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 PDF

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CN108452805B
CN108452805B CN201710087506.4A CN201710087506A CN108452805B CN 108452805 B CN108452805 B CN 108452805B CN 201710087506 A CN201710087506 A CN 201710087506A CN 108452805 B CN108452805 B CN 108452805B
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郭旺
黄集权
李国京
江亚斌
兰海
陈剑
石明
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Fujian Institute of Research on the Structure of Matter of CAS
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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
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    • 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
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    • 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
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    • 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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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

NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst, preparation method and application thereof
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
Figure BDA0001227887320000091
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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