CN115636949A - Preparation method and application of metal organic framework - Google Patents
Preparation method and application of metal organic framework Download PDFInfo
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- CN115636949A CN115636949A CN202211461447.XA CN202211461447A CN115636949A CN 115636949 A CN115636949 A CN 115636949A CN 202211461447 A CN202211461447 A CN 202211461447A CN 115636949 A CN115636949 A CN 115636949A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 8
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910007926 ZrCl Inorganic materials 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a metal organic framework X \8834, uiO-66- (NH) based on a mixed organic ligand 2 ) 2 From 2, 5-diaminoterephthalic acid ((NH) 2 ) 2 -BDC) and 5,10,15, 20-tetrakis (4-carboxyphenyl) metalloporphyrin or porphyrin are organic ligands, and the metal organic framework material is prepared by a one-pot method; the framework material presents an approximate octahedral structure, and the main structure of the framework material is UiO-66- (NH) 2 ) 2 In the framework structure (NH) 2 ) 2 -a portion of the positions of the BDC ligand is substituted with PdTCPP ligand; the metal isThe organic framework material has larger specific surface area and excellent visible light absorption capacity, is suitable for photocatalytic water splitting hydrogen production application, and has a photocatalytic hydrogen production rate of 1126 mu mol g under visible light irradiation ‑1 h ‑1 (ii) a The catalytic performance of four cycle periods is not obviously reduced, and the cycle stability is better; the preparation method has simple process, the yield is up to more than 80 percent, and the method is worthy of market popularization.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a metal organic framework X \8834andUiO-66- (NH) 2 ) 2 And the application thereof in the field of photocatalytic hydrogen production.
Background
Global energy and environmental issues have attracted considerable attention and become a focus of academic research. The consumption of fossil energy causes energy problems. Solar energy is considered a promising clean energy source. However, the utilization and conversion efficiency of solar energy is limited, and its utilization and storage pose significant challenges. The use of TiO has been reported since 1972 by Fujishima and Honda 2 Great progress has been made since the pioneering work of photocatalysts for solar energy conversion. Photocatalytic hydrogen production is an effective way to utilize solar energy. Semiconductor materials based on photoresponse have received a great deal of attention in recent years. The photocatalytic hydrogen production can convert solar energy into chemical energy, and becomes a friendly way for solving energy and environmental crisis. At present, researchers have developed many materials as photocatalysts, the earliest studies being based on TiO 2 Semiconductor materials and modifications thereof. However, finding new, highly efficient photocatalytic hydrogen production catalysts remains a challenge.
Up to now, photocatalysts such as TiO 2 ZnO, cdS, carbon nitride (C) 3 N 4 ) And the composite material or the heterojunction material thereof shows excellent photocatalytic hydrogen production performance. However, the properties of these materials have yet to be further improved. In order to solve these problems, research in recent years has focused mainly on the design and synthesis of highly efficient photocatalysts. The Metal Organic Framework (MOF) material is a porous material, also called porous coordination polymer, and has higher contentSpecific surface area and porosity. MOF materials have found widespread use in gas adsorption/separation, sensing, catalysis, etc. over the past 20 years. In addition, MOF materials have also been applied to CO 2 Reduction, organic transformation, hydrogenation, photocatalysis and the like. The photocatalytic hydrogen production is a simple and convenient hydrogen production method. Compared with the traditional inorganic semiconductor, the MOF as the photocatalyst has the advantages that (1) the high porosity of the MOF is favorable for the exposure of active sites and catalytic reaction; (2) the structure adjustability of the MOF enables the light absorption range to be adjustable; (3) The porous structure of the MOF shortens the charge transfer path, thereby improving the separation of photo-generated electrons-holes (e-h); (4) The co-catalyst or photosensitizer may be modified on the pore or backbone to facilitate the separation of the e-h pairs.
The reduction of water (hydrogen production) and the oxidation of water (oxygen production) are the two half-reactions of water decomposition. The hydrogen production reaction of the MOF photocatalyst is the main half reaction. Ultraviolet, visible and near infrared light account for 5%, 45% and 50% of sunlight, respectively. Because the proportion of ultraviolet light is relatively small, the design and preparation of photocatalysts with visible light or near infrared light response are always the focus of research. Porphyrin is a class of organic macromolecules with highly conjugated pi-electrons, has the advantages of excellent visible light absorption capacity, easy modification and the like, and is a very important organic ligand for constructing MOFs. The constructed porphyrin MOFs can combine the advantages of porphyrin with the structural characteristics of MOFs, so that the porphyrin MOFs has excellent catalytic performance in the field of photocatalysis. The amino group is another group with visible light absorption capability, and the metal organic framework material containing the amino group has visible light capture capability.
In summary, although the metal-organic framework constructed by porphyrin and organic ligand containing amino group has been widely applied in the field of hydrogen production by photocatalytic water splitting, a variety of MOFs and their composite materials have been designed and developed. The metal organic framework is constructed by the mixed ligand consisting of porphyrin and organic ligand containing amino, so that the visible light absorption capability of the material is expected to be further improved, and the photocatalytic performance is further improved.
Disclosure of Invention
To overcomeThe invention provides a metal organic framework X \8834; uiO-66- (NH) 2 ) 2 The preparation method and the application of the material in the field of hydrogen production by photocatalytic water decomposition.
In order to achieve the purpose, the invention adopts the technical scheme that: metal organic skeleton X8834, uiO-66- (NH) 2 ) 2 The preparation method comprises the following steps: reacting ZrCl 4 、(NH 2 ) 2 Adding BDC, metalloporphyrin or porphyrin, benzoic acid and DMF into a polytetrafluoroethylene reactor according to a molar ratio of 1.51 to 2.52 of (1.08 to 0.16) 2 ) 2 Wherein X is metalloporphyrin or porphyrin;
preferably, the metalloporphyrin comprises PdTCPP, cuTCPP and ZnTCPP, and the porphyrin is TCPP;
metal organic skeleton X8834, uiO-66- (NH) 2 ) 2 Prepared by the preparation method;
the invention also provides a metal organic framework X \8834, uiO-66- (NH) 2 ) 2 The application in the aspect of photocatalytic hydrogen production is as follows: mixing X8834, uiO-66- (NH) 2 ) 2 Dispersing in a solution consisting of TEOA and PBS according to the volume ratio of 1 to 4-6, adding 1-3% of Pt as a cocatalyst, pumping a reaction system to a vacuum state by using a vacuum pump, and starting a light source;
preferably, the light source is a 300W xenon lamp, and lambda is more than or equal to 400 nm.
The beneficial effects obtained by the invention are as follows:
the metal organic skeleton prepared by the invention is X \8834andUiO-66- (NH) 2 ) 2 Is similar to octahedral structure, presents deep purple, has uniform size, can be controlled at about 200 nm, and is due to (NH) in mixed ligand 2 ) 2 The concentration of-BDC is much higher than PdTCPP, preferably UiO-66- (NH) 2 ) 2 Nucleation causes the material to assume an approximately octahedral structure. But due to the presence of metalloporphyrin or porphyrin in the system, in UiO-66- (NH) 2 ) 2 In the nucleation process of (A), metalloporphyrin or porphyrin and (NH) 2 ) 2 -BDC competes with Zr 6 Cluster-bound to participate in the growth process due to Zr 6 The clusters are highly symmetrical and connected, so that UiO-66- (NH) 2 ) 2 Can still maintain a three-dimensional structure, the framework material presents an approximate octahedral structure, and the main structure of the framework material is UiO-66- (NH) 2 ) 2 In the framework structure (NH) 2 ) 2 -a portion of the positions of the BDC ligand are substituted by metalloporphyrin or porphyrin ligands; the metal organic framework has a large specific surface area and excellent visible light absorption capacity, under the irradiation of visible light, triethanolamine (TEOA) is used as a sacrificial agent, 1% Pt is added as a cocatalyst, PBS with the concentration of 50 mM is used as a buffer solution, the photocatalytic hydrogen production performance of the framework material is measured under the condition that the volume ratio of TEOA to PBS is 1 -1 h -1 The cycle performance test shows that the material is not obviously reduced after four cycles, so that the material is proved to have better cycle stability and be suitable for the field of hydrogen production by photocatalytic water splitting; the preparation process is simple and feasible, the yield is up to more than 80%, and the method is worthy of market popularization.
Drawings
FIG. 1 shows an octahedral metal organic skeleton UiO-66- (NH) 2 ) 2 SEM picture of (1);
FIG. 2 shows an octahedral metal-organic framework PdTCPP \8834; uiO-66- (NH) in example 1 of the present invention 2 ) 2 SEM picture of (1);
FIG. 3 shows an octahedral metal organic skeleton PdTCPP 8834and UiO-66- (NH) in example 1 of the present invention 2 ) 2 (ii) a power spectrum analysis map of (a);
FIG. 4 shows PdTCPP 8834; uiO-66- (NH) in example 1 of the present invention 2 ) 2 Ultraviolet-visible absorption spectrum of (a);
FIG. 5 shows PdTCPP \8834, uiO-66- (NH) in example 1 of the present invention 2 ) 2 (addition of 1% of Pt Co-catalyst) photocatalytic decomposition of Water to Hydrogen production RateA rate map;
FIG. 6 shows PdTCPP \8834, uiO-66- (NH) in example 1 of the present invention 2 ) 2 Four-cycle activity profiles of photocatalytic splitting of water to produce hydrogen (addition of 1%;
FIG. 7 shows an octahedral metal organic framework CuTCPP 8834; uiO-66- (NH) in example 2 of the present invention 2 ) 2 SEM picture of (1);
FIG. 8 shows the octahedral metal-organic framework ZnTCPP 8834; uiO-66- (NH) in example 3 of the present invention 2 ) 2 SEM picture of (1);
FIG. 9 shows the octahedral metal-organic framework TCPP \8834; uiO-66- (NH) in example 4 of the present invention 2 ) 2 SEM picture of (1);
figure 10 is an XRD spectrum of several octahedral metal-organic frameworks according to examples of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1: octahedral metal-organic framework PdTCPP 8834and UiO-66- (NH) 2 ) 2 Preparation of (2)
Reacting ZrCl 4 （30 mg），(NH 2 ) 2 -BDC (30 mg), pdTCPP (10 mg), benzoic acid (500 mg) and DMF (2 mL) are added into a polytetrafluoroethylene reactor with the volume of 20 mL and stirred for 15 min, then the reactor is transferred into a reaction kettle, the reaction kettle is heated in an oven with the temperature of 120 ℃ for 12 h, after the temperature is cooled to room temperature, a sample is collected by centrifugal separation, the sample is washed with DMF and ethanol for three times respectively, and finally, the sample is placed in a vacuum drying oven with the temperature of 80 ℃ for 48 h, and the obtained product is the octahedral metal organic framework PdTCPP \8834, uiO-66- (NH-H 2 ) 2 The yield was 82%.
Example 2: octahedral metal-organic framework CuTCPP 8834and UiO-66- (NH) 2 ) 2 Preparation of
Reacting ZrCl 4 （30 mg），(NH 2 ) 2 BDC (30 mg), cuTCPP (10 mg), benzoic acid (500 mg) and DMF (2 mL) were charged to a Teflon reactor with a volume of 20 mL and stirred for 15 min, then the reactor was transferred to a reaction kettle which was oven-dried at 120 deg.CHeating for 12 h, cooling to room temperature, centrifuging to collect sample, washing with DMF and ethanol for three times, and standing in 80 deg.C vacuum drying oven for 48 h to obtain octahedral metal-organic framework CuTCPP 8834, uiO-66- (NH-66) 2 ) 2 The yield was 80%.
Example 3: octahedral metal-organic framework ZnTCPP 8834and UiO-66- (NH) 2 ) 2 Preparation of
Reacting ZrCl 4 （30 mg），(NH 2 ) 2 adding-BDC (30 mg), znTCPP (10 mg), benzoic acid (500 mg) and DMF (2 mL) into a polytetrafluoroethylene reactor with the volume of 20 mL and stirring for 15 min, then transferring the reactor into a reaction kettle, heating the reaction kettle in an oven at 120 ℃ for 12 h, after the temperature is cooled to room temperature, collecting a sample by centrifugal separation, washing the sample with DMF and ethanol for three times respectively, and finally placing the sample in a vacuum drying oven at 80 ℃ for 48 h to obtain the octahedral metal-organic framework ZnTCPP 8834UiO-66- (NH-C) of the octahedral shape 2 ) 2 The yield was 85%.
Example 4: octahedral metal-organic framework TCPP 8834, uiO-66- (NH) 2 ) 2 Preparation of
Reacting ZrCl 4 （30 mg），(NH 2 ) 2 -BDC (30 mg), TCPP (10 mg), benzoic acid (500 mg) and DMF (2 mL) were added to a Teflon reactor with a volume of 20 mL and stirred for 15 min, then the reactor was transferred to a reaction kettle, the reaction kettle was heated in an oven at 120 ℃ for 12 h, after the temperature was cooled to room temperature, a sample was collected by centrifugation, the sample was washed three times with DMF and ethanol, and finally, the sample was placed in a vacuum oven at 80 ℃ for 48 h, and the product obtained was the octahedral metal-organic framework TCPP \8834, uiO-66- (NH-N 2 ) 2 The yield was 84%.
5mg of PdTCPP \8834andUiO-66- (NH) prepared in example 1 were taken 2 ) 2 Dispersing into a solution consisting of 20 mL TEOA and 80 mL PBS, performing ultrasonic dispersion, adding 1% Pt as a cocatalyst, pumping the reaction system to a vacuum state by using a vacuum pump, and starting a light source (a 300W xenon lamp, lambda is more than or equal to 400 nm); by constant temperature coolingWhile the circulating pump maintained the reaction temperature at 6 ℃ and the hydrogen content was measured by on-line gas chromatography (GC-7920, TCD) during the reaction; the result shows that PdTCPP \8834; uiO-66- (NH) 2 ) 2 (addition of 1% of Pt promoter) exhibits excellent photocatalytic hydrogen production performance at a hydrogen production rate of up to 1126. Mu. Mol g -1 h -1 The excellent catalytic performance is attributed to the existence of PdTCPP and amino, so that the framework material has excellent visible light absorption capacity, and the Pt cocatalyst can be used as an electron capture center, thereby greatly improving the separation efficiency of photo-generated electron holes.
The above detailed description is intended to illustrate the present invention, not to limit the present invention, and any modifications and changes made within the spirit of the present invention and the scope of the claims fall within the scope of the present invention.
Claims (6)
1. Metal organic framework X8834and UiO-66- (NH) 2 ) 2 The preparation method is characterized by comprising the following steps: reacting ZrCl 4 、(NH 2 ) 2 Adding BDC, metalloporphyrin or porphyrin, benzoic acid and DMF into a polytetrafluoroethylene reactor according to a molar ratio of 1.51 to 2.52 of (1.08 to 0.16) 2 ) 2 And X is metalloporphyrin or porphyrin.
2. The method of claim 1, wherein the metalloporphyrin comprises PdTCPP, cuTCPP, znTCPP and the porphyrin is TCPP.
3. Metal organic framework X8834and UiO-66- (NH) 2 ) 2 Prepared by the preparation method of any one of claims 1 to 2.
4. The metal-organic framework X \8834; uiO-66- (NH) as claimed in claim 3 2 ) 2 The application in the aspect of photocatalytic hydrogen production.
5. The use according to claim 4, characterized in that the method is: mixing X8834, uiO-66- (NH) 2 ) 2 Dispersing the mixture into a solution consisting of TEOA and PBS according to the volume ratio of 1 to 4 to 6, adding 1 to 3 percent of Pt as a cocatalyst, pumping the reaction system to a vacuum state by using a vacuum pump, and starting a light source.
6. The use according to claim 5, wherein the light source is a 300W xenon lamp with a lambda ≥ 400 nm.
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| CN108620136A (en) * | 2018-05-21 | 2018-10-09 | 西北师范大学 | The preparation and application of copper porphyrin functional metal organic frame/composite titania material |
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| Title |
|---|
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