CN110152737A - The modified ZnCdS nanosphere composite material of Zr-MOF and its application - Google Patents
The modified ZnCdS nanosphere composite material of Zr-MOF and its application Download PDFInfo
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- CN110152737A CN110152737A CN201910389547.8A CN201910389547A CN110152737A CN 110152737 A CN110152737 A CN 110152737A CN 201910389547 A CN201910389547 A CN 201910389547A CN 110152737 A CN110152737 A CN 110152737A
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000002077 nanosphere Substances 0.000 title claims abstract description 39
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 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 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 239000013207 UiO-66 Substances 0.000 abstract description 50
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000004246 zinc acetate Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052726 zirconium 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
- B01J31/16—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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/51—
-
- B01J35/617—
-
- B01J35/647—
-
- 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
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/48—Zirconium
-
- 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 invention discloses a kind of bimetallic sulfide based composites, using one step hydro thermal method be prepared for a kind of bimetallic sulfide nanosphere with using Zr as the composite material of the metal organic frame (MOF) of metal center, the preparation and its application in Photocatalyzed Hydrogen Production that ZnCdS nanosphere and organic framework materials form the nanocomposite catalytic of heterojunction structure, belong to nano material preparation technology and green energy resource field.It is raw material the invention firstly uses zirconium chloride and terephthalic acid (TPA), by solvent-thermal process square block Zr metal-organic framework material (abbreviation UIO-66 (Zr)), the nanocomposite of ZnCdS nanosphere modified metal organic frame UIO-66 (Zr) is then further synthesized using cadmium acetate and zinc acetate.The nanocomposite shows excellent catalytic activity in Photocatalyzed Hydrogen Production.
Description
Technical field
The invention belongs to nano material preparation technology and green energy resource fields, and in particular to a kind of modified ZnCdS of Zr-MOF
The preparation method of nanosphere composite material and its application in Photocatalyzed Hydrogen Production.
Background technique
The energy be human survival, life and develop tiny step difficulty from energy carrier.The exploitation and utilization of fossil energy makes
Problem of environmental pollution it is more serious, in order to cope with fossil fuel increasingly depleted and environmental aspect further deterioration, people
A large amount of research has been carried out to green and renewable energy.In renewable energy, solar energy be the largest can production of resources, with
One kind that photocatalysis hydrogen production technology based on semiconductor is widely regarded as converting solar energy into chemical fuel is promising
Approach, rationally designing sustainable effective visible light responsive photocatalyst is still a challenging task.
Bimetallic sulfide has good environment as a kind of typical non precious metal semiconducting polymer photochemical catalyst
Friendly, surface be synthetic, good physical and chemical stability and unique characteristic electron, however, original bimetallic sulfide
There is also some limitations, and if specific surface area is not high, the active specy electronics that light excitation generates during light-catalyzed reaction is empty
Cave low separation efficiency, electric charge carrier transfer ability are weak etc., directly result in catalytic activity reduction.It a series of is asked to solve this
Topic, there have been many researchs, such as pass through control Cd0.5Zn0.5The pattern of S, doped precious metal, and with other semiconductors
It is compound, Cd0.5Zn0.5The photocatalysis performance of S has obtained a degree of raising.Regrettably, Cd0.5Zn0.5The light of S photochemical catalyst
Catalytic activity is also far from satisfying the basic demand of practical application.Therefore, Cd is developed0.5Zn0.5The new way of S Photocatalyst
Diameter is very important；Metal-organic framework (MOFs) has high specific surface area, tunable aperture, the high activity exposed
The characteristics such as center and flexible structure, thus cause people to its photocatalysis field extensive concern, however, due to UIO-66
(Zr) band gap is big (3.5 eV), can only absorb ultraviolet light, and the application in terms of visible light catalytic is restricted.Therefore, we will
The Zr-MOF material is connected with semiconductor material bimetallic sulfide, so as to improve the visible light-responded of Zr-MOF, as
Photochemical catalyst has the MOFs of high-specific surface area not only can be to avoid the aggregation of semi-conductor nano particles, but also can provide more
Reaction center and catalytic active center, to improve photocatalysis performance.
Summary of the invention
In view of the above technical problems, the present invention introduces Zr base MOF material (being denoted as UIO-66 (Zr) below) into bimetallic
Sulfide nanosphere, the introducing of the material provide more activated centres and effective electric charge transfer, so that composite material
Catalytic activity be improved significantly.
For material, it is micro- to have synthesized nanometer with bimetallic sulfide ZnCdS and metal organic frame UIO-66 (Zr) by the present invention
Ball is grown on ZnCdS/UIO-66 (Zr) nanocomposite of the special building form on the surface square block Zr base MOF.
Wherein, Zr base MOF material, can be used as the semiconductor of photochemical catalyzing, have excellent thermostabilization in water
Property, chemical stability and structural stability, are a kind of up-and-coming photochemical catalysts.ZnCdS solid solution under visible light illumination,
Very strong catalytic activity, chemical stability with higher are shown to water-splitting hydrogen manufacturing and degradable organic pollutant.But it is former
Having some limitations property of beginning ZnCdS, such as active sites poor dispersion, electron hole low separation efficiency, photoexcited charge carrier mobility
Ability is weak etc..Therefore, the MOF of high-specific surface area is introduced to overcome the low specific surface of quantity of photogenerated charge carrier present in ZnCdS
Long-pending and quickly compound disadvantage；And UIO-66 (Zr) can not obtain excellent production hydrogen activity since light absorption is limited, the present invention
It is compound with the progress of bimetallic sulfide, preferably to separate charge and activating reaction object.
To achieve the above object, the technical solution adopted by the present invention are as follows:
First by a step solvent structure square block metal-organic framework material UIO-66 (Zr), then by UIO-66 (Zr)
It is added under the synthesis condition of bimetallic sulfide, obtains ZnCdS nanosphere by solvent-thermal method and be grown on metal having machine frame
Novel ZnCdS/UIO-66 (Zr) composite photo-catalyst on frame surface, wherein UIO-66 (Zr) remains the spy of its high-ratio surface
Point, when additional amount is 40%-70%, the specific surface area range of obtained composite material is 128.05-450.53 m2/g。
The preparation method of the modified ZnCdS nanosphere composite material of UIO-66 (Zr) of the present invention includes following
Step:
(1) it weighs zirconium chloride and terephthalic acid (TPA) is dissolved in DMF, ultrasound is transferred to 50mL to after being completely dissolved
Ptfe autoclave liner in, seal heating, product is washed with DMF and methanol repeatedly, in vacuum drying
It is dried in case, obtains UIO-66 (Zr).
(2) UIO-66 obtained in step (1) (Zr) is dissolved in the water, is ultrasonically treated to obtain suspending liquid A；Weigh cadmium acetate
And zinc acetate, be dispersed in water, be stirred until homogeneous and disperse to obtain suspension B, after suspension B is added in suspending liquid A, stirring one
The section time adds dropwise sodium sulfide solution, continues stir process to form homogeneous mixture solotion.
(3) mixed solution that step (2) obtains is transferred in ptfe autoclave liner, is added in baking oven
Heat treatment.It is cooled to room temperature, it is multiple with pure water and ethanol washing, then dry in an oven.
UIO-66 (Zr) modified ZnCdS nanosphere composite material is applied in Photocatalyzed Hydrogen Production the present invention also provides a kind of
On application.Specific steps include the following: under visible light illumination, to have carried out hydrogen manufacturing in closing quartz reaction system, passed through
The temperature of reaction system is maintained at 5-8 DEG C by cooling circulating water, and UIO-66 (Zr) modified ZnCdS nanosphere composite material is urged
Agent is dispersed in the aqueous solution of vulcanized sodium and sodium sulfite, and wherein vulcanized sodium and sodium sulfite are continuously being stirred as sacrifice agent
Mix it is lower completely removed air, using the 300W Xe arc lamp of 420 nm optical filters (CEL-HXF300) as light source, using online
Gas chromatography (FULI, GC-7920) carries out liberation of hydrogen analysis, and the modified ZnCdS nanosphere of UIO-66 (Zr) is compound as the result is shown
Excellent Photocatalyzed Hydrogen Production activity is presented in material.
The present invention provides advanced composite material (ACM)s of a kind of Photocatalyzed Hydrogen Production and preparation method thereof, and are applied to light and urge
Change and produce hydrogen, preparation method is rationally simple, and H2-producing capacity is obviously improved, with excellent Photocatalyzed Hydrogen Production activity.
The present invention is compound using a kind of modified ZnCdS nanosphere of square block UIO-66 (Zr) of simple solvent structure
Photochemical catalyst, has high specific surface area and more active sites, and the composite material of synthesis has excellent under visible light
H2-producing capacity, can be widely used in green energy resource field.
Reaction mechanism: the modified ZnCdS nanosphere composite photo-catalyst of the square block UIO-66 (Zr) of this patent preparation exists
Extremely excellent catalytic activity is shown in Photocatalyzed Hydrogen Production, it is mainly different due to being constituted between UIO-66 (Zr) and ZnCdS
Matter structure, i.e., during illumination reaction, the conduction band and valence band of UIO-66 (Zr) and ZnCdS generate electrons and holes, due to
The electrode potential reason of UIO-66 (Zr) conduction band is more negative, and the electronics on conduction band is transmitted directly to the conduction band of ZnCdS, and produces in valence band
The sacrifice agent in raw hole and addition is compound.I.e. significantly improving for photocatalytic activity is attributable to during illumination reaction
On ZnCdS and the interface UIO-66 (Zr) charge efficiently separate and shift and the extension of Photoinduced Charge carrier lifetime.
In addition, ZnCdS@UIO-66 (Zr) photochemical catalyst have under visible light illumination good stability and it is good can
Recyclability.MOF based compound nano material environment remediation and novel photocatalysis material in terms of have wide application
Prospect.
Detailed description of the invention
Fig. 1: for catalyst Z nCdS, UIO-66 (Zr) made from embodiment 1, the modified ZnCdS nanosphere of UIO-66 (Zr)
The X-ray diffractogram of composite material.
Fig. 2: for the scanning electron microscope of UIO-66 made from embodiment 1 (Zr) modified ZnCdS nanosphere composite material ZU-50
Figure.
Fig. 3: for the transmission electron microscope of UIO-66 made from embodiment 1 (Zr) modified ZnCdS nanosphere composite material ZU-50
Figure.
Fig. 4: for the N of UIO-66 made from embodiment 1 (Zr) modified ZnCdS nanosphere composite material2Adsorption-desorption is bent
Line.
Fig. 5: the ultraviolet-visible for UIO-66 made from embodiment 1 (Zr) modified ZnCdS nanosphere composite material is unrestrained anti-
Penetrate spectrogram.
Fig. 6: for catalyst Z nCdS made from embodiment 1, the modified ZnCdS nanosphere of UIO-66 (Zr), UIO-66 (Zr)
The infared spectrum of composite material ZU-50.
Fig. 7: for catalyst Z nCdS made from embodiment 1, the modified ZnCdS nanosphere of UIO-66 (Zr), UIO-66 (Zr)
The photoelectricity flow graph of composite material.
Fig. 8: for catalyst Z nCdS made from embodiment 1, the modified ZnCdS nanosphere of UIO-66 (Zr), UIO-66 (Zr)
Exchange-impedance diagram of composite material.
Fig. 9: for catalyst Z nCdS made from embodiment 2, the modified ZnCdS nanosphere of UIO-66 (Zr), UIO-66 (Zr)
The H2-producing capacity histogram of composite material.
Specific embodiment
Embodiment 1
1) it weighs 1 mmol zirconium chloride and 1 mmol terephthalic acid (TPA) is dissolved in 30 mL DMF, it is ultrasonic to complete
It after fully dissolved, is transferred in the ptfe autoclave liner of 50 mL, seals, be put into baking oven, 120 DEG C add
24 h of heat, are cooled to room temperature, and product is washed repeatedly with DMF and methanol respectively, are dried in vacuo in 80 DEG C, obtaining metal has machine frame
Frame Zr-MOF is named as UIO-66 (Zr).
2) weigh 80.7 mg, 121 mg, 181.5 mg respectively, 282.3 mg UIO-66 obtained in step (1) (Zr) in
In four beakers (respectively representing UIO-66 (Zr) additional amount and accounting for the molar ratio of composite material is 40%, 50%, 60%, 70%), it is added 5
ML water is ultrasonically treated to obtain finely dispersed suspending liquid A 1, A2, A3, A4, separately takes four beakers, weighs 0.5 mmol acetic acid respectively
Cadmium and 0.5 mmol zinc acetate measure 15 mL water, stir 30 min to suspension B1, B2, B3, the B4 of being uniformly dispersed to obtain, and then will
B1, B2, B3, B4, which are respectively corresponded, is added to corresponding A1, A2, A3, stirs 1 h in A4,5 mL vulcanized sodium are added dropwise dropwise respectively afterwards
Solution (0.3M) continues 2 h of stir process to form uniform mixed solution.
3) the uniform mixed solution that step (2) obtains is transferred to the ptfe autoclave liner of 50 mL
In, heat 4 h in 160 DEG C of baking ovens.It is cooled to room temperature, it is multiple with pure water and ethanol washing, then at 80 DEG C
It is dried overnight in vacuum drying oven.Sample is labeled as ZU-40, ZU-50, ZU-60, ZU-70, respectively indicates UIO-66 (Zr) additional amount
Molar ratio is 40%, 50%, 60%, 70% in the composite.In addition, when being added without metal-organic framework material UIO-66 (Zr)
Synthesize original bimetallic sulfide Zn0.5Cd0.5S。
Fig. 1 is the modified ZnCdS nanosphere of catalyst Z nCdS, UIO-66 (Zr) made from embodiment 1, UIO-66 (Zr)
The X-ray diffractogram of composite material.(it can be seen that with the presence of the characteristic peak of obvious UIO-66 and ZnCdS in composite material,
Both illustrate it is compound after do not destroy the structure of script, and with the increase of UIO-66 mole, feature in the composite
Peak is also more obvious).
Fig. 3: for the transmission electron microscope picture of UIO-66 made from embodiment 1 (Zr) modified ZnCdS nanosphere composite material.
(this it appears that square block UIO-66 and ZnCdS nanosphere, mapping figure are respectively in selected areas from transmission plot
The distribution situation of Cd, S, Zn, Zr various elements, ZnCdS nanosphere are distributed mainly on selected areas surrounding, therefore Cd, S,
Tri- kinds of elements of Zn compare concentration in the distribution of region surrounding, and square block UIO-66 is mainly at the middle part of selected areas, therefore Zr element
Integrated distribution is in the middle part of region).
Embodiment 2
1) composite catalyst obtained in embodiment 1 is carried out to the Photocatalyzed Hydrogen Production of visible light.
2) hydrogen manufacturing experiment under visible light illumination, has been carried out in closing quartz reaction system, it will by cooling circulating water
The temperature of reaction system is maintained at 6 DEG C, and 50 mg catalyst are dispersed in the water-soluble of 0.25 M vulcanized sodium and 0.35 M sodium sulfite
In liquid (80mL), wherein vulcanized sodium and sodium sulfite are completely removed air, with continuous stirring as sacrifice agent with 420
The 300W Xe arc lamp of nm optical filter (CEL-HXF300) be light source, using online gas chromatography (FULI, GC-7920) into
The analysis of row liberation of hydrogen.It is primary every sampling in 1 hour after illumination starts, it obtains producing hydrogen histogram shown in Fig. 5.It can be concluded that UIO-66
(Zr) the product ZU-50 hydrogen output being added when weight is 50% is 4333.93 μm of olh-1·g-1。
Claims (9)
1. a kind of Zr-MOF modified ZnCdS nanosphere composite material, which is characterized in that the composite material is bimetallic vulcanization
The composite material of object nanosphere and metal organic frame Zr-MOF heterojunction structure.
2. Zr-MOF according to claim 1 modified ZnCdS nanosphere composite material, which is characterized in that described
Bimetallic sulfide nanosphere is bimetallic sulfide ZnCdS nanosphere, having a size of 10 nm -15nm.
3. Zr-MOF according to claim 1 modified ZnCdS nanosphere composite material, which is characterized in that metal has
Machine frame Zr-MOF is the metal-organic framework material that Zr is metal center.
4. Zr-MOF according to claim 3 modified ZnCdS nanosphere composite material, which is characterized in that described
Metal organic frame Zr-MOF is porous box structure, and pore size is 2 nm -50 nm, specific surface area 550-570
m2/g。
5. Zr-MOF according to claim 1 modified ZnCdS nanosphere composite material, which is characterized in that metal has
Shared molar ratio is respectively 0-70% to machine frame Zr-MOF in the composite.
6. Zr-MOF according to claim 1 modified ZnCdS nanosphere composite material, which is characterized in that metal has
Machine frame Zr-MOF is to dissolve zirconium chloride and terephthalic acid (TPA) in solvent DMF, then the hydro-thermal at 100-130 DEG C in reaction kettle
It reacts obtained by 20-25h.
7. Zr-MOF according to claim 1 modified ZnCdS nanosphere composite material, which is characterized in that bimetallic
The preparation method of the composite material of sulfide nanosphere metal organic frame Zr-MOF heterojunction structure is by cadmium acetate and second
The aqueous solution of sour zinc is added in metal organic frame Zr-MOF material, is stirred that vulcanized sodium is added dropwise after suspended emulsion, is obtained uniformly
Solution；Uniform solution is transferred in polytetrafluoroethylene (PTFE), hydro-thermal 3-5h obtains bimetallic sulfide and receives at 150-180 DEG C
The composite material of meter Wei Qiu and metal organic frame Zr-MOF heterojunction structure.
8. Zr-MOF according to claim 1-7 modified ZnCdS nanosphere composite material is produced in photocatalysis
Application on hydrogen.
9. application according to claim 8, which is characterized in that under visible light illumination, will be reacted by cooling circulating water
The temperature of system is maintained at 5-8 DEG C, and bimetallic sulfide based composites are dispersed in the aqueous solution of vulcanized sodium and sodium sulfite
In, continuously stir and visible light under produce hydrogen.
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| CN115990522A (en) * | 2022-12-10 | 2023-04-21 | 福州大学 | Preparation and application of MOF/CdZnS composite material |
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| CN110652988A (en) * | 2019-09-25 | 2020-01-07 | 三峡大学 | Preparation method and application of superfine bimetal sulfide microsphere loaded NiS film |
| CN110918126A (en) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst |
| CN110918125A (en) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | Preparation method of UiO-66 loaded tin sulfide nanoparticle photocatalyst |
| CN110918126B (en) * | 2019-12-23 | 2022-06-14 | 西北师范大学 | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst |
| CN111185199A (en) * | 2020-01-22 | 2020-05-22 | 天津理工大学 | Z-type heterojunction photocatalyst and preparation method and application thereof |
| CN115888833A (en) * | 2022-10-31 | 2023-04-04 | 淮北师范大学 | CdS/Mn-MOF composite photocatalyst and preparation method and application thereof |
| CN115888833B (en) * | 2022-10-31 | 2024-02-27 | 淮北师范大学 | CdS/Mn-MOF composite photocatalyst and preparation method and application thereof |
| CN115990522A (en) * | 2022-12-10 | 2023-04-21 | 福州大学 | Preparation and application of MOF/CdZnS composite material |
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