CN105148956A - Efficient photocatalytic-water-splitting hydrogen production catalyst and preparation method thereof - Google Patents
Efficient photocatalytic-water-splitting hydrogen production catalyst and preparation method thereof Download PDFInfo
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- CN105148956A CN105148956A CN201510633425.0A CN201510633425A CN105148956A CN 105148956 A CN105148956 A CN 105148956A CN 201510633425 A CN201510633425 A CN 201510633425A CN 105148956 A CN105148956 A CN 105148956A
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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 copper phosphide and titanium dioxide nanocrystalline compound-type photocatalytic-water-splitting hydrogen production catalyst and a preparation method thereof, and belongs to the technical field of nano-catalysts. The preparation method includes the steps that copper nitrate is prepared into copper hydroxide, copper hydroxide and sodium hypophosphite are calcined at certain temperature and under nitrogen protection, and then a product is rinsed, centrifuged and dried to obtain product copper phosphide; then, copper phosphide and anatase titanium dioxide nanocrystals are mixed and ground evenly to obtain the catalyst through preparation. The reaction rate of photocatalytic-water-splitting hydrogen production can be increased to 7.94 mmol h<-1>g<-1> from 0.74 mmol h<-1>g<-1> of pure titanium dioxide, and is increased by over 10 times. In this way, the catalyst is used as a new technological means for solving energy crisis, having potential industry applicability and producing environmentally-friendly novel energy.
Description
Technical field
The invention belongs to nanocatalyst technical field, be specifically related to a kind of phosphorized copper and titanium dioxide nanocrystalline compound photocatalysis Decomposition aquatic products hydrogen catalyst and preparation method thereof.
Background technology
Titanium dioxide is the excellent material of a kind of photocatalysis performance, and it is nontoxic but also relative low price not only, and raw material sources are very abundant again, and in the earth, abundance is higher, and its whiteness is very high.It is a kind of semi-conducting material of excellent performance, is to apply maximum materials in photolysis water hydrogen field, is the ideal material solving energy crisis and produce clean energy resource.But, the situation of exist actually is that titanium dioxide uses its photochemical catalyzing efficiency extremely low as photochemical catalyst decomposition water, be difficult to meet industrial requirement, mainly because the very fast compound of the light induced electron that excites under ultraviolet light of titanium dioxide and hole, luminous energy can not be effectively utilized, cause photochemical catalyzing effect very undesirable, so need to make improvements and design.
Summary of the invention
In order to the problem that the photochemical catalyzing hydrogen generation efficiency solving titanium deoxide catalyst existence in prior art is extremely low, the present invention conducts in-depth research the mechanism that optically catalytic TiO 2 decomposes aquatic products hydrogen, after having paid a large amount of original works, and then complete the present invention.
High efficiency photocatalysis of the present invention decomposes aquatic products hydrogen catalyst, is be prepared into Kocide SD by copper nitrate, Kocide SD again with inferior sodium phosphate roasting under uniform temperature and nitrogen protection, then product to be washed, dry product phosphorized copper; Phosphorized copper again with anatase titania nanocrystalline mixed grinding even.The present invention can make photocatalysis Decomposition aquatic products hydroformylation reaction rate by the 0.74mmolh of pure titinium dioxide
-1g
-1bring up to 7.94mmolh
-1g
-1, performance raising has exceeded 10 times.Therefore the present invention is that one has the potential industrial applicability of solution energy crisis, and is a kind of new technical means producing the environment-friendly novel energy.
A kind of high efficiency photocatalysis of the present invention decomposes the preparation method of aquatic products hydrogen catalyst, and its step is as follows:
(1) get copper nitrate solid particle to stir in reaction vessel and within 10 ~ 50 minutes, make it dissolve completely, continue the sodium hydroxide solution 50 ~ 100 milliliters adding 0.2 ~ 0.6 mole often liter under stirring, the mole dosage of copper nitrate and NaOH than being 1:2 ~ 5, then continuing stirring and within 2 ~ 5 hours, obtains suspension;
(2) suspension that step (1) obtains is spent deionized water centrifugal 3 ~ 5 times, then with centrifugal 1 ~ 3 time of ethanol washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours again;
(3) desciccate step (2) obtained and inferior sodium phosphate (NaH
2pO
2h
2after the ratio mixing of O) pressed powder 1:5 ~ 10 in mass ratio, grinding evenly;
(4) product getting step (3) gained roasting 1 ~ 2 hour under the argon-mixed protection of nitrogen, argon gas or nitrogen, 300 ~ 350 degrees celsius;
(5) step (4) roasting afterproduct is spent deionized water centrifugal 3 ~ 5 times, then with centrifugal 1 ~ 2 time of ethanol washing, dry phosphorized copper (Cu after abandoning supernatant
3p);
(6) block polymer (P123) of 2.0 ~ 2.8 grams of oxirane and methyl oxirane is joined in the diethylene glycol (DEG) of 80 ~ 160 milliliters, and then add 3 ~ 6 milliliters of titanium tetrachloride aqueous solutions (the mass concentration >99% of titanium tetrachloride), the last concentrated ammonia liquor (aqueous solution containing ammonia mass fraction 25% ~ 28%) adding 3 ~ 6 milliliters again, reacts 3 ~ 5 hours in the oil bath of 200 ~ 230 degrees Celsius;
(7) in the mixed liquor in step (6), add the acetone of 50 ~ 80 milliliters, then centrifugal 4 ~ 6 times of acetone washing, to abandon after supernatant under 80 ~ 100 degrees celsius dry 10 ~ 15 hours again;
(8) by the roasting 2 ~ 5 hours under 450 ~ 650 degrees celsius of the desciccate in step (7), anatase titania nanocrystalline (grain size is 10 ~ 20 nanometers (nm)) is obtained;
(9) by the product (anatase titania is nanocrystalline) in step (8) and the product (phosphorized copper (Cu in step (5)
3p)) with the mixed rear grinding even (45 ~ 60 minutes) of the ratio of mass ratio 100:0.1 ~ 15, thus photocatalysis Decomposition aquatic products hydrogen catalyst of the present invention is obtained.
The test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph is moored through Beijing, photochemical catalyst prepared by the present invention titanium dioxide that catalysis photocatalytic water speed ratio is simple under triethanolamine does the condition of sacrifice agent has had and has significantly improved, and the raising of performance has exceeded 10 times.
The present invention can make photochemical catalyzing efficiency greatly improve, and further meets industrial requirement.Composite catalyst system inhibits the compound in light induced electron and hole in titanium dioxide under ultraviolet excitation greatly, improves the separative efficiency of photo-generated carrier, luminous energy is effectively utilized, and then improve the speed of its photochemical catalyzing.Therefore the present invention is very significant innovation and creation.
Accompanying drawing explanation
Fig. 1: pure Cu
3p, TiO
2and 2wt%Cu
3p-TiO
2digital pictures, great changes will take place can to find out sample appearance color, black be that we prepare pure Cu
3p sample, comparatively shallow we of color prepare pure TiO
2, color be grey be the 2wt%Cu that we prepare
3p-TiO
2sample, Cu a small amount of as seen
3the color of P on sample has very large impact.
Fig. 2: pure Cu
3p, TiO
2with 0.125 ~ 5wt%Cu
3p-TiO
2the hydrogen-producing speed phenogram of sample; Clearly can find out that from figure our modified sample hydrogen-producing speed is than simple Cu
3p, TiO
2be greatly improved.
Fig. 3: 0.5wt%Cu
3p-TiO
2cyclical stability phenogram; As can be seen from the figure our properties of sample is very stable, does not decay through 5 loop test performances.
Fig. 4: figure (a) and figure (b) are pure TiO
2and 0.5wt%Cu
3p-TiO
2sample transmission Electronic Speculum figure; Pure TiO can be found out from figure (a)
2grain size be the nanocrystalline of 10 ~ 20 nanometers (nm), from figure (b) can find out spacing of lattice (d), d=0.230nm is Cu
3[202] crystal face of P, d=0.196nm is Cu
3[113] crystal face of P, d=0.350nm is TiO
2[101] crystal face, demonstrate Cu
3p and TiO
2both hetero-junctions compound fine formed.
Fig. 5: pure TiO
2and 0.5wt%Cu
3p-TiO
2fluorescence spectrum phenogram; The sample that photoluminescence spectrum intensity indicates our compound inhibits the compound in light induced electron and hole greatly, thus improves the utilization ratio of luminous energy.
Fig. 6: sample 0.5wt%Cu
3p-TiO
2element Surface scan (mapping) phenogram and tunnel scanning electron microscope diagram (SEM); Mapping figure is the pattern of corresponding SEM, directly shows all existence of Cu, P, Ti, O element in composite sample and its distribution situation is also very clear, thus the sample having confirmed us is further Cu
3p and TiO
2compound.
Fig. 7: Cu
3p and TiO
2the phenogram of X-ray diffractometer (XRD); As can be seen from the figure Cu
3p and TiO
2be pure phase, corresponding PDF card numbering: 65-3628 and 21-1272.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
(1) get 0.4689 gram of copper nitrate and put into 250 ml beakers stirring 10 minutes, add the sodium hydroxide solution 100 milliliters of 0.25 mole often liter under then continuing stirring condition, continue stirring 2 hours;
(2) suspension of step (1) is spent deionized water centrifugal 3 times, centrifugal 2 times of ethanol washing, after outwelling supernatant, put into dry 12 hours of the baking oven of 80 degrees Celsius;
(3) step (2) dried product and inferior sodium phosphate (quality of inferior sodium phosphate: the quality=5:1 of step (2) dried product) are ground evenly in mortar;
(4) product getting step (3) gained puts into the roasting 1 hour under 300 degree of conditions of tube furnace with nitrogen protection device;
(5) product after step (4) roasting is spent deionized water centrifugal 3 times, centrifugal 2 times of ethanol washing, obtains product phosphorized copper (Cu
3p), the Cu of pure phase is detected as through X-ray diffractometer (XRD)
3p;
(6) block polymer (P123) of the oxirane of 2.4 grams and methyl oxirane is added in 80 milliliters of diethylene glycol (DEG)s, and then add the titanium tetrachloride solution (mass concentration of titanium tetrachloride is 99.5%) of 4 milliliters, add the concentrated ammonia liquor (be the aqueous solution of 25% containing ammonia mass fraction) of 4 milliliters subsequently again, the oil bath of then putting into 220 degree reacts 3 hours under agitation;
(7) in the mixed liquor in step (6), add the acetone of 80 milliliters, then use acetone centrifuge washing 4 times, then put into 80 degree of baking ovens dry 12 hours;
(8) roasting under the 450 degree of conditions of the desciccate in step (7) is obtained the nanocrystalline (TiO of anatase titania in 2 hours
2) TiO of pure phase is detected as through X-ray diffractometer (XRD)
2, characterize through transmission electron microscope (TEM) TiO that particle diameter is 10 ~ 20 nanometers
2nanocrystalline
(9) product be mixed to form by the product in step (8) in even suspension (pure phase titanium dioxide nanocrystalline 0.1 gram, 90 ml waters, 10 milliliters of mass fractions are the triethanolamine of 99.5%) and step (5) is mixed to form even suspension, and phosphorized copper 0.1 gram, 90 ml waters, 10 milliliters of mass fractions are the triethanolamine of 99.5%) test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph is moored respectively through Beijing.Pure titinium dioxide (TiO prepared by the present invention
2) nanocrystalline catalysis photocatalytic water hydrogen-producing speed is 0.74mmolh
-1g
-1; Pure phase phosphorized copper (Cu
3p) nanocrystalline catalysis photocatalytic water hydrogen-producing speed is 0.05mmolh
-1g
-1.
Embodiment 2
Step (1) ~ (8) with embodiment 1, by the product (pure phase titanium dioxide (TiO in step (8)
2) product (pure phase phosphorized copper (Cu in nanocrystalline and step (5)
3p) mass ratio is (quality of titanium dioxide: the quality=100:0.125 of phosphorized copper), and in mortar, grinding mixes and namely obtains sample 0.125wt%Cu for 45 minutes
3p/TiO
2; By 0.1 gram of this catalyst, 90 ml waters, 10 milliliters of mass fractions be 99.5% triethanolamine be mixed to form even suspension, moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing.The catalysis photocatalytic water speed of photocatalysis Decomposition aqua prepared by the present invention is 7.149mmolh
-1g
-1, than simple titanium dioxide hydrogen-producing speed 0.74mmolh
-1g
-1have and significantly improved, improved effect and exceeded 9 times.
Embodiment 3
Step (1) ~ (8) with embodiment 1, by the product (pure phase titanium dioxide (TiO in step (8)
2) product (pure phase phosphorized copper (Cu in nanocrystalline and step (5)
3p) mass ratio is (quality of titanium dioxide: the quality=100:0.5 of phosphorized copper), and in mortar, grinding mixes and namely obtains sample 0.5wt%Cu for 45 minutes
3p/TiO
2; By 0.1 gram of this catalyst, 90 ml waters, 10 milliliters of mass fractions be 99.5% triethanolamine be mixed to form even suspension, moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing.The catalysis photocatalytic water speed of photocatalysis Decomposition aqua prepared by the present invention is 7.939mmolh
-1g
-1, than simple titanium dioxide hydrogen-producing speed 0.74mmolh
-1g
-1have and significantly improved, improved effect and exceeded 10 times.
Embodiment 4
Step (1) ~ (8) with embodiment 1, by the product (pure phase titanium dioxide (TiO in step (8)
2) product (pure phase phosphorized copper (Cu in nanocrystalline and step (5)
3p) mass ratio is (quality of titanium dioxide: the quality=100:1 of phosphorized copper), and in mortar, grinding mixes and namely obtains sample 1wt%Cu for 45 minutes
3p/TiO
2; By 0.1 gram of this catalyst, 90 ml waters, 10 milliliters of mass fractions be 99.5% triethanolamine be mixed to form even suspension, moor the test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing.The catalysis photocatalytic water speed of photocatalysis Decomposition aqua prepared by the present invention is 7.698mmolh
-1g
-1, than simple titanium dioxide hydrogen-producing speed 0.74mmolh
-1g
-1have and significantly improved, improved effect and exceeded 10 times.
Embodiment 5
Step (1) ~ (8) with embodiment 1, by the product (pure phase titanium dioxide (TiO in step (8)
2) product (phosphorized copper (pure phase Cu in nanocrystalline and step (5)
3p) mass ratio is (quality of titanium dioxide: the quality=100:2 of phosphorized copper), and in mortar, grinding mixes and namely obtains sample 2wt%Cu for 45 minutes
3p/TiO
2; The triethanolamine being 99.5% by 0.1 gram of this catalyst and 90 ml waters and 10 milliliters of mass fractions is mixed to form even suspension, moors the test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing.The catalysis photocatalytic water speed of photocatalysis Decomposition aqua prepared by the present invention is 6.673mmolh
-1g
-1, than simple titanium dioxide hydrogen-producing speed 0.74mmolh
-1g
-1have and significantly improved, improved effect and exceeded 9 times.
Embodiment 6
Step (1) ~ (8) with embodiment 1, by the product (pure phase titanium dioxide (TiO in step (8)
2) product (pure phase phosphorized copper (Cu in nanocrystalline and step (5)
3p) mass ratio is (quality of titanium dioxide: the quality=100:5 of phosphorized copper), and in mortar, grinding mixes and namely obtains sample 5wt%Cu for 45 minutes
3p/TiO
2; The triethanolamine being 99.5% by 0.1 gram of this catalyst and 90 ml waters and 10 milliliters of mass fractions is mixed to form even suspension, moors the test of luxuriant and rich with fragrance Lay light system for producing hydrogen and the detection of Japanese Shimadzu GC-81 type chromatograph through Beijing.The catalysis photocatalytic water speed of photocatalysis Decomposition aqua prepared by the present invention is 5.354mmolh
-1g
-1, than simple titanium dioxide hydrogen-producing speed 0.74mmolh
-1g
-1have and significantly improved, improved effect and exceeded 7 times.
To sum up prepare example, we draw following conclusion further:
(1) mass ratio of titanium dioxide and phosphorized copper has individual optimal value scope, i.e. the quality of titanium dioxide: quality=100:0.125 ~ 5 of phosphorized copper;
(2) purity of phosphorized copper and the performance of the pattern of titanium dioxide nanocrystalline to this catalyst have material impact;
(3) adding of sacrifice agent triethanolamine good synergy is played to photochemical catalyzing performance.
Claims (7)
1. high efficiency photocatalysis decomposes a preparation method for aquatic products hydrogen catalyst, and its step is as follows:
(1) get copper nitrate solid particle to stir in reaction vessel and within 10 ~ 50 minutes, make it dissolve completely, continue the sodium hydroxide solution 50 ~ 100 milliliters adding 0.2 ~ 0.6 mole often liter under stirring, the mole dosage of copper nitrate and NaOH than being 1:2 ~ 5, then continuing stirring and within 2 ~ 5 hours, obtains suspension;
(2) suspension that step (1) obtains is spent deionized water centrifugal 3 ~ 5 times, then with centrifugal 1 ~ 3 time of ethanol washing, dry after abandoning supernatant;
(3) grind even after the ratio of desciccate step (2) obtained and inferior sodium phosphate pressed powder 1:5 ~ 10 in mass ratio mixes;
(4) by the roasting under the argon-mixed protection of nitrogen, argon gas or nitrogen of step (3) products therefrom;
(5) step (4) roasting afterproduct is spent deionized water centrifugal 3 ~ 5 times, then with centrifugal 1 ~ 2 time of ethanol washing, after drying, obtain phosphorized copper Cu3P;
(6) the block polymer P123 of 2.0 ~ 2.8 grams of oxirane and methyl oxirane is joined in the diethylene glycol (DEG) of 80 ~ 160 milliliters, and then add 3 ~ 6 milliliters of titanium tetrachloride solutions, the last concentrated ammonia liquor adding 3 ~ 6 milliliters again, reacts 3 ~ 5 hours in the oil bath of 200 ~ 230 degrees Celsius;
(7) in the mixed liquor in step (6), the acetone of 50 ~ 80 milliliters is added, then centrifugal 4 ~ 6 times of acetone washing, then under 80 ~ 100 degrees celsius dry 10 ~ 15 hours;
(8) desciccate in step (7) is carried out roasting, obtain anatase titania nanocrystalline;
(9) namely the product in the product in step (8) and step (5) is evenly obtained high efficiency photocatalysis with the mixed rear grinding of the ratio of mass ratio 100:0.1 ~ 15 and decompose aquatic products hydrogen catalyst.
2. a kind of high efficiency photocatalysis as claimed in claim 1 produces the preparation method of hydrogen decomposition water catalyst, it is characterized in that: step (2) is under 80 ~ 100 degrees celsius dry 10 ~ 15 hours.
3. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: step (4) is roasting 1 ~ 2 hour under 300 ~ 350 degrees celsius.
4. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: step (8) is roasting 2 ~ 5 hours under 450 ~ 650 degrees celsius.
5. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: the milling time of step (9) is 45 minutes ~ 60 minutes.
6. a kind of high efficiency photocatalysis as claimed in claim 1 decomposes the preparation method of aquatic products hydrogen catalyst, it is characterized in that: in step (9), the mass ratio of titanium dioxide and phosphorized copper is 100:0.125 ~ 5.
7. high efficiency photocatalysis decomposes an aquatic products hydrogen catalyst, it is characterized in that: be prepared by the method for claim 1 ~ 6 described in any one.
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| CN107376957A (en) * | 2017-06-27 | 2017-11-24 | 青岛鲁润中科环境工程技术开发有限公司 | The preparation method and application of red phosphorus cladding titanium dioxide nano fiber catalysis material |
| CN108193219A (en) * | 2017-12-27 | 2018-06-22 | 黄河科技学院 | Phosphorized copper modified titanic oxide optoelectronic pole and preparation method thereof and the application in photoelectrocatalysis decomposes water |
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| CN108483404A (en) * | 2018-04-20 | 2018-09-04 | 中国科学技术大学 | A kind of preparation method of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet |
| CN110252359A (en) * | 2019-06-17 | 2019-09-20 | 四川大学 | A kind of preparation method of sulfur-bearing cadmium hetero-junctions photodissociation aquatic products hydrogen catalyst |
| CN110252359B (en) * | 2019-06-17 | 2020-04-03 | 四川大学 | Preparation method of catalyst for photolysis of water to produce hydrogen by using cadmium sulfide-containing heterojunction |
| CN112774732A (en) * | 2021-01-29 | 2021-05-11 | 胡国强 | Ti-MOF/Rh-Al2O3Preparation method of composite catalyst |
| CN112774732B (en) * | 2021-01-29 | 2023-04-11 | 江西新节氢能源科技有限公司 | Ti-MOF/Rh-Al 2 O 3 Preparation method of composite catalyst |
| CN115449630A (en) * | 2022-08-12 | 2022-12-09 | 上海师范大学 | Method for selective metal leaching of photocatalysis nitrile-amine-containing solution system |
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