CN117772261B - g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst - Google Patents
g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst Download PDFInfo
- Publication number
- CN117772261B CN117772261B CN202410212052.9A CN202410212052A CN117772261B CN 117772261 B CN117772261 B CN 117772261B CN 202410212052 A CN202410212052 A CN 202410212052A CN 117772261 B CN117772261 B CN 117772261B
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- supported
- ptco
- sheet material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 229910002837 PtCo Inorganic materials 0.000 title claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 150000003057 platinum Chemical class 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of photocatalyst preparation, and particularly relates to an application of a g-C 3N4 supported PtCo diatomic photocatalyst as an ammonia borane hydrolysis hydrogen production catalyst, wherein the g-C 3N4 supported PtCo diatomic photocatalyst preparation method comprises the following steps: the preparation method comprises the steps of preparing a g-C 3N4 nano sheet material by a thermal polymerization method, dispersing the g-C 3N4 nano sheet material in a mixed solution filled with water and ethanol, adding cobalt salt and sodium borohydride, carrying out light reduction, separating, washing and vacuum drying to obtain a g-C 3N4 supported Co single-atom nano sheet material, dispersing the Co single-atom nano sheet material in the mixed solution filled with water and ethanol, adding platinum salt, carrying out light reduction, separating, washing and vacuum drying to obtain the g-C 3N4 supported PtCo double-atom photocatalyst. The invention prepares the PtCo diatomic photocatalyst supported by g-C 3N4 by two-step photo-reduction, and realizes the highest known catalytic activity and the highest cycling stability of ammonia borane.
Description
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to an application of a g-C 3N4 supported PtCo diatomic photocatalyst as a catalyst for producing hydrogen by ammonia borane hydrolysis.
Background
The current energy structure with fossil energy as a main body causes great pressure on the environment, which causes serious environmental pollution problems, ever-increasing energy crisis and ecological health threats. Therefore, changing the current energy structure, reducing the dependence on fossil energy, and actively developing and popularizing the application of renewable energy becomes a key way for solving the series of problems. Among the many renewable energy sources, hydrogen energy is considered as a powerful competitor to future energy sources due to its cleanliness, high energy density, and renewable nature, and is one of the ideal choices for achieving renewable energy utilization. However, the problem of storing and transporting hydrogen energy has been a major obstacle limiting its use on a large scale. In recent years, researchers have found that ammonia borane has suitable thermodynamic properties and has a high hydrogen storage density of 19.6 wt% while being stable at room temperature for convenient storage and transportation. Nevertheless, the problems of high catalyst cost, slow kinetic reaction and high energy input remain in the hydrolysis hydrogen production process of ammonia borane.
Defects and deficiencies of the prior art:
1. in the process of producing hydrogen by ammonia borane hydrolysis, a large amount of energy is consumed by pyrolysis, and the hydrogen release kinetics process of the metal catalyst is slow, so that the overall reaction efficiency is low.
2. Conventional nanoparticle catalysts have a limitation in that atoms react mainly at the surface of the particles, and thus their atom utilization efficiency is low. This results in the need for more particulate catalyst in practical applications to achieve the desired catalytic activity, adding significant cost to the catalysis.
Compared with the traditional granular catalyst, the monoatomic catalyst has obvious advantages in the aspect of improving the atom utilization rate, but has complex preparation technology and poor catalytic stability, and the problems also need to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an application of a g-C 3N4 supported PtCo diatomic photocatalyst as an ammonia borane hydrolysis hydrogen production catalyst, wherein the g-C 3N4 supported PtCo diatomic photocatalyst is obtained by a two-step photo-reduction method.
The invention is realized by the following technical scheme:
The invention firstly provides an application method of a g-C 3N4 supported PtCo diatomic photocatalyst as an ammonia borane hydrolysis hydrogen production catalyst.
G-C 3N4 is taken as an excellent photocatalyst, can effectively absorb light energy and provides enough energy to drive catalytic reaction; the PtCo diatomic structure is introduced, so that the activity of the catalyst is greatly improved, higher atom utilization rate is realized through accurate atomic arrangement, and the catalysis cost is reduced; the synergistic effect of Pt and Co with a diatomic structure further enhances the stability of the catalyst and ensures the durability in the reaction process. These advantages make the g-C 3N4 supported PtCo diatomic photocatalyst of the invention exhibit excellent photocatalytic ammonia borane hydrogen production performance.
Further, the preparation method of the g-C 3N4 supported PtCo diatomic photocatalyst comprises the following steps:
(1) Dispersing g-C 3N4 nano-sheet material in a container filled with a water-ethanol mixed solution, performing ultrasonic treatment at room temperature for 0.5-1 h, and stirring at a rotating speed of 1000-1500 rpm for 1-3 h to obtain a solution a; the concentration of the g-C 3N4 nano sheet material in the solution a is 20-65 mu mol/mL;
(2) Adding cobalt nitrate and sodium borohydride into the solution a, wherein the concentration of the cobalt nitrate in the solution a is 1-3 mu mol/mL, the concentration of the sodium borohydride is 0.2-0.5 mu mol/mL, stirring at the room temperature for 1-3 hours at the rotating speed of 1000-1500 rpm, and then placing under a xenon lamp for illumination; after illumination is finished, separating out a sample, cleaning, and vacuum drying to obtain a Co nano sheet material supported by g-C 3N4;
(3) Dispersing the Co nano-sheet material supported by g-C 3N4 in a container filled with a water-ethanol mixed solution, performing ultrasonic treatment at room temperature for 0.5-1 h, and stirring at a rotating speed of 1000-1500 rpm for 1-3 h to obtain a solution b; the concentration of the Co nano sheet material supported by the g-C 3N4 in the solution b is 20-65 mu mol/mL;
(4) And (3) adding chloroplatinic acid into the solution b, wherein the concentration of the chloroplatinic acid in the solution b is 0.3-1 mu mol/mL, stirring at room temperature for 2-3 h at a rotating speed of 1000-1500 rpm, illuminating under a xenon lamp, separating out a sample after illumination is finished, cleaning, and drying in vacuum to obtain the PtCo diatomic photocatalyst supported by g-C 3N4.
Further, the g-C 3N4 nano-sheet material is 1-2 nm thick and is prepared by a thermal polymerization method.
Further, the preparation method of the g-C 3N4 nano sheet material comprises the following steps: placing urea into a crucible with a cover, heating to 550-600 ℃ in a muffle furnace at a speed of 2-3 ℃/min, sintering for 240-300 min, and naturally cooling to room temperature; grinding the obtained product into powder, heating to 480-520 ℃ at the speed of 10-20 ℃/min, sintering for 120-180 min, naturally cooling to room temperature, and collecting a sample to obtain the g-C 3N4 nano sheet material.
Further, the volume ratio of water to ethanol in the water-ethanol mixed solution is 4:1-8:1.
Further, the illumination time in the step (2) and the step (4) is 20-40 min, the illumination wavelength is 420-800 nm, the distance between the light source and the liquid level is 10-25 cm, and the liquid level optical power is 80-150 mu W/cm 2. Preferably, the illumination time is 25-30 min, the distance between the light source and the liquid surface is 12-15 cm, and the light power of the liquid surface is 100-110 mu W/cm 2.
Further, the time of the vacuum drying in the step (2) and the step (4) is 2-4 hours, the vacuum degree is 5 x 10 -2~3*10-3 Kpa, and the temperature is 40-60 ℃.
The invention has the advantages and positive effects that:
The invention aims at the problems of high energy input and low metal catalytic activity of pyrolysis in the existing ammonia borane hydrolysis hydrogen production technology, in particular to the problems of complex preparation process and poor cycle stability of a single-atom catalyst. The invention prepares the PtCo diatomic photocatalyst supported by g-C 3N4 by a simple two-step photo-reduction preparation method, and realizes the highest known catalytic activity (conversion frequency: 3053: mol H2·molpt -1·min-1) and the highest cycling stability (conversion number: 307982 mol H2·molPt −1) of ammonia borane.
Drawings
FIG. 1 is an electron microscope image of PtCo SA/CN photocatalyst, wherein a in FIG. 1 is a high resolution projection electron microscope (HRTEM) image; b in fig. 1 is a spherical aberration correcting high angle annular dark field scanning transmission electron microscope (AC-STEM);
FIG. 2 shows the near-edge spectrum and the extended-edge spectrum of the L 3 side of the Pt element in the PtCo SA/CN photocatalyst;
FIG. 3 is a near-edge spectrum and an extended-edge spectrum of the K-edge of Co element in PtCo SA/CN photocatalyst;
FIG. 4 is an X-ray diffraction pattern (XRD) of CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalyst powders;
FIG. 5 is an X-ray photoelectron spectrometer (XPS) spectrum of Pt and Co in the PtCo SA/CN photocatalyst, wherein a in FIG. 5 is a spectrum of an X-ray photoelectron spectrometer (XPS) spectrum of Pt element of the PtCo SA/CN photocatalyst; FIG. 5 b is a spectrum of an X-ray photoelectron spectrometer (XPS) of the Co element of the PtCo SA/CN photocatalyst;
FIG. 6 is a graph of ammonia borane hydrogen production time for CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalysts;
FIG. 7 is a graph showing the shift frequency (TOF) of ammonia borane production by CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalysts.
Detailed Description
For a better understanding of the present invention, the present invention will be described in further detail below with reference to the accompanying drawings. The features in the cases can be combined with each other without conflict. The starting materials used in the examples below were all commercially available analytically pure starting materials.
Example 1
A preparation method of a g-C 3N4 supported PtCo diatomic (PtCo SA/CN) photocatalyst comprises the following specific operations:
(1) Preparing a g-C 3N4 nano sheet material (CN) with the thickness of 1-2 nm by using a thermal polymerization method: 10 g urea was placed in a covered crucible, heated to 550 ℃ in a muffle furnace at a rate of 2.5 ℃/min, sintered 240: 240 min, and naturally cooled to room temperature. Grinding the obtained product into powder, heating to 500 ℃ at the speed of 10 ℃/min, sintering to 120 min, naturally cooling to room temperature, and collecting a sample to obtain a g-C 3N4 nanosheet material (CN);
(2) Dispersing 300 mg g-C 3N4 nanosheet material (CN) in a beaker filled with a mixed solution of 40 mL water and 10 mL ethanol, performing ultrasonic treatment at room temperature for 1h, and stirring at a rotation speed of 1500 rpm for 3 h to obtain a solution a;
(3) Adding 127 mu mol of cobalt nitrate and 20 mu mol of sodium borohydride into the solution a, continuously stirring for 3 hours at a rotating speed of 1500 rpm, then placing under a xenon lamp for illumination of 30 min, wherein the wavelength of illumination light needs to be controlled within a range of 420-800 nm, and the beaker mouth needs to be completely covered by transparent glass; the light source is 15 cm from the liquid level, and the liquid level optical power is 100 mu W/cm 2; after illumination, separating out a sample by adopting a suction filtration mode, flushing the sample for 3 times by using ethanol after suction filtration, removing residual metal salt solution, and vacuum-drying 4h (the vacuum degree is 3 x 10 -3 Kpa, and the temperature is 60 ℃), thereby obtaining a Co nano sheet material supported by g-C 3N4;
(4) Dispersing 300 mg dried g-C 3N4 supported Co nano-sheet material in a mixed solution of 40 mL water and 10 mL ethanol, performing ultrasonic treatment at room temperature for 1h, and stirring at a rotating speed of 1500 rpm for 3 h to obtain a solution b;
(5) Adding chloroplatinic acid of 15 mu mol into the solution b, stirring at a rotation speed of 1500 rpm at room temperature for 3 h, and then carrying out illumination of 30 min under a xenon lamp, wherein the wavelength of illumination light is controlled within a range of 420-800 nm, and the beaker mouth is completely covered by light-transmitting glass; the light source is 15 cm from the liquid level, and the liquid level optical power is 100 mu W/cm 2; after illumination, a sample is separated by adopting a suction filtration mode, the sample is washed by ethanol for 3 times after the suction filtration, residual metal salt solution is removed, and 4h (the vacuum degree is 3 x 10 -3 Kpa and the temperature is 60 ℃) is dried in vacuum, so that the g-C 3N4 supported PtCo diatomic nanosheet material, namely the g-C 3N4 supported PtCo diatomic (PtCo SA/CN) photocatalyst is obtained.
FIG. 1 is an electron microscope image of PtCo SA/CN photocatalyst prepared in example 1, wherein a in FIG. 1 is a high resolution projection electron microscope (HRTEM) image; b in fig. 1 is a spherical aberration correcting scanning transmission electron microscope (AC-STEM). The high-resolution projection electron microscope (HRTEM) image shows that no metal nano particles appear on the surface of the g-C 3N4, and the spherical aberration correction scanning transmission electron microscope image shows the random distribution of Pt and Co single atoms, which proves that the photocatalyst prepared by the invention is in a double-atom state and no metal particles or clusters exist.
Fig. 2 shows near-edge spectrum and extended-edge spectrum tests of the L 3 side of the Pt element in the PtCo SA/CN photocatalyst prepared in example 1, fig. 3 shows near-edge spectrum and extended-edge spectrum tests of the K side of the Co element in the PtCo SA/CN photocatalyst prepared in example 1, and it can be seen from fig. 2 and 3 that both the Pt and Co elements in the catalyst prepared in example 1 are in a single atomic state.
The inductive coupling plasma test was performed on the PtCo SA/CN photocatalyst prepared in example 1, and the results are shown in Table 1, wherein the Pt element loading amount in the PtCo SA/CN photocatalyst is 0.92 wt%, and the Co element loading amount is 2.41 wt%.
TABLE 1 PtCo SA/CN inductively coupled plasma test to obtain Pt and Co loadings
FIG. 5 is an X-ray photoelectron spectrometer (XPS) spectrum of Pt and Co in the PtCo SA/CN photocatalyst prepared in example 1, wherein a in FIG. 5 is a spectrum of an X-ray photoelectron spectrometer (XPS) spectrum of Pt element in the PtCo SA/CN photocatalyst; b in fig. 5 is a spectrum of an X-ray photoelectron spectrometer (XPS) of Co element in the PtCo SA/CN photocatalyst, the spectrum showing non-zero valence chemical states of Pt and Co element.
Comparative example 1
A preparation method of a g-C 3N4 supported Pt atom (Pt SA/CN) photocatalyst, which comprises the following specific operations:
(1) Preparing a g-C 3N4 nano sheet material (CN) with the thickness of 1-2 nm by using a thermal polymerization method: the specific preparation method is the same as in example 1.
(2) Dispersing 300 mg g-C 3N4 nanosheet material (CN) in a beaker filled with a mixed solution of 40mL water and 10 mL ethanol, carrying out ultrasonic treatment at room temperature for 1h, stirring for 3 h at a rotating speed of 1500 rpm, adding 50 mu mol of chloroplatinic acid, continuously stirring for 3 h at a rotating speed of 1500 rpm, carrying out illumination on a sample under a xenon lamp for 30min, controlling the wavelength of the illumination light within a range of 420-800 nm, and completely covering the mouth of the beaker with transparent glass. The light source is spaced from the liquid surface 15 cm and the liquid surface optical power is 100 mu W/cm 2. And after illumination is finished, separating out the sample by adopting a suction filtration mode. After suction filtration, the samples were rinsed 3 times with ethanol to remove residual metal salt solution. 4h (vacuum 3 x 10 -3 Kpa, temperature 60 ℃) were dried under vacuum and the resulting g-C 3N4 supported Pt atom (Pt SA/CN) photocatalyst was collected.
The Pt SA/CN photocatalyst prepared in comparative example 1 was subjected to inductively coupled plasma test, and the result is shown in table 2, in which the Pt element loading amount is 3.33 wt%.
TABLE 2 Pt SA/CN inductive coupling plasma test to obtain Pt loadings
Comparative example 2
A preparation method of a g-C 3N4 supported Co atom (Co SA/CN) photocatalyst comprises the following specific operations:
(1) Preparing a g-C 3N4 nano sheet material (CN) with the thickness of 1-2 nm by using a thermal polymerization method: the specific preparation method is the same as in example 1.
(2) 300 G-C 3N4 nano-sheet material of mg is dispersed in a beaker filled with a mixed solution of 40 mL water and 10 mL ethanol, ultrasonically stirred at room temperature for 1h, then stirred at 1500 rpm for 3 h, then 150 mu mol of cobalt nitrate and 20 mu mol of sodium borohydride are added, and the rotation speed for 3 h is continued at 1500 rpm. And then carrying out 30 min of illumination on the sample under a xenon lamp, wherein the wavelength of the illumination light is controlled within the range of 420-800 nm, and the beaker mouth is completely covered by light-transmitting glass. The light source is spaced from the liquid surface 15 cm and the liquid surface optical power is 100 mu W/cm 2. And after illumination is finished, separating out the sample by adopting a suction filtration mode. After suction filtration, the samples were rinsed 3 times with ethanol to remove residual metal salt solution. And vacuum drying 4h (vacuum degree is 3 x 10 -3 Kpa, temperature is 60 ℃), and collecting the obtained g-C 3N4 supported Co atom (Co SA/CN) photocatalyst.
The Co SA/CN photocatalyst prepared in comparative example 2 was subjected to inductively coupled plasma test, and the Co element loading in the Co SA/CN photocatalyst was 3.33 wt% as shown in Table 3.
TABLE 3 Co SA/CN inductively coupled plasma test to obtain Co loading
FIG. 4 is an X-ray diffraction (XRD) pattern of CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalyst powder, showing that only standard diffraction peaks corresponding to (100) and (002) crystal planes of g-C 3N4 appear in the pattern, while no metal diffraction peaks of Pt and Co are observed in the pattern.
Application example
The photocatalytic ammonia borane hydrogen production performance research comprises the following specific steps: 5 mg CN, 5 mg Pt SA/CN, 5 mg Co SA/CN and 5 mg PtCo SA/CN photocatalysts are respectively dispersed in 5 mL water, are ultrasonically treated to be milky suspension in a photocatalytic tube, 18.48 mg (0.6 mmol) ammonia borane is added under 298K normal pressure, then the catalytic system is sealed, photocatalysis is initiated by irradiation of LED white light with the power density of 180 mu W/cm 2, the temperature of the reaction system is controlled to be 25 ℃ (+/-0.5 ℃), the yield of hydrogen is quantified by utilizing a drainage method, the time is consumed for 2.5 min, and 1.8 mmol of hydrogen is generated. The catalytic activity is shown in FIG. 6 and FIG. 7.
Fig. 6 shows the time curves of ammonia borane hydrogen production of CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalysts, fig. 6 shows that PtCo SA/CN exhibits optimal catalytic performance, fig. 7 shows the conversion frequency (TOF) of ammonia borane hydrogen production of CN, pt SA/CN, co SA/CN, ptCo SA/CN photocatalysts, fig. 7 shows that PtCo SA/CN catalyst realizes 3053 mol H2·molpt -1·min-1, which is a world record value under the current normal temperature differential pressure condition.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Claims (5)
- The application of 1.g-C 3N4 supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst is characterized in that the preparation method of g-C 3N4 supported PtCo diatomic photocatalyst comprises the following steps:(1) Dispersing g-C 3N4 nano-sheet material in a container filled with a water-ethanol mixed solution, performing ultrasonic treatment at room temperature for 0.5-1 h, and stirring for 1-3 h to obtain a solution a; the concentration of the g-C 3N4 nano sheet material in the solution a is 20-65 mu mol/mL; the thickness of the g-C 3N4 nano sheet material is 1-2 nm, and the material is prepared by adopting a thermal polymerization method;(2) Adding cobalt nitrate and sodium borohydride into the solution a, wherein the concentration of the cobalt nitrate in the solution a is 1-3 mu mol/mL, the concentration of the sodium borohydride is 0.2-0.5 mu mol/mL, stirring at room temperature for 1-3 h, and then placing under a xenon lamp for illumination; after illumination is finished, separating out a sample, cleaning, and vacuum drying to obtain a Co nano sheet material supported by g-C 3N4;(3) Dispersing the Co nano-sheet material supported by g-C 3N4 in a container filled with a water-ethanol mixed solution, performing ultrasonic treatment at room temperature for 0.5-1 h, and stirring for 1-3 h to obtain a solution b; the concentration of the Co nano sheet material supported by the g-C 3N4 in the solution b is 20-65 mu mol/mL;(4) And adding chloroplatinic acid into the solution b, wherein the concentration of the chloroplatinic acid in the solution b is 0.3-1 mu mol/mL, stirring for 2-3 hours at room temperature, illuminating under a xenon lamp, separating out a sample after illumination is finished, cleaning, and drying in vacuum to obtain the PtCo diatomic photocatalyst supported by g-C 3N4.
- 2. The use according to claim 1, wherein the preparation method of the g-C 3N4 nanosheet material is: the urea is placed into a crucible, heated to 550-600 ℃ in a muffle furnace at a speed of 2-3 ℃/min, sintered for 240-300 min, and naturally cooled to room temperature; grinding the obtained product into powder, heating to 480-520 ℃ at the speed of 10-20 ℃/min, sintering for 120-180 min, naturally cooling to room temperature, and collecting a sample to obtain the g-C 3N4 nano sheet material.
- 3. The use according to claim 1, wherein the volume ratio of water to ethanol in the water-ethanol mixed solution is 4:1-8:1.
- 4. The use according to claim 1, wherein the illumination time in step (2) and step (4) is 20-40 min, the illumination wavelength is 420-800 nm, the light source is 10-25 cm from the liquid surface, and the liquid surface optical power is 80-150 μw/cm 2.
- 5. The method of claim 1, wherein the vacuum drying in step (2) and step (4) is performed for 2-4 hours at a vacuum of 5 x 10 -2~3×10-3 KPa and a temperature of 40-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410212052.9A CN117772261B (en) | 2024-02-27 | 2024-02-27 | g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410212052.9A CN117772261B (en) | 2024-02-27 | 2024-02-27 | g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117772261A CN117772261A (en) | 2024-03-29 |
| CN117772261B true CN117772261B (en) | 2024-04-26 |
Family
ID=90394910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410212052.9A Active CN117772261B (en) | 2024-02-27 | 2024-02-27 | g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117772261B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560131A (en) * | 2019-09-18 | 2019-12-13 | 安徽工业大学 | Method for dehydrogenating ammonia borane by visible light catalysis of CoPt nanosheet catalyst |
| CN114904574A (en) * | 2022-06-23 | 2022-08-16 | 江苏大学 | Platinum monoatomic/cluster modified photosensitization system and preparation method and application thereof |
| CN115532298A (en) * | 2022-10-13 | 2022-12-30 | 天津理工大学 | Preparation method of diatom cluster photocatalyst |
| CN116474811A (en) * | 2023-04-24 | 2023-07-25 | 广东奥柏科技有限公司 | High-efficiency bimetallic catalyst and application thereof in ammonia borane alcoholysis hydrogen production |
| CN116550357A (en) * | 2023-02-15 | 2023-08-08 | 浙江农林大学 | Preparation method and application of g-C3N4 nanosheet photocatalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102232964B1 (en) * | 2019-01-04 | 2021-03-29 | 서울대학교산학협력단 | Single atom catalyst and method of forming the same |
-
2024
- 2024-02-27 CN CN202410212052.9A patent/CN117772261B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560131A (en) * | 2019-09-18 | 2019-12-13 | 安徽工业大学 | Method for dehydrogenating ammonia borane by visible light catalysis of CoPt nanosheet catalyst |
| CN114904574A (en) * | 2022-06-23 | 2022-08-16 | 江苏大学 | Platinum monoatomic/cluster modified photosensitization system and preparation method and application thereof |
| CN115532298A (en) * | 2022-10-13 | 2022-12-30 | 天津理工大学 | Preparation method of diatom cluster photocatalyst |
| CN116550357A (en) * | 2023-02-15 | 2023-08-08 | 浙江农林大学 | Preparation method and application of g-C3N4 nanosheet photocatalyst |
| CN116474811A (en) * | 2023-04-24 | 2023-07-25 | 广东奥柏科技有限公司 | High-efficiency bimetallic catalyst and application thereof in ammonia borane alcoholysis hydrogen production |
Non-Patent Citations (1)
| Title |
|---|
| "Highly efficient hydrolysis of ammonia borane using ultrafine bimetallic RuPd nanoalloys encapsulated in porous g-C3N4";Yong-Ting Li等;《Fuel》;20201001;第277卷;1-11 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117772261A (en) | 2024-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | A review on H2 production through photocatalytic reactions using TiO2/TiO2-assisted catalysts | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN111185210A (en) | Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof | |
| CN112774682B (en) | Aluminum-cobalt composite catalyst and preparation method and application thereof | |
| Liu et al. | TiO 2/gC 3 N 4 heterojunction hollow porous nanofibers as superior visible-light photocatalysts for H 2 evolution and dye degradation | |
| Liu et al. | Deposition of CdS and Au nanoparticles on TiO2 (B) spheres towards superior photocatalytic performance | |
| CN113058601B (en) | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting | |
| CN111715287B (en) | ZIF-67/GO photocatalytic-photothermal composite film and preparation method and application thereof | |
| CN117772261B (en) | g-C3N4Application of supported PtCo diatomic photocatalyst as ammonia borane hydrolysis hydrogen production catalyst | |
| CN109847753B (en) | Porous Co @ C nano material and preparation method and application thereof | |
| CN115518690B (en) | Cu (copper) alloy 7 S 4 -MOF composite material and preparation method and application thereof | |
| Jiang et al. | A living photocatalyst derived from CaCu3Ti4O12 for CO2 hydrogenation to methanol at atmospheric pressure | |
| CN113559856B (en) | Preparation method of barium titanate/silver iodate heterojunction photocatalyst | |
| CN115090318A (en) | Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area | |
| CN113398968A (en) | MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof | |
| CN113117672A (en) | Branched alkane reforming photo-thermal catalyst and preparation method and application thereof | |
| CN110787821A (en) | Graphite-phase nitrogen carbide/cadmium sulfide photocatalytic nanocomposite material with burr-like structure and preparation method and application thereof | |
| CN115193466B (en) | Bimetallic hydrogen evolution catalyst and preparation method thereof | |
| CN115318308B (en) | Simple solvothermal method for preparing In (OH) 3 /CdIn 2 S 4 Composite catalyst | |
| CN114797930B (en) | Catalyst for efficiently degrading organic matters under natural light and preparation method thereof | |
| CN112756002B (en) | Element-doped transition metal sulfide ultrathin sheet and preparation and application thereof | |
| CN116333308B (en) | Donor-pi-acceptor type covalent triazine framework material and preparation method and application thereof | |
| RU2800948C1 (en) | Catalyst, method for its preparation, and method for photocatalytic production of hydrogen | |
| CN117443413A (en) | SrWO 4 /MoS 2 Photocatalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |