CN112892607A - Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof - Google Patents
Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof Download PDFInfo
- Publication number
- CN112892607A CN112892607A CN202110057935.3A CN202110057935A CN112892607A CN 112892607 A CN112892607 A CN 112892607A CN 202110057935 A CN202110057935 A CN 202110057935A CN 112892607 A CN112892607 A CN 112892607A
- Authority
- CN
- China
- Prior art keywords
- mof
- cds
- composite material
- rgo
- hydrogen production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 42
- 239000011206 ternary composite Substances 0.000 title claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- -1 polytetrafluoroethylene Polymers 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 238000005079 FT-Raman Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011218 binary composite Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a stable ternary composite material for hydrogen production by photocatalytic water decomposition, which is prepared by compounding MOF-808 and reduced graphene oxide with a CdS semiconductor material under a low-temperature hydrothermal condition. The composite material can be kept stable under the condition of light radiation, has excellent light corrosion resistance, does not use high-boiling-point organic solvent in the synthesis process, and does not pollute the environment. The composite material has a lower band gap value than pure CdS, can effectively respond to visible light, and enhances the absorption of light. By compounding the CdS with the MOF-808 and the RGO, the effective catalytic activity area of the CdS is increased, the migration distance of photon-generated carriers is shortened, the migration rate of the carriers is greatly increased, the quantum utilization efficiency is improved, and the photocatalytic hydrogen production activity of the composite material is further improved. The performance test of photocatalytic hydrogen production by water decomposition shows that the ternary composite material has excellent photocatalytic hydrogen production performance.
Description
Technical Field
The invention belongs to the field of catalytic material preparation, and particularly relates to a stable ternary composite material with excellent hydrogen production performance by photocatalytic water decomposition and prepared by compounding a CdS semiconductor material with MOF-808 and RGO, and a preparation method thereof.
Background
The abuse of fossil fuel leads the environmental problem to be increasingly aggravated, and along with the improvement of the environmental awareness of people and the increasing exhaustion of the fossil fuel, the environment is developed and the environmental protection can be realizedThe biological energy source is particularly important. Solar energy is a cheap clean energy source, but the energy density of solar energy is low, and the solar energy is not easy to store and use, and needs to be converted into a high-density energy form. Hydrogen energy has attracted much attention as a high-density, renewable and clean energy source for scholars at home and abroad. Compared with other energy conversion forms, the clean energy H is prepared by utilizing solar energy to decompose water2Is one of the hottest novel energy conversion forms studied at present. Most of the catalysts for preparing hydrogen by decomposing water through photocatalysis are concentrated in d0Compounds of electronic configuration (e.g. Ti)4+，Zr5+，Nb5+Etc.) and d10P-block metal compounds of electronic configuration (e.g. Ga)3+，In3+Etc.) and transition metal oxides and sulfides (e.g., TiO)2ZnO, CdS), etc. In the semiconductor materials, CdS has a narrow band gap (2.4eV), can effectively respond to visible light, and has a proper hydrogen-production conduction band position, so that CdS becomes used for preparing H2One of the most numerous materials. However, in the process of photocatalytic reaction, the wide use of CdS is limited by the rapid recombination of photogenerated electrons and holes, light radiation corrosion and the like. People generally improve the activity and stability of CdS by using methods of compounding other nano materials with CdS, regulating the appearance of a semiconductor, adding a cocatalyst for modification, doping elements and the like. For example, the reported composite materials such as CdS/RGO have larger specific surface area, excellent charging property and higher carrier mobility due to Reduced Graphene Oxide (RGO), and can improve the separation efficiency of photo-generated electrons and holes, so that the CdS/RGO shows enhanced photocatalytic activity. However, the synthesis methods and processes for these materials are complex, energy-consuming, and often involve the use of large amounts of organic solvents such as dimethyl sulfoxide and the like. Not only has high cost, but also pollutes the environment. Therefore, the preparation of the composite CdS material with simple process, stability and high efficiency is particularly important for photocatalytic hydrogen production.
Metal organic framework Materials (MOFs) are novel porous materials with many advantages such as high porosity and large specific surface area. Many researchers use it for photocatalytic hydrogen production and the like. Some MOFs are capable of exhibiting semiconductor-like characteristics by themselves, but showCertain photocatalytic activity, but the activity requirement of photocatalytic hydrogen production cannot be met. Most MOFs do not have visible light response, so in order to improve the application of the MOFs in photocatalytic hydrogen production, other semiconductor nano materials are required to be compounded to further improve the photocatalytic hydrogen production performance based on the MOFs. Compared with the traditional semiconductor photocatalytic material, the MOFs-based composite material has higher porosity and larger specific surface area, is beneficial to the adhesion growth of semiconductor nano materials, and can even highly disperse small-size semiconductor nano materials in MOFs holes so as to reduce the agglomeration of the semiconductor nano materials and increase the reaction active sites of the composite material. Moreover, the porosity of the MOFs can not only endow the MOFs-based composite material with more reactive active sites, but also enhance the adsorption and activation of the MOFs to reaction substrates, shorten the migration distance of photon-generated carriers, reduce the recombination rate of the carriers, accelerate the charge transfer rate, improve the quantum utilization efficiency and greatly improve the photocatalytic activity of the composite material. Such as reported C3N4semiconductor/MOF materials such as/MIL-101 (Fe) exhibit excellent photocatalytic activity through the synergistic effect of the semiconductor and MOF materials. Therefore, the composite photocatalytic material taking MOFs as the substrate has a great application prospect.
Disclosure of Invention
The invention provides a preparation method of a stable ternary composite material for hydrogen production by photocatalytic water decomposition. The invention aims to provide a ternary composite material photocatalyst which is simple in process, low in preparation cost, small in pollution and good in stability, and has excellent hydrogen production performance by photocatalytic water decomposition.
The invention aims to prepare a ternary composite material CdS/MOF-808/RGO with high stability and excellent photocatalytic water splitting hydrogen production performance by compounding MOF-808 with large specific surface area and porosity and RGO molecules with high electron mobility under a low-temperature hydrothermal condition by using a narrow-bandgap semiconductor CdS with a proper reduction potential, and the ternary composite material CdS/MOF-808/RGO is recorded as CM 8R. Different from a pure CdS and CdS binary composite material, the composite material can utilize the mass ratio of RGO and MOF-808 and CdS and MOF-808/RGO to regulate the composition structure and the hydrogen production performance by photocatalytic water decomposition of the ternary composite material. Moreover, compared with the pure CdS, the CM8R has stronger interface interaction, the interface interaction between the CdS and MOF-808 can inhibit the recombination of photo-generated electrons and holes, reduce the occurrence of CdS photo-corrosion, effectively prevent the photo-corrosion of CdS nano-particles and enhance the stability of the ternary composite photocatalyst. By compounding the CdS with the MOF-808 and the RGO, the effective catalytic activity area of the CdS is increased, the carrier migration rate is greatly increased, the separation of photo-generated electrons and holes is promoted, and the photocatalytic hydrogen production activity of the composite material is further improved. The application discloses a preparation method of the novel high-stability ternary composite material with excellent performance for hydrogen production by photocatalytic water decomposition.
The invention relates to a ternary composite material which is constructed based on CdS, RGO and MOF-808 and has high stability and excellent hydrogen production performance by photocatalytic water decomposition, which is prepared by compounding MOF-808 and RGO molecules under a low-temperature hydrothermal condition by using a CdS semiconductor material. The ternary material may be represented as CdS/MOF-808/RGO, noted as CM 8R.
In the CM8R ternary material, MOF-808 is regular octahedral microcrystal, CdS nanoparticles and RGO are highly dispersed on the surface of the MOF-808, and the morphological structure of the MOF-808 is not changed. The size of CdS in CM8R is smaller than that of pure CdS (about 150nm), the size of CdS is gradually increased along with the increase of CdS content, the range is about 30-50nm, the attaching amount of the CdS nano particles on the MOF-808 surface is obviously increased, and the surface roughness of CM8R is increased compared with that of MOF-808. In particular, the roughness of the CM8R material is obviously increased after RGO complex modification. MOF-808 and CM8R exist in a microporous structure, N2The adsorption-desorption curve follows the typical type I isotherm. When the RGO and CdS nanoparticles are attached to the surface of the MOF-808 more, part of the RGO and CdS nanoparticles are easily attached to the holes of the MOF-808 to cause hole blockage, so that the BET area of the CM8R is reduced along with the increase of the content of the CdS and the RGO, and the BET surface area of the prepared CM8R material is different (300 m) according to the mass ratio of the MOF-808/RGO to the CdS2-500m2). In the ternary material CM8R of the invention, the band gap value is lower than that of MOF-808(4.09eV) and CdS (2.3eV), the energy required for the electrons to be excited from a valence band to a conduction band is lower, and the complex energy is more complexThe composite material shows better visible light response.
The synthesis method of the ternary composite material CM8R comprises the following steps:
step 1: accurately weighing Reduced Graphene Oxide (RGO) and ethanol, mixing in a polytetrafluoroethylene lining, and performing ultrasonic mixing to obtain a mixed solution 1 for later use;
wherein the mass ratio of RGO to ethanol is 1: 6300;
step 2: accurately weighing MOF-808, dispersing into the mixed solution 1 in the step 1, and performing ultrasonic mixing uniformly to obtain a mixed solution 2 for later use;
wherein the mass ratio of RGO to MOF-808 is 1-3: 200;
and step 3: putting the polytetrafluoroethylene lining containing the mixed solution 2 into a stainless steel kettle, then putting the reaction kettle into a drying oven at the temperature of 120-130 ℃, keeping for 12-16h, naturally cooling, filtering the product, washing the product for a plurality of times by water and absolute ethyl alcohol respectively, and finally drying the product in a vacuum drying oven to obtain a MOF-808/RGO composite material, which is recorded as M8R;
according to the difference of the mass percentages of the RGO and the MOF-808, the molecular weight is recorded as M8R0.5-M8R1.5；
And 4, step 4: accurately weighing M8R obtained in step 3, and dispersing into Cd (CH)3COO)2·2H2Ultrasonically mixing the O in the water solution uniformly to obtain a suspension 3 for later use;
wherein, Cd (CH)3COO)2·2H2The mass ratio of O to M8R is 0.5-3: 2;
and 5: accurately weighing thioacetamide, dispersing into the suspension 3 in the step 4, stirring for 0.5-2h in water bath at 50-60 ℃, cooling to room temperature, centrifuging the precipitate, washing with water and ethanol for several times, and drying in a vacuum oven to obtain the ternary composite material CdS/MOF-808/RGO, which is recorded as CM 8R.
Wherein thioacetamide is reacted with Cd (CH)3COO)2·2H2The mass ratio of O was 0.43: 1.
The structure and properties of the product were analyzed by XRD, FT-IR, FT-Raman, SEM, TEM, XPS, DRS, BET, and GC, etc.
The ternary composite material CM8R prepared by the method is used for preparing hydrogen from water.
The invention has the advantages that:
1. the ternary composite material prepared by the low-temperature hydrothermal method has good light corrosion resistance stability, no high-boiling-point organic solvent is used in the synthetic process, no environmental pollution is caused, and the preparation process is green, safe and environment-friendly;
2. the ternary composite material prepared by the invention has a smaller band gap value, can effectively respond to visible light, improves the number of photon-generated carriers, and the composite RGO molecules can effectively promote the transfer of electrons, further improve the separation rate of photon-generated electrons and holes, improve the quantum utilization efficiency and further improve the photocatalytic activity of the composite material.
3. The ternary composite material can control the appearance, composition structure and photocatalytic hydrogen production activity of the ternary composite material by regulating the mass ratio of CdS, RGO and MOF-808, and can realize efficient and stable photocatalytic hydrogen production by water decomposition under proper conditions.
Drawings
FIG. 1(a) is an XRD pattern of GO reduction to RGO; (b) are powder diffraction patterns of CdS, MOF-808 and the prepared part of samples.
FIG. 2(a) FT-IR spectra of CdS, MOF-808 and portions of the samples prepared; (b) is GO, RGO, CdS, MOF-808 and 0.5-CM8R1FT-Raman spectrum of (1).
FIG. 3 is an SEM image of MOF-808, CdS and a series of composite samples. (a) Is MOF-808, (b) is CdS, (c-g) is 0.2, 0.4, 0.5, 0.6, 0.8-CM8, (h) is 0.5-CM8R1。
FIGS. 4(a-c) are MOF-808, CdS, 0.5-CM8R1A TEM image of (B); (d) is 0.5-CM8R1HRTEM image of the sample; (e-f) is 0.5-CM8R1HAADF-STEM plots of the samples and their corresponding EDS element mapping images, MOF-808, CdS and composite showed the same characteristics as SEM.
FIG. 5 shows MOF-808, CdS, 0.5-CM8R1XPS spectra of (a). (a) Is a full map of three samples; (b) is an energy spectrum of Cd 3 d; (c) is a power spectrum diagram of S2 p; (d) is Zr 3d energy spectrum.
FIG. 6(a) is a DRS map of MOF-808, CdS and a series of composite samples; (b) is CdS, 0.5-CM8 and 0.5-CM8R1Tauc diagram of the ternary composite; (c) tauc diagram for MOF-808; (d) is MOF-808, CdS and a series of composite samples N2Adsorption-desorption isotherms.
FIG. 7 is a graph of data of the MOF-808, CdS and a series of composite samples tested for photocatalytic activity and stability under the irradiation of visible light. (a) As the hydrogen production (μmol) of the sample varied with time; (b) is a histogram of the photocatalytic hydrogen production rate corresponding to MOF-808, CdS and a series of composite samples; (c) is 0.5-CM8R under irradiation of visible light1A four-cycle catalytic hydrogen production reaction data diagram of the composite catalyst and the pure CdS; (d) is an enlarged view of CdS circulating hydrogen production in the graph (c).
FIG. 8 shows 0.5-CM8R1XRD and SEM images of the composite material after four times of circulation catalytic hydrogen production. (a) XRD patterns, and (b) and (c) are SEM images.
FIG. 9 is CdS, MOF-808, 0.5-CM8, 0.5CM8R1EIS Nyquist plot and transient photocurrent plot for the sample. (a) An EIS Nyquist curve is obtained; (b) is a transient photocurrent graph.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Comparative example 1: only CdS complexes with MOF-808 to form binary composite CM 8.
0.1839g of Cd (CH) are accurately weighed3COO)2·2H2O (about 0.69mmol) was added to 40mL of deionized water, sonicated, and then 0.5g, 0.25g, 0.2g, 0.167g, 0.125g of MOF-808 was accurately weighed out and dispersed in the above solution for 0.5 h. Finally, accurately weighing 0.0781g of CH3CSNH2(1.04mmol) was added to the suspension and stirred in a water bath at 60 ℃ for 0.5 h. After cooling to room temperature, the precipitate was centrifuged, washed three times with water and ethanol and then dried under vacuum at 50 ℃ overnight. The binary composite CdS/MOF-808, denoted as X-CM8, was obtained. Five samples were based on CdS (in Cd (CH)) produced3COO)2·2H2O mass) and MOF-808, respectively recorded as 0.2-CM8, 0.4-CM8, 0.5-CM8, 0.6-CM8 and 0.8-CM 8.
Example 1
Firstly, accurately weighing 5mg of RGO, dispersing the RGO into 40mL of ethanol solution, then putting the RGO into 50mL of polytetrafluoroethylene lining, carrying out ultrasonic treatment for 1h, then accurately weighing 1.00g, 0.50g and 0.33g of MOF-808, respectively adding the MOF-808 into three polytetrafluoroethylene linings, and carrying out ultrasonic mixing uniformly; then putting the three polytetrafluoroethylene linings into a steel kettle respectively, keeping the three polytetrafluoroethylene linings in an oven at 120 ℃ for 12 hours, naturally cooling, washing the product with water and absolute ethyl alcohol respectively for three times, and finally drying in a vacuum oven at 50 ℃ to obtain the MOF-808/RGO composite material which is recorded as M8RY. The three samples were designated M8R according to the mass percentage of RGO and MOF-808 added0.5，M8R1And M8R1.5(ii) a 0.1839g of Cd (CH) are accurately weighed3COO)2·2H2O (about 0.69mmol) is added to 40mL of deionized water, dissolved by ultrasonic, and then the composite material M8R is accurately weighedYThe mass of (A) is 0.5g, 0.25g, 0.2g, 0.167g, 0.125g, dispersing into the above solution, ultrasonic treating for 0.5h, and finally accurately weighing 0.0781g CH3CSNH2(1.04mmol) was added to the suspension and stirred in a water bath at 60 ℃ for 0.5 h. After cooling to room temperature, the precipitate was centrifuged, washed three times with water and ethanol and then dried under vacuum at 50 ℃ overnight. Obtaining CdS/MOF-808/RGO composite material, which is recorded as X-CM8RY. Five samples were based on CdS (in Cd (CH)) produced3COO)2·2H2Mass of O) and M8RYThe mass ratios of (A) to (B) are respectively recorded as 0.2-CM8RY，0.4-CM8RY，0.5-CM8RY，0.6-CM8RY，0.8-CM8RY. Under the reaction conditions, X-CM8RYThe yield is highest, the morphology is regular and uniform, and the method is the optimal reaction condition.
Example 2: the temperature for the recombination of RGO with MOF-808 was 130 ℃ compared to example 1.
Firstly, accurately weighing 5mg RGO, dispersing the RGO into 40mL ethanol solution, then placing the solution into 50mL polytetrafluoroethylene lining, carrying out ultrasonic treatment for 1h, and then preparingRespectively adding 1.00g, 0.50g and 0.33g of MOF-808 into three polytetrafluoroethylene inner liners, and ultrasonically mixing uniformly; then putting the three polytetrafluoroethylene linings into a steel kettle respectively, keeping the three polytetrafluoroethylene linings in a drying oven at 130 ℃ for 12 hours, after natural cooling, washing the product with water and absolute ethyl alcohol respectively for three times, and finally drying the product in a vacuum drying oven at 50 ℃ to obtain an MOF-808/RGO composite material which is recorded as M8RYThe yield was slightly lower than that of example 1. The three samples were designated M8R according to the mass percentage of RGO and MOF-808 added0.5，M8R1And M8R1.5(ii) a 0.1839g of Cd (CH) are accurately weighed3COO)2·2H2O (about 0.69mmol) is added to 40mL of deionized water, dissolved by ultrasonic, and then the composite material M8R is accurately weighedYThe mass of (2) was 0.5g, 0.25g, 0.2g, 0.167g, 0.125g, dispersed in the above solution, and sonicated for 0.5 h. Finally, accurately weighing 0.0781g of CH3CSNH2(1.04mmol) was added to the suspension and stirred in a water bath at 60 ℃ for 0.5 h. After cooling to room temperature, the precipitate was centrifuged, washed three times with water and ethanol and then dried under vacuum at 50 ℃ overnight. Obtaining CdS/MOF-808/RGO composite material, which is recorded as X-CM8RY. Five samples were based on CdS (in Cd (CH)) produced3COO)2·2H2Mass of O) and M8RYThe mass ratios of (A) to (B) are respectively recorded as 0.2-CM8RY，0.4-CM8RY，0.5-CM8RY，0.6-CM8RY，0.8-CM8RY. The yield was close to that of example 1.
Example 3: the temperature of the CdS complexed with MOF-808/RGO was 50 ℃ compared to example 1.
Firstly, accurately weighing 5mg of RGO, dispersing the RGO into 40mL of ethanol solution, then putting the RGO into 50mL of polytetrafluoroethylene lining, carrying out ultrasonic treatment for 1h, then accurately weighing 1.00g, 0.50g and 0.33g of MOF-808, respectively adding the MOF-808 into three polytetrafluoroethylene linings, and carrying out ultrasonic mixing uniformly; then putting the three polytetrafluoroethylene linings into a steel kettle respectively, keeping the three polytetrafluoroethylene linings in an oven at 120 ℃ for 12 hours, naturally cooling, washing the product with water and absolute ethyl alcohol respectively for three times, and finally drying in a vacuum oven at 50 ℃ to obtain the MOF-808/RGO composite material which is recorded as M8RY. The three samples were designated M8R according to the mass percentage of RGO and MOF-808 added0.5，M8R1And M8R1.5(ii) a 0.1839g of Cd (CH) are accurately weighed3COO)2·2H2O (about 0.69mmol) is added to 40mL of deionized water, dissolved by ultrasonic, and then the composite material M8R is accurately weighedYThe mass of (2) was 0.5g, 0.25g, 0.2g, 0.167g, 0.125g, dispersed in the above solution, and sonicated for 0.5 h. Finally, accurately weighing 0.0781g of CH3CSNH2(1.04mmol) was added to the suspension and stirred in a water bath at 50 ℃ for 0.5 h. After cooling to room temperature, the precipitate was centrifuged, washed three times with water and ethanol and then dried under vacuum at 50 ℃ overnight. Obtaining CdS/MOF-808/RGO composite material, which is recorded as X-CM8RY. Five samples were based on CdS (in Cd (CH)) produced3COO)2·2H2Mass of O) and M8RYThe mass ratios of (A) to (B) are respectively recorded as 0.2-CM8RY，0.4-CM8RY，0.5-CM8RY，0.6-CM8RY，0.8-CM8RY. The yield was close to that of example 1.
Example 4: photocatalytic hydrogen production activity and stability test
Under the irradiation of simulated visible light, Pt is photo-deposited by taking lactic acid as a sacrificial agent as a cocatalyst, the hydrogen production performance of a test sample is photo-catalyzed in an aqueous solution, and 50mg of prepared photocatalyst (pure CdS and MOF-808 are used as blank controls) is added into a 250mL sealed reactor containing 90mL and 10mL of lactic acid. Reduction of H by light2PtCl61 wt% Pt was supported on the surface of the photocatalyst as a co-catalyst. Before the experiment, the whole reaction system was evacuated until the system pressure stabilized. Finally, the sealed reactor was irradiated with a 300W Xe lamp with a 400nm filter to cut off the light in the ultraviolet region. The gas produced was automatically analyzed by gas chromatography (GC-7900, Kexiao, China) connected to the above reaction system. In 5h, the MOF-808 has no hydrogen production activity, the pure CdS shows lower hydrogen production activity, and after the CdS and the MOF-808 are compounded, the composite material also shows excellent hydrogen production activity even if the content of the CdS is very low, wherein the hydrogen production activity is the best when the mass ratio of the CdS to the MOF-808 is 1: 2. This is achieved byIn addition, when the mass ratio of CdS to MOF-808 is 1:2, the hydrogen production activity of the composite material is further improved after a small amount of RGO is compounded. Wherein when the mass percentage of RGO to MOF-808 is 1% (i.e., 0.5-CM 8R)1) The ternary composite material has the highest hydrogen production activity. The photocatalytic stability test is consistent with the photocatalytic activity test method, and four times of cyclic hydrogen production experiments are continuously carried out under the irradiation of visible light, and the sacrificial agent is not replaced in the period. The result shows that after four hydrogen production experiments, the hydrogen production amount of CM8R in 5h is basically unchanged, excellent light stability is shown, the hydrogen production amount of pure CdS is obviously reduced, and the photo-induced corrosion is serious. This shows that the ternary composite photocatalyst CM8R prepared by the invention has excellent stability and photocatalytic activity.
Example 1, example 2, and example 3 all gave the desired product, wherein the mass ratio of RGO to MOF-808 in example 1 was 1:100, and Cd (CH)3COO)2·2H2When the mass ratio of O to MOF-808/RGO is 0.92:1, the obtained composite material has the best photocatalytic activity performance.
Table 1 is a summary of the specific surface areas of some of the samples prepared according to the invention
TABLE 1
FIG. 1(a) is an XRD pattern of GO reduction to RGO, which was successfully reduced to RGO; (b) the powder diffraction patterns of CdS, MOF-808 and some of the prepared samples show that a series of samples are successfully prepared.
FIG. 2(a) FT-IR spectra of CdS, MOF-808 and a portion of the samples prepared, confirming the successful complexation of CdS with MOF-808 in the inventive material. (b) Is GO, RGO, CdS, MOF-808 and 0.5-CM8R1The FT-Raman spectrogram of (A) proves the successful combination of the RGO in the material of the invention.
FIG. 3 is an SEM image of MOF-808, CdS and a series of composite samples. (a) Is MOF-808, (b) is CdS, (c-g) is 0.2, 0.4, 0.5, 0.6, 0.8-CM8, (h) is 0.5-CM8R1. CdS nanoparticles and RGO can be seen to be uniformly distributed on the surface of MOF-808, and assembledThe morphological structure of post-MOF-808 was unchanged.
FIGS. 4(a-c) are MOF-808, CdS, 0.5-CM8R1A TEM image of (B); (d) is 0.5-CM8R1HRTEM image of the sample; (e-f) is 0.5-CM8R1HAADF-STEM plots of the samples and their corresponding EDS element mapping images, MOF-808, CdS and composite showed the same characteristics as SEM. EDS element mapping revealed that the mapping images of Cd, S, C, O and Zr had the same shape, which again demonstrated a ternary composite of 0.5-CM8R1The successful preparation.
FIG. 5 shows MOF-808, CdS, 0.5-CM8R1XPS spectra of (a). (a) Is a full map of three samples, and can be seen that 0.5-CM8R1The material has C, O, Zr, Cd and S elements. (b) Is a spectrogram of Cd 3d, and shows that the chemical state of CdS is Cd2+(ii) a (c) Is a spectrum diagram of S2 p, and shows that the chemical state of CdS is S2-(ii) a (d) Is a spectrum diagram of Zr 3d, and shows that the zirconium in the MOF-808 is Zr4+Exists in the form of (1); 0.5-CM8R compared to CdS and MOF-8081The Cd 3d, S2 p and Zr 3d characteristic peaks of the composite material all showed slight shifts pointing to higher binding energies, which indicates that stronger interfacial interactions exist between CdS, MOF-808 or RGO. The interface interaction can inhibit the recombination of photo-generated electrons and holes, reduce the occurrence of CdS photo-corrosion and enhance the stability of the material.
FIG. 6(a) is a DRS map of MOF-808, CdS and a series of composite samples, and it can be seen that the response range of the ternary composite material to visible light wavelength is widened; (b) is CdS, 0.5-CM8 and 0.5-CM8R1The Tauc diagram of the ternary composite material is calculated to obtain the band gap value of the material, and 0.5-CM8 and 0.5-CM8R can be seen1The band gap values are all smaller than that of CdS, and (c) is a Tauc graph of MOF-808, and the band gap value of the MOF-808 is seen to be 4.09eV which is far larger than that of the CdS and the composite material;
(d) is MOF-808, CdS and a series of composite samples N2And (3) an adsorption-desorption isotherm, wherein the pure CdS curve is a type II isotherm, which indicates that the pure CdS nonporous structure, and MOF-808 and a series of composite samples conform to the typical type I isotherm, which indicates that the microporous structure exists.
Figure 7 is a drawing of a MOF-808,and a data graph of photocatalytic activity and stability test of CdS and a series of composite samples under the irradiation of visible light. (a) The hydrogen production amount (mu mol) of the sample is changed along with time, so that the MOF-808 has no hydrogen production activity, and the hydrogen production amount of pure CdS is 34.05 mu mol within 5 hours; after the CdS is only compounded with the MOF-808, the hydrogen production amount of the composite material is also obviously improved, wherein the hydrogen evolution of the 0.5-CM8 composite material reaches the maximum 83.98 mu mol (2.47 times of that of pure CdS); after the CdS is compounded with MOF-808 and RGO, the hydrogen production in 5h is further improved, wherein 0.5-CM8R1The hydrogen evolution of the composite reached a maximum of 142.11 μmol (4.17 times higher than for pure CdS). (b) Is a histogram of the photocatalytic hydrogen production rate corresponding to MOF-808, CdS and a series of composite samples. 0.5-CM8R1The hydrogen evolution rate of the composite material reaches 1136.89 mu mol.h-1gCdS -1The highest values of (b) are CdS (136.21. mu. mol. h)-1gCdS -1) And 0.5-CM8 (671.84. mu. mol. h)-1gCdS -1) Photocatalytic assay of H28.35 and 1.69 times the rate. (c) Is 0.5-CM8R under irradiation of visible light1And a four-cycle catalytic hydrogen production reaction data diagram of the composite catalyst and the pure CdS. After 4 cycles, 0.5-CM8R1The hydrogen yield of the composite material in 5h is still as high as 137.46 mu mol, which is reduced by 4.65 mu mol compared with the first time, and the hydrogen yield of CdS in 5h after 4 cycles is only 22.41 mu mol, which is reduced by 11.64 mu mol compared with the first time. (d) Is an enlarged view of CdS circulating hydrogen production in the graph (c).
FIG. 8 shows 0.5-CM8R1XRD and SEM images of the composite material after four times of circulation catalytic hydrogen production. (a) The XRD shows that the structures of the materials before and after the ternary composite catalytic hydrogen production cycle are not changed. (b) And (c) is an SEM image, so that the appearance of the ternary composite material is not changed before and after the hydrogen is catalytically produced, and the ternary composite material has stronger light corrosion resistance.
FIG. 9 is CdS, MOF-808, 0.5-CM8, 0.5CM8R1EIS Nyquist plot and transient photocurrent plot for the sample. (a) Are EIS Nyquist curves, 0.5-CM8 and 0.5-CM8R1The composite material has a smaller radius of curvature than pure CdS and MOF-808. 0.5-CM8R1The composite material has a minimum radius of semi-circleMing 0.5-CM8R1The composite material is capable of more efficient charge separation. (b) For the transient photocurrent graph, it can be seen that 0.5-CM8R1The composite material exhibits an optimum photocurrent intensity. The compound of CdS, MOF-808 and RGO can improve the separation efficiency of light-induced interface charges; through 4 switching light cycles, 0.5-CM8R1The photoresponse of the composite photocatalyst is kept stable, and the ternary composite material disclosed by the invention is shown to have excellent photochemical stability.
Claims (8)
1. A stable ternary composite material for hydrogen production by photocatalytic water decomposition is characterized in that MOF-808 is a regular octahedral microcrystal, CdS nanoparticles and RGO are highly dispersed on the surface of the MOF-808, and the size of the CdS nanoparticles is 30-50 nm.
2. A preparation method of a stable ternary composite material for hydrogen production by photocatalytic water decomposition is characterized by comprising the following steps:
step 1: accurately weighing Reduced Graphene Oxide (RGO) and ethanol, mixing in a polytetrafluoroethylene lining, and performing ultrasonic mixing to obtain a mixed solution 1 for later use;
step 2: accurately weighing MOF-808, dispersing into the mixed solution 1 in the step 1, and performing ultrasonic mixing uniformly to obtain a mixed solution 2 for later use;
and step 3: putting the polytetrafluoroethylene lining containing the mixed solution 2 into a stainless steel kettle, putting the reaction kettle into an oven for reaction, naturally cooling after the reaction is finished, filtering the product, washing the product with water and absolute ethyl alcohol for a plurality of times respectively, and finally drying the product in a vacuum oven to obtain an MOF-808/RGO composite material which is recorded as M8R;
and 4, step 4: accurately weighing M8R obtained in step 3, and dispersing into Cd (CH)3COO)2·2H2Ultrasonically mixing the O in the water solution uniformly to obtain a suspension 3 for later use;
and 5: accurately weighing thioacetamide, dispersing into the suspension 3 in the step 4, stirring for reaction in a water bath, cooling to room temperature, centrifuging the precipitate, washing with water and ethanol for several times, and drying in a vacuum oven to obtain the ternary composite material CdS/MOF-808/RGO, wherein the ternary composite material is recorded as CM 8R.
3. The preparation method according to claim 2, wherein the mass ratio of RGO to ethanol in step 1 is 1: 6300.
4. The method of claim 2, wherein in step 2, the mass ratio of RGO to MOF-808 is 1-3: 200.
5. The method as claimed in claim 2, wherein in step 3, the reaction temperature in the oven is 120-130 ℃, and the reaction time is 12-16 h.
6. The method according to claim 2, wherein in step 4, Cd (CH)3COO)2·2H2The mass ratio of O to M8R is 0.5-3: 2.
7. The method of claim 2, wherein in step 5 thioacetamide is reacted with Cd (CH)3COO)2·2H2The mass ratio of O is 0.43:1, the water bath temperature is 50-60 ℃, and the stirring time is 0.5-2 h.
8. Use of the stable photocatalytic hydrogen production by water splitting ternary composite material according to claim 1 for hydrogen production from water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110057935.3A CN112892607A (en) | 2021-01-15 | 2021-01-15 | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110057935.3A CN112892607A (en) | 2021-01-15 | 2021-01-15 | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112892607A true CN112892607A (en) | 2021-06-04 |
Family
ID=76113830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110057935.3A Pending CN112892607A (en) | 2021-01-15 | 2021-01-15 | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112892607A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736095A (en) * | 2021-09-01 | 2021-12-03 | 成都理工大学 | Method for degrading and detecting organophosphorus pesticide by using Fe-CDs and MOF-808 composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266787A (en) * | 2010-06-07 | 2011-12-07 | 付文甫 | Preparation method of novel noble-metal-free catalyst for photolysis of water to produce hydrogen |
| CN111408395A (en) * | 2020-03-13 | 2020-07-14 | 沈阳化工大学 | RGO/Cu5FeS4/g-C3N4Preparation method of ternary composite photocatalyst |
-
2021
- 2021-01-15 CN CN202110057935.3A patent/CN112892607A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266787A (en) * | 2010-06-07 | 2011-12-07 | 付文甫 | Preparation method of novel noble-metal-free catalyst for photolysis of water to produce hydrogen |
| CN111408395A (en) * | 2020-03-13 | 2020-07-14 | 沈阳化工大学 | RGO/Cu5FeS4/g-C3N4Preparation method of ternary composite photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 王方平: "基于MOF-808复合纳米材料的制备及其光催化性能的研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736095A (en) * | 2021-09-01 | 2021-12-03 | 成都理工大学 | Method for degrading and detecting organophosphorus pesticide by using Fe-CDs and MOF-808 composite material |
| CN113736095B (en) * | 2021-09-01 | 2022-12-09 | 成都理工大学 | Method for degrading and detecting organophosphorus pesticide by using Fe-CDs and MOF-808 composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113634258B (en) | Catalyst for generating ethylene by photocatalytic reduction of carbon dioxide and preparation method thereof | |
| CN108671955B (en) | Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN111389442A (en) | P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof | |
| CN111437884A (en) | Composite photocatalyst and preparation method thereof | |
| CN116139867B (en) | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof | |
| CN110756203A (en) | Ni2P/Mn0.3Cd0.7S photocatalytic water splitting composite catalyst and preparation method and application thereof | |
| CN113145138A (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN112675831A (en) | Preparation method of MOF-derived zinc oxide composite titanium dioxide heterojunction and application of heterojunction in photoelectric water decomposition | |
| CN112892608A (en) | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof | |
| CN114160169B (en) | Preparation method and application of covalent organic framework material encapsulated molybdenum-sulfur cluster | |
| CN113694925B (en) | Porous titanium dioxide-cuprous oxide composite material and preparation method and application thereof | |
| CN112588324B (en) | Method for preparing composite photocatalyst CdS/ZIF-8 by one-pot method and application thereof | |
| CN113351210A (en) | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction | |
| CN112892607A (en) | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof | |
| CN111389409B (en) | Preparation method and application of bismuth vanadate photocatalyst with surface modified by cobalt-copper oxide | |
| He et al. | In situ grown CdS on 2D Cd-based porphyrin MOFs enhances the significant separation and transfer of charge carriers with an appropriate heterojunction during photocatalytic hydrogen evolution | |
| CN114653383B (en) | Indium zinc sulfide photocatalyst co-modified by cobalt tungstate and cobaltosic oxide on surface as well as preparation method and application thereof | |
| CN114950439B (en) | High-efficiency photolysis water hydrogen production MOF TiO 2 NiO material and preparation method and application thereof | |
| CN114425392B (en) | Carbon-nitrogen based composite material, preparation method and application thereof | |
| CN111617778B (en) | Preparation method of hydrothermally synthesized flower-rod-shaped sulfur indium zinc photocatalyst | |
| CN113398968A (en) | MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof | |
| CN111495391A (en) | Composite photocatalyst and preparation method and application thereof | |
| CN114849785B (en) | Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst | |
| CN116371425B (en) | CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210604 |
|
| RJ01 | Rejection of invention patent application after publication |