CN114890465A - Preparation method and application of transition metal doped titanium dioxide with fixed form - Google Patents

Preparation method and application of transition metal doped titanium dioxide with fixed form Download PDF

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CN114890465A
CN114890465A CN202210634597.XA CN202210634597A CN114890465A CN 114890465 A CN114890465 A CN 114890465A CN 202210634597 A CN202210634597 A CN 202210634597A CN 114890465 A CN114890465 A CN 114890465A
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titanium dioxide
transition metal
doped titanium
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precipitate
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唐量
陈文倩
王佳俊
吴秋雨
吴明红
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a preparation method and application of transition metal doped titanium dioxide with a fixed form, which comprises the following steps: (1) firstly, taking Ti-based MOF as a precursor, immersing the Ti-based MOF into a transition metal salt solution, and carrying out ultrasonic treatment for 1-2h to ensure that metal ions of the transition metal salt solution enter an MIL-125 pore channel of the Ti-based MOF to form turbid liquid, wherein metal is contained in the turbid liquidThe salt solution is Fe (NO) 3 ) 3 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 Or Zn (NO) 3 ) 2 One or more of (a); (2) placing the obtained suspension in a vacuum oven for vacuum drying treatment to obtain a solid sample, washing the solid sample with methanol, and then centrifuging to obtain a precipitate; (3) and drying the precipitate at room temperature, and calcining the dried precipitate to obtain the titanium dioxide doped with the transition metal. The transition metal doped titanium dioxide prepared by the method effectively reduces the band gap width of the titanium dioxide, and the electrocatalytic performance of the titanium dioxide is greatly improved.

Description

Preparation method and application of transition metal doped titanium dioxide with fixed form
Technical Field
The invention relates to the field of titanium dioxide preparation, in particular to a preparation method and application of transition metal doped titanium dioxide with a fixed form.
Background
Since the 21 st century, the economic rapid development consumes a large amount of stone resources such as petroleum, coal, natural gas and the like, and simultaneously brings serious environmental pollution, thereby seriously restricting the sustainable development of the society. Therefore, the development and exploration of new energy materials are difficult to solve the current energy and environmental problems,
titanium dioxide is an inorganic substance which is widely applied to the processes of paint, plastics, paper making, printing ink, chemical fiber, rubber, cosmetics and the like. TiO has been reported since 1972 by Fujishima and Honda in Japan 2 TiO is generated by the phenomenon that the electrode can decompose water to generate hydrogen under the irradiation of ultraviolet light 2 Because the catalyst is nontoxic, low in price, high in chemical and thermal stability and obviously superior to other catalytic materials, the catalyst attracts general attention of medical researchers worldwide. TiO 2 2 Long cycle life, durability, is a preferred electrode material. However, in practical applications, TiO 2 Has larger band gap (3.0-3.2eV), low quantum efficiency and easy recombination of photogenerated electrons and holes. Therefore, the synthetic preparation of titanium dioxide materials with good electrocatalytic properties remains a difficult task.
TiO with fixed shape doped by relevant transition metal ions at home and abroad through investigation 2 The preparation and application of the materials are generally based on literature reports and patent findingsThe sol-gel method, the electrochemical doping method, the solid phase synthesis method, the hydrothermal method and other methods have the problems of too complex synthesis method procedures, difficult control of the synthesized mosaic appearance, overhigh synthesis temperature and the like.
In view of the above, the present invention provides a method for preparing titanium dioxide doped with transition metal and having a fixed morphology and an application thereof.
Disclosure of Invention
The invention aims to provide a preparation method and application of transition metal doped titanium dioxide with a fixed form, aiming at the defects of the prior art, wherein the preparation method is simpler and easier to operate compared with the traditional synthesis method, and the electrocatalytic performance of a titanium dioxide material is improved.
In order to solve the technical problems, the following technical scheme is adopted:
a preparation method of transition metal doped titanium dioxide with fixed morphology comprises the following steps:
(1) taking Ti-based MOF as a precursor, immersing the Ti-based MOF into a transition metal salt solution, and carrying out ultrasonic treatment for 1-2h to ensure that metal ions of the transition metal salt solution enter MIL-125 pore channels of the Ti-based MOF to form a suspension, wherein the metal salt solution is Fe (NO) 3 ) 3 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 Or Zn (NO) 3 ) 2 One or more of (a);
(2) placing the obtained suspension in a vacuum oven for vacuum drying treatment to obtain a solid sample, washing the solid sample with methanol, and then centrifuging to obtain a precipitate;
(3) and drying the precipitate at room temperature, and calcining the dried precipitate to obtain the titanium dioxide doped with the transition metal.
Further, the concentration of the metal salt solution is 0.1-0.2M.
Further, in the step (2), the temperature of the suspension liquid in a vacuum oven for vacuum drying treatment is controlled to be 75-90 ℃, and the time of the drying treatment is controlled to be 2.5-3.5 h.
Further, in the step (2), the number of times of washing the solid sample with methanol is controlled to be 3 to 5.
Further, in the step (3), the dried precipitate is calcined and placed in a muffle furnace for carrying out the calcination treatment, the temperature of the calcination treatment is controlled to be 450-.
Further, in the step (1), the precursor Ti-based MOF is prepared by the following method: putting isopropyl titanate, terephthalic acid and dimethylformyl into a Teflon reaction kettle, uniformly stirring, carrying out hydrothermal reaction in an oven at 150 ℃ for 24h, washing with dimethylformyl and ethanol for 3 times respectively, and finally carrying out vacuum drying at 150 ℃ for 3h to obtain a precursor Ti-based MOF of titanium dioxide doped with transition metal ions.
Further, the solvent adopted by the isopropyl titanate, the terephthalic acid and the dimethylformyl is absolute methanol.
Further, the molar ratio of isopropyl titanate to terephthalic acid is 1: 3.5.
further, the fixed form of the titanium dioxide is the fixed form of the precursor Ti-based MOF.
According to another technical scheme of the invention, the transition metal doped titanium dioxide with a fixed form is applied to the electrocatalytic performance.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the invention relates to a preparation method and application of transition metal doped titanium dioxide with a fixed form. The transition metal doped titanium dioxide prepared by the method effectively reduces the band gap width of the titanium dioxide, and the electrocatalytic performance of the titanium dioxide is greatly improved.
The method comprises the steps of preparing titanium dioxide with a fixed form by taking Ti-based MOF as a precursor, immersing the precursor into a transition metal salt solution, ultrasonically washing and drying, calcining at a proper temperature to obtain the titanium dioxide with the fixed form doped with transition metal ions, measuring the electrocatalytic performance of the titanium dioxide with the fixed form doped with the transition metal ions in a KOH alkaline electrolyte with the concentration of 1M, and comparing the electrocatalytic performance of the titanium dioxide with the fixed form not doped with the transition metal ions. The result shows that the electrocatalytic performance of the titanium dioxide with fixed form doped by the transition metal ions prepared by the invention is far superior to that of the titanium dioxide with fixed form not doped by the transition metal ions.
Drawings
The invention will be further described with reference to the accompanying drawings in which:
FIG. 1 is a comparison of a transition metal ion doped titanium dioxide prepared in accordance with the present invention, before and after calcination, in fixed morphology.
FIG. 2 is a comparative XRD plot of transition metal ion doped titanium dioxide with fixed morphology prepared according to the present invention.
FIG. 3 is a TEM image of the titania precursor MIL-125 prepared by the present invention.
FIG. 4 is a TEM image of transition metal ion doped titania with fixed morphology prepared according to the present invention.
FIG. 5 EDS picture of transition metal ion doped titanium dioxide with fixed morphology prepared by the present invention.
FIG. 6 is a graph showing the results of electrocatalytic performance of transition metal ion-doped titanium dioxide having a fixed morphology and titanium dioxide having a fixed morphology prepared according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
As shown in fig. 1 to 5, a method for preparing transition metal doped titanium dioxide having a fixed morphology, comprising the steps of:
(1) firstly, Ti-based MOF is taken as a precursor, and the Ti-based MOF is MIL-125. Immersing the Ti-based MOF into a transition metal salt solution and carrying out ultrasonic treatment for 1-2h, so that metal ions of the transition metal salt solution enter MIL-125 pore channels of the Ti-based MOF to form a suspension, wherein the metal salt solution is Fe (NO3)3, Co (NO3)2, Ni (NO3) 2 、Cu(NO 3 ) 2 Or Zn (NO) 3 ) 2 The concentration of the metal salt solution is 0.1-0.2M.
(2) And (3) placing the obtained suspension in a vacuum oven for vacuum drying treatment, wherein the temperature of the suspension in the vacuum oven for vacuum drying treatment is controlled to be 75-90 ℃, and the time of the drying treatment is controlled to be 2.5-3.5h, so as to obtain a solid sample.
Washing the solid sample with methanol, controlling the number of times of washing the solid sample with methanol to be 3-5 times, and then centrifuging to obtain a precipitate;
(3) and drying the precipitate at room temperature, calcining the dried precipitate, placing the calcined dried precipitate in a muffle furnace for calcination, controlling the temperature of the calcination to be 500 ℃ plus one year, controlling the time of the calcination to be 2.5-3.5h, raising the temperature of the muffle furnace to be 500 ℃ plus one year at the speed of 2 ℃/min, and finally obtaining the titanium dioxide doped with the transition metal.
Further, in the step (1), the precursor Ti-based MOF is prepared by the following method: the solvent adopted by the isopropyl titanate, the terephthalic acid and the dimethylformyl is anhydrous methanol, and the molar ratio of the isopropyl titanate to the terephthalic acid is 1: 3.5. putting isopropyl titanate, terephthalic acid and dimethylformyl into a Teflon reaction kettle, uniformly stirring, carrying out hydrothermal reaction in an oven at 150 ℃ for 24h, washing with dimethylformyl and ethanol for 3 times respectively, and finally carrying out vacuum drying at 150 ℃ for 3h to obtain a precursor Ti-based MOF of titanium dioxide doped with transition metal ions. The fixed form of the titanium dioxide is the fixed form of a precursor Ti-based MOF.
The process for the preparation of transition metal doped titanium dioxide having a fixed morphology is illustrated in detail by the following examples.
Example 1
(1) Preparation of MIL-125: stirring 3g of terephthalic acid, 1.56mL of isopropyl titanate, 6mL of anhydrous ethanol, 54mL of anhydrous ethanol and dimethyl formyl for 30min until the materials are uniformly mixed, placing the mixture in a 100mL Teflon reaction kettle for reacting for 24h at 150 ℃, taking the suspension after the reaction is completely cooled, adding 30mL of methanol into the suspension, stirring for 1h, centrifuging, and drying for 3h at 150 ℃ in vacuum to obtain white MIL-125 powder.
(2) Mixing: 200mg of MIL-125 powder was put in 1mL of Cu (NO) 3 ) 2 In the solution (concentration of 0.1M), the solution is fully mixed by ultrasonic treatment for 1 h.
(3) And (3) calcining: and (3) drying the mixture prepared in the step (2) at 80 ℃ in vacuum for 3h, washing the dried mixture with methanol for three times, centrifuging the washed mixture to obtain a precipitate, drying the precipitate at room temperature, and calcining the precipitate in a muffle furnace at 450 ℃ for 3h to obtain the titanium dioxide doped with transition metal ions and having a fixed form.
Referring to FIGS. 2-5, the present example uses Cu (NO) 3 ) 2 The solution is used as a metal salt solution to obtain Cu-TiO 2 And ordinary TiO 2 XRD contrast pattern of (see fig. 2).
TEM image of the resulting titanium dioxide precursor MIL-125 (see FIG. 3).
TEM image of the resulting transition metal ion doped titanium dioxide with fixed morphology (see fig. 4).
EDS map of the resulting transition metal ion doped titanium dioxide with fixed morphology (see fig. 5).
Referring to FIG. 6, (a) the prepared transition metal ion doped titanium dioxide Cu-TiO with fixed morphology is taken 2 6mg，Cu-TiO 2 Then mixed with 330uL water, 110uL ethanol and 40uL Nafion ice-water bath for ultrasonic treatment for 15min to form uniform ink.
(b) Preparing an electrode slice: and (3) uniformly coating 120uL (4) of ink on the foamed nickel, and airing at room temperature.
(c) And (3) performance testing: KOH with the concentration of 1M is used as electrolyte, a graphite electrode is used as a counter electrode, and a mercury-mercury oxide electrode is used as a reference electrode.
The results show, with reference to FIG. 6, that the present invention is applicablePrepared transition metal ion doped titanium dioxide Cu-TiO with fixed form 2 The electrocatalytic performance of the titanium dioxide is far superior to that of titanium dioxide with a fixed form without doping of transition metal ions.
Example 2
(1) Preparation of MIL-125: stirring 2.8g of terephthalic acid, 1.6mL of isopropyl titanate, 6mL of absolute ethyl alcohol, 54mL of absolute ethyl alcohol and dimethyl formyl for 30min until the mixture is uniformly mixed, placing the mixture in a 100mL Teflon reaction kettle to react for 24h at 150 ℃, taking the suspension after the reaction is completely cooled, adding 30mL of methanol into the suspension, stirring for 1h, centrifuging, and drying for 3h at 150 ℃ in vacuum to obtain white MIL-125 powder.
(2) Mixing: putting 180mgMIL-125 powder in 1mL of Fe (NO) 3 ) 3 In the solution (concentration of 0.1M), the solution is fully mixed by ultrasonic treatment for 2 h.
(3) And (3) calcining: and (3) drying the mixture prepared in the step (2) in vacuum at 80 ℃ for 3.5h, washing the dried mixture with methanol for four times, centrifuging the washed mixture to obtain a precipitate, drying the precipitate at room temperature, and calcining the precipitate in a muffle furnace at 500 ℃ for 3h to obtain the titanium dioxide doped with transition metal ions and having a fixed form.
Example 3
(1) Preparation of MIL-125: stirring 3g of terephthalic acid, 1.6mL of isopropyl titanate, 6mL of anhydrous ethanol, 54mL of anhydrous ethanol and dimethylformamide for 30min until the materials are uniformly mixed, placing the mixture in a 100mL Teflon reaction kettle for reacting for 24h at 150 ℃, taking the suspension after the reaction is completely cooled, adding 30mL of methanol into the suspension, stirring for 1h, centrifuging, and drying for 3h at 150 ℃ in vacuum to obtain white MIL-125 powder.
(2) Mixing: 220mgMIL-125 powder is put into 1mL Co (NO) 3 ) 2 And Ni (NO) 3 ) 2 The mixed solution (concentration: 0.1M) was subjected to ultrasonic treatment for 1.5 hours to mix thoroughly.
(3) And (3) calcining: and (3) drying the mixture prepared in the step (2) in vacuum at 80 ℃ for 3.5h, washing the dried mixture with methanol for five times, centrifuging the dried mixture to obtain a precipitate, drying the precipitate at room temperature, and calcining the precipitate in a muffle furnace at 480 ℃ for 3h to obtain the titanium dioxide doped with transition metal ions and having a fixed form.
Example 4
(1) Preparation of MIL-125: stirring 3g of terephthalic acid, 1.55mL of isopropyl titanate, 6mL of anhydrous ethanol, 54mL of anhydrous ethanol and dimethyl formyl for 30min until the materials are uniformly mixed, placing the mixture in a 100mL Teflon reaction kettle for reacting for 24h at 150 ℃, taking the suspension after the reaction is completely cooled, adding 30mL of methanol into the suspension, stirring for 1h, centrifuging, and drying for 3h at 150 ℃ in vacuum to obtain white MIL-125 powder.
(2) Mixing: 200mg of MIL-125 powder was put in 1mL of Cu (NO) 3 ) 2 And Zn (NO) 3 ) 2 The mixed solution (concentration: 0.1M) was subjected to ultrasonic treatment for 1.5 hours to mix thoroughly.
(3) And (3) calcining: and (3) drying the mixture prepared in the step (2) in vacuum at 80 ℃ for 3h, washing the dried mixture with methanol for five times, centrifuging the dried mixture to obtain a precipitate, drying the precipitate at room temperature, and calcining the precipitate in a muffle furnace at 480 ℃ for 3h to obtain the titanium dioxide doped with the transition metal ions and having a fixed form.
Example 5
(1) Preparation of MIL-125: stirring 3g of terephthalic acid, 1.5mL of isopropyl titanate, 6mL of anhydrous ethanol, 54mL of anhydrous ethanol and dimethyl formyl for 30min until the materials are uniformly mixed, placing the mixture in a 100mL Teflon reaction kettle for reacting for 24h at 150 ℃, taking the suspension after the reaction is completely cooled, adding 30mL of methanol into the suspension, stirring for 1h, centrifuging, and drying for 3h at 150 ℃ in vacuum to obtain white MIL-125 powder.
(2) Mixing: 200mg of MIL-125 powder is put into 1mL of Ni (NO) 3 ) 2 And Cu (NO) 3 ) 2 The mixed solution (concentration: 0.1M) was subjected to ultrasonic treatment for 1.5 hours to mix thoroughly.
(3) And (3) calcining: and (3) drying the mixture prepared in the step (2) in vacuum at 80 ℃ for 3h, washing the dried mixture with methanol for five times, centrifuging the dried mixture to obtain a precipitate, drying the precipitate at room temperature, and calcining the precipitate in a muffle furnace at 480 ℃ for 3h to obtain the titanium dioxide doped with the transition metal ions and having a fixed form.
Similarly, examples 2-5, transition metal ion doped titanium dioxide Fe-TiO with fixed morphology prepared using different types of metal salt solutions and their associated reaction conditions 2 ，Co-TiO 2 ，Ni-TiO 2 ，Zn-TiO 2 Or mixed Co thereof x Ni y -TiO 2 ，Cu x Zn y -TiO 2 And Ni x Cu y -TiO 2 The electrocatalytic performance of the catalyst is far superior to that of the catalystTitanium dioxide with a fixed morphology without transition metal ion doping. The method has the advantages of simple process steps, simple operation, low production cost and low synthesis temperature, and the obtained sample has stable appearance. The transition metal doped titanium dioxide obtained by the method effectively reduces the band gap width of the titanium dioxide, and the electrocatalytic performance of the titanium dioxide is greatly improved.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.

Claims (10)

1. The preparation method of the titanium dioxide doped with the transition metal and having the fixed morphology is characterized by comprising the following steps:
(1) firstly taking Ti-based MOF as a precursor, immersing the Ti-based MOF into a transition metal salt solution, and carrying out ultrasonic treatment for 1-2h to ensure that metal ions of the transition metal salt solution enter an MIL-125 pore channel of the Ti-based MOF to form a suspension, wherein the metal salt solution is Fe (NO) 3 ) 3 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 Or Zn (NO) 3 ) 2 One or more of (a);
(2) placing the obtained suspension in a vacuum oven for vacuum drying treatment to obtain a solid sample, washing the solid sample with methanol, and then centrifuging to obtain a precipitate;
(3) and drying the precipitate at room temperature, and calcining the dried precipitate to obtain the titanium dioxide doped with the transition metal.
2. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 1, characterized in that: the concentration of the metal salt solution is 0.1-0.2M.
3. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 1, characterized in that: in the step (2), the suspension is placed in a vacuum oven to be subjected to vacuum drying treatment, the temperature is controlled to be 75-90 ℃, and the drying treatment time is controlled to be 2.5-3.5 h.
4. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 1, characterized in that: in the step (2), the number of times that the solid sample is washed with methanol is controlled to be 3 to 5.
5. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 1, characterized in that: in the step (3), the dried precipitate is calcined and placed in a muffle furnace for carrying out the calcination, the temperature of the calcination is controlled to be 450-.
6. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 1, characterized in that: in the step (1), the precursor Ti-based MOF is prepared by the following method: putting isopropyl titanate, terephthalic acid and dimethylformyl into a Teflon reaction kettle, uniformly stirring, carrying out hydrothermal reaction in an oven at 150 ℃ for 24h, washing with dimethylformyl and ethanol for 3 times respectively, and finally carrying out vacuum drying at 150 ℃ for 3h to obtain a precursor Ti-based MOF of titanium dioxide doped with transition metal ions.
7. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 6, characterized in that: the solvent adopted by the isopropyl titanate, the terephthalic acid and the dimethyl formyl is absolute methanol.
8. The method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 6, characterized in that: the molar ratio of the isopropyl titanate to the terephthalic acid is 1: 3.5.
9. the method of producing transition metal doped titanium dioxide with a fixed morphology according to claim 6, characterized in that: the fixed form of the titanium dioxide is the fixed form of a precursor Ti-based MOF.
10. The use of transition metal doped titanium dioxide with a fixed morphology for electrocatalytic properties.
CN202210634597.XA 2022-06-07 2022-06-07 Preparation method and application of transition metal doped titanium dioxide with fixed form Pending CN114890465A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003821A (en) * 2023-02-23 2023-04-25 西安交通大学 MOF nano material and preparation method thereof, preparation method and application of metal-loaded single-atom MOF nano material

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