CN108452805B - NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst, preparation method and application thereof - Google Patents
NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst, preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002071 nanotube Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 7
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 239000011858 nanopowder Substances 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 11
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000011941 photocatalyst Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C01B2203/10—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
- C01B2203/1094—Promotors or activators
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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
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- Chemical & Material Sciences (AREA)
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- 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 invention relates to a NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst, preparation method and application thereofThe catalyst is made of Ni (NO)3)2And HTNT. The invention also provides a preparation method of the catalyst, the photocatalyst is prepared by in-situ reaction through a hydrothermal method, and the prepared catalyst is a uniform one-dimensional nanotube. The NiTiO prepared by the method3/TiO2The nanotube catalyst has stable structure and property, can be repeatedly used for catalyzing the hydrogen production reaction by photolysis, and still has good stability after being recycled for multiple times.
Description
Technical Field
The invention belongs to the field of semiconductor photocatalysis, and particularly relates to NiTiO for photolyzing water to produce hydrogen3/TiO2A nano composite catalyst, a preparation method and application thereof.
Background
The large consumption of non-renewable fossil energy makes energy exhaustion and serious environmental pollution a big problem facing the world at present. Seeking environmentally friendly renewable energy sources becomes the best choice to solve energy crisis and environmental problems. Hydrogen has attracted considerable attention as the cleanest energy source. The direct utilization of solar light to decompose water to produce hydrogen is considered to be an effective way to solve the problems of energy crisis and environmental pollution. The catalytic action of the photocatalyst can not be separated in the process of decomposing water by utilizing the solar light. The existing found catalyst has the problems of poor stability, low photoelectric conversion efficiency, great environmental hazard, high synthesis cost, light corrosion and the like, so that the catalyst cannot be applied on a large scale. Titanium dioxide has the characteristics of low cost, stable chemical properties, no pollution and the like, and is considered as a promising photocatalyst. However, titanium dioxide has a relatively broad valence band and is limited in its light absorption, and a promoter is generally added to increase the absorption of visible light and increase the light absorption efficiency.
In order to improve the catalytic efficiency of the photocatalyst, CN103872174A (application No. 201210552885.7) provides an Au-modified TiO having visible light absorption characteristics2A method for preparing a nanorod array photo-anode material. Using Au quantum dot pairs to TiO2Surface and bottom are modified together to add TiO2In the absorption range of visible light range, the efficiency of photolysis of water is improved. CN102513129A (application No. 201110393837.3) provides a photocatalytic TiO2/Cu2The preparation method of the O composite film improves the photocatalytic hydrogen production performance by modifying Pt. However, the above catalysts require noble metals and are expensive to prepare. In addition, most of the catalysts cannot be recycled, and the purpose of environmental protection and economy cannot be achieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides NiTiO for photolyzing water to produce hydrogen3/TiO2The catalyst has the advantages of improving the efficiency of photolysis of water to produce hydrogen, being recyclable, being environment-friendly and economical and the like, and the preparation method has mild reaction conditions and simple operation steps.
In order to achieve the above purpose, the invention provides the following technical scheme:
NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst is NiTiO3With TiO2The nanocomposite of (1).
According to the invention, the NiTiO3/TiO2NiTiO in catalyst3/TiO2The molar ratio of (1) to (0-0.055) may be other than 0; preferably (0.005-0.045) 1; more preferably (0.01-0.030): 1; more preferably (0.012-0.025): 1.
According to the invention, the NiTiO3/TiO2TiO in catalyst2The phases are anatase phases.
According to the invention, the NiTiO3/TiO2The catalyst is a one-dimensional nanotube. The length of the nanotube can be between 100 and 800 nm; the inner diameter may be 3-5 nm.
According to the invention, the NiTiO3/TiO2The catalyst has a large specific surface area which can be 80-150m2/g。
The catalyst of the invention has the following advantages:
(1) the NiTiO3/TiO2Catalyst vs. TiO2Has higher photocatalysis efficiency. Wherein the NiTiO contained in the catalyst3Can effectively improve TiO2Photocatalytic efficiency of the nanotubes;
(2) the NiTiO3/TiO2The catalyst can be TiO2The hydrogen production rate of the nanotube is improved by at least 15 times and is at least 60 times of that of the P25 powder;
(3) the NiTiO3/TiO2The catalyst has stable structure, and the phenomenon of photoetching is not found in the using process;
(4) the NiTiO3/TiO2The catalyst can be recycled for more than 4 times, for example, at least 5 times, and the effect of photolyzing water to produce hydrogen is not obviously reduced.
The invention also provides the NiTiO as described above3/TiO2Method for preparing catalyst, the NiTiO3/TiO2The catalyst is prepared by taking a protonated titanate nanotube (hereinafter referred to as 'HTNT') as a precursor through a hydrothermal in-situ reaction method.
According to the invention, the method comprises the following preparation steps:
1) preparing an HTNT comprising the steps of:
1a) adding TiO into the mixture2Carrying out hydrothermal reaction with an alkaline solution; separating to obtain titanate nanotubes after the reaction is finished;
1b) washing the titanate nano tube obtained in the step 1a) with water, and washing away redundant alkali; then washing with acid liquor to obtain protonized titanate nanotubes; washing with water again, washing with an organic solvent, and drying to obtain HTNT;
2) preparation of NiTiO3/TiO2A catalyst precursor comprising: mixing HTNT with Ni (NO)3)2Mixing the solutions, stirring, adding alkali solution to adjust pH of the reaction solution, stirring, filtering, and adding H2Cleaning O and organic solvent, and drying to obtain NiTiO3/TiO2A catalyst precursor;
3) preparation of NiTiO by annealing treatment3/TiO2A catalyst, comprising: mixing the above NiTiO3/TiO2Calcining the catalyst precursor to obtain the NiTiO3/TiO2A catalyst.
In step 1a), preferably, the alkaline solution may be an aqueous NaOH solution; the concentration of the alkaline solution can be 5-10 mol/L;
preferably, the TiO is2Can be nano powder;
preferably, the TiO is2The ratio (g: mL) of the mass of (2) to the volume of the alkaline solution may be (2.0 to 3.5): (40-100), preferably (2.5-3.0): (60-90), for example, 2.5: 80;
preferably, the temperature of the hydrothermal reaction is 120-300 ℃, preferably 160-240 ℃, and as an illustrative example, the temperature of the hydrothermal reaction is 160 ℃;
preferably, the hydrothermal reaction time may be 1.5 to 24 hours, and as an illustrative example, the hydrothermal reaction time is 24 hours.
Preferably, the separation can be suction filtration using a vacuum pump;
in step 1b), the water is preferably distilled water;
preferably, the acid solution can be a nitric acid aqueous solution prepared by mixing concentrated nitric acid and water at any ratio; the concentration of the aqueous nitric acid solution may be 0.001mol/L to 0.1mol/L, preferably 0.005mol/L to 0.05mol/L, for example 0.01 mol/L;
preferably, the organic solvent is not particularly limited as long as it does not react with the product. Preferably, the solvent is a solvent inert to the reaction reagents. As an illustrative example, the organic solvent may be selected from one or more of nitrile solvents (e.g., acetonitrile), aromatic hydrocarbon solvents (e.g., benzene, toluene), alcohol solvents (e.g., methanol, ethanol, isopropanol, n-propanol), ether solvents (e.g., diethyl ether), ester solvents (e.g., ethyl acetate), halogenated hydrocarbon solvents (e.g., dichloromethane, carbon tetrachloride). Further preferably, the organic solvent is ethanol.
In step 2), the Ni (NO)3)2The concentration of the solution may be 0.0001 to 0.1mol/L, preferably 0.001 to 0.015 mol/L;
preferably, the Ni (NO)3)2The molar ratio to HTNT may be 0: 1-0.05: 1, preferably 0.01: 1-0.02: 1, more preferably 0.018: 1;
preferably, the HTNT is reacted with Ni (NO)3)2The reaction time may be 5-24h, as an illustrative example 24 h;
preferably, the alkali solution can be ammonia water, NaHCO3Aqueous solution, Na2CO3One or more of aqueous solutions, for example, aqueous ammonia;
preferably, adding alkali liquor to adjust the pH of the reaction solution to 9-11;
preferably, the reaction solution may be further stirred for 1 hour or more after the pH is adjusted to 9 to 11, for example, for 2 hours, 5 hours or 10 hours;
preferably, the organic solvent used for washing in said step 2) has the definition as described above in step 1).
In step 3), preferably, the calcination temperature may be 300-;
preferably, the calcination time may be 1 hour or more, for example, 2 hours.
The invention also provides the NiTiO as described above3/TiO2Use of the catalyst, the NiTiO3/TiO2The catalyst can be used for catalyzing photolysis of water to produce hydrogen.
The invention has the beneficial effects that:
1. NiTiO of the invention3/TiO2The catalyst has stable structure and no photoetching phenomenon. The hydrogen production effect by photolysis of water is not obviously attenuated after the hydrogen production is recycled for more than 4 times.
2.NiTiO3/TiO2The catalyst is presented as a unique one-dimensional nano-tubular structure, and the structure can obviously improve the light utilization efficiency of the catalyst, thereby improving the TiO2The efficiency of photolysis of water hydrogen.
3.NiTiO3/TiO2The preparation of the catalyst is carried out at a lower temperature, and no toxic noble metal is introduced as a cocatalyst in the reaction process, so that the energy consumption is reduced, and the environment is not seriously influenced.
Drawings
FIG. 1 is an XRD pattern of the S1-S9 samples; wherein, (a) is XRD pattern of S1-S9 sample, and (b) and (c) are partial enlarged views.
Figure 2 is an XRD pattern of the S9 sample.
FIGS. 3(a) and (b) are transmission electron micrographs of S0 and S5, respectively.
FIG. 4 is a graph showing the change with time of the hydrogen production amounts of the samples S0 to S9 in example 11.
FIG. 5 shows the hydrogen production of the S0-S9 samples of example 11 as a function of NiTiO in the catalyst3Graph of content variation.
FIG. 6 is a graph of the cyclic catalytic hydrogen production of the S5 catalyst.
Detailed Description
The invention discloses NiTiO for photolyzing water to produce hydrogen3/TiO2The catalyst is measured by the following photocatalytic test method to obtain the photocatalytic efficiency:
i) 0.01-1g of the NiTiO of the present invention3/TiO2The catalyst is added into a photocatalytic reactor in a photocatalytic system, and then 100mL of pure water or a cavity sacrificial agent aqueous solution with the volume fraction of 5% -50% is added into the photocatalytic reactor, wherein the cavity sacrificial agent can be methanol, ethanol, acetic acid, lactic acid and the like.
ii) starting a vacuum pump connected with the photocatalytic system and simultaneously starting stirring to remove air in the system until the pressure value reaches negative one atmosphere and no bubbles emerge at the liquid level in the reactor.
And iii) starting the magnetic control glass air pump to promote the air flow in the system, so that the air is uniformly dispersed, placing a xenon lamp light source simulating natural light above the reactor, and starting the xenon lamp to start the photocatalytic reaction.
iv) carrying out timing sampling analysis on gas generated by water decomposition in the system by utilizing a gas chromatograph of the photocatalytic system, sampling once every 1h, sampling and analyzing 10 times for each sample, and determining the type and the content of a gas product of the water decomposition reaction of the photocatalysis.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the examples are all commercially available materials.
The XRD of the samples of the examples was characterized using a miniflex-600 powder diffractometer.
The transmission electron microscopy of the examples was characterized using a scanning transmission electron microscope Tecnai G2F 20.
The Ni, Ti content analytical testing of the samples of the examples was characterized using an Ultima 2 inductively coupled full spectrum plasma spectrometer.
Example 1 (preparation of HTNT)
320g of NaOH was weighed and dissolved in 1000mL of distilled water at room temperature with stirring to prepare an 8mol/L NaOH solution. 2.5g of TiO are added into 10 100mL reaction kettles2And (3) nano powder and 80mL of the NaOH solution are added, and the reaction kettle is moved into a blast drying oven to carry out hydrothermal reaction for 24 hours at 160 ℃. And after the reaction, carrying out suction filtration by using a vacuum pump to obtain the titanate nanotube.
Washing the hydrothermally prepared titanate nanotubes for 3 times by distilled water, and washing off redundant NaOH. And then washing with 0.01mol/L nitric acid for 10 times, so that sodium in the titanate nanotubes can be fully replaced by hydrogen in the nitric acid, namely, the titanate is protonated. Washing with distilled water for 5 times and ethanol for 3 times, and drying to obtain HTNT named S0.
Example 2
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.001mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S1.
Example 3
1g HTNT was mixed with 40mL of 0.002mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2The photocatalyst is named as S2.
Example 4
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.003mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S3.
Example 5
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.004mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S4.
Example 6
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.005mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S5.
Example 7
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.006mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S6.
Example 8
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.007mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S7.
Example 9
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.008mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S8.
Example 10
1g of the HTNT synthesized in example 1 was mixed with 40mL of 0.015mol/L Ni (NO)3)2Mixing the solutions, magnetically stirring for 24 hr, adding ammonia water solution dropwise to adjust pH to 9-11, stirring for 5 hr, vacuum filtering, and adding H2And repeatedly washing with O and ethanol, and drying. And annealing the suction filtration product by using a tube furnace. Calcining for 2h at 450 ℃ to obtain one-dimensional tubular NiTiO3/TiO2Photocatalyst, designation S9. Example 11 (elemental analysis and photocatalytic Hydrogen production test)
0.1g of the catalysts S0-S9 prepared as described in examples 1-10 above were weighed out and tested for photocatalytic hydrogen production efficiency using the test method described above, and the test results are shown in FIGS. 4 and 5.
As can be seen from FIG. 4, the hydrogen production of the catalyst increased with time, while pure TiO2The hydrogen production amount of (S0) hardly changes with an increase in time; and with NiTiO3An increase in the content, an increase in the amount of hydrogen production with time; further, within a certain range, e.g. NiTiO3With TiO2When x is in the range of 0 to 0.0177 in the molar ratio (x:1) of (A) to (B), with NiTiO3The hydrogen production increases with an increase in the content.
As can be seen from FIG. 5, NiTiO3/TiO2The hydrogen production rate of the catalyst is along with the NiTiO3The content increases and then decreases, while in NiTiO3With TiO2The highest hydrogen production rate is achieved when the molar ratio of (A) to (B) is 0.0177: 1.
The catalysts S0-S9 prepared in examples 1-10 above were subjected to ICP content analysis and the results are shown in Table 1.
TABLE 1 NiTiO in S1-S9 samples3With TiO2In a molar ratio of
Example 12 (catalyst cycle catalyzed hydrogen production test)
And (3) filtering and recovering the S5 catalyst after the catalytic hydrogen production test, drying and directly using the catalyst for the next catalytic hydrogen production test, wherein the test result is shown in figure 6.
From the figure 6, the catalyst has no obvious reduction of the hydrogen production effect after five times of photocatalytic cycles, the performance of the catalyst is stable, the catalyst can be recycled for many times, and the catalytic activity is almost unchanged.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. NiTiO for photolyzing water to produce hydrogen3/TiO2The catalyst is characterized in that the catalyst is NiTiO3With TiO2The nanocomposite of (a); NiTiO in catalyst3/TiO2The molar ratio of (0-0.055) is 1 and not 0;
the NiTiO3/TiO2The catalyst is a one-dimensional nanotube;
the length of the nanotube is between 100 and 800 nm; the inner diameter is 3-5 nm.
2. The NiTiO compound of claim 13/TiO2Catalyst, characterized in that the catalyst contains NiTiO3/TiO2The molar ratio of (0.005-0.045) to (1).
3. The NiTiO compound of claim 23/TiO2Catalyst, characterized in that the catalyst contains NiTiO3/TiO2The molar ratio of (0.01-0.030) to (1).
4. The NiTiO compound of claim 33/TiO2Catalyst, characterized in that the catalyst contains NiTiO3/TiO2The molar ratio of (0.012-0.025) to 1.
5. The NiTiO compound of claim 13/TiO2Catalyst, characterized in that the NiTiO3/TiO2TiO in catalyst2Phase of anataseAnd (4) phase(s).
6. A NiTiO according to any one of claims 1 to 53/TiO2Catalyst, characterized in that the NiTiO3/TiO2The specific surface area of the catalyst is 80-150m2/g。
7. A NiTiO according to any one of claims 1 to 63/TiO2The preparation method of the catalyst is characterized in that the catalyst is prepared by taking a protonated titanate nanotube (HTNT) as a precursor by a hydrothermal in-situ reaction method;
the method specifically comprises the following preparation steps:
1) preparing protonated titanate nanotubes (HTNT), which comprises the following steps:
1a) adding TiO into the mixture2Carrying out hydrothermal reaction with an alkaline solution; separating to obtain titanate nanotubes after the reaction is finished;
1b) washing the titanate nano tube obtained in the step 1a) with water, and washing away redundant alkali; then washing with acid liquor to obtain protonized titanate nanotubes; washing with water again, washing with an organic solvent, and drying to obtain HTNT;
2) preparation of NiTiO3/TiO2A catalyst precursor comprising: mixing HTNT with Ni (NO)3)2Mixing the solutions, stirring, adding alkali solution to adjust pH of the reaction solution, stirring, filtering, and adding H2Cleaning O and organic solvent, and drying to obtain NiTiO3/TiO2A catalyst precursor;
3) preparation of NiTiO by annealing treatment3/TiO2A catalyst, comprising: mixing the above NiTiO3/TiO2Calcining the catalyst precursor to obtain the NiTiO3/TiO2A catalyst.
8. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that in the step 1a), the alkaline solution is NaOH aqueous solution;
the concentration of the alkaline solution is 5-10 mol/L.
9. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that in the step 1a), the TiO2Is nano powder;
the TiO is2The ratio of the mass of (2.0 to 3.5) g to the volume of the alkaline solution is: (40-100) mL.
10. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that the temperature of the hydrothermal reaction is 120-300 ℃.
11. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that in the step 1b), the water is distilled water;
the acid solution is a nitric acid aqueous solution prepared by mixing concentrated nitric acid and water at any ratio.
12. The NiTiO compound of claim 73/TiO2A method for preparing a catalyst, characterized in that, in step 2), the Ni (NO) is3)2The concentration of the solution is 0.0001-0.1 mol/L.
13. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that in the step 2), the alkali liquor is ammonia water and NaHCO3Aqueous solution, Na2CO3One or more of aqueous solutions;
adding alkali liquor to adjust the pH of the reaction solution to 9-11.
14. The NiTiO compound of claim 73/TiO2The preparation method of the catalyst is characterized in that in the step 3), the calcination temperature is 300-600 ℃.
15. The NiTiO of claim 113/TiO2Of catalystsThe preparation method is characterized in that in the step 1a), the TiO2The ratio of the mass of (2.5 to 3.0) g to the volume of the alkaline solution is: (60-90) mL;
the temperature of the hydrothermal reaction is 160-240 ℃;
in the step 1b), the concentration of the nitric acid aqueous solution is 0.001-0.1 mol/L;
the organic solvent is selected from one or more of nitrile solvents, aromatic hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents and halogenated hydrocarbon solvents;
in step 2), the Ni (NO)3)2The concentration of the solution is 0.001-0.015 mol/L;
the alkali liquor is ammonia water;
in the step 3), the calcination temperature is 350-450 ℃.
16. The NiTiO of claim 153/TiO2The preparation method of the catalyst is characterized in that in the step 1a), the TiO2The ratio of the mass of (2.5 g) to the volume of the alkaline solution is: 80 mL;
the hydrothermal reaction temperature is 160 ℃;
in the step 1b), the concentration of the nitric acid aqueous solution is 0.005mol/L-0.05 mol/L;
the organic solvent is ethanol;
in step 2), the Ni (NO)3)2Molar ratio to HTNT 0.018: 1;
in the step 3), the calcination temperature is 450 ℃.
17. Use of a catalyst according to any of claims 1 to 6, wherein the NiTiO is3/TiO2The catalyst is used for catalyzing photolysis of water to produce hydrogen.
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