CN109046424A - A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof - Google Patents
A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 122
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 58
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 26
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 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 13
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006303 photolysis reaction Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 239000003708 ampul Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001052 transient effect Effects 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
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof.Its technical solution is: by Ti3AlC2It is placed in polytetrafluoroethyllining lining, hydrofluoric acid solution, the Ti that will be obtained is added3C2TxAnnealing, obtains TiO2/Ti3C2Compound.By zirconium chloride, n,N-Dimethylformamide and mixed in hydrochloric acid, zirconium chloride solution is obtained.By TiO2/Ti3C2Compound is added in zirconium chloride solution, and stirring obtains Zr4+/TiO2/Ti3C2Mixed solution.2- amino terephthalic acid (TPA) and the n,N-Dimethylformamide are mixed, organic ligand solution is obtained.To Zr4+/TiO2/Ti3C2Organic ligand solution is added in mixed solution and carries out hydro-thermal reaction to get the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.Present invention process is simple and strong operability, made product can significantly improve the separation of photo-generate electron-hole pair in photocatalytic process, has excellent visible photocatalysis water hydrogen manufacturing performance.
Description
Technical field
The invention belongs to composite photo-catalyst technical fields.More particularly to a kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/
Ti3C2Composite photo-catalyst and preparation method thereof.
Background technique
A large amount of burnings of fossil fuel bring global energy shortages and problem of environmental pollution, and searching is clean can
The energy persistently substituted is the hot spot of current research, while being also the demand that present society rapidly develops.It simulates in nature
Photosynthesis is to convert solar energy into a kind of important channel of Hydrogen Energy using photochemical catalyzing.But water oxygenization half
Reaction is due to being related to four electronic transfer process and more difficult generation.Therefore, finding stable, efficient photochemical catalyst is to realize photocatalysis
One of key factor of water decomposition.
Metal-organic framework materials (Metal-organic frameworks, be abbreviated as MOFs) be by metal ion with
A kind of porous material with three-dimensional space network shape structure that organic ligand bridging is constituted.Due to its with high porosity,
The features such as big specific surface area and regulatable structural unit and the extensive concern by researcher.Zirconium-based metallic-organic frame
Material (UiO-66-NH2) it is a kind of MOFs for just having under ultraviolet light and carrying out photocatalytic water hydrogen production potential itself.But it is single
UiO-66-NH2Photochemical catalyst is also faced with some problems, for example optical response range is narrow, photo-generate electron-hole pair it is compound several
Rate height and quantum yield are low etc..In order to improve these problems, further increase the efficiency of photodissociation aquatic products hydrogen, rational choice other half
Conductor material, synthesis composite photo-catalyst are a kind of simple and easy methods, such as studies have reported that: by MoS2Introduce UiO-
66-NH2Obtain composite photo-catalyst MoS2/UiO-66-NH2/G(Hao,Xuqiang,et al.Peculiar synergetic
effect of MoS2 quantum dots and graphene on Metal-Organic Frameworks for
photocatalytic hydrogen evolution.Applied Catalysis B:Environmental210(2017):
45-56.), by Cd0.2Zn0.8S introduces UiO-66-NH2Middle synthesis obtains and Cd0.2Zn0.8S/UiO-66-NH2(Su,Yun,et
al.Cd0.2Zn0.8S@UiO-66-NH2 nanocomposites as efficient and stable visible-light-
driven photocatalyst for H2 evolution and CO2 reduction.Applied Catalysis B:
, but above-mentioned report solution problem above still not yet in effect Environmental200 (2017): 448-457).
Summary of the invention
The present invention is directed to overcome prior art defect, and it is an object of the present invention to provide a kind of preparation process is simple and the height of strong operability
Effect produces the UiO-66-NH of hydrogen2/TiO2/Ti3C2The preparation method of composite photo-catalyst can effectively improve with the made product of this method
Single UiO-66-NH2Electric conductivity and light absorpting ability, the separation of photo-generate electron-hole pair in photocatalytic process can be promoted,
With excellent visible photocatalysis water hydrogen manufacturing performance.
To achieve the above object, technical solution of the present invention comprises the concrete steps that:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (40~60), first by the Ti3AlC2It is placed in polytetrafluoro
In ethylene liner, hydrofluoric acid solution is added, stirs 24~48h, then with the alternately washing 5~8 of deionized water and dehydrated alcohol
It is secondary, it is centrifuged, it is dry, obtain Ti3C2Tx。
Step 2: by the Ti3C2TxIt is placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is
400~800 DEG C, the time of annealing is 2~4h, obtains TiO2/Ti3C2Compound.
Step 3: pressing zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid is 1: 10: 60, by four chlorination
Zirconium, the n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution.
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (1~5): 100, it will be described
TiO2/Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2Mixed solution.
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2-
Amino terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution.
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (1~3):
1, to the Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-NH2/
TiO2/Ti3C2The precursor solution of composite photo-catalyst.
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst is transferred to reaction kettle
Interior carry out hydro-thermal reaction, the temperature of hydro-thermal reaction are 120~140 DEG C, and the time of hydro-thermal reaction is 16~32h；Be centrifuged, wash,
It is dry, obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
The concentration of the hydrofluoric acid is 40wt%.
The nitrogen contains N2Amount is 99.5vol%.
Due to the adoption of the above technical scheme, the beneficial effects of the present invention are:
(1) present invention first uses under nitrogen atmosphere and makes annealing treatment Ti3C2Tx, TiO is obtained in situ2/Ti3C2Compound.Then
By TiO2/Ti3C2Compound is added in zirconium chloride solution, adds organic ligand solution, is lauched in 120~140 DEG C of conditions
16~32h of thermal response to get highly effective hydrogen yield UiO-66-NH2/TiO2/Ti3C2Composite photo-catalyst, therefore simple process can be grasped
The property made is good.
(2) present invention makes annealing treatment Ti in a nitrogen atmosphere3C2Tx, TiO is obtained in situ2/Ti3C2Compound.Due to TiO2/
Ti3C2Composite surface has hydrophilic functional group abundant, makes UiO-66-NH2Ti can be uniformly attached to3C2Surface.Load has
Black TiO2/Ti3C2After compound, compared to single UiO-66-NH2, UiO-66-NH2/TiO2/Ti3C2Composite photo-catalyst
Light absorpting ability have and be obviously improved.Simultaneously as in the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Complex light is urged
Agent interface forms Schottky barrier, effectively increases the separative efficiency of photo-generate electron-hole pair, prepared efficient production
The UiO-66-NH of hydrogen2/TiO2/Ti3C2The photolysis water hydrogen efficiency of composite photo-catalyst is 298~412 μm of olg-1·h-1。
Therefore, present invention process is simple and strong operability, the UiO-66-NH of prepared highly effective hydrogen yield2/TiO2/
Ti3C2Composite photo-catalyst can improve single UiO-66-NH2Electric conductivity and light absorpting ability, significantly improve photocatalysis
The separation of photo-generate electron-hole pair in journey has excellent visible photocatalysis water hydrogen manufacturing performance.
Detailed description of the invention
Fig. 1 is a kind of UiO-66-NH of highly effective hydrogen yield prepared by the present invention2/TiO2/Ti3C2The SEM of composite photo-catalyst
Photo；
Fig. 2 is the UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The TEM photo of composite photo-catalyst；
Fig. 3 is the UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The ultraviolet-ray visible absorbing of composite photo-catalyst
Spectrum；
Fig. 4 is the UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The Decay figure of composite photo-catalyst；
Fig. 5 is the UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The photodissociation aquatic products hydrogen of composite photo-catalyst is living
Property figure.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments, not to the limit of its protection scope
System.
To avoid repeating, will first unite involved in present embodiment in relation to the detection method of material and made product
One is described as follows:
The concentration of the hydrofluoric acid is 40wt%；
The nitrogen contains N2Amount is 99.5vol%.
The UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2The inspection of the photocatalysis Decomposition aquatic products hydrogen activity of composite photo-catalyst
Survey method is: by the UiO-66-NH of the highly effective hydrogen yield of 20mg2/TiO2/Ti3C2Composite photo-catalyst is added to 50mL methanol and goes
(V in the mixed solution of ionized waterMethanol=12.5mL, VDeionized water=37.5mL), wherein methanol is as electronics sacrifice agent.Then to mixed
It closes in solution and is passed through nitrogen half an hour, to exclude the oxygen in solution.Quartz ampoule is irradiated to 3h under 500W xenon lamp again and carries out light
Catalysis reaction, sample detection hydrogen.When test, quartz ampoule top tank air is extracted using 250 μ L sample injectors and is injected into gas-chromatography
In instrument, the standard hydrogen area in obtained peak area and gas chromatograph is converted to get photocatalysis Decomposition aquatic products hydrogen
Rate.
It is repeated no more in embodiment.
Embodiment 1
A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof.The preparation side
The step of method, is:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (40~45), first by the Ti3AlC2It is placed in polytetrafluoro
In ethylene liner, hydrofluoric acid solution is added, stirs 24~30h, then with the alternately washing 5~8 of deionized water and dehydrated alcohol
It is secondary, it is centrifuged, it is dry, obtain Ti3C2Tx。
Step 2: by the Ti3C2TxIt is placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is
400~500 DEG C, the time of annealing is 2~2.5h, obtains TiO2/Ti3C2Compound.
Step 3: pressing zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid is 1: 10: 60, by four chlorination
Zirconium, the n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution.
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (1~2.5): 100, by institute
State TiO2/Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2It mixes molten
Liquid.
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2-
Amino terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution.
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (1~1.5)
: 1, to the Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-
NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst.
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst is transferred to reaction kettle
Interior carry out hydro-thermal reaction, the temperature of hydro-thermal reaction are 120~125 DEG C, and the time of hydro-thermal reaction is 16~20h；Be centrifuged, wash,
It is dry, obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
Fig. 1 is a kind of UiO-66-NH of highly effective hydrogen yield manufactured in the present embodiment2/TiO2/Ti3C2Composite photo-catalyst
SEM photograph；Fig. 2 is the UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The TEM photo of composite photo-catalyst；Fig. 3 is
The UiO-66-NH of highly effective hydrogen yield shown in Fig. 12/TiO2/Ti3C2The uv-visible absorption spectra of composite photo-catalyst；Fig. 4 is Fig. 1
The UiO-66-NH of shown highly effective hydrogen yield2/TiO2/Ti3C2The Decay figure of composite photo-catalyst；Fig. 5 is efficiently to produce shown in Fig. 1
The UiO-66-NH of hydrogen2/TiO2/Ti3C2The photodissociation aquatic products hydrogen activity figure of composite photo-catalyst.
It will be seen from figure 1 that UiO-66-NH2Even particulate dispersion is in Ti3C2Surface, so that made product remains with centainly
Exposed active site is conducive to the progress of light-catalyzed reaction.Figure it is seen that UiO-66-NH2/TiO2/Ti3C2Interface
Formation, UiO-66-NH2、TiO2And Ti3C2It is in close contact.From Fig. 3, (I indicates pure UiO-66-NH2, II indicates the product) it and can
To find out, the light absorpting ability of the product is compared to pure UiO-66-NH2Have and be obviously improved, there is good visible light
Responding ability.From fig. 4, it can be seen that the transient state fluorescence lifetime of the product is compared to pure UiO-66-NH2It is significantly improved, says
Bright introducing TiO2/Ti3C2After compound, due to the presence of Schottky barrier, photo-generate electron-hole is greatly reduced to dividing
From efficiency, be conducive to photolysis water hydrogen reaction.From fig. 5, it can be seen that the photocatalytic hydrogen production by water decomposition efficiency of the product is than pure
UiO-66-NH2Improve 81 times.
Product shown in Fig. 1 is after tested: photocatalytic hydrogen production by water decomposition efficiency is 407 μm of olg-1·h-1。
The made product of the present embodiment is after tested: photocatalytic hydrogen production by water decomposition efficiency is 355~412 μm of olg-1·h-1。
Embodiment 2
A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof.The preparation side
The step of method, is:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (45~50), first by the Ti3AlC2It is placed in polytetrafluoro
In ethylene liner, hydrofluoric acid solution is added, stirs 30~36h, then with the alternately washing 5~8 of deionized water and dehydrated alcohol
It is secondary, it is centrifuged, it is dry, obtain Ti3C2Tx。
Step 2: by the Ti3C2TxIt is placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is
500~600 DEG C, the time of annealing is 2.5~3h, obtains TiO2/Ti3C2Compound.
Step 3: pressing zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid is 1: 10: 60, by four chlorination
Zirconium, the n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution.
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (1.5~3): 100, by institute
State TiO2/Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2It mixes molten
Liquid.
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2-
Amino terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution.
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (1.5~2)
: 1, to the Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-
NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst.
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst is transferred to reaction kettle
Interior carry out hydro-thermal reaction, the temperature of hydro-thermal reaction are 125~130 DEG C, the time of hydro-thermal reaction is 20~for 24 hours；Be centrifuged, wash,
It is dry, obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
The made product of the present embodiment is after tested: photocatalytic hydrogen production by water decomposition efficiency is 335~392 μm of olg-1·h-1。
Embodiment 3
A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof.The preparation side
The step of method, is:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (50~55), first by the Ti3AlC2It is placed in polytetrafluoro
In ethylene liner, hydrofluoric acid solution is added, stirs 36~42h, then with the alternately washing 5~8 of deionized water and dehydrated alcohol
It is secondary, it is centrifuged, it is dry, obtain Ti3C2Tx。
Step 2: by the Ti3C2TxIt is placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is
600~700 DEG C, the time of annealing is 3~3.5h, obtains TiO2/Ti3C2Compound.
Step 3: pressing zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid is 1: 10: 60, by four chlorination
Zirconium, the n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution.
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (2~4.5): 100, by institute
State TiO2/Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2It mixes molten
Liquid.
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2-
Amino terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution.
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (2~2.5)
: 1, to the Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-
NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst.
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst is transferred to reaction kettle
Interior carry out hydro-thermal reaction, the temperature of hydro-thermal reaction are 130~135 DEG C, and the time of hydro-thermal reaction is 24~28h；Be centrifuged, wash,
It is dry, obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
The made product of the present embodiment is after tested: photocatalytic hydrogen production by water decomposition efficiency is 318~375 μm of olg-1·h-1。
Embodiment 4
A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof.The preparation side
The step of method, is:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (55~60), first by the Ti3AlC2It is placed in polytetrafluoro
In ethylene liner, hydrofluoric acid solution is added, stirs 42~48h, then with the alternately washing 5~8 of deionized water and dehydrated alcohol
It is secondary, it is centrifuged, it is dry, obtain Ti3C2Tx。
Step 2: by the Ti3C2TxIt is placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is
700~800 DEG C, the time of annealing is 3.5~4h, obtains TiO2/Ti3C2Compound.
Step 3: pressing zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid is 1: 10: 60, by four chlorination
Zirconium, the n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution.
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (2.5~5): 100, by institute
State TiO2/Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2It mixes molten
Liquid.
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2-
Amino terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution.
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (2.5~3)
: 1, to the Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-
NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst.
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst is transferred to reaction kettle
Interior carry out hydro-thermal reaction, the temperature of hydro-thermal reaction are 135~140 DEG C, and the time of hydro-thermal reaction is 28~32h；Be centrifuged, wash,
It is dry, obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
The made product of the present embodiment is after tested: photocatalytic hydrogen production by water decomposition efficiency is 298~353 μm of olg-1·h-1。
The beneficial effect of present embodiment is:
(1) present embodiment first uses and makes annealing treatment Ti under nitrogen atmosphere3C2Tx, TiO is obtained in situ2/Ti3C2It is compound
Object.Then by TiO2/Ti3C2Compound is added in zirconium chloride solution, adds organic ligand solution, at 120~140 DEG C
Under the conditions of 16~32h of hydro-thermal reaction to get highly effective hydrogen yield UiO-66-NH2/TiO2/Ti3C2Composite photo-catalyst, therefore technique is simple
Single, operability is good.
(2) present embodiment makes annealing treatment Ti in a nitrogen atmosphere3C2Tx, TiO is obtained in situ2/Ti3C2Compound.
Due to TiO2/Ti3C2Composite surface has hydrophilic functional group abundant, makes UiO-66-NH2Ti can be uniformly attached to3C2Table
Face.Load has black TiO2/Ti3C2After compound, compared to single UiO-66-NH2, UiO-66-NH2/TiO2/Ti3C2It is compound
The light absorpting ability of photochemical catalyst, which has, to be obviously improved.Simultaneously as in the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2
Composite photo-catalyst interface forms Schottky barrier, effectively increases the separative efficiency of photo-generate electron-hole pair, prepared
Highly effective hydrogen yield UiO-66-NH2/TiO2/Ti3C2The photolysis water hydrogen efficiency of composite photo-catalyst is 298~412 μm of olg-1·h-1。
Therefore, present embodiment simple process and strong operability, the UiO-66-NH of prepared highly effective hydrogen yield2/
TiO2/Ti3C2Composite photo-catalyst can improve single UiO-66-NH2Electric conductivity and light absorpting ability, significantly improve light
The separation of photo-generate electron-hole pair in catalytic process has excellent visible photocatalysis water hydrogen manufacturing performance.
Claims (4)
1. a kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2The preparation method of composite photo-catalyst, which is characterized in that described
Preparation method comprises the concrete steps that:
Step 1: pressing Ti3AlC2: the molar ratio of hydrofluoric acid is 1: (40~60), first by the Ti3AlC2It is placed in polytetrafluoroethylene (PTFE)
In lining, hydrofluoric acid solution is added, stirs 24~48h, is then alternately washed 5~8 times with deionized water and dehydrated alcohol, from
The heart, it is dry, obtain Ti3C2Tx；
Step 2: by the Ti3C2TxIt being placed in crucible, makes annealing treatment in a nitrogen atmosphere, the temperature of annealing is 400~
800 DEG C, the time of annealing is 2~4h, obtains TiO2/Ti3C2Compound；
Step 3: press zirconium chloride: n,N-Dimethylformamide: the molar ratio of hydrochloric acid be 1: 10: 60, by the zirconium chloride,
The n,N-Dimethylformamide and the mixed in hydrochloric acid are ultrasonically treated 2~3min, obtain zirconium chloride solution；
Step 4: pressing the TiO2/Ti3C2Compound: the mass ratio of the zirconium chloride is (1~5): 100, by the TiO2/
Ti3C2Compound is added in the zirconium chloride solution, is stirred 1~2h, is obtained Zr4+/TiO2/Ti3C2Mixed solution；
Step 5: pressing 2- amino terephthalic acid (TPA): the molar ratio of the n,N-Dimethylformamide is 1: 60, by the 2- amino
Terephthalic acid (TPA) and n,N-Dimethylformamide mixing, are ultrasonically treated 2~3min, obtain organic ligand solution；
Step 6: pressing the Zr4+/TiO2/Ti3C2Mixed solution: the volume ratio of the organic ligand solution is (1~3): 1, to
The Zr4+/TiO2/Ti3C2The organic ligand solution is added in mixed solution, stirs 1~2h, obtains UiO-66-NH2/
TiO2/Ti3C2The precursor solution of composite photo-catalyst；
Step 7: by the UiO-66-NH2/TiO2/Ti3C2The precursor solution of composite photo-catalyst be transferred in reaction kettle into
Row hydro-thermal reaction, the temperature of hydro-thermal reaction are 120~140 DEG C, and the time of hydro-thermal reaction is 16~32h；Centrifugation, washing, drying,
Obtain the UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst.
2. the UiO-66-NH of highly effective hydrogen yield as described in claim 12/TiO2/Ti3C2The preparation method of composite photo-catalyst,
The concentration for being characterized in that the hydrofluoric acid is 40wt%.
3. the UiO-66-NH of highly effective hydrogen yield as described in claim 12/TiO2/Ti3C2The preparation method of composite photo-catalyst,
Be characterized in that the nitrogen contains N2Amount is 99.5vol%.
4. a kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst, it is characterised in that the highly effective hydrogen yield
UiO-66-NH2/TiO2/Ti3C2Composite photo-catalyst be any one of according to claim 1~3 described in highly effective hydrogen yield
UiO-66-NH2/TiO2/Ti3C2The UiO-66-NH of highly effective hydrogen yield prepared by the preparation method of composite photo-catalyst2/TiO2/
Ti3C2Composite photo-catalyst.
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