CN108579775B - Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof - Google Patents
Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application 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 219
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 106
- 239000002057 nanoflower Substances 0.000 title claims abstract description 78
- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 62
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 61
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 30
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 10
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 8
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- GMMZXKSNKIUKOW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(C)O Chemical compound [O-2].[O-2].[Ti+4].C(C)O GMMZXKSNKIUKOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000004332 silver Substances 0.000 abstract description 11
- 229910052709 silver Inorganic materials 0.000 abstract description 11
- -1 silver ions Chemical class 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005285 chemical preparation method Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- 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
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- 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
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- 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
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- 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
- C01B2203/1082—Composition of support materials
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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
Abstract
The invention discloses a preparation method of a silver phosphate/silver/titanium dioxide nanoflower composite material. The silver phosphate/silver/titanium dioxide nanoflower composite material prepared by the invention is a Z-Scheme heterostructure compounded by three components of ultramicro silver phosphate nanoparticles, silver nanoparticles and titanium dioxide nanoflowers. The titanium dioxide nanoflowers are formed by self-assembling ultrathin titanium dioxide nanosheets, provide large specific surface area and are rich in a large number of oxygen vacancies. A small amount of silver ions are reduced by the titanium dioxide nanoflower oxygen vacancies and uniformly reduced and deposited on the surface of the titanium dioxide nanoflower, the titanium dioxide nanoflower and the titanium dioxide nanoflower are in close interface contact, and then a layer of silver phosphate nanoparticles is coated on the surface of the silver nanoparticles by a simple chemical coprecipitation method. The silver phosphate/silver/titanium dioxide nanoflower composite material provided by the invention is an efficient and stable photoelectric conversion material, adopts a simple chemical preparation method, is simple in preparation process, easy to control reaction conditions, and is suitable for large-scale preparation and industrial production.
Description
Technical Field
The invention relates to a silver phosphate/silver/titanium dioxide nanoflower composite material and a preparation method and application thereof, and belongs to the technical field of nano materials and photocatalysis.
Background
Energy problems are a resource on which humans rely for survival and development to be important. Solar energy has the advantages of being clean, inexpensive, renewable, etc., and thus, efficient and rapid utilization, conversion, and storage of solar energy is a goal of efforts. The semiconductor photocatalysis technology is the core of chemical conversion and storage of solar energy, and the semiconductor material is utilized to absorb the solar energy and convert the solar energy into other new energy sources which are pollution-free and renewable, so that the semiconductor photocatalysis technology is considered to be one of the main means for solving the energy crisis of human beings at present.
Silver phosphate is widely applied to the fields of water treatment, water photolysis, waste gas treatment, antibiosis and the like as a novel visible light response semiconductor photocatalytic material. The photocatalyst has the advantages of high photocatalytic activity, adjustable morphology and the like, the quantum efficiency of photocatalytic water decomposition is up to 90%, and the oxygen evolution rate is 3 times and 8 times of that of bismuth vanadate and tungsten oxide respectively, so that the photocatalyst has important research significance and application prospect. However, silver ions are easily reduced into silver simple substance by photo-generated electrons excited by self light, so that the silver phosphate loses activity, and the photocatalytic activity of the silver phosphate is greatly limited.
Titanium dioxide has been most widely used in the field of photocatalysis in the past decades, but large-scale industrialization of titanium dioxide has been limited due to the problems of narrow spectral response range, low light utilization rate, serious recombination of photo-generated carriers, and the like. At present, a large number of researchers improve the photocatalytic performance of titanium dioxide through various strategies, and the main methods include morphology control, precious metal deposition and semiconductor compounding. Among them, the preparation of a nanomaterial of a titanium dioxide hierarchical nanoflower structure of a suitable size is considered as a new strategy to improve the photocatalytic performance of titanium dioxide, since it exhibits unique physicochemical properties: the method has the advantages of low light reflectivity, better improvement of physical light absorption, provision of more reaction sites and active sites and the like. The light absorption range of the titanium dioxide can be widened to a certain extent, and the service life of the photogenerated carrier current of the titanium dioxide is prolonged. This makes their use in the field of photocatalysis of great interest. In addition, the composite construction of heterostructures of titanium dioxide with other semiconductors is considered to be the most effective means for increasing the photocatalytic activity of titanium dioxide. For example, silver phosphate is deposited on the surface of titanium dioxide to construct a heterostructure, a photon-generated carrier separation channel can be constructed between the titanium dioxide and the heterostructure, and the photocatalytic activity of the titanium dioxide and the heterostructure is effectively improved
Reducing silver ions into silver nanoparticles by using oxygen vacancy defects on the surface of the titanium dioxide nanoflower, depositing the silver nanoparticles on the surface of the titanium dioxide nanoflower, and then depositing a layer of silver phosphate on the surface of the silver nanoparticles on the surface of the titanium dioxide nanoflower by a chemical coprecipitation method. The method is simple to operate, non-toxic, efficient and capable of realizing large-area production.
Disclosure of Invention
The invention aims to solve the problems, provides a preparation method of a silver phosphate/silver/titanium dioxide nanoflower composite material, and solves the problems of insufficient light absorption of titanium dioxide, low light utilization rate, poor silver phosphate stability, difficult photocatalyst recovery and the like in the prior art.
The invention adopts the following technical scheme; a preparation method of an ultramicro nano silver phosphate/silver/titanium dioxide nano flower composite material comprises the following steps:
step 1: adding isopropanol into diethylenetriamine, uniformly stirring, adding diisopropyl di (acetylacetonate) titanate, wherein the volume ratio of the isopropanol to the diethylenetriamine to the diisopropyl di (acetylacetonate) titanate is 1260-2520: 1-10: 45-360, uniformly stirring, pouring into a reaction kettle, carrying out solvent heat treatment for 24-36 hours at 200-220 ℃, washing, drying, heating the obtained nano material to an annealing temperature at 1-10 ℃/min, wherein the annealing temperature is 450 ℃, and the annealing time is 2 hours, thus obtaining the precursor oxygen-rich vacancy titanium dioxide nano flower material.
Step 2: stirring and dispersing a precursor titanium dioxide nanoflower material in 30mL of ethanol; weighing 200-400 mg of silver nitrate, and dissolving the silver nitrate into a solution of ammonia water with the mass fraction of 1-2% and the volume of 10ml to obtain a silver-ammonia solution; dropwise adding the silver ammonia solution into the titanium dioxide ethanol dispersion liquid; dropwise adding 0.2-0.4 mol/L sodium dihydrogen phosphate solution with the volume of 10mL into the mixed solution under the stirring state, wherein the mass ratio of silver nitrate to titanium dioxide nanoflower precursor is 1: 2-4, chemically depositing silver phosphate particles, standing, centrifugally cleaning, placing in an oven at 60 ℃, and drying for 12 hours to obtain the silver phosphate/titanium dioxide nanoflower composite material.
Further, in the step 1, the reaction temperature is 200 ℃, the reaction time is 24 hours, and the volume ratio of the isopropanol, the diethylenetriamine and the diisopropyl di (acetylacetonate) titanate is 1260:1: 45.
Further, in the step 2, 200mg of silver nitrate, 1% of ammonia water by mass, 0.2mol/l of sodium dihydrogen phosphate concentration and a ratio of the silver nitrate to the titanium dioxide nanoflower are 1: 2.
The ultramicro nano silver phosphate/silver/titanium dioxide nanoflower composite material is characterized in that the titanium dioxide nanoflowers are composed of anatase-phase titanium dioxide nanosheets, and the thickness of the titanium dioxide nanosheets is 2-9 nm; the silver phosphate nano particles coat the silver nano particles to form nano particles with the size of 1-4 nm, and the nano particles are loaded on the surface of the titanium dioxide nano sheet to form a heterojunction.
The silver phosphate/silver/titanium dioxide nanoflower composite material is applied as a photocatalyst: the water decomposition hydrogen production, the water decomposition oxygen production, the pollutant degradation, the biological antibiosis, the photoelectricity water decomposition and the organic matter synthesis and other related fields.
The invention has the beneficial effects that: the invention provides a simple method for preparing an ultramicro nano silver phosphate/silver/titanium dioxide nano flower material. Firstly, preparing oxygen-rich vacancy titanium dioxide nanoflowers serving as a carrier through a simple one-step solvothermal method, reducing a part of silver ions to silver nanoparticles through oxygen vacancies rich in the titanium dioxide nanoflowers to deposit the silver nanoparticles on the surfaces of the titanium dioxide nanoflowers, and then depositing a layer of silver phosphate on the surfaces of the silver nanoparticles through a chemical coprecipitation method. The titanium dioxide nanoflower carrier is formed by self-assembling anatase-phase titanium dioxide nanosheets, has a three-dimensional hierarchical structure, can expand the absorption range of visible light of the titanium dioxide nanoflower, increases the multiple scattering performance of light, quickly transfers photoelectrons, and increases more adsorption sites and reaction sites. On the other hand, the silver nanoparticles deposited on the surface of the titanium dioxide nanoflower are used as electron hole recombination media of the titanium dioxide nanoflower and the silver phosphate, so that holes in the titanium dioxide nanoflower and electrons in the silver phosphate are compounded and annihilated, and photo-generated electrons and holes with super-strong redox capabilities of the titanium dioxide nanoflower and the silver phosphate are left. The silver phosphate/silver/titanium dioxide is compounded to form a Z-Scheme heterostructure, so that the separation of a photon-generated carrier is promoted, photo-generated electrons and holes are efficiently utilized to participate in an oxidation-reduction reaction, and the photocatalytic performance of the composite material is improved. In addition, the preparation method of the material is simple, the size is easy to control and the industrial production is facilitated, so that the production cost of the ultramicro nano silver phosphate/silver/titanium dioxide nanoflower composite material is greatly reduced, the photocatalytic performance of the ultramicro nano silver phosphate/silver/titanium dioxide nanoflower composite material is remarkably improved, and the material has a great application prospect.
Drawings
Fig. 1 shows the X-ray diffraction pattern (XRD) of the silver phosphate/silver/titanium dioxide nanoflower composite prepared in example 1.
FIG. 2 XPS Ag peak spectra for composites made in example 1;
fig. 3 shows a Scanning Electron Microscope (SEM) image of the silver phosphate/silver/titanium dioxide nanoflower composite prepared in example 1.
Fig. 4 and 5 show Transmission Electron Micrographs (TEMs) of the silver phosphate/silver/titanium dioxide nanoflower composite prepared in example 1 at different magnifications.
Fig. 6 is a graph of the oxygen production by hydrolysis of silver phosphate/silver/titanium dioxide nanoflower composite prepared in example 1 as a photocatalyst.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples. The following examples are intended to illustrate the present invention, but 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.
Example 1:
step 1: to 31.5mL of isopropyl alcohol was added 0.025mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 1.125mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The obtained mixed solution was poured into a reaction vessel and solvent-heat treated at 200 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, heating the reactant at the speed of 1 ℃/min and the heat treatment temperature of 450 ℃, and annealing the reactant for 2 hours to obtain the precursor titanium dioxide nanoflower material.
Step 2: step 2: stirring and dispersing 100mg of precursor titanium dioxide nanoflower material in 30mL of ethanol, and dispersing the precursor titanium dioxide nanoflower material uniformly by moderate ultrasound; weighing 200mg of silver nitrate, and dissolving the silver nitrate into a solution with the mass fraction of 1% and the volume of 10ml of ammonia water to obtain a silver-ammonia solution; dropwise adding a fresh silver ammonia solution into the titanium dioxide ethanol dispersion liquid until silver ions are completely adsorbed; under the stirring state, 0.2mol/L sodium dihydrogen phosphate solution with the volume of 10mL is dripped into the mixed solution, the dripping speed is controlled to be about 1 drop/3 seconds, silver phosphate particles are chemically deposited, the mixture is kept stand, centrifugally cleaned and placed in an oven at the temperature of 60 ℃ for drying for 12 hours, and the silver phosphate/silver/titanium dioxide nanoflower composite material is obtained.
FIG. 1 composite obtained in example 1The XRD pattern of the material can see the peaks of two phases of silver phosphate and titanium dioxide, and the XRD diffraction patterns of the two phases and standard Ag3PO4And anatase TiO2The characteristic peaks of elemental silver were not observed, which is probably due to too small Ag content.
Fig. 2 shows the XPS Ag peak separation spectrum of the composite material prepared in example 1, which shows that the prepared composite material contains a small amount of silver, which is reduced by the oxygen vacancies enriched in the titanium dioxide nanoflower.
FIG. 3 is an SEM image of the composite material obtained in example 1, and it can be seen that the size of the titanium dioxide nanoflower is 500-1000 nm, and the existence of silver phosphate and silver nanoparticles is not observed, which may be caused by the small size of the silver phosphate and silver nanoparticles.
Fig. 4 and 5 are Transmission Electron Microscope (TEM) images of the ultrafine silver phosphate/silver/titanium dioxide nanoflower composite prepared in example 1, and it can be seen from the TEM images that silver nanoparticles are coated on silver nanoparticles to form nanoparticles with a size of 2-4 nm, and the nanoparticles are loaded on the surface of a titanium dioxide nanosheet to form a heterojunction.
50mg of the silver phosphate/silver/titanium dioxide nanoflower composite material prepared in the embodiment is ultrasonically dispersed in 100mL of deionized water, 200mg of silver nitrate is added into the dispersion liquid to serve as an electron capture agent, the dispersion liquid obtained after the ultrasonic dispersion is uniform is transferred into a photocatalytic reactor, the photocatalytic reactor is placed in the dark for standing for 30 minutes, and the whole device is vacuumized. And placing the nano silver phosphate/silver/titanium dioxide nano flower composite material under the illumination, sampling once every 30 minutes, and detecting the amount of generated oxygen by using gas chromatography, thereby drawing a curve graph of the oxygen generated by the nano silver phosphate/silver/titanium dioxide nano flower composite material through photocatalytic decomposition under the illumination. FIG. 6 is a graph of oxygen produced by photocatalytic decomposition of water obtained by the test, and it can be seen that the composite material shows good water decomposition performance.
Example 2
Step 1: to 31.5mL of isopropyl alcohol was added 0.025mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 1.125mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The obtained mixed solution was poured into a reaction vessel and solvent-heat treated at 200 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, heating the reactant at the speed of 1 ℃/min and the heat treatment temperature of 450 ℃, and annealing the reactant for 2 hours to obtain the precursor titanium dioxide nanoflower material.
Step 2: step 2: stirring and dispersing 100mg of precursor titanium dioxide nanoflower material in 30mL of ethanol, and dispersing the precursor titanium dioxide nanoflower material uniformly by moderate ultrasound; weighing 400mg of silver nitrate, and dissolving the silver nitrate into a solution of ammonia water with the mass fraction of 2% and the volume of 10ml to obtain a silver-ammonia solution; dropwise adding a fresh silver ammonia solution into the titanium dioxide ethanol dispersion liquid until silver ions are completely adsorbed; under the stirring state, 0.4mol/L sodium dihydrogen phosphate solution with the volume of 10mL is dripped into the mixed solution, the dripping speed is controlled to be about 1 drop/3 seconds, silver phosphate particles are chemically deposited, the mixture is kept stand, centrifugally cleaned and placed in an oven at the temperature of 60 ℃ for drying for 12 hours, and the silver phosphate/silver/titanium dioxide nanoflower composite material is obtained.
According to the characterization, the titanium dioxide nanoflower material is 500-1000 nm in size and is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of each nanosheet is 2-9 nm. The silver phosphate nano particles coat the silver nano particles to form nano particles with the size of 1-3 nm, and the nano particles are loaded on the surface of the titanium dioxide nano sheet to form a heterojunction. The material XRD diffraction pattern and standard anatase phase TiO2And the characteristic peaks of the standard silver phosphate coincide.
The method of example 1 is used for photocatalytic decomposition of aquatic oxygen, and shows good water decomposition performance.
Example 3
Step 1: to 31.5mL of isopropyl alcohol was added 0.125mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 4.5mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The resulting mixed solution was poured into a reaction vessel and subjected to solvothermal treatment at 220 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, heating the reactant at the speed of 10 ℃/min and the heat treatment temperature of 450 ℃, and annealing the reactant for 2 hours to obtain the precursor titanium dioxide nanoflower material.
Step 2: stirring and dispersing 100mg of precursor titanium dioxide nanoflower material in 30mL of ethanol, and dispersing the precursor titanium dioxide nanoflower material uniformly by moderate ultrasound; weighing 200mg of silver nitrate, and dissolving the silver nitrate into a solution with the mass fraction of 1% and the volume of 10ml of ammonia water to obtain a silver-ammonia solution; dropwise adding a fresh silver ammonia solution into the titanium dioxide ethanol dispersion liquid until silver ions are completely adsorbed; under the stirring state, 0.2mol/L sodium dihydrogen phosphate solution with the volume of 10mL is dripped into the mixed solution, the dripping speed is controlled to be about 1 drop/3 seconds, silver phosphate particles are chemically deposited, the mixture is kept stand, centrifugally cleaned and placed in an oven at the temperature of 60 ℃ for drying for 12 hours, and the silver phosphate/silver/titanium dioxide nanoflower composite material is obtained.
According to the characterization, the titanium dioxide nanoflower material is 500-1000 nm in size and is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of each nanosheet is 2-9 nm. The small-size silver phosphate nano particles are uniformly dispersed on the titanium dioxide nano flower piece to form a heterojunction structure, the particle size of the ultramicro silver phosphate particles is 1-4 nm, and an XRD diffraction pattern of the material and a standard anatase phase TiO phase2And the characteristic peaks of the standard silver phosphate coincide.
Example 4
Step 1: to 31.5mL of isopropyl alcohol was added 0.125mL of diethylenetriamine (EDTA), and the mixture was stirred for 10 min. To the solution was added 4.5mL of diisopropyl di (acetylacetonate) titanate. Stirring was continued for 10 min. The resulting mixed solution was poured into a reaction vessel and subjected to solvothermal treatment at 220 ℃ for 24 hours. And after the reaction is finished, washing the precipitate for three times by using deionized water and absolute ethyl alcohol respectively, placing the washed precipitate in a 60 ℃ oven, drying the washed precipitate for 24 hours, finally placing the reactant in a muffle furnace, heating the reactant at the speed of 10 ℃/min and the heat treatment temperature of 450 ℃, and annealing the reactant for 2 hours to obtain the precursor titanium dioxide nanoflower material.
Step 2: step 2: stirring and dispersing 100mg of precursor titanium dioxide nanoflower material in 30mL of ethanol, and dispersing the precursor titanium dioxide nanoflower material uniformly by moderate ultrasound; weighing 400mg of silver nitrate, and dissolving the silver nitrate into a solution of ammonia water with the mass fraction of 2% and the volume of 10ml to obtain a silver-ammonia solution; dropwise adding a fresh silver ammonia solution into the titanium dioxide ethanol dispersion liquid until silver ions are completely adsorbed; under the stirring state, 0.4mol/L sodium dihydrogen phosphate solution with the volume of 10mL is dripped into the mixed solution, the dripping speed is controlled to be about 1 drop/3 seconds, silver phosphate particles are chemically deposited, the mixture is kept stand, centrifugally cleaned and placed in an oven at the temperature of 60 ℃ for drying for 12 hours, and the silver phosphate/silver/titanium dioxide nanoflower composite material is obtained.
According to the characterization, the titanium dioxide nanoflower material is 500-1000 nm in size and is formed by self-assembling ultrathin titanium dioxide nanosheets, and the thickness of each nanosheet is 2-9 nm. The silver phosphate nano particles coat the silver nano particles to form nano particles with the size of 1-4 nm, and the nano particles are loaded on the surface of the titanium dioxide nano sheet to form a heterojunction. The material XRD diffraction pattern and standard anatase phase TiO2And the characteristic peaks of the standard silver phosphate coincide.
The method of example 1 is used for photocatalytic decomposition of aquatic oxygen, and shows good water decomposition performance.
Claims (5)
1. A preparation method of an ultramicro nano silver phosphate/silver/titanium dioxide nano flower composite material is characterized by comprising the following steps:
step 1: adding isopropanol into diethylenetriamine, uniformly stirring, adding diisopropyl di (acetylacetonate) titanate, wherein the volume ratio of the isopropanol to the diethylenetriamine to the diisopropyl di (acetylacetonate) titanate is 1260-2520: 1-10: 45-360, uniformly stirring, pouring into a reaction kettle, carrying out solvent heat treatment for 24-36 hours at 200-220 ℃, washing, drying, heating the obtained nano material to an annealing temperature at 1-10 ℃/min, wherein the annealing temperature is 450 ℃, and the annealing time is 2 hours, so as to obtain a precursor oxygen-rich vacancy titanium dioxide nano flower material;
step 2: stirring and dispersing a precursor titanium dioxide nanoflower material in 30mL of ethanol; weighing 200-400 mg of silver nitrate, and dissolving the silver nitrate into a solution of ammonia water with the mass fraction of 1-2% and the volume of 10ml to obtain a silver-ammonia solution; dropwise adding the silver ammonia solution into the titanium dioxide ethanol dispersion liquid; dropwise adding 0.2-0.4 mol/L sodium dihydrogen phosphate solution with the volume of 10mL into the mixed solution under the stirring state, wherein the mass ratio of silver nitrate to the titanium dioxide nanoflower precursor is 1: 2-4, chemically depositing silver phosphate particles, standing, centrifugally cleaning, placing in an oven at 60 ℃, and drying for 12 hours to obtain the ultramicro nano silver phosphate/silver/titanium dioxide nanoflower composite material.
2. The method of claim 1, wherein in step 1 the reaction temperature is 200 ℃, the reaction time is 24 hours, and the volume ratio of isopropanol, diethylenetriamine and diisopropyl di (acetylacetonate) titanate is 1260:1: 45.
3. The method as claimed in claim 1, wherein in step 2, the ratio of silver nitrate to titanium dioxide nanoflower is 1:2, the mass fraction of ammonia water is 1%, the concentration of sodium dihydrogen phosphate is 0.2mol/l, and the ratio of silver nitrate to titanium dioxide nanoflower is 200 mg.
4. The ultramicro nano silver phosphate/silver/titanium dioxide nanoflower composite material prepared by the method of claim 1, wherein the titanium dioxide nanoflower is composed of anatase-phase titanium dioxide nanosheets, and the thickness of the titanium dioxide nanosheets is 2-9 nm; the silver phosphate nano particles coat the silver nano particles to form nano particles with the size of 1-4 nm, and the nano particles are loaded on the surface of the titanium dioxide nano sheet to form a heterojunction.
5. The application of the ultramicro nano silver phosphate/silver/titanium dioxide nano flower composite material prepared by the method as claimed in claim 1 as a photocatalyst is characterized by comprising hydrogen production by decomposing water, oxygen production by decomposing water, pollutant degradation, biological antibiosis, photoelectric water decomposition and organic matter synthesis.
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| CN103301861A (en) * | 2013-06-29 | 2013-09-18 | 上海荣富新型材料有限公司 | Preparation method of trace silver phosphate sensitized titanium dioxide photocatalyst |
| CN104258886A (en) * | 2014-09-16 | 2015-01-07 | 上海电力学院 | Silver phosphate/oxygen vacancy type titanium dioxide compound photocatalyst and preparation method thereof |
| CN106391067A (en) * | 2016-07-01 | 2017-02-15 | 上海电力学院 | AgI-Ag3PO4/OV-TiO2 compound photocatalyst and preparation method thereof |
| CN107824181A (en) * | 2017-10-26 | 2018-03-23 | 上海应用技术大学 | A kind of preparation method of visible-light photocatalyst |
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| CN101648139A (en) * | 2009-09-03 | 2010-02-17 | 福州大学 | Novel visible catalyst-silver phosphate and preparation method thereof |
| CN103301861A (en) * | 2013-06-29 | 2013-09-18 | 上海荣富新型材料有限公司 | Preparation method of trace silver phosphate sensitized titanium dioxide photocatalyst |
| CN104258886A (en) * | 2014-09-16 | 2015-01-07 | 上海电力学院 | Silver phosphate/oxygen vacancy type titanium dioxide compound photocatalyst and preparation method thereof |
| CN106391067A (en) * | 2016-07-01 | 2017-02-15 | 上海电力学院 | AgI-Ag3PO4/OV-TiO2 compound photocatalyst and preparation method thereof |
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