CN106944108A - The preparation of ternary non-crystaline amorphous metal/nano titania catalytic composite material and its application in photolysis water hydrogen - Google Patents
The preparation of ternary non-crystaline amorphous metal/nano titania catalytic composite material and its application in photolysis water hydrogen Download PDFInfo
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- 239000005300 metallic glass Substances 0.000 title claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 5
- 238000006303 photolysis reaction Methods 0.000 title abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 title abstract description 3
- 230000003197 catalytic effect Effects 0.000 title description 3
- 239000011941 photocatalyst Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002114 nanocomposite Substances 0.000 claims abstract description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 6
- 238000007772 electroless plating Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003643 water by type Substances 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000015096 spirit Nutrition 0.000 claims description 5
- 229910003087 TiOx Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 235000011083 sodium citrates Nutrition 0.000 claims description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229910001096 P alloy Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000006392 deoxygenation reaction Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- -1 potassium hypophosphites Chemical class 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 229910018104 Ni-P Inorganic materials 0.000 description 4
- 229910018536 Ni—P Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical class O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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 kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst and its application in photolysis water hydrogen.Described ternary non-crystaline amorphous metal is Pd Ni P alloys prepared by electroless plating method, and ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst is prepared by low-temperature solid-phase method.The nano composite photo-catalyst of the present invention shows higher hydrogen-producing speed during photocatalytic water.Compared with prior art, the hydrogen-producing speed of photochemical catalyst of the invention is 3.5 times of nano titanium dioxide powder hydrogen-producing speed under the same terms.The nano composite photo-catalyst of the present invention effectively increases photocatalytic activity using Pd Ni P ternary non-crystaline amorphous metals.The present invention prepares composite photo-catalyst using low-temperature solid-phase method, with technique is simple, equipment is simple, simple operation and other advantages, is applicable industrialized production.
Description
Technical field
The invention belongs to photocatalysis technology field, it is related to a kind of Pd-Ni-P ternarys non-crystaline amorphous metal and nano titanium oxide
The preparation method of composite photo-catalyst and its application in light decomposes aquatic products hydrogen.
Background technology
(1) non-crystaline amorphous metal has excellent mechanical property, electric property, magnetic performance and chemical property.Research shows,
Amorphous alloy has obvious catalytic action to some chemical reactions.Pd-Ni-P alloys can shape in very wide compositing range
Into amorphous structure, its excellent physical-chemical performance all has a good application prospect in terms of machinery, electro-catalysis.This
Invention prepares Pd-Ni-P ternary non-crystaline amorphous metals using electroless plating method, and its process is simple, and equipment requirement is simple.
(2) with expanding economy and the growth of population, traditional fossil fuel result in a series of pollution problem, sternly
The sustainable development of human society is threaten again.Therefore, facing mankind huge energy crisis and environmental problem.Hydrogen is not only
With cleaning, reproducible advantage, had good burning performance, the features such as energy conversion rate is high while also having, be considered as optimal
Clean energy resource.In recent years, photocatalytic hydrogen production by water decomposition is increasingly paid close attention to by researcher.The invention provides a kind of new light
The preparation method of catalyst, obtains the nano composite photo-catalyst of a class better performances.
(3) nano titanium oxide is a kind of new high-performance inorganic nanometer materials, is both had with general nano material
Standby skin effect, quantum size effect and macro quanta tunnel effect, has the unique photocatalytic of semi-conducting material, light again
The premium properties such as electric transformational and photocatalysis stability, so nano titanium oxide is the conductor photocatalysis material of most study
Material.Novel photocatalyst is developed, it is all possessed good photocatalysis Decomposition aquatic products hydrogen under ultraviolet light and radiation of visible light
Performance, tool is of great significance.Ternary non-crystaline amorphous metal/nano titania that the present invention is prepared using low-temperature solid-phase method is multiple
The speed that closing light catalyst decomposes aquatic products hydrogen is higher.
The content of the invention
It is an object of the invention to provide a kind of Pd-Ni-P ternarys non-crystaline amorphous metal/titanic oxide nano compound photocatalyst
Preparation method.Ternary non-crystaline amorphous metal is obtained by electroless plating method, then ternary non-crystaline amorphous metal/dioxy is prepared using low-temperature solid-phase method
Change titanium nano composite photo-catalyst.This method is simple to operate, and can be realized by adjusting technological parameter to ternary non-crystaline amorphous metal
The precise control of non-crystaline amorphous metal content in component and nano composite photo-catalyst.
The preparation method of novel photocatalyst of the present invention comprises the following steps：
(1) 0.5~10g hypophosphites is added into 10~200mL to go from obtained solution A in water；
(2) it is slowly added dropwise in the inorganic palladium salts of 0.01~0.2g after 0.1~5.0mL concentrated hydrochloric acids, 10~60min of stirring, drop
Plus 0.5~10mL ammonia spirits, continue to stir after 10~60min, solution becomes colorless, obtained solution B；
(3) l0~200mL deionized waters are heated to after 40~80 DEG C in water-bath, sequentially add 0.5~10g boron
Solids is treated in acid, 0.5~10g inorganic nickels, 0.5~10g sodium citrates, 0.5~5g ammonium chlorides, 0.5~5g ammonium sulfate, stirring
Matter is completely dissolved rear obtained solution C；
(4) solution B and solution C are mixed, by add sodium hydroxide solution adjust the pH value of mixed solution for 7.0~
9.0 scopes, obtained solution D；
(5) solution A is added in solution D, 1~12h is reacted at room temperature, solid matter is put into 60 DEG C of baking after filtering
Dried in case after 1~10h, obtain non-crystaline amorphous metal；
(6) obtained non-crystaline amorphous metal is put into nano titanium dioxide powder according to 0.1~5.0wt% mass percent
Ball milling in ball grinder, controls drum's speed of rotation for 100~1000r/min, after 30~300min of ball milling, is made three before heat treatment
First non-crystaline amorphous metal/titanic oxide nano compound material；
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances
In, in 99.99% high pure nitrogen (flow is 1~5L/min), 300~500 DEG C of scopes are heated to, and be incubated 0.5~6h.
After furnace cooling, final ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst is obtained.
Hypophosphites described in step (1) is one kind in preferred sodium hypophosphite, potassium hypophosphite.Described in step (2)
Inorganic palladium salt be one or more of any combination in preferred palladium bichloride, palladium nitrate, palladium sulfate.Described in step (3)
Inorganic nickel is one or more of any combination in preferred nickel chloride, nickel sulfate, nickel nitrate.
Compared with the conventional method, the invention has the advantages that：
(1) photochemical catalyst prepared by the present invention has good photocatalysis hydrogen production performance, and hydrogen-producing speed is higher；
(2) present invention prepares photochemical catalyst using low-temperature solid-phase method, and technique is simple, equipment is simple, simple to operate.
Brief description of the drawings
Fig. 1 is X-ray diffractogram spectrogram, and Fig. 2 is hydrogen-producing speed curve map.Curve 1, curve 2, curve 3 are respectively in Fig. 1
The ternary non-crystaline amorphous metal of preparation, nano titanium dioxide powder, the X of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst
X ray diffraction collection of illustrative plates.Curve 1, curve 2, curve 3 respectively ternary non-crystaline amorphous metal, nano titanium dioxide powder, ternary are non-in Fig. 2
The hydrogen-producing speed curve of peritectic alloy/titanic oxide nano compound photocatalyst (embodiment 1).
Embodiment
Below by embodiment, the present invention will be further described, and its purpose, which is only that, more fully understands present disclosure
The protection domain being not intended to limit the present invention.
Embodiment 1：
(1) 1g potassium hypophosphites are added to obtained solution A in 25mL deionized waters.
(2) it is slowly added dropwise in 0.016g palladium nitrates after 0.4mL concentrated hydrochloric acids, stirring 10min, 0.75mL ammoniacal liquor is added dropwise molten
Liquid, continues to stir after 20min, solution becomes colorless, obtained solution B.
(3) 20mL deionized waters are heated to after 50 DEG C in water-bath, sequentially add 1g boric acid, 1g nickel sulfate hexahydrates,
1g sodium citrates, 0.75g ammonium chlorides, 0.75g ammonium sulfate, stirring obtained solution C after solid matter is completely dissolved.
(4) solution B and solution C are mixed, the pH value that mixed solution is adjusted by adding sodium hydroxide solution is 8.0, system
Obtain solution D.
(5) solution A is added in solution D, 4h is reacted at room temperature, solid matter is put into 60 DEG C of baking oven after filtering
Dry after 3h, obtain non-crystaline amorphous metal.
(6) obtained non-crystaline amorphous metal and nano titanium dioxide powder are put into ball milling according to 1.2wt% mass percent
Ball milling in tank, controls drum's speed of rotation for 400r/min, and after ball milling 60min, ternary non-crystaline amorphous metal/dioxy before heat treatment is made
Change titanium nanometer composite material.
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances
In, in 99.99% high pure nitrogen (flow is 2L/min), 300 DEG C are heated to, and be incubated 1h.After furnace cooling, obtain
Final ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst.
Photocatalytic hydrogen production by water decomposition performance test is carried out at room temperature：99.99% height is passed through into 30% methanol solution
Pure nitrogen gas deoxygenation 50min, in this, as sacrifice agent.The methanol solutions of 100mL 30% of deoxygenation are taken, and it is non-to add 20mg ternarys
Moved into after peritectic alloy/titanic oxide nano compound photocatalyst, ultrasonic 30min in quartz glass reactor.In 500W mercury lamps
Under irradiation, using drainage, relation curve such as Fig. 2 curve 3 institute of the hydrogen-producing speed with the photocatalytic degradation time is obtained by calculating
Show.
Embodiment 2：
(1) 2g sodium hypophosphites are added to obtained solution A in 50mL deionized waters.
(2) it is slowly added dropwise in 0.028g palladium bichlorides after 0.8mL concentrated hydrochloric acids, stirring 20min, 1.5mL ammonia spirits is added dropwise,
Continue to stir after 30min, solution becomes colorless, obtained solution B.
(3) 40mL deionized waters are heated to after 60 DEG C in water-bath, sequentially add 2g boric acid, 2g nickel nitrates, 2g lemons
Lemon acid sodium, 1.5g ammonium chlorides, 1.5g ammonium sulfate, stirring obtained solution C after solid matter is completely dissolved.
(4) solution B and solution C are mixed, by adding the pH value that flaky sodium hydrate adjusts mixed solution to be 7.5, are made
Solution D.
(5) solution A is added in solution D, 4h is reacted at room temperature, solid matter is put into 60 DEG C of baking oven after filtering
Dry after 3h, obtain non-crystaline amorphous metal.
(6) obtained non-crystaline amorphous metal and nano titanium dioxide powder are put into ball milling according to 2.0wt% mass percent
Ball milling in tank, controls drum's speed of rotation for 400r/min, and after ball milling 120min, ternary non-crystaline amorphous metal/bis- before heat treatment are made
TiOx nano composite.
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances
In, in 99.99% high pure nitrogen (flow is 2L/min), 400 DEG C are heated to, and be incubated 2h.After furnace cooling, obtain most
Whole ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst.
Photocatalytic hydrogen production by water decomposition performance test is carried out at room temperature：99.99% height is passed through into 30% methanol solution
Pure nitrogen gas deoxygenation 50min, in this, as sacrifice agent.The methanol solutions of 100mL 30% of deoxygenation are taken, and it is non-to add 20mg ternarys
Moved into after peritectic alloy/titanic oxide nano compound photocatalyst, ultrasonic 30min in quartz glass reactor.In 500W mercury lamps
Under irradiation, the hydrogen produced by being collected using drainage obtains relation of the hydrogen-producing speed with the photocatalytic degradation time by calculating
Curve.
Embodiment 3：
(1) 5g potassium hypophosphites are added to obtained solution A in 125mL deionized waters.
(2) it is slowly added dropwise in 0.056g palladium sulfates after 3.2mL concentrated hydrochloric acids, stirring 30min, 6mL ammonia spirits is added dropwise, after
After continuous stirring 40min, solution becomes colorless, obtained solution B.
(3) 100mL deionized waters are heated to after 70 DEG C in water-bath, sequentially add 5g boric acid, 5g nickel chlorides, 5g lemons
Lemon acid sodium, 3.75g ammonium chlorides, 3.75g ammonium sulfate, stirring obtained solution C after solid matter is completely dissolved.
(4) solution B and solution C are mixed, by adding the pH value that flaky sodium hydrate adjusts mixed solution to be 7.0, are made
Solution D.
(5) solution A is added in solution D, 6h is reacted at room temperature, solid matter is put into 60 DEG C of baking oven after filtering
Dry after 5h, obtain non-crystaline amorphous metal.
(6) obtained non-crystaline amorphous metal and nano titanium dioxide powder are put into ball milling according to 0.6wt% mass percent
Ball milling in tank, controls drum's speed of rotation for 500r/min, and after ball milling 200min, ternary non-crystaline amorphous metal/bis- before heat treatment are made
TiOx nano composite.
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances
In, in 99.99% high pure nitrogen (flow is 3L/min), 350 DEG C are heated to, and be incubated 3h.After furnace cooling, obtain most
Whole ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst.
Photocatalytic hydrogen production by water decomposition performance test is carried out at room temperature：99.99% height is passed through into 30% methanol solution
Pure nitrogen gas deoxygenation 50min, in this, as sacrifice agent.The methanol solutions of 100mL 30% of deoxygenation are taken, and it is non-to add 20mg ternarys
Moved into after peritectic alloy/titanic oxide nano compound photocatalyst, ultrasonic 30min in quartz glass reactor.In 500W mercury lamps
Under irradiation, the hydrogen produced by being collected using drainage obtains relation of the hydrogen-producing speed with the photocatalytic degradation time by calculating
Curve.
Embodiment 4：
(1) 10g sodium hypophosphites are added to obtained solution A in 200mL deionized waters.
(2) it is slowly added dropwise in 0.02g palladium bichlorides after 4.5mL concentrated hydrochloric acids, stirring 50min, 8.5mL ammonia spirits is added dropwise,
Continue to stir after 60min, solution becomes colorless, obtained solution B.
(3) 200mL deionized waters are heated to after 80 DEG C in water-bath, sequentially add 10g boric acid, the water sulfuric acid of 10g six
Nickel, 10g sodium citrates, 5g ammonium chlorides, 5g ammonium sulfate, stirring obtained solution C after solid matter is completely dissolved.
(4) solution B and solution C are mixed, by adding the pH value that flaky sodium hydrate adjusts mixed solution to be 9.0, are made
Solution D.
(5) solution A is added in solution D, 12h is reacted at room temperature, solid matter is put into 60 DEG C of baking oven after filtering
After middle dry 8h, non-crystaline amorphous metal is obtained.
(6) obtained non-crystaline amorphous metal and nano titanium dioxide powder are put into ball milling according to 5.0wt% mass percent
Ball milling in tank, controls drum's speed of rotation for 600r/min, and after ball milling 240min, ternary non-crystaline amorphous metal/bis- before heat treatment are made
TiOx nano composite.
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances
In, in 99.99% high pure nitrogen (flow is 5L/min), 450 DEG C are heated to, and be incubated 5h.After furnace cooling, obtain most
Whole ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst.
Photocatalytic hydrogen production by water decomposition performance test is carried out at room temperature：99.99% height is passed through into 30% methanol solution
Pure nitrogen gas deoxygenation 50min, in this, as sacrifice agent.The methanol solutions of 100mL 30% of deoxygenation are taken, and it is non-to add 20mg ternarys
Moved into after peritectic alloy/titanic oxide nano compound photocatalyst, ultrasonic 30min in quartz glass reactor.In 500W mercury lamps
Under irradiation, the hydrogen produced by being collected using drainage obtains relation of the hydrogen-producing speed with the photocatalytic degradation time by calculating
Curve.
Claims (9)
1. a kind of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst, it is characterised in that：Three are obtained by electroless plating method
First non-crystaline amorphous metal, then ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst, the photocatalysis is prepared using low-temperature solid-phase method
Agent has preferable hydrogen-producing speed.
2. the preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 1, its feature
It is to comprise the following steps：
(1) hypophosphites is added to from obtained solution A in water；
(2) appropriate concentrated hydrochloric acid is slowly added dropwise in inorganic palladium salt, after stirring a period of time, ammonia spirit is added dropwise, continues to stir one
After the section time, solution becomes colorless, obtained solution B；
(3) certain deionized water is heated to after uniform temperature in water-bath, sequentially adds boric acid, inorganic nickel, lemon
Sour sodium, ammonium chloride, ammonium sulfate, stirring obtained solution C after solid matter is completely dissolved；
(4) solution B and solution C are mixed, the pH value of mixed solution, obtained solution D is adjusted by adding sodium hydroxide solution；
(5) solution A is added in solution D, reacted at room temperature certain time, solid matter is put into baking oven after filtering and done
It is dry, obtain non-crystaline amorphous metal；
(6) obtained non-crystaline amorphous metal and nano titanium dioxide powder are put into ball in ball grinder according to certain mass percent
Mill, control drum's speed of rotation, ball milling for a period of time after, be made heat treatment before ternary non-crystaline amorphous metal/nano titania be combined
Material；
(7) obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) is put into high temperature process furnances,
In high pure nitrogen, uniform temperature, and held for some time are heated to, after furnace cooling, final ternary non-crystaline amorphous metal/bis- are obtained
TiOx nano composite photo-catalyst.
3. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
Be characterised by that the hypophosphites described in step (1) is one kind in preferred sodium hypophosphite, potassium hypophosphite, solution A be 10~
200mL goes what is obtained from dissolving 0.5~10g hypophosphites in water.
4. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
It is one or more of any in preferred palladium bichloride, palladium nitrate, palladium sulfate to be characterised by the inorganic palladium salt described in step (2)
Combination, is slowly added dropwise in the inorganic palladium salts of 0.01~0.2g after 0.1~5.0mL concentrated hydrochloric acids, 10~60min of stirring, and dropwise addition 0.5~
10mL ammonia spirits, continue to stir after 10~60min, solution becomes colorless, obtained solution B.
5. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
It is one or more of any in preferred nickel chloride, nickel sulfate, nickel nitrate to be characterised by the inorganic nickel described in step (3)
Combination, l0~200mL deionized waters are heated to after 40~80 DEG C in water-bath, sequentially add 0.5~10g boric acid, 0.5~
10g inorganic nickels, 0.5~10g sodium citrates, 0.5~5g ammonium chlorides, 0.5~5g ammonium sulfate, stirring treat that solid matter is completely molten
Obtained solution C after solution.
6. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
It is characterised by step (4), the pH value by mixed solution adjusts most 7.0~9.0 scopes, obtained solution D.
7. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
1~12h of reaction at room temperature described in step (5) is characterised by, solid matter is put into 60 DEG C of baking oven after filtering and done
After dry 1~10h, non-crystaline amorphous metal is obtained.
8. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
Be characterised by described in step (6) by the matter of obtained non-crystaline amorphous metal and nano titanium dioxide powder according to 0.1~5.0wt%
Amount percentage is put into ball milling in ball grinder, controls drum's speed of rotation for 100~1000r/min, after 30~300min of ball milling, is made
Ternary non-crystaline amorphous metal/titanic oxide nano compound material before heat treatment.
9. a kind of preparation method of ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst as claimed in claim 2, its
It is characterised by being put into obtained ternary non-crystaline amorphous metal/titanic oxide nano compound material in step (6) described in step (7)
In high temperature process furnances, in 99.99% high pure nitrogen (flow is 1~5L/min), 300~500 DEG C of scopes are heated to, and protect
0.5~6h of temperature, after furnace cooling, obtains final ternary non-crystaline amorphous metal/titanic oxide nano compound photocatalyst.
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| CN108671925A (en) * | 2018-05-28 | 2018-10-19 | 国网山东省电力公司电力科学研究院 | Nano-TiO2Amorphous acid bronze alloy composite photocatalyst material and preparation method thereof and purposes |
| CN108686662A (en) * | 2018-05-28 | 2018-10-23 | 国网山东省电力公司电力科学研究院 | Nano TiO 2-amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes |
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| WO2020039229A1 (en) * | 2018-08-20 | 2020-02-27 | Karunarathna Randika | Photocatalytic water splitting by combining semiconductor nano-structures with fabricated metal and/or metal alloy or waste metal and/or metal alloy to generate hydrogen gas |
| CN109082652A (en) * | 2018-10-31 | 2018-12-25 | 西南石油大学 | A kind of surface amorphous alloy conductive layer technology of preparing of non-conductive matrix |
| CN110433852B (en) * | 2019-09-05 | 2022-11-15 | 西南石油大学 | Graphite-phase carbon nitride-loaded atomic-level bimetallic catalyst and preparation method and application thereof |
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| EP2703078A1 (en) * | 2012-09-03 | 2014-03-05 | Saudi Basic Industries Corporation | Photocatalyst comprising gold-palladium alloy, method for preparation, photolysis system |
| CN106378148B (en) * | 2016-08-29 | 2018-11-13 | 北方工业大学 | Preparation method of dendritic nanocrystal supported ternary alloy nanoparticle photocatalytic material |
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| CN108671925A (en) * | 2018-05-28 | 2018-10-19 | 国网山东省电力公司电力科学研究院 | Nano-TiO2Amorphous acid bronze alloy composite photocatalyst material and preparation method thereof and purposes |
| CN108686662A (en) * | 2018-05-28 | 2018-10-23 | 国网山东省电力公司电力科学研究院 | Nano TiO 2-amorphous zirconium-base alloy composite photocatalyst material and preparation method thereof and purposes |
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