CN107670696A - A kind of (NH of metal-organic framework materials UIO 662The preparation method of)/bar-shaped cadmium sulfide composite photo-catalyst - Google Patents
A kind of (NH of metal-organic framework materials UIO 662The preparation method of)/bar-shaped cadmium sulfide composite photo-catalyst Download PDFInfo
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- CN107670696A CN107670696A CN201710880425.XA CN201710880425A CN107670696A CN 107670696 A CN107670696 A CN 107670696A CN 201710880425 A CN201710880425 A CN 201710880425A CN 107670696 A CN107670696 A CN 107670696A
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 77
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 title abstract description 15
- 239000000463 material Substances 0.000 title abstract description 11
- 239000013207 UiO-66 Substances 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000002171 ethylene diamines Chemical class 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 7
- 229940107698 malachite green Drugs 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to a kind of (NH of metal-organic framework materials UIO 662) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation, including step：The preparation of bar-shaped cadmium sulfide (CdS NRs), (NH of UIO 662) preparation and the (NH of UIO 662) bar-shaped the cadmium sulfide ((NH of CdS@UIO 66 of doping2)) preparation of composite photo-catalyst.The beneficial effects of the invention are as follows：The preparation method is relatively simple, and preparation condition is easily controlled, the prepared (NH of UIO 662) bar-shaped cadmium sulfide (CdS NRs) composite catalyst of doping has the advantages that non-secondary pollution, photocatalysis efficiency is high, there is certain application value.
Description
Technical field
The invention belongs to nano material preparation and applied technical field, it is related to a kind of metal-organic framework materials UIO-66
(NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation method.
Background technology
Photocatalysis technology, which is increasingly becoming, curbs environmental pollution and one of the technology of most critical of energy shortage problem, and draws
The widely studied of domestic and international scientist is sent out.Many research work concentrate on high efficiency photocatalyst search and it is appropriately designed on,
Because directly driving reaction to have proved to be a kind of science using solar radiation, effective and green method.It is a kind of typical
II-VI semiconductors, due to its suitable band gap (2.4eV) and its electronics and optical property, CdS conducts in the past few decades
The material of practical application is furtherd investigate, and is particularly used to convert solar energy into chemical energy under visible light illumination.
But research shows there are still the utilization that Railway Project limits pure CdS particles, such as：CdS particles tend to gather
Collection, causes surface area to reduce；High recombination rate and the photoetch tendency of photo-generate electron-hole pair also greatly limit it and widely should
With.Many trials have been done to improve CdS activity and stability, such as CdS particles have been embedded in polymeric matrix, synthesis
CdS quantum dot, and combined with other compositions (such as noble metal, semiconductor and carbon material)；Therefore CdS and other semiconductors combination
Turn into study hotspot.Wherein, semiconductors coupling is that the semiconductor progress of two or more different energy band is mutually compound.
After semiconductors coupling, light induced electron and hole are flowed into another semiconductor energy level from a semiconductor energy level, promote photoproduction
Electronics has expanded spectral response range, so as to further improve the quantum yield of photochemical catalyst, and then has improved light and urge to separation
Change efficiency.Recently, nano composite material such as SnO2- CdS, TiO2- CdS, ZnO-CdS, α-Fe2O3- CdS is through research by as having
Desired photochemical catalyst.However it has been found that the conventional technology of preparing that Prior efforts person uses is related to the program of complexity, it is substantial amounts of organic
Solvent such as DMSO, crystallinity is improved usually using heat treatment, its energy expenditure is high, may cause seriously to pollute.Above seldom
It is proved to stability and the catalytic efficiency for successfully enhancing CdS, therefore the nano composite material for exploring CdS is very significant
's.
By metal ion and the metal organic framework (MOFs) being self-assembly of of organic ligand, because it is unique physico
Learn for example high pore volume of property, high-specific surface area, structure adaptability and flexibility and have a wide range of applications, including gas absorption,
Separation, chemical co-ordination, linear optics property and catalysis.MOFs can be used as catalyst in itself, and it is light-catalysed fabulous time
Thing is selected, research shows that some MOFs can be used as semiconductor, and is excited by the light of organic contact body or metal cluster to transmit electricity
Son.Further, it is also possible to introduce metal organic frame in the avtive spot of Photoactive metal material and semiconductor nanoparticle.With biography
The semiconductor light-catalyst of system is compared, and MOFs is advantageous in that the surface area with superelevation, and narrow micropore is distributed in
Single dispersing optical active substance is formed on MOFs, is advantageous to its catalytic activity and selectivity.Importantly, as light-catalyzed reaction
Organic porous material, they can also provide approach for the migration of photoinduced electron, so as to promote separation of charge, improve photocatalysis effect
Rate.Recent semiconductor@MOF structure, such as ZnO@ZIF-8 and TiO2@MOF-5 have been synthesized, due to their cooperative effect,
Show very big advantage.Literature survey finds that the photocatalytic activity of CdS-MOF nano composite materials is not yet thoroughly studied.This
In we prepare it is a kind of on cadmium sulfide nano-stick wrap up MOF NEW TYPE OF COMPOSITE photochemical catalyst, UiO-66 (NH2) stability height,
Using it as research object, the results showed that, prepared CdS-MOF nano composite materials show sizable conversion ratio, to light
Catalyst has high selectivity.Therefore, it is very significant to research and develop this new composite photo-catalyst.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, the present invention provides a kind of metal-organic framework materials
UIO-66(NH2The preparation method of)/bar-shaped cadmium sulfide composite photo-catalyst.
A technical scheme is used by the present invention solves its technical problem：A kind of UIO-66 (NH2) the bar-shaped sulphur of doping
The preparation method of cadmium (CdS NRs) composite photo-catalyst, comprises the following steps：
(1) preparation of bar-shaped cadmium sulfide (CdS NRs)：By CdCl2·2.5H2O and CH4N2S is added to 60mL ethylenediamines
Sealed in 100mL autoclaves, shift 160 DEG C of autoclave, reaction time 48h.By gained yellow powder with water and ethanol wash with
Remove impurity, centrifugal filtration it is dry product；
(2)UIO-66(NH2) preparation：By ZrCl4It is dissolved in 2- amino-terephthalic acid (TPA) in DMF (50mL), then
Solution is transferred in 100mL autoclaves, and autoclave is sealed and heats 24h in 120 DEG C of baking oven.Obtained sample is with anhydrous
Methanol cleans several times, to ensure that the DMF molecules of closing remove, is then dried under vacuum (100 DEG C, 12h)；
(3)UIO-66(NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation：It will be done in step (1)
(the CdS NRs) of certain mass after dry, ZrCl4It is dissolved in 2- amino-terephthalic acid (TPA) in DMF (50mL), then solution
It is transferred in 100ml autoclaves, autoclave is sealed and heats 24h in 120 DEG C of baking oven.Obtained sample absolute methanol
Cleaning several times, with ensure closing DMF molecules remove, centrifugal filtration it is dry product.
Further, CdCl in described step (1)2·2.5H2O and CH4N2S mol ratio is 1：3；
Further, ZrCl in described step (2) (3)4Mol ratio with 2- amino-terephthalic acid (TPA) is 1:1；
Further, UIO-66 (NH in described step (3)2):CdS mass ratioes be respectively 5wt%, 10wt%,
15wt%.
Further, hydrothermal temperature is 120 DEG C in described step (3), reaction time 24h.
Metal-organic framework materials UIO-66 (NH2The application of)/bar-shaped cadmium sulfide composite catalyst, for photocatalytic degradation
Malachite green (MG) solution, is carried out as steps described below：
Weigh 20mg catalyst to be put into test tube, 50mL 25mg/L MG solution is added, with 420nm optical filters
500W xenon lamps carry out photocatalytic degradation reaction as light source.Dark reaction time is 30min, after illumination, time sample is taken per 20min, is entered
Row centrifugation, and then survey its absorbance.
The beneficial effects of the invention are as follows：The preparation method is relatively simple, and preparation condition is easily controlled, prepared UIO-66
(NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping has the advantages that pollution-free, high catalytic efficiency, have certain
Application value.Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the UIO-66 (NH that the embodiment of the present invention 1 is prepared2) bar-shaped cadmium sulfide (CdS NRs) complex light of doping
The scanning electron microscope (SEM) photograph (a) and transmission electron microscope picture (b) of catalyst；
Fig. 2 is the UIO-66 (NH that the embodiment of the present invention 1 is prepared2) bar-shaped cadmium sulfide (CdS NRs) complex light of doping
The X-ray diffractogram of catalyst；
Fig. 3 is the UIO-66 (NH that the embodiment of the present invention 1 is prepared2) bar-shaped cadmium sulfide (CdS NRs) complex light of doping
The activity figure of catalyst degradation malachite green.
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
(1) preparation of bar-shaped cadmium sulfide (CdS NRs)：By 20.25mmol CdCl2·2.5H2O (4.62g) and
60.75mmol CH4N2S (4.62g) is added in the 100mL autoclaves of 60mL ethylenediamines and sealed, and shifts 160 DEG C of autoclave, instead
48h between seasonable.Gained yellow powder is washed with water and ethanol to remove impurity, centrifugal filtration it is dry product；
(2)UIO-66(NH2) preparation：By ZrCl4(0.2332g, 1.0mmol) and 2-NH2- terephthalic acid (TPA)
(0.1812g, 1.0mmol) is dissolved in DMF (50mL), and then solution is transferred in 100ml autoclaves, by autoclave sealing simultaneously
24h is heated in 120 DEG C of baking oven.Obtained sample is cleaned several times with absolute methanol, to ensure that the DMF molecules of closing remove,
Then dried under vacuum (100 DEG C, 12 hours)；
(3)UIO-66(NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation：It will be done in step (1)
The bar-shaped cadmium sulfide (CdS NRs) of 1.812g after dry, ZrCl4(0.2332g, 1.0mmol) and 2-NH2- BDC (0.1812g,
1.0mmol) it is dissolved in DMF (50mL), then solution is transferred in 100ml autoclaves, autoclave is sealed and at 120 DEG C
24h is heated in baking oven.Obtained sample is cleaned several times with absolute methanol, and to ensure that the DMF molecules of closing remove, centrifugal filtration is done
It is dry to obtain product.
Scanning electron microscope (SEM) photograph is as shown in figure 1, as can be seen from Fig., UIO-66 (NH prepared by present embodiment2) doping it is bar-shaped
The pattern of cadmium sulfide (CdS NRs) composite photo-catalyst is bar-shaped cadmium sulfide Surface coating UIO-66 (NH2), and be distributed more equal
It is even.
X ray diffracting spectrum is as shown in Fig. 2 as seen from the figure, the UIO-66 (NH of preparation2) the bar-shaped cadmium sulfide (CdS of doping
NRs) composite photo-catalyst XRD diffraction can be seen in the figure there are UIO-66 (NH at 7.53 °2) characteristic diffraction peak, 24.8 °,
26.5 °, 28.2 °, 43.9 ° with 48.2 ° of characteristic diffraction peaks for being bar-like cadmium sulfide (CdS NRs).Therefore, UIO-66 can be proved
(NH2) be combined with each other with bar-shaped cadmium sulfide (CdS NRs), and not changing itself crystal formation, this is consistent with the result of Electronic Speculum.
(4) photocatalytic degradation malachite green (MG)
20mg different catalysts are weighed respectively to be put into test tube, are added 50ml 25mg/L MB solution, are filtered with 420nm
The 500W xenon lamps of mating plate carry out photocatalytic degradation reaction as light source.Dark reaction time is 30min, after illumination, every
20min takes time sample, and the high speed centrifugation under the conditions of 5000rpm, takes supernatant liquor to survey its concentration with ultraviolet-uisible spectrophotometer
Change.As seen from Figure 3, in 30 minutes malachite green degradation rate to reach 99.9%, it is seen that prepared CdS UIO-66
(NH2) composite photo-catalyst has higher photocatalytic activity.
Claims (5)
- A kind of 1. UIO-66 (NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation method, it is characterised in that Comprise the following steps：(1) preparation of bar-shaped cadmium sulfide (CdS NRs)：By CdCl2·2.5H2O and CH4N2S is added to the 100mL of 60mL ethylenediamines Sealed in autoclave, be warming up to 160 DEG C, reaction time 48h.Gained yellow powder is washed to remove impurity with water and ethanol, Centrifugal filtration it is dry product；(2)UIO-66(NH2) preparation：By ZrCl4It is dissolved in 2- amino-terephthalic acid (TPA) in DMF (50mL), then solution It is transferred in 100mL autoclaves, autoclave is sealed and heats 24h in 120 DEG C of baking oven.Obtained sample absolute methanol Cleaning several times, to ensure that the DMF molecules of closing remove, is then dried under vacuum (100 DEG C, 12h)；(3)UIO-66(NH2) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping preparation：After being dried in step (1) Certain mass (CdS NRs), ZrCl4It is dissolved in 2- amino-terephthalic acid (TPA) in DMF (50mL), then solution shifts Into 100mL autoclaves, autoclave is sealed and heats 24h in 120 DEG C of baking oven.Obtained sample is cleaned with absolute methanol Several times, with ensure closing DMF molecules remove, centrifugal filtration it is dry product.
- A kind of 2. UIO-66 (NH according to claim 12) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping Preparation method, it is characterized in that：CdCl in described step (1)2·2.5H2O and CH4N2S mol ratio is 1：3.
- A kind of 3. UIO-66 (NH according to claim 12) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping Preparation method, it is characterized in that：ZrCl in described step (2), (3)4Mol ratio with 2- amino-terephthalic acid (TPA) is 1:1.
- A kind of 4. UIO-66 (NH according to claim 12) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping Preparation method, it is characterized in that：The quality of bar-shaped cadmium sulfide (CdS NRs) is 1~5g in described step (3), and UIO-66 (NH2):CdS mass ratioes are respectively 5wt%, 10wt%, 15wt%.
- A kind of 5. UIO-66 (NH according to claim 12) bar-shaped cadmium sulfide (CdS NRs) composite photo-catalyst of doping Preparation method, it is characterized in that：Hydrothermal temperature is 120 DEG C, reaction time 24h.
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| CN108579819A (en) * | 2018-05-21 | 2018-09-28 | 西南石油大学 | A kind of Fe3O4- N adulterates Ni/Zn-MOFs/g-C3N4The preparation method of composite photocatalyst material |
| CN108671960A (en) * | 2018-05-02 | 2018-10-19 | 中山大学 | A kind of high hydrothermal stability MOFs catalyst, the method for preparing and preparing chemicals for cellulose conversion |
| CN108752599A (en) * | 2018-08-31 | 2018-11-06 | 南京邮电大学 | A kind of high length-diameter ratio metal organic frame crystalline material and preparation method thereof |
| CN108772104A (en) * | 2018-06-12 | 2018-11-09 | 常州大学 | A kind of preparation method of tri- dish alkene polymer NTP NEW TYPE OF COMPOSITE photochemical catalysts of rodlike cadmium sulfide CdS NRs/ |
| CN108855216A (en) * | 2018-06-11 | 2018-11-23 | 福州大学 | Metal organic frame MIL-101 (Cr) optic catalytic composite material and the preparation method and application thereof of cadmium sulfide package |
| CN108927178A (en) * | 2018-06-21 | 2018-12-04 | 三峡大学 | A kind of In-situ sulphiding method of metal-organic framework material prepares the method and application of NiS/CdS composite catalyst |
| CN108993604A (en) * | 2018-08-10 | 2018-12-14 | 淮阴师范学院 | High visible-light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application |
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| CN109046424B (en) * | 2018-08-09 | 2021-02-19 | 武汉科技大学 | UiO-66-NH for high-efficiency hydrogen production2/TiO2/Ti3C2Composite photocatalyst and preparation method thereof |
| CN108993604A (en) * | 2018-08-10 | 2018-12-14 | 淮阴师范学院 | High visible-light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application |
| CN108993604B (en) * | 2018-08-10 | 2021-07-20 | 淮阴师范学院 | High visible light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application thereof |
| CN108752599A (en) * | 2018-08-31 | 2018-11-06 | 南京邮电大学 | A kind of high length-diameter ratio metal organic frame crystalline material and preparation method thereof |
| CN110124740A (en) * | 2019-06-12 | 2019-08-16 | 常州大学 | Cerium dopping NH2The preparation method of-UiO-66/ indium sulfide zinc composite visible light catalyst |
| CN113070042A (en) * | 2021-04-28 | 2021-07-06 | 广东工业大学 | CdS quantum dot/MIL-101 (Cr) composite material and preparation method and application thereof |
| CN113398996A (en) * | 2021-06-21 | 2021-09-17 | 华东交通大学 | CdS @ UIO-66-NH2Preparation method of core-shell composite material |
| CN115845926A (en) * | 2023-02-14 | 2023-03-28 | 北京理工大学唐山研究院 | Application of cadmium sulfide composite UIO-66 (Ce) catalyst |
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