CN115305478B - Preparation method of recyclable efficient composite platinum catalyst and application of recyclable efficient composite platinum catalyst in electrocatalysis - Google Patents

Preparation method of recyclable efficient composite platinum catalyst and application of recyclable efficient composite platinum catalyst in electrocatalysis Download PDF

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CN115305478B
CN115305478B CN202210803712.1A CN202210803712A CN115305478B CN 115305478 B CN115305478 B CN 115305478B CN 202210803712 A CN202210803712 A CN 202210803712A CN 115305478 B CN115305478 B CN 115305478B
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高广刚
尹迪
刘红
范林林
宫孟娣
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Abstract

The invention provides a preparation method of a recyclable efficient composite platinum catalyst, which comprises the following steps of II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Is used for preparing catalyst Pt/Mo 2 C/Mo 2 N@C-N. The application prepares the platinum-based electrocatalyst (Pt/Mo) 2 C/Mo 2 N@C-N) which shows excellent electrocatalytic activity at a current density of 10 mA cm ‑2 When the overpotential is only 13 mV, the electrocatalytic effect is higher than that of a commercial Pt/C catalyst; in addition, pt/Mo 2 C/Mo 2 N@C-N can regenerate the precursor [ Pt ] after oxidation-reduction reaction in acetonitrile/dichloromethane/hydrogen peroxide mixed solution II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The method is used for preparing the catalyst in the next cycle, and finally realizes the recycling of the element platinum. The performance of the catalyst after circulation is almost unchanged.

Description

Preparation method of recyclable efficient composite platinum catalyst and application of recyclable efficient composite platinum catalyst in electrocatalysis
Technical Field
The invention belongs to the technical field of synthesis of recyclable platinum catalysts, and particularly relates to a preparation method of a recyclable efficient composite platinum catalyst and an electrocatalytic application thereof.
Background
Currently, platinum-based materials have made them one of the most promising electrocatalysts due to their excellent electrocatalytic activity. However, the large-scale use of platinum-based materials is limited due to the low abundance and high price of platinum elements in nature. Therefore, the effective recovery of the platinum-based electrocatalyst is the most effective method for solving the scarce platinum resource, and is also a technical problem to be solved in the catalyst field.
The platinum catalyst prepared by the prior art is mainly recovered by the following three methods:
(1) A high-temperature melting smelting method; (2) acid dissolution; (3) electrochemical recovery method. Although the above-described techniques have proven to be effective in the recovery of platinum, there are still drawbacks in practice, such as high-temperature melting, which is not only energy-intensive, but also leads to the emission of toxic gases (e.g., hydrogen fluoride) that severely pollute the environment. The acid dissolution technology inevitably uses hydrochloric acid, sulfuric acid, nitric acid, aqua regia and other highly corrosive acids in the operation process, so that the equipment cost is high, and harmful emissions (such as hydrogen chloride steam, chlorine, sulfur dioxide, nitric oxide, nitrogen dioxide and the like) are released in the recovery process. Electrochemical recovery processes typically use corrosive or toxic electrolytes, which can also lead to emissions of harmful substances and secondary pollution.
The Pt/C of the platinum catalyst commonly used in the prior art has 20 percent of Pt content, high Pt content and high cost,
the recovery of Pt/C catalyst is typically accomplished by dissolving the spent Pt/C catalyst electrochemically or at high temperature (150 ℃) in a dilute acid solution to extract Pt, which is then deposited onto the carbon material. However, during this cycle, the electrochemical properties of the recovered Pt/C catalyst are greatly reduced due to Pt agglomeration and weak forces between Pt and the carbon of the substrate material [Mater. Chem. Phys. 2022, 276, 125439]。
In summary, the platinum-based catalyst prepared in the prior art has high Pt content and high cost, and has high cost, large environmental pollution and high risk for operators when platinum is recovered, and the recovered platinum-based material has a large particle size (more than 50 mm) generally, so that the electrochemical property is greatly reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a recyclable efficient composite platinum catalyst and application thereof in electrocatalysis, and the following aims are achieved: the composite platinum catalyst is prepared, the dosage of Pt is reduced while the catalytic effect is ensured, the recovery method is environment-friendly, the number of times of recycling is large, and the catalytic performance of the catalyst prepared from the recovered catalyst precursor is almost unchanged.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a recyclable efficient composite platinum catalyst comprises [ Pt II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Is used for preparing catalyst Pt/Mo 2 C/Mo 2 N@C-N.
The following is a further improvement of the above technical scheme:
the [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The preparation method comprises the steps of mixing tetrammine platinum chloride and (C 4 H 9 N) 4 [Mo 8 O 26 ]Dissolving in water, stirring at room temperature for 24 hr, filtering to obtain yellow filtrate, standing at 4deg.C for one week to obtain pale yellow transparent crystal [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]。
The tetrammine platinum chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]The mass ratio of (2) is 10-12:1; the mass volume ratio of the tetrammine platinum chloride to the water is 0.07-0.08 g/1 mL.
The catalyst Pt/Mo 2 C/Mo 2 N@C-N is prepared by mixing graphite phase carbon nitride with [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Adding into isopropanol, and controlling illumination intensity at 145-155mW/cm at room temperature 2 Stirring at 470-500r/min for 0.9-1.1 hr, centrifuging the obtained mixture, washing the separated solid powder with methanol three times, vacuum drying at 55-65deg.C for 1.8-2.2 hr, and vacuum drying at 55-65deg.CCalcining for 1.9-2.1h at 590-610 ℃ in CO atmosphere to obtain the catalyst Pt/Mo 2 C/Mo 2 N@C-N。
The graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The mass ratio of (2) is 1:0.9-1.1; the mass volume ratio of the graphite phase carbon nitride to the isopropanol is 1 mg/58-62 mL.
The mass content of Pt in the catalyst is 1.55-1.6%.
Said (C) 4 H 9 N) 4 [Mo 8 O 26 ]The preparation method comprises dissolving sodium molybdate dihydrate in water, adding tetrabutylammonium bromide, stirring at 74-76 ℃ for 9-11 min, and forming white precipitate; filtering under normal pressure, adding the obtained white precipitate directly into acetone at 44-46 deg.C, stirring slowly until the precipitate is dissolved, crystallizing the dissolved solution at 4deg.C in dark at low temperature for about one week to obtain crystal (C) 4 H 9 N) 4 [Mo 8 O 26 ]。
The mass ratio of the sodium molybdate dihydrate to the water is 1:4.3-4.5; the mass ratio of the sodium molybdate dihydrate to the tetrabutylammonium bromide is 1:0.66-0.67; the volume ratio of the water to the acetone is 1:2.2-2.3; the stirring speed is 110-130 r/min.
The catalyst prepared by the method is applied to electrocatalysis.
The invention adopts octamolybdic acid anion ([ Mo) 8 O 26 ] 4- ) As a novel carrier of platinum, the carrier and platinum are further converted and recovered simultaneously by utilizing a mild oxidation-reduction reaction. The invention first employs octamolybdate (formula (C) 4 H 9 N) 4 [Mo 8 O 26 ]) With platinum-containing compounds [ Pt (NH) 3 ) 4 ]Cl 2 Formation of [ Pt ] by crystallization reaction in solution II (NH 3 ) 4 ] 2 [Mo 8 O 26 ](abbreviated as Mo) 8 Pt) crystalline material. Then the prepared crystal material is reduced in carbon monoxide atmosphere to obtain the compound platinum-based catalyst Pt/Mo with cubic configuration 2 C/Mo 2 N@C-N, morphology and structure analysis show that nano-scale platinum particles are distributed on molybdenum carbide and molybdenum nitride substrates and can be used for electrocatalytic hydrogen production reaction. After the reaction, pt/Mo is added 2 C/Mo 2 N@C-N is dissolved in acetonitrile/dichloromethane/hydrogen peroxide mixed solution, crystallization reaction is carried out at normal temperature, and the most original crystal material [ Pt ] can be obtained again II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Thereby realizing the recycling of the platinum catalyst in a simple, effective and environment-friendly way.
Compared with the prior art, the invention has the following beneficial effects:
the application designs a brand new polyoxometallate Mo 8 Pt is an ideal recovery medium for renewable high-efficiency platinum-based electrocatalysts. Mo is added with 8 Pt is used as a precursor to carry out simple reduction reaction on graphite phase carbon nitride to prepare the platinum-based electrocatalyst (Pt/Mo) with nano cubic structure 2 C/Mo 2 N@C-N) which shows excellent electrocatalytic activity at a current density of 10 mA cm -2 When the overpotential is only 13 mV, the electrocatalytic effect is higher than that of a commercial Pt/C catalyst.
In addition, pt/Mo 2 C/Mo 2 N@C-N can regenerate precursor Mo after oxidation-reduction reaction in acetonitrile/dichloromethane/hydrogen peroxide mixed solution 8 Pt is used for preparing the catalyst in the next cycle, and finally, the recycling of the element Pt is realized. The performance of the catalyst after circulation is almost unchanged, and the current density of the composite catalyst after five times of circulation is 10 mA cm -2 At this time, the overpotential was still only 13 mV.
In the catalyst prepared by the application, the mass percentage of Pt is 1.55-1.6%, preferably 1.58%, and the Pt content is low and the production cost is low.
Drawings
FIG. 1 Mo prepared according to the invention 8 Is a infrared spectrogram of (2);
FIG. 2 is a diagram of Mo prepared according to the present invention 8 A crystal map of Pt under an optical microscope;
FIG. 3 Mo prepared according to the present invention 8 Molecular structure diagram of Pt;
FIG. 4 Pt/Mo prepared according to the present invention 2 C/Mo 2 N@C-N XRD pattern;
FIG. 5 Pt/Mo prepared according to the present invention 2 C/Mo 2 N@C-N TEM (a) and HRTEM (b) images;
FIG. 6 Pt/Mo prepared according to the present invention 2 C/Mo 2 N@C-N XPS plot;
wherein a is XPS map of C1 s; b is an XPS diagram of N1 s, c is an XPS diagram of Mo 3d, and d is an XPS diagram of Pt 4 f;
FIG. 7 Pt/Mo prepared according to the present invention 2 C/Mo 2 N@C-N and commercial Pt/C electrochemical performance comparison plots;
FIG. 8 Mo before and after multiple cycles 8 XRD pattern of Pt;
FIG. 9 Pt/Mo before and after multiple cycles 2 C/Mo 2 N@C-N electrochemical performance diagram.
Detailed Description
Example 1
1. (C 4 H 9 N) 4 [Mo 8 O 26 ](abbreviated as Mo) 8 ) Is characterized by the following steps:
Mo 8 reference to the preparation of (C)J. Am. Chem. Soc. 1976, 98, 8291–8293]。
Sodium molybdate dihydrate (5 g,20.7 mmol) was dissolved in 22 mL water (ph=4.7) and then 3.34 g (10.4 mmol) tetrabutylammonium bromide C was added 16 H 36 BrN. After stirring at 75 ℃ for 10 minutes, a white precipitate formed; filtering under normal pressure, directly adding the obtained white precipitate into acetone heated to 45deg.C of 50 mL, stirring at low speed (120 r/min) until the precipitate is dissolved, placing the dissolved solution in refrigerator fresh-keeping layer (temperature is regulated to 4deg.C), crystallizing at low temperature in dark place for about one week to obtain crystal Mo 8 . The infrared spectrum is shown in figure 1, 500 and 500 cm -1 Up to 1000 cm -1 Characteristic peaks at wavelength and Mo reported in literature 8 Is consistent with the characteristic peak of the (C).
2. [Pt II (NH 3 ) 4 ] 2 [Mo 8 O 26 ](simple)Written as Mo 8 Pt) preparation and structural characterization:
platinum tetrammine chloride 1.1. 1.1 g and Mo 0.1 g 8 Dissolved in 15 mL water. After stirring at room temperature for 24 hours, filtration was performed to obtain a yellow filtrate. Standing the filtrate in a refrigerator at 4deg.C for one week to obtain pale yellow transparent crystal Mo 8 Pt (see fig. 2). The structure test is carried out on the pale yellow transparent crystal by utilizing an X-ray single crystal diffractometer, and the data is analyzed to obtain the accurate structure of the crystal, namely the pale yellow transparent crystal is prepared fromβ[ Mo ] 8 O 26 ] 4- Anions and two [ Pt ] II (NH 3 ) 4 ] 2+ The cationic composition, its club-polyhedral diagram is shown in figure 3.
3. Platinum/molybdenum carbide/molybdenum nitride @ carbon-nitrogen (Pt/Mo) 2 C/Mo 2 N@C-N) preparation:
0.1 mg of Mo and 0. 0.1 mg of graphite phase carbon nitride 8 Pt is added into 6 mL isopropanol, and the illumination intensity is controlled to be 150 mW/cm at room temperature 2 Stirring at 480 r/min for 1h, centrifuging the obtained mixture, washing the separated solid powder with methanol for three times, vacuum drying at 60 ℃ for 2h, and calcining at 600 ℃ for 2h in CO atmosphere to finally obtain the nanocomposite Pt/Mo2C/Mo2N@C-N catalyst with a hollow cubic structure. The prepared catalyst was characterized by X-ray powder diffraction (XRD), transmission Electron Microscopy (TEM) and photoelectron spectroscopy (XPS). Wherein in the XRD pattern Mo is present at 34.2 °, 37.8 °, 39.6 °, 52.7 °, 56.2 °, 60.2 ° and 69.3 ° 2 Characteristic diffraction peaks for C appear at 36.8 °, 44.3 °, and 60.0 °, corresponding to Mo 2 Diffraction peaks for N (see fig. 4); the TEM image as in FIG. 5a shows Pt/Mo 2 C/Mo 2 N@C-N catalyst is a hollow cube structure with a size of about 600 nm, while FIG. 5b shows lattice fringes of 2.7A, 2.4A, and 2.2A, respectively with Mo at the sample interface 2 C (002) crystal face, mo 2 (111) crystal face of N and Pt 0 The (111) crystal face matching is good. In addition, to further determine the electrocatalyst Pt/Mo 2 C/Mo 2 XPS measurement of the composition of N@C-N and the valence of Pt on the samplesTest, as in FIG. 6a, pt/Mo 2 C/Mo 2 N@C-N high resolution C1 s XPS spectrum can be decomposed into 3 peaks (281.6 eV, 284.5 eV and 285.5 eV) corresponding to Mo-C, C =C and C-N, respectively, indicating that the samples are other than Mo 2 In addition to C, there are also some elemental C. The 3 peaks shown in the XPS spectrum of N1 s (FIG. 6 b) can be attributed to pyridine N (398.0 eV), pyrrole N (399.3 eV) and quaternary ammonium N (401.5 eV), respectively, indicating N doping in the sample, except that the peak at 395.0 eV can be attributed to Mo-N. From FIG. 6c, it can be seen that the 228.5 eV and 231.5 eV peaks of Mo 3d XPS spectrum are attributable to Mo 2 The Mo-C bond in C and the 229.2 eV and 232.6 eV peaks correspond to Mo 2 Mo-N in N. The Pt 4f spectrum consists of peaks at 70.7 eV and 73.9 eV, which can be attributed to metallic Pt 0 Species (fig. 6 d). The three types of characterization mutually authenticate the Pt/Mo composite electrocatalyst prepared by the invention 2 C/Mo 2 N@C-N was successfully prepared.
Pt/Mo prepared by the invention 2 C/Mo 2 N@C-N material, by ICP measurement, contains 1.58% of Pt by mass.
4. Electrochemical performance test:
taking Pt/Mo prepared by 2 mg 2 C/Mo 2 N@C-N electrocatalyst is dispersed in 4 mL isopropanol dispersant, the mixed solution is coated on the surface of a glassy carbon electrode after ultrasonic homogenization, a three-electrode system is adopted, the electrocatalytic Hydrogen (HER) performance of the catalyst is measured through an electrochemical workstation, and the test result is shown in FIG. 7, and the current density is 10 mA cm -2 When Pt/Mo 2 C/Mo 2 N@C-N (Pt content of 1.58%) had a minimum overpotential of only 13 mV, which was lower than that of commercial Pt/C (Pt content of 20%) catalysts (38 mV).
5. Pt/Mo 2 C/Mo 2 For Mo in N@C-N material 8 Regeneration and recovery of Pt:
Pt/Mo after electrochemical testing of 50 mg (after electrocatalytic hydrogen production) 2 C/Mo 2 N@C-N was dissolved in 3 mL acetonitrile, 1mL dichloromethane and 1mL H 2 O 2 （H 2 O 2 30% by mass) of the mixture, stirring 2.2h, filtering, and filteringStanding the solution in a refrigerator at 4deg.C for one week to obtain pale yellow transparent crystal Mo 8 Pt is Mo after 1 cycle 8 Pt; mo is recycled by the method of the step 3 8 Conversion of Pt to Pt/Mo 2 C/Mo 2 N@C-N, which is a catalyst after 1 cycle, was tested for electrocatalytic hydrogen production according to the procedure of step 4. And (5) recycling the regenerated product by using the method of the step (5), so that the regenerated product can be recycled for a plurality of times.
The present application performed 5 regeneration cycles and performed 1, 3 and 5 cycles of Mo 8 Pt was XRD tested and showed Mo before and after cycling 8 The crystal phase structure of Pt remains almost unchanged (see fig. 8). At the same time, for the composite catalyst Pt/Mo after 1 time, 3 times and 5 times circulation 2 C/Mo 2 N@C-N was tested for electrocatalytic hydrogen production performance (see FIG. 9). The results show that the composite catalyst Pt/Mo is subjected to five times of circulation 2 C/Mo 2 N@C-N has substantially unchanged hydrogen production performance, and has a current density of 10 mA cm -2 At this time, the overpotential was still only 13 mV.

Claims (3)

1. A preparation method of a recyclable efficient composite platinum catalyst is characterized by comprising the following steps of: comprises [ Pt II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Is used for preparing catalyst Pt/Mo 2 C/Mo 2 N@C-N preparation;
the [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The preparation method comprises the steps of mixing tetrammine platinum chloride and (C 4 H 9 N) 4 [Mo 8 O 26 ]Dissolving in water, stirring at room temperature for 24 hr, filtering to obtain yellow filtrate, standing at 4deg.C for one week to obtain pale yellow transparent crystal [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The method comprises the steps of carrying out a first treatment on the surface of the The tetrammine platinum chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]The mass ratio of (2) is 10-12:1; the mass volume ratio of the tetrammine platinum chloride to the water is 0.07-0.08 g/1 mL;
the catalyst Pt/Mo 2 C/Mo 2 N@C-N is prepared by mixing graphite phase carbon nitride with [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Adding into isopropanol, and controlling illumination intensity at 145-155mW/cm at room temperature 2 Stirring at 470-500r/min for 0.9-1.1 hr, centrifuging the obtained mixture, washing the separated solid powder with methanol three times, vacuum drying at 55-65deg.C for 1.8-2.2 hr, and calcining at 590-610 deg.C under CO atmosphere for 1.9-2.1 hr to obtain catalyst Pt/Mo 2 C/Mo 2 N@C-N；
The graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The mass ratio of (2) is 1:0.9-1.1; the mass volume ratio of the graphite phase carbon nitride to the isopropanol is 1 mg/58-62 mL.
2. The method for preparing the recyclable efficient composite platinum catalyst, which is characterized by comprising the following steps of: the mass content of Pt in the catalyst is 1.55-1.6%.
3. Use of the catalyst prepared by the process of claim 1 in electrocatalysis.
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CN113529102A (en) * 2021-07-15 2021-10-22 广东工业大学 Metal and nitrogen co-doped molybdenum carbide catalyst and preparation method and application thereof

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