CN105964305B - 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 47
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019441 ethanol Nutrition 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 235000011187 glycerol Nutrition 0.000 claims abstract description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 8
- 229920006362 Teflon® Polymers 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000001035 drying 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 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 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
- 238000002156 mixing Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 150000001412 amines Chemical class 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
- 230000003197 catalytic effect Effects 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
- 150000001875 compounds Chemical class 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
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity 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
- 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
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography 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
-
- B01J35/39—
-
- 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
Abstract
The present invention relates to a kind of novel ZnIn2S4/NH2- MIL-125 (Ti) composite visible light catalyst, belongs to photocatalysis technology field.It is characterized in that, ZnIn2S4For nano-sheet, it is evenly distributed in block-like NH2The surface-MIL-125 (Ti), NH2The mass percent of-MIL-125 (Ti) is 20.0-60.0%.Preparation method: a certain amount of butyl titanate and 2- amino terephthalic acid (TPA) are dissolved in the mixed solution of n,N-Dimethylformamide and methanol by the first step, and crystallization 48h at 150 DEG C, obtains NH in autoclave2-MIL-125(Ti)；Second step, by the NH of above-mentioned synthesis2- MIL-125 (Ti) ultrasonic disperse is in a certain amount of ethyl alcohol, then a certain amount of glycerine, inidum chloride, zinc chloride, thioacetamide are sequentially added under stiring, the crystallization 10h at 180-200 DEG C in autoclave, obtained solid product obtain ZnIn after being filtered, washed and dried drying2S4/NH2- MIL-125 (Ti) composite visible light catalyst.Preparation method of the invention is environmental-friendly, simple process.The composite catalyst of preparation has very high visible light catalysis activity, has potential application value in using solar energy photocatalytic hydrogen manufacturing.
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 technique
Demand of the mankind to the energy is increasing, and it is extremely urgent to find new energy.Hydrogen Energy is due to high-energy, cleaning etc.
Feature and become substitute fossil fuels future type clean energy resource.TiO is used from Fujishima in 1972 etc.2Single Crystalline Electrodes are real
Since existing photochemical catalyzing (A. Fujishima and K. Honda,Nature, 1972,238:37-38), light is urged
Change extensive concern of the hydrogen production by water decomposition by various countries.But TiO2The ultraviolet light for accounting for sunlight total amount 3%-5%, the sun can only be absorbed
Energy utilization rate is low, it is difficult to industrial applications.Since visible light accounts for about the 45% of sunlight total amount, it develops visible light-responded
, high efficiency photocatalyst have become the research hotspot of recent photocatalysis research field.
Ternary metal sulfide ZnIn2S4Because there is unique layer structure, suitable forbidden bandwidth, have in visible region
The series of advantages such as relatively strong absorption, cause the great interest of photocatalysis field researcher in recent years.Studies have shown that ZnIn2S4?
Higher catalytic activity is presented in terms of the photocatalytic degradation of photocatalysis hydrolytic hydrogen production and organic pollutant, and golden with binary
Belong to testing sulphide ratio, there is better photochemical stability.But single ZnIn2S4Photogenerated charge be easy compound, quantum efficiency
It is low.At present by metal ion mixing, noble metal loading and with the methods of semiconductors coupling to ZnIn2S4It is modified, one
Determine to improve its photocatalysis performance in degree, but is still unable to satisfy the requirement of practical application, therefore, ZnIn2S4Photocatalysis
Performance still needs to further increase.
Metal organic framework (MOFs) is the coordination polymer formed by metal oxygen-containing group and organic ligand.Because of its tool
Have the advantages that high specific surface area, high porosity and structure are easily adjusted and is widely used in gas absorption, separation, medicament transport, catalysis
Equal fields.In addition, recently the study found that some metal-organic framework materials also have characteristic of semiconductor, in organic pollutant
Photocatalytic degradation, photocatalysis hydrolytic hydrogen production and photo catalytic reduction CO2Deng reaction in show certain photocatalytic activity.But with biography
The inorganic semiconductor photochemical catalyst of system is compared, and the active site of MOFs is less, and photocatalytic activity is very low.By MOFs material with it is inorganic
Semiconductor material is compounded to form heterojunction structure, by the synergistic effect of two kinds of materials, can effectively facilitate photoproduction electricity on catalyst
The separation of lotus, to improve its photocatalytic activity.Recently, some MOF based composites are 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. be successfully synthesized, and show
Photocatalytic activity more higher than corresponding monomer.However, up to the present, preparation and its photocatalysis about MOF based composites
The report of performance study is still less.
NH2- MIL-125 (Ti) is one kind that a kind of oxygen-containing group by metal Ti and organic ligand are formed by coordinate bond
Semiconductor material with three-dimensional 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.Preparation side of the invention
Method, environmental-friendly, simple process.In addition, the photochemical catalyst of preparation has high visible light catalysis activity, solar energy is being utilized
There is potential application value in catalyzing manufacturing of hydrogen.
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 its preparation side
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
Composition below: NH2The quality of-MIL-125 (Ti) is ZnIn2S4The 20.0-60.0 % of quality.
A kind of ZnIn of the present invention2S4/NH2The preparation method of-MIL-125 (Ti) composite visible light catalyst, feature exist
In with preparation process below and step:
A. NH2The preparation of-MIL-125 (Ti)
(a) under room temperature, weigh 2.201 g 2- amino terephthalic acid (TPA) be dissolved in n,N-Dimethylformamide with
The proportion of methanol is in 9:1 mixed solution；
(b) butyl titanate of 2.4 ml is added dropwise in above-mentioned solution；
(c) it after above-mentioned solution being stirred 0.5 h, moves in the autoclave of teflon gasket, at 150 DEG C
48 h of crystallization；
(d) solid product obtained respectively washs 3 times through filtering, N,N-dimethylformamide and ethyl alcohol and 24 h vacuum are dry
NH is obtained after dry2- MIL-125 (Ti) catalyst.
B. ZnIn2S4/NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
(a) by calculating, 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 the proportion of ethyl alcohol and glycerine is 3:1；
(b) 0.136 g ZnCl is added in above-mentioned mixed liquor2With 0.586 g InCl3.4H2O stirs 1 h；
(c) thioacetamide of 0.302 g is added in above-mentioned solution and stirs 1 h；
(d) gained mixture is transferred in the autoclave of teflon gasket, the crystallization at 180-200 DEG C
React 10 h；
(e) solid product obtained is dried in vacuo through filtering, ethanol washing and 24 h, and ZnIn is finally made2S4/NH2-
MIL-125 (Ti) composite visible light catalyst.
ZnIn2S4/NH2The photocatalysis performance of-MIL-125 (Ti) composite visible light catalyst is tested:
ZnIn is evaluated by the way that photocatalysis hydrolytic hydrogen production can be seen below2S4/NH2- MIL-125 (Ti) composite visible light catalyst
Photocatalysis performance.Active testing tests the III AG type photolysis water hydrogen of Lab solar- in Beijing Bo Feilai Science and Technology Ltd.
It is carried out in system.Detailed process is as follows: firstly, dispersing 100 ml using triethanolamine as sacrifice agent for 50 mg photochemical catalysts
In reaction solution, and by the suspension of formation under dark condition ultrasound 30min.Then reaction system is vacuumized.Then, it opens
Light source (300W xenon lamp, λ > 420nm) carries out photocatalytic water experiment.In experiment, is sampled, passed through by on-line acquisition system every 1h
Gas chromatograph detects hydrogen output.By the reaction of 4h, the highest hydrogen-producing speed of composite catalyst can reach 1783.0 μm of ol
g-1h-1。
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map 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.
Specific embodiment
After now specific embodiments of the present invention are described in detail.
Embodiment 1
A. NH2The preparation of-MIL-125 (Ti)
(1) under room temperature, 2.201 g 2- amino terephthalic acid (TPA)s are dissolved in the N of 36 ml, N- dimethyl formyl
In the mixed solution of amine and 4 ml methanol；
(2) 2.4 ml butyl titanates are added dropwise in above-mentioned solution；
(3) it after above-mentioned solution being stirred 0.5 h, moves in the autoclave of the teflon gasket of 100ml,
48 h of crystallization at 150 DEG C；
(4) solid product obtained respectively washs 3 times through filtering, N,N-dimethylformamide and ethyl alcohol and 24 h vacuum are dry
NH is obtained after dry2- MIL-125 (Ti) catalyst.
B. ZnIn2S4/40%NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
(1) by the NH of above-mentioned synthesis20.169 g of-MIL-125 (Ti) catalyst, ultrasonic disperse is in 15 ml ethyl alcohol and 5
In the mixed solution of ml glycerine；
(2) 0.136 g ZnCl is added in above-mentioned mixed liquor2With 0.586 gInCl3.4H2O stirs 1 h；
(3) 0.302 g thioacetamide is added in above-mentioned solution and stirs 1 h；
(4) gained mixture is transferred in the autoclave of teflon gasket, the crystallization at 180 DEG C
10 h；
(5) solid product obtained is dried in vacuo through filtering, ethanol washing and 24 h, and ZnIn is finally made2S4/40%
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 the same as embodiment 1 for operating process
By the NH of above-mentioned synthesis2- MIL-125 (Ti) catalyst 0.085g, ultrasonic disperse is in 15 ml ethyl alcohol and 5 ml the third three
In the mixed solution of alcohol.
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 the same as embodiment 1 for operating process
By the NH of above-mentioned synthesis20.127 g of-MIL-125 (Ti) catalyst, ultrasonic disperse is in 15 ml ethyl alcohol and 5 ml third
In the mixed solution of triol.
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 the same as embodiment 1 for operating process
By the NH of above-mentioned synthesis20.254 g of-MIL-125 (Ti) catalyst, ultrasonic disperse is in 15 ml ethyl alcohol and 5 ml third
In the mixed solution of triol.
Comparative example
(1) by 0.136 gZnCl2With 0.586 gInCl3.4H2O is dissolved in the mixing of 15 ml ethyl alcohol and 5 ml glycerine
In solution, 1 h is stirred；
(2) 0.302 g thioacetamide is added in above-mentioned solution and stirs 1 h, be transferred to 100 ml polytetrafluoroethylene (PTFE)
In the autoclave of liner, 10 h of crystallization at 180 DEG C；
(3) solid product obtained is filtered, and is washed, dry, and ZnIn is finally made2S4Visible light catalyst.
Referring to attached drawing 1, Fig. 1 is gained ZnIn in present example 1-42S4/NH2- MIL-125 (Ti) photochemical catalyst and right
The XRD spectra of ratio.From fig. 1, it can be seen that the diffraction maximum position of comparative example and ZnIn2S4Standard card (JCPDS No. 65-
2023) corresponding (006), (102), (104), (108) and (110) crystal face meet, and illustrate that the sample of comparative example synthesis is
Pure ZnIn2S4.And in the XRD spectrum of sample synthesized by embodiment 1-4, while there is ZnIn2S4And NH2-MIL-125(Ti)
Diffraction maximum, show ZnIn2S4/NH2- MIL-125 (Ti) composite photo-catalyst successfully synthesizes.
Referring to attached drawing 2 and 3, Fig. 2 is pure NH2The SEM of-MIL-125 (Ti) schemes, it can be seen that the NH of synthesis2-MIL-125
(Ti) be in bulk morphologies, about 1 μm of particle size.Fig. 3 is the resulting ZnIn of present example 12S4/40% NH2-MIL-125(Ti)
The SEM of composite photo-catalyst schemes, it will thus be seen that the ZnIn of nano-sheet2S4Successfully it is supported on blocky NH2-MIL-125(Ti)
On surface.
Referring to attached drawing 4, Fig. 4 is the EDS spectrogram of 1 gained catalyst of present example.It can be seen that synthesized sample
It is made of Zn, In, Ti, C, O and S element.
Referring to attached drawing 5, Fig. 5 is that the photocatalysis performance of catalyst obtained by present example 1-4 and comparative example compares figure.From figure
In it is found that ZnIn2S4/NH2- MIL-125 (Ti) composite material 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 up to 1783.0 μm of ol g-1h-1。
Claims (2)
1. a kind of ZnIn2S4/NH2- MIL-125 (Ti) composite visible light catalyst, it is characterised in that there is composition below: NH2-
The quality of MIL-125 (Ti) is ZnIn2S4The 20.0-60.0% of quality；
ZnIn2S4/NH2The preparation method of-MIL-125 (Ti) composite visible light catalyst has preparation process below and step
It is rapid:
A.NH2The preparation of-MIL-125 (Ti)
(a) under room temperature, the 2- amino terephthalic acid (TPA) for weighing 2.201g is dissolved in n,N-Dimethylformamide and methanol
Volume proportion is in 9:1 mixed solution；
(b) butyl titanate of 2.4ml is added dropwise in above-mentioned solution；
(c) it after above-mentioned solution being stirred 0.5h, moves in the autoclave of teflon gasket, crystallization is anti-at 150 DEG C
Answer 48h；
(d) solid product obtained is respectively washed 3 times through filtering, N,N-dimethylformamide and ethyl alcohol and is obtained after being dried in vacuo for 24 hours
NH2- MIL-125 (Ti) catalyst；
B.ZnIn2S4/NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
(a) by calculating, 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 the volume proportion of ethyl alcohol and glycerine is 3:1；
(b) 0.136g ZnCl is added in above-mentioned mixed liquor2With 0.586g InCl3.4H2O stirs 1h；
(c) thioacetamide of 0.302g is added in above-mentioned solution and stirs 1h；
(d) gained mixture is transferred in the autoclave of teflon gasket, the crystallization at 180-200 DEG C
10h；
(e) solid product obtained is through filtering, ethanol washing and is for 24 hours dried in vacuo, and ZnIn is finally made2S4/NH2-MIL-125
(Ti) composite visible light catalyst.
2. a kind of ZnIn2S4/NH2The preparation method of-MIL-125 (Ti) composite visible light catalyst, which is characterized in that have with
Under preparation process and step:
A.NH2The preparation of-MIL-125 (Ti)
(a) under room temperature, the 2- amino terephthalic acid (TPA) for weighing 2.201g is dissolved in n,N-Dimethylformamide and methanol
Volume proportion is in 9:1 mixed solution；
(b) butyl titanate of 2.4ml is added dropwise in above-mentioned solution；
(c) it after above-mentioned solution being stirred 0.5h, moves in the autoclave of teflon gasket, crystallization is anti-at 150 DEG C
Answer 48h；
(d) solid product obtained is respectively washed 3 times through filtering, N,N-dimethylformamide and ethyl alcohol and is obtained after being dried in vacuo for 24 hours
NH2- MIL-125 (Ti) catalyst；
B.ZnIn2S4/NH2The preparation of-MIL-125 (Ti) composite visible light catalyst
(a) by calculating, 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 the volume proportion of ethyl alcohol and glycerine is 3:1；
(b) 0.136g ZnCl is added in above-mentioned mixed liquor2With 0.586g InCl3.4H2O stirs 1h；
(c) thioacetamide of 0.302g is added in above-mentioned solution and stirs 1h；
(d) gained mixture is transferred in the autoclave of teflon gasket, the crystallization at 180-200 DEG C
10h；
(e) solid product obtained is through filtering, ethanol washing and is for 24 hours dried in vacuo, and ZnIn is finally made2S4/NH2-MIL-125
(Ti) composite visible light catalyst.
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