CN110227495A - A kind of copper-rich modifying defect titanium dioxide, cuprous sulfide hetero-junctions produce the preparation method of hydrogen catalyst - Google Patents
A kind of copper-rich modifying defect titanium dioxide, cuprous sulfide hetero-junctions produce the preparation method of hydrogen catalyst Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 70
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000007547 defect Effects 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001257 hydrogen Substances 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 5
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- -1 poly(ethylene glycol) Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920006358 Fluon Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C01B2203/1076—Copper or zinc-based 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention is that a kind of copper-rich modifying defect titanium dioxide, cuprous sulfide hetero-junctions produce the preparation method of hydrogen catalyst, and Cu is doped in the wide bandgap semiconductor TiO with good light absorpting ability2In, and being artificially introduced surface defect makes Cu reduction in part be exposed to TiO2Surface then carries out vulcanizing treatment and forms Cu doping vario-property defect TiO2、Cu2S hetero-junctions makes catalyst play highest catalytic efficiency by the control to Cu doping content, carries out vulcanizing treatment to catalyst, forms Cu doping vario-property defect TiO2、Cu2S hetero-junctions plays hetero-junctions and doping vario-property and acts synergistically, to obtain higher photocatalysis efficiency.The method of the present invention is simple and environmentally-friendly, inexpensive；Catalytic effect is obvious, is swift in response, and has many advantages, such as that repeatability is high；This catalyst, which produces hydrogen to visible light catalytic water decomposition, has potential using value.
Description
Technical field
The invention belongs to the preparation of nano material and application fields, more particularly to a kind of copper-rich modifying defect titanium dioxide
Titanium, cuprous sulfide hetero-junctions produce the preparation method of hydrogen catalyst.
Background technique
With the development of industry, increasingly depleted energy reserves and increasingly severe environmental pollution are that people to be faced
Two big challenges.Fossil energy is used as always the main body of the energy and increasingly consumes for a long time, has been difficult to meet permanent energy confession
It answers, on the other hand, fossil fuel generates a large amount of CO while burning generates the energy2、SO2Equal pernicious gases, this brings again
Pollution problems such as " greenhouse effects "[1].Therefore, two above how is solved the problems, such as to realization sustainable development and safeguards ecological ring
Border harmony have own strategic significance, and develop and the use of clean reproducible energy is to solve the problems, such as these two aspects effective way.
Sunlight is most abundant and sustainable use energy source for human society.People pass through manual simulation's photosynthesis
It proposes and converts solar energy into the solar battery technology of electricity, convert light energy into the photothermal conversion technology of thermal energy and by light
The PhotoelectrochemicalTechnique Technique of chemical energy can be converted into[2].Hydrogen (H2) it is that one kind has high fuel value, efficient energy carrier,
Product after burning is only that water does not have any harmful components, this makes hydrogen become a kind of very superior clean energy resource.Hydrogen Energy at present
Production mainly by coal, natural gas reformation come, this will necessarily aggravate the consumption of non-regeneration energy and bring environment
Pollution problem.Since Honda is reported in TiO2After water can generate hydrogen by photoelectrolysis on electrode, TiO2Semiconductor material
Due to characteristics such as its photochemical stability, nontoxic and cheap prices, and becomes a kind of and potentially can be applied to the sunlight energy
The catalysis material that conversion and environment are cured[3].However, this system still faces lot of challenges such as: how to overcome TiO2Width
Bandgap semiconductor characteristic expands its spectral response range, reduces the high recombination rate of light induced electron and hole and accelerates hot carrier
The problems such as diffusion rate.This patent develops an easy-to-use synthetic route to prepare high Cu doping vario-property defect TiO2、
Cu2S hetero-junctions visible light catalytic water decomposition produces hydrogen catalyst.By adjusting position and the concentration of Cu doping and surface defect, come
Adjustment and expansion visible absorption range；By in Cu doping vario-property defect TiO2Cu is constructed in nanostructure2The half of S hetero-junctions
Conductor photocatalytic system obtains efficient separation of charge efficiency.
[1]Blankenship R E,Tiede D M,Barber J,et al.Comparing photosynthetic
and photovoltaic efficiencies and recognizing the potential for improvement
[J].science,2011,332(6031):805-809.
[2]Maeda K,Domen K.Photocatalytic water splitting:recent progress and
future challenges[J].The Journal of Physical Chemistry Letters,2010,1(18):
2655-2661.
[3]Fujishima A,Honda K.Photolysis-decomposition of water at the
surface of an irradiated semiconductor[J].Nature,1972,238(5385):37-38.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of richness Cu modifying defect TiO2, Cu2S hetero-junctions
The preparation method of hydrogen catalyst is produced, this method is simple and easy, and yield is higher, prepared Cu doping vario-property defect TiO2、Cu2S is different
There is matter knot visible light catalyst preferable visible light catalytic water decomposition to produce hydrogen effect.
The object of the present invention is achieved like this: the preparation method of the catalyst the following steps are included:
(1), Cu doping vario-property TiO2F127 (poly- (the second of 1.6g is added into 30mL alcohol solvent for the preparation of nanostructure
Glycol) poly- (the propylene glycol)-block- poly(ethylene glycol) of-block-, molecular weight: 13000) and the copper acetate of 0.2g, stirred at 60 DEG C
It mixes 1 hour, revolving speed 500rpm dissolves it sufficiently；The glacial acetic acid (98%) and 0.7mL of 2.3mL is added into solution again
Hydrochloric acid (36%), 3.5mL TBT (butyl titanate) continue stirring 30 minutes, revolving speed is still 500rpm；Mixed solution is moved
Enter in electric drying oven with forced convection, under the conditions of 60 DEG C, be dried 24 hours, obtains Cu doping TiO2Collosol and gel；By what is obtained
Cu adulterates TiO2Collosol and gel sample is transferred to Muffle furnace and carries out high-temperature calcination processing, is warming up to 450 DEG C simultaneously with the rate of 5 DEG C/min
Heat preservation 4 hours, it is cooling to obtain Cu doping TiO2Nanostructure sample；
(2), Cu doping vario-property defect TiO2Cu made from step (1) is adulterated TiO by the preparation of nanostructure2Nanostructure
Sample is mixed with the sodium borohydride (analysis is pure) of 300mg and is uniformly ground 1 hour, obtains mixing sample；Under the protection of argon gas
It is warming up to 300 DEG C using tube furnace with the rate of 10 DEG C/min to calcine above-mentioned mixing sample 30 minutes, obtained sample is packed into
20mL deionized water is added in 50mL centrifuge tube, places 36 hours, reacts it sufficiently；Centrifugal treating is carried out to sample after reaction,
Its centrifugal rotational speed 5000rpm, centrifugation time 3min abandon supernatant, and sediment cleans with deionized water and be ultrasonically treated 3min, weight
Multiple primary above-mentioned centrifugation, deionized water cleaning process, then be centrifuged, drain under natural conditions and formed --- Cu doping vario-property defect
TiO2Nanostructure.
(3), Cu doping vario-property defect TiO2、Cu2S hetero-junctions visible light catalytic water decomposition produces the preparation of hydrogen catalyst, will walk
Suddenly Cu doping vario-property defect TiO made from (2)21:2 is mixed nanostructure sample in molar ratio with thiocarbamide, will mix sample 1.2g
It is added in 30ml hydrazine hydrate aqueous solution (20%), continuing magnetic force stirs 30min at room temperature, and suspension is then sealed in 50ml spy
In the stainless steel autoclave of fluon liner, 180 DEG C and heated at constant temperature are heated to the heating rate of 5 DEG C/min in electronics baking oven
24 hours, then cooled to room temperature；The sediment prepared is centrifuged 15min with 5000rpm, respectively with deionized water and
Ethanol washing is three times, 12 hours dry in 70 DEG C of electronics baking oven；Obtaining final sample is Cu doping vario-property defect TiO2、
Cu2S hetero-junctions visible light catalytic water decomposition produces hydrogen catalyst.
1, above-mentioned steps (1), (2), reagent dosage is not scalable in (3).
2, above-mentioned steps (1), (2), reagent is that analysis is pure in (3), without being further processed.
The present invention has the advantages that:
1, the purity is high of catalyst sample synthesized by the method for the present invention, synthesis technology is simple and advanced, is put forward for the first time Cu and mixes
Miscellaneous modifying defect TiO2、Cu2S hetero-junctions plays synergistic effect visible light catalytic and decomposes aquatic products hydrogen.
2, method of the invention is simple and environmentally-friendly, inexpensive；Detection is rapid, repeatability is high；To making water under visible light conditions
It decomposes and produces hydrogen with very wide application prospect.
Detailed description of the invention
Fig. 1 is Cu doping vario-property defect TiO of the present invention2、Cu2S heterojunction photocatalyst XRD diagram；
Fig. 2 is Cu doping vario-property defect TiO of the present invention2、Cu2S heterojunction photocatalyst solid uv drs figure；
Fig. 3 is Cu doping vario-property defect TiO of the present invention2、Cu2S heterojunction photocatalyst TEM image and high-resolution TEM figure
Picture；
Fig. 4 is Cu doping vario-property defect TiO of the present invention2、Cu2S heterojunction photocatalyst Photocatalyzed Hydrogen Production performance schematic diagram；
Specific embodiment
The specific embodiment that the invention will now be described in detail with reference to the accompanying drawings:
A kind of Cu doping vario-property defect TiO2、Cu2The preparation method of S heterojunction photocatalyst: the preparation method includes following
Step:
(1), Cu doping vario-property TiO2F127 (poly- (the second of 1.6g is added into 30mL alcohol solvent for the preparation of nanostructure
Glycol) poly- (the propylene glycol)-block- poly(ethylene glycol) of-block-, molecular weight: 13000) and the copper acetate of 0.2g, stirred at 60 DEG C
It mixes 1 hour, revolving speed 500rpm dissolves it sufficiently；The salt of acetic acid (35%) and 0.7mL of 2.3mL is added into solution again
The TBT (butyl titanate) of sour (36%), 3.5mL continue stirring 30 minutes, and revolving speed is still 500rpm；Mixed solution is moved into
It in electric drying oven with forced convection, under the conditions of 60 DEG C, is dried 24 hours, obtains Cu doping TiO2Collosol and gel；The Cu that will be obtained
Adulterate TiO2Collosol and gel sample is transferred to Muffle furnace and carries out high-temperature calcination processing, is warming up to 450 DEG C with the rate of 5 DEG C/min and protects
Temperature 4 hours, it is cooling to obtain Cu doping TiO2Nanostructure sample；
(2), Cu doping vario-property defect TiO2Cu made from step (1) is adulterated TiO by the preparation of nanostructure2Nanostructure
Sample is mixed with the sodium borohydride (analysis is pure) of 300mg and is uniformly ground 1 hour, obtains mixing sample；Under the protection of argon gas
It is warming up to 300 DEG C using tube furnace with the rate of 10 DEG C/min to calcine above-mentioned mixing sample 30 minutes, obtained sample is packed into
20mL deionized water is added in 50mL centrifuge tube, places 36 hours, reacts it sufficiently；Centrifugal treating is carried out to sample after reaction,
Its centrifugal rotational speed 5000rpm, centrifugation time 3min abandon supernatant, and sediment cleans with deionized water and be ultrasonically treated 3min, weight
Multiple primary above-mentioned centrifugation, deionized water cleaning process, then be centrifuged, drain under natural conditions and formed --- Cu doping vario-property defect
TiO2Nanostructure.
(3),.Cu doping vario-property defect TiO2、Cu2S hetero-junctions visible light catalytic water decomposition produces the preparation of hydrogen catalyst, will
Cu doping vario-property defect TiO made from step (2)21:2 is mixed nanostructure sample in molar ratio with thiocarbamide, will mix sample
1.2g is added in 30ml hydrazine hydrate aqueous solution (20%), and continuing magnetic force stirs 30min at room temperature, is then sealed in suspension
In the stainless steel autoclave of 50ml teflon liner, 180 DEG C and perseverance are heated to the heating rate of 5 DEG C/min in electronics baking oven
Temperature heating 24 hours, then cooled to room temperature.By the sediment prepared with 5000rpm be centrifuged 15min, spend respectively from
Sub- water and ethanol washing are three times, 12 hours dry in 70 DEG C of electronics baking oven.Obtaining final sample is Cu doping vario-property defect
TiO2、Cu2S hetero-junctions visible light catalytic water decomposition produces hydrogen catalyst.
Using X-ray diffraction (XRD), solid uv drs, transmission electron microscope and high-resolution transmission electron microscopy
Mirror characterizes the Cu doping vario-property defect TiO of above method preparation2、Cu2S heterojunction photocatalyst, can from the XRD diagram picture of Fig. 1 sample
To find out,
1, reagent dosage is not scalable in above-mentioned steps (1) (2) (3).
2, reagent is that analysis is pure in above-mentioned steps (1) (2) (3), without being further processed.
Claims (1)
1. the preparation method of a kind of copper-rich modifying defect titanium dioxide, cuprous sulfide hetero-junctions production hydrogen catalyst, it is characterised in that:
Method includes the following steps:
(1), Cu doping vario-property TiO2The polyethers F127 and 0.2g of 1.6g are added into 30mL alcohol solvent for the preparation of nanostructure
Copper acetate, stir 1 hour at 60 DEG C, revolving speed 500rpm dissolves it sufficiently；The ice second of 2.3mL is added into solution again
The hydrochloric acid (38%) of sour (98%) and 0.7mL, 3.5mL butyl titanate (97%) continue to stir 30 minutes, revolving speed is still
500rpm；Mixed solution is moved into electric drying oven with forced convection, under the conditions of 60 DEG C, is dried 24 hours, Cu doping is obtained
TiO2Collosol and gel；Obtained Cu is adulterated into TiO2Collosol and gel sample be transferred to Muffle furnace carry out high-temperature calcination processing, with 5 DEG C/
The rate of min is warming up to 450 DEG C and keeps the temperature 4 hours, cooling to obtain Cu doping TiO2Nanostructure；
(2), Cu doping vario-property defect TiO2Cu made from step (1) is adulterated TiO by the preparation of nanostructure2Nanostructure sample
It mixes with the sodium borohydride of 300mg and uniformly grinds 1 hour, obtain mixing sample；Under the protection of argon gas using tube furnace with
The rate of 10 DEG C/min is warming up to 300 DEG C and calcines above-mentioned mixing sample 30 minutes, and obtained sample is packed into 50mL centrifuge tube, adds
Enter 20mL deionized water, places 36 hours, react it sufficiently；Centrifugal treating, centrifugal rotational speed are carried out to sample after reaction
5000rpm, centrifugation time 3min, abandon supernatant, and sediment cleans and is ultrasonically treated with deionized water 3min, is repeated once above-mentioned
Centrifugation, deionized water cleaning process, then be centrifuged, it is drained under natural conditions and forms Cu doping vario-property defect TiO2Nanostructure；
(3), Cu doping vario-property defect TiO2、Cu2S hetero-junctions visible light catalytic water decomposition produces the preparation of hydrogen catalyst, by step
(2) Cu doping vario-property defect TiO made from21:2 is mixed nanostructure sample in molar ratio with thiocarbamide, and mixing sample 1.2g is added
Enter in 30ml hydrazine hydrate aqueous solution (20%), continuing magnetic force stirs 30min at room temperature, and suspension is then sealed in 50ml Teflon
In the stainless steel autoclave of grand liner, 180 DEG C and heated at constant temperature 24 are heated to the heating rate of 5 DEG C/min in electronics baking oven
Hour, then cooled to room temperature；The sediment prepared is centrifuged 15min with 5000rpm, uses deionized water and second respectively
Alcohol washs three times, 12 hours dry in 70 DEG C of electronics baking oven；Obtaining final sample is Cu doping vario-property defect TiO2、Cu2S
Hetero-junctions visible light catalytic water decomposition produces hydrogen catalyst.
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| CN201910615457.6A CN110227495A (en) | 2019-07-09 | 2019-07-09 | A kind of copper-rich modifying defect titanium dioxide, cuprous sulfide hetero-junctions produce the preparation method of hydrogen catalyst |
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