis performance, but still cannot meet the requirement of actual application, therefore, ZnIn2S4Photocatalysis
Performance still needs to improve further.
Metallic organic framework (MOFs) is the coordination polymer formed by metal oxygen-containing group and organic ligand.Because it has
The advantages such as high specific surface area, high porosity and structure easily tune are had to be widely used in gas absorption, separation, medicament transport, catalysis
In field.Additionally, study discovery recently, some metal-organic framework materials also have characteristic of semiconductor, at organic pollution
Photocatalytic degradation, photocatalysis hydrolytic hydrogen production and photo catalytic reduction CO2Certain photocatalytic activity is shown Deng in reaction.But with biography
The inorganic semiconductor photocatalyst of system is compared, and the avtive spot of MOFs is less, and photocatalytic activity is the lowest.By MOFs material with inorganic
Semi-conducting material is compounded to form heterojunction structure, by the cooperative effect of bi-material, can effectively facilitate photoproduction electricity on catalyst
The separation of lotus, thus improve its photocatalytic activity.Recently, some MOF based composites such as: ZnO@ZIF-8 (W. W. Zhan,
Q. Kuang, J. Z. Zhou, X. J. Kong, Z. X. Xie and L. S. Zheng,J .Am.Chem.Soc., 2013, 135, 1926-1933), Cu3(BTC)2@TiO2 (R. Li , J. H.Hu , M.
S. Deng, H. L. Wang, X. J. Wang, Y. L. Hu, H. L. Jiang, J. Jiang , Q. Zhang ,
Y. Xie and Y. J. Xiong, Adv.Mater., 2014, 26, 4783-4788)、 BiVO4@MIL-101 (Y.
L. Xu, M. M. Lv, H. B. Yang, Q. Chen, X. T. Liu and F. Y. Wei, RSC Adv.,
2015, 5, 43473-43479)、 Bi2WO6@UiO-66 (Z. Sha, J. L. Sun, H. S. O. Chan, S.
Jaenicke and J. S. Wu, RSC Adv., 2014, 4, 64977-64984)、 BiOBr@UiO-66 (Z.
Sha and J. S. Wu, RSC Adv., 2015, 5, 39592-39600)、 UiO-66@g-C3N4 (R. Wang ,
L. N. Gu , J. J. Zhou , X. L. Liu , F. Teng , C. H. Li , Y. H. Shen and Y. P.
Yuan, Adv.Mater. Interfaces, 2015,2, 1500037)、 CdS@UiO-66-NH2 (L. J.
Shen, S. J. Liang, W. M.Wu, R. W. Liang and L. Wu, J. Mater. Chem. A,
2013,1,11473-11482) and MoS2@UiO-66@CdS (L. J. Shen, M. B. Luo, Y. H. Liu, R.
W. Liang, F. F. Jing and L. Wu, Appl. Catal. B: Environ., 2015, 166-
167,445-453) etc. it has been successfully synthesized, and has shown photocatalytic activity more higher than corresponding monomer.But, it is up till now
Only, the most less about the preparation of MOF based composites and the report of Photocatalytic Performance Study thereof.
NH2The one that-MIL-125 (Ti) is a kind of oxy radical by metal Ti and organic ligand is formed by coordinate bond
There is the semi-conducting material of 3-D solid structure, under visible light conditions can photolysis water hydrogen, but its quantum efficiency is low causes
Photocatalytic activity is low.Based on above-mentioned technical background, the novel ZnIn of the convenient solvent structure of first passage of the present invention2S4/
NH2-MIL-125 (Ti) composite visible light catalyst, and have studied its visible photocatalysis water hydrogen manufacturing performance.The preparation of the present invention
Method, environmental friendliness, technique is simple.Additionally, the photocatalyst of preparation has high visible light catalysis activity, utilizing solar energy
Photocatalysis hydrogen production has potential using value.
Summary of the invention
It is an object of the invention to provide a kind of ZnIn2S4/NH2-MIL-125 (Ti) composite visible light catalyst and preparation side thereof
Method.
The present invention is to provide a kind of ZnIn2S4/NH2-MIL-125 (Ti) composite visible light catalyst, it is characterised in that have
Following composition: NH2The quality of-MIL-125 (Ti) is ZnIn2S4The 20.0-60.0 % of quality.
One ZnIn of the present invention2S4/NH2The preparation method of-MIL-125 (Ti) composite visible light catalyst, its feature exists
In, there is following preparation process and step:
A. NH2The preparation of-MIL-125 (Ti)
A, under () room temperature condition, the 2-amino p-phthalic acid weighing 2.201 g is dissolved in DMF and methanol
Proportioning be in 9:1 mixed solution;
B the butyl titanate of 2.4 ml is added dropwise in above-mentioned solution by ();
C (), by after above-mentioned solution stirring 0.5 h, moves in the autoclave of teflon gasket, crystallization at 150 DEG C
React 48 h;
D solid product that () obtains is after filtration, N,N-dimethylformamide and ethanol respectively wash 3 times and 24 h vacuum drying
Obtain NH2-MIL-125 (Ti) catalyst.
B. ZnIn2S4/NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
A () passes through to calculate, according to ZnIn2S4The 20.0-60.0 % of mass percent weigh the NH of above-mentioned synthesis2-MIL-125
(Ti) catalyst, ultrasonic disperse is in the mixed solution that proportioning is 3:1 of ethanol and glycerol;
B () adds 0.136 g ZnCl in above-mentioned mixed liquor2With 0.586 g InCl3.4H2O, stirs 1 h;
C the thioacetamide of 0.302 g is joined and stirs 1 h in above-mentioned solution by ();
D gained mixture is transferred in the autoclave of teflon gasket by (), crystallization at 180-200 DEG C
10 h;
E solid product that () obtains, through filtration, washing with alcohol and 24 h vacuum drying, finally prepares ZnIn2S4/NH2-MIL-
125 (Ti) composite visible light catalyst.
ZnIn2S4/NH2The photocatalysis performance test of-MIL-125 (Ti) composite visible light catalyst:
ZnIn is evaluated by photocatalysis hydrolytic hydrogen production can be seen below2S4/NH2The light of-MIL-125 (Ti) composite visible light catalyst
Catalytic performance.Active testing experiment is in the Lab solar-III AG type photolysis water hydrogen system of Beijing Bo Feilai Science and Technology Ltd.
On carry out.Detailed process is as follows: first, and 50 mg photocatalysts are scattered in 100 ml reaction with triethanolamine as sacrifice agent
In liquid, and the suspension ultrasonic 30min under dark condition that will be formed.Then to response system evacuation.Then, light source is opened
(300W xenon lamp, λ > 420nm) carry out photocatalytic water experiment.In experiment, sampled by on-line acquisition system every 1h, pass through gas phase
Chromatograph detection hydrogen output.By the reaction of 4h, the highest hydrogen-producing speed of composite catalyst can reach 1783.0 μm ol g- 1h-1。
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of example 1-4 and comparative example.
Fig. 2 is scanning electron microscope (SEM) picture of comparative example.
Fig. 3 is the SEM picture of embodiment 1.
Fig. 4 is X-ray energy spectrum (EDS) figure of embodiment 1.
Fig. 5 is the photocatalysis performance comparison curves of embodiment 1-4 and comparative example.
Detailed description of the invention
After now the specific embodiment of the present invention being described in detail.
Embodiment 1
A. NH2The preparation of-MIL-125 (Ti)
(1) under room temperature condition, 2.201 g 2-amino p-phthalic acids are dissolved in 36 ml DMF and
In the mixed solution of 4 ml methanol;
(2) 2.4 ml butyl titanates are added dropwise in above-mentioned solution;
(3) by after above-mentioned solution stirring 0.5 h, in the autoclave of the teflon gasket moving to 100ml, 150
Crystallization 48 h at DEG C;
(4) solid product obtained is after filtration, N,N-dimethylformamide and ethanol respectively wash 3 times and 24 h vacuum drying
Obtain NH2-MIL-125 (Ti) catalyst.
B. ZnIn2S4/40%NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
(1) by the NH of above-mentioned synthesis2-MIL-125 (Ti) catalyst 0.169 g, ultrasonic disperse is at 15 ml ethanol and 5 ml third
In the mixed solution of triol;
(2) in above-mentioned mixed liquor, 0.136 g ZnCl is added2With 0.586 gInCl3.4H2O, stirs 1 h;
(3) 0.302 g thioacetamide is joined above-mentioned solution stirs 1 h;
(4) gained mixture is transferred in the autoclave of teflon gasket, crystallization 10 h at 180 DEG C;
(5) solid product obtained, through filtration, washing with alcohol and 24 h vacuum drying, finally prepares ZnIn2S4/40%NH2-
MIL-125 (Ti) composite visible light catalyst.
Embodiment 2
A. NH2The preparation of-MIL-125 (Ti)
Operating process is such as embodiment 1
B. ZnIn2S4/20%NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
Except for the following differences, remaining is with embodiment 1 in operating process
NH by above-mentioned synthesis2-MIL-125 (Ti) catalyst 0.085g, ultrasonic disperse is at 15 ml ethanol and 5 ml glycerol
In mixed solution.
Embodiment 3
A. NH2The preparation of-MIL-125 (Ti)
Operating process is such as embodiment 1
B. ZnIn2S4/30%NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
Except for the following differences, remaining is with embodiment 1 in operating process
NH by above-mentioned synthesis2-MIL-125 (Ti) catalyst 0.127 g, ultrasonic disperse is at 15 ml ethanol and 5 ml glycerol
Mixed solution in.
Embodiment 4
A. NH2The preparation of-MIL-125 (Ti)
Operating process is such as embodiment 1
B. ZnIn2S4/60%NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
Except for the following differences, remaining is with embodiment 1 in operating process
NH by above-mentioned synthesis2-MIL-125 (Ti) catalyst 0.254 g, ultrasonic disperse is at 15 ml ethanol and 5 ml glycerol
Mixed solution in.
Comparative example
(1) by 0.136 gZnCl2With 0.586 gInCl3.4H2O is dissolved in 15 ml ethanol and the mixed solution of 5 ml glycerol
In, stir 1 h;
(2) 0.302 g thioacetamide is joined above-mentioned solution stirs 1 h, transfer to 100 ml teflon gaskets
Autoclave in, crystallization 10 h at 180 DEG C;
(3) solid product obtained, through filtering, washs, and is dried, finally prepares ZnIn2S4Visible light catalyst.
Seeing accompanying drawing 1, Fig. 1 is gained ZnIn in present example 1-42S4/NH2-MIL-125 (Ti) photocatalyst and comparative example
XRD spectra.From fig. 1, it can be seen that the diffraction maximum position of comparative example and ZnIn2S4Standard card (JCPDS No. 65-2023) phase
Corresponding (006), (102), (104), (108) and (110) crystal face meets, and illustrates that the sample that comparative example synthesizes is pure
ZnIn2S4.And in the XRD figure spectrum of the sample synthesized by embodiment 1-4, ZnIn occurs simultaneously2S4And NH2-MIL-125's (Ti)
Diffraction maximum, shows ZnIn2S4/NH2-MIL-125 (Ti) composite photo-catalyst successfully synthesizes.
Seeing accompanying drawing 2 and 3, Fig. 2 is pure NH2The SEM figure of-MIL-125 (Ti), it can be seen that the NH of synthesis2-MIL-125
(Ti) in bulk morphologies, particle size about 1 μm.Fig. 3 is the ZnIn of present example 1 gained2S4/40% NH2-MIL-125(Ti)
The SEM figure of composite photo-catalyst, it will thus be seen that the ZnIn of nano-sheet2S4Successfully it is supported on block NH2-MIL-125(Ti)
On surface.
Seeing accompanying drawing 4, Fig. 4 is the EDS spectrogram of present example 1 gained catalyst.It can be seen that synthesized sample
Elementary composition by Zn, In, Ti, C, O and S.
Seeing accompanying drawing 5, Fig. 5 is present example 1-4 and the photocatalysis performance comparison diagram of comparative example gained catalyst.From figure
Knowable in, ZnIn2S4/NH2-MIL-125 (Ti) composite is than single ZnIn2S4And NH2-MIL-125 (Ti) has higher
Photocatalytic activity.And work as NH2When the mass percent of-MIL-125 (Ti) is 40%, the photocatalysis performance of composite photo-catalyst
Most preferably, on optimum catalyst, hydrogen production rate reaches 1783.0 μm ol g-1h-1。
Claims (2)
1. a ZnIn2S4/NH2-MIL-125 (Ti) composite visible light catalyst, it is characterised in that there is following composition:
NH2The quality of-MIL-125 (Ti) is ZnIn2S4The 20.0-60.0 % of quality.
2. a ZnIn2S4/NH2The preparation method of-MIL-125 (Ti) composite visible light catalyst, it is characterised in that have with
Under preparation process and step:
A. NH2The preparation of-MIL-125 (Ti)
A, under () room temperature condition, the 2-amino p-phthalic acid weighing 2.201 g is dissolved in DMF and methanol
Proportioning be in 9:1 mixed solution;
B the butyl titanate of 2.4 ml is added dropwise in above-mentioned solution by ();
C (), by after above-mentioned solution stirring 0.5 h, moves in the autoclave of teflon gasket, crystallization at 150 DEG C
React 48 h;
D solid product that () obtains is after filtration, N,N-dimethylformamide and ethanol respectively wash 3 times and 24 h vacuum drying
Obtain NH2-MIL-125 (Ti) catalyst;
B. ZnIn2S4/NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
A () passes through to calculate, according to ZnIn2S4The 20.0-60.0 % of mass percent weigh the NH of above-mentioned synthesis2-MIL-125
(Ti) catalyst, ultrasonic disperse is in the mixed solution that proportioning is 3:1 of ethanol and glycerol;
B () adds 0.136 g ZnCl in above-mentioned mixed liquor2With 0.586 g InCl3.4H2O, stirs 1 h;
C the thioacetamide of 0.302 g is joined and stirs 1 h in above-mentioned solution by ();
D gained mixture is transferred in the autoclave of teflon gasket by (), crystallization at 180-200 DEG C
10 h;
E solid product that () obtains, through filtration, washing with alcohol and 24 h vacuum drying, finally prepares ZnIn2S4/NH2-MIL-
125 (Ti) composite visible light catalyst.
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