CN114717600B - Preparation of carbon-supported small-particle nano metal rhenium catalyst and application of catalyst in hydrogen production by water electrolysis - Google Patents
Preparation of carbon-supported small-particle nano metal rhenium catalyst and application of catalyst in hydrogen production by water electrolysis Download PDFInfo
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- CN114717600B CN114717600B CN202210531945.0A CN202210531945A CN114717600B CN 114717600 B CN114717600 B CN 114717600B CN 202210531945 A CN202210531945 A CN 202210531945A CN 114717600 B CN114717600 B CN 114717600B
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Abstract
The invention discloses a method for preparing a carbon-supported small-particle metal rhenium catalyst, which comprises the steps of dissolving a rhenium source in a water-ethanol mixed solution, dispersing a carbon material in the mixed solution, and stirring for 10-12 h at 75-85 ℃; washing and drying the reaction product to obtain a precursor material; then spreading the precursor material between two layers of carbon paper, fixing the precursor material in a flash furnace, and after introducing protective gas, setting the electrifying time to be 3-10 s, wherein the working current is 10-20 mA, and the target temperature is 800-1200 ℃; and (3) after the flash firing is finished, obtaining the carbon-supported small-particle nano metal rhenium catalyst. According to the invention, the carbon material is used as a carrier, and the carbon-supported small-particle nano metal rhenium catalyst is obtained by an adsorption-flash burning two-step method, so that the preparation process is simple and quick, and the problems of difficult operation, time consumption and complexity of the traditional preparation method are avoided; the prepared catalyst is used in hydrolysis hydrogen production reaction, and has excellent catalytic performance and good stability.
Description
Technical Field
The invention relates to preparation of a nano metal rhenium catalyst, in particular to preparation of a carbon-supported small-particle nano metal rhenium catalyst, which is mainly used for catalyzing water electrolysis hydrogen production reaction, and belongs to the technical field of composite materials and water electrolysis hydrogen production reaction.
Background
The large-scale exploitation and combustion of fossil fuels bring about serious energy crisis and environmental problems, and the development and utilization of new energy have become a necessary solution. Hydrogen is a highly desirable fuel as a highly efficient, clean energy source. The electrolysis of water to produce hydrogen by electrocatalytic technology is a widely used means at present, and a high-efficiency catalyst is needed to promote the dissociation process of water and promote the production of hydrogen. The existing hydrogen evolution catalysts such as platinum-carbon catalysts are expensive, and limit large-scale application and popularization.
The transition metal is widely distributed and relatively low in price, so that the transition metal-based catalyst has great development potential. At present, the research on transition metal-based catalysts is very extensive, such as nickel, cobalt, tungsten, molybdenum and the like. Rhenium-based catalysts are also a very potential transition metal catalyst. However, the pure metal rhenium block has poor electrocatalytic hydrogen evolution performance, and a rhenium/carbon mixture can be obtained by utilizing a carbon carrier, but the performance of the pure metal rhenium block is still deficient, and a certain lifting space exists. The small particle Nano-sized metallic rhenium may exhibit better catalytic capability, but the preparation process of the small particle Nano-sized material is difficult to control, for example, rhenium disulfide, which requires precise manual control, and is difficult to quickly and simply realize in a short time (Nano Energy, 2019, 58:660-668), which is complicated and time-consuming. Therefore, the rapid and convenient preparation of the small-particle nano metal rhenium is an urgent technology, and the practical application of the rhenium-based catalyst can be greatly expanded.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-supported small-particle metal rhenium catalyst, which realizes simple and rapid preparation of carbon-supported small-particle metal rhenium nanoparticles by an adsorption-flash two-step method so as to solve the problem of complex preparation process of the traditional small-particle metal rhenium;
the invention also aims to research the performance of the carbon-supported small-particle metal rhenium catalyst for catalyzing water to prepare hydrogen so as to expand the application of the catalyst.
1. Preparation of carbon-supported small particle metal rhenium catalyst
According to the method for preparing the carbon-supported small-particle metal rhenium catalyst, a rhenium source is firstly dissolved in a water-ethanol mixed solution, then a carbon material is dispersed in the mixed solution, and the mixture is stirred for 10-12 hours at 75-85 ℃; washing and freeze-drying the reaction product to obtain a precursor material; then spreading the precursor material between two layers of carbon paper, fixing the precursor material in a flash furnace, and after introducing protective gas, setting the electrifying time to be 3-10 s, wherein the working current is 10-20 mA, and the target temperature is 800-1200 ℃; and after the flash firing is finished, the carbon-supported small-particle nano metal rhenium catalyst is obtained and is marked as Re/CNTs.
The rhenium source is rhenium pentachloride, ammonium perrhenate, rhenium disulfide and the like; the carbon material is carbon nano tube, carbon nano cage, graphene oxide and the like; the mass ratio of the rhenium source to the carbon material is 7:1-14:1.
In the water-ethanol mixed solution, the volume percentage of ethanol is 89-91%.
And freeze-drying or vacuum drying at 55-65 ℃ is adopted for drying.
The shielding gas is argon or nitrogen.
FIG. 1 is a TEM image of the prepared carbon nanotube-supported small particle rhenium metal Re/CNTs catalyst. TEM shows that deep black small particles grow on the carbon nano tube, and the diameter of the small particles can reach about 5nm at minimum.
FIG. 2 is an XRD pattern of the prepared carbon nanotube-supported small particle rhenium metal Re/CNTs catalyst. The XRD pattern shows that the metal particles in the catalyst are rhenium metal.
2. Catalytic Activity of carbon-supported Small particle Metal rhenium catalysts
The catalyst Re/CNTs (prepared in yi example 1) is coated on a working electrode, and current is introduced into the working electrode in a solvent liquid phase environment to carry out catalytic hydrogen production reaction, wherein the solvent is sulfuric acid solution of 0.5 mol/L or potassium hydroxide solution of 1 mol/L.
FIG. 3 shows the results of the catalytic activity and stability test of Re/CNTs catalyst. As can be seen from FIG. 3, the catalyst Re/CNTs was in an acidic environment, 10mA/cm 2 The overpotential is 99mV at current density, and has excellent catalytic activity. In alkaline environment, current density is 10mA/cm 2 89mV shows that the catalyst has better catalytic activity in alkaline environment and extremely small performance attenuation after 10000 cycles, thus proving that the catalyst has good stability.
In summary, the method utilizes the carbon material as the carrier, and after adsorbing the rhenium metal source, the method rapidly flashes in the flash furnace to realize the rapid conversion from the precursor to the catalyst within the second time scale, thereby obtaining the carbon-supported small-particle nano metal rhenium catalyst, having simple and rapid preparation process and avoiding the problems of difficult operation, time consumption and complexity of the traditional preparation method; the prepared catalyst is used in hydrolysis hydrogen production reaction, and has excellent catalytic performance and good stability.
Drawings
FIG. 1 is a TEM image of carbon nanotube-supported small particle rhenium metal Re/CNTs catalysts.
FIG. 2 is an XRD phase characterization of carbon nanotube-supported small particle rhenium metal Re/CNTs catalysts.
FIG. 3 shows the results of the catalytic activity and stability test of carbon nanotube-supported small particle rhenium metal Re/CNTs catalysts.
Detailed Description
The preparation of the catalyst Re/CNTs of the present invention and its activity in hydrolysis hydrogen production reactions are further illustrated by the following examples.
Example 1
90mg of rhenium pentachloride was dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of carbon nanotubes were dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. And (5) washing and freeze-drying. About 20mg of precursor was obtained;
spreading 5mg of precursor on the carbon paper, covering another piece of carbon paper, and placing the double-layer carbon paper with the precursor on a platform in the inner cavity of the flash furnace for fixing. Under the protection of argon atmosphere, setting working current of 14mA, target temperature of 800 ℃ and electrifying time of 4s. Obtaining the carbon nano tube loaded small particle nano metal rhenium catalyst Re/CNTs after 4 s;
coating Re/CNTs catalyst on the working electrode, and introducing current in 0.5 mol/L sulfuric acid solution phase environment to catalyze hydrogen production reaction, 10mA/cm 2 At current density, the overpotential is 99 mV; introducing current into a 1 mol/L potassium hydroxide solution phase environment to perform catalytic hydrogen production reaction, wherein the current is 10mA/cm 2 At current density, the overpotential was 89 mV.
Example 2
70mg of rhenium pentachloride is dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of carbon nano tubes are dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. And (5) washing and freeze-drying. 5mg of precursor is taken to be clamped between two pieces of carbon paper, and under the protection of argon atmosphere, the working current is set to 14mA, the target temperature is 800 ℃, and the electrifying time is set to 4s. Example 2 was obtained. In an acidic environment, 10mA/cm 2 At current density, the overpotential was 136mV. In alkaline environment, current density is 10mA/cm 2 At 113mV.
Example 3
90mg of rhenium pentachloride is dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of graphene oxide is dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. And (5) washing and freeze-drying. 5mg of precursor is clamped between two pieces of carbon paper, and under the protection of argon atmosphere, the working current is set to be 14mA,Target temperature 800 ℃, and energizing time 4s. Example 3 was obtained. In an acidic environment, 10mA/cm 2 At current density, the overpotential was 117mV. In alkaline environment, current density is 10mA/cm 2 103mV.
Example 4
90mg of rhenium pentachloride was dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of carbon nanotubes were dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. Washed and dried in a vacuum oven at 60 ℃. 5mg of precursor is taken to be clamped between two pieces of carbon paper, and under the protection of argon atmosphere, the working current is set to 14mA, the target temperature is 800 ℃, and the electrifying time is set to 4s. Example 4 was obtained. In an acidic environment, 10mA/cm 2 At current density, the overpotential was 101mV. In alkaline environment, current density is 10mA/cm 2 93mV.
Example 5
60mg of ammonium perrhenate was dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of carbon nanotubes were dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. And (5) washing and freeze-drying. 5mg of precursor is taken to be clamped between two pieces of carbon paper, and under the protection of nitrogen atmosphere, the working current is set to 14mA, the target temperature is 800 ℃, and the electrifying time is set to 4s. Example 4 was obtained. In an acidic environment, 10mA/cm 2 At current density, the overpotential was 104mV. In alkaline environment, current density is 10mA/cm 2 97mV.
Example 6
90mg of rhenium pentachloride was dissolved in a mixed solution of 20ml of ethanol and 2ml of water, and 8mg of carbon nanotubes were dispersed in the solution. The mixture was stirred overnight at 80℃in an oil bath. And (5) washing and freeze-drying. 5mg of precursor is taken to be clamped between two pieces of carbon paper, and under the protection of argon atmosphere, the working current is set to 13mA, the target temperature is 850 ℃, and the electrifying time is 5s. Example 2 was obtained. In an acidic environment, 10mA/cm 2 At current density, the overpotential was 142mV. In alkaline environment, current density is 10mA/cm 2 127mV.
Claims (5)
1. A preparation method of a carbon-supported small-particle metal rhenium catalyst comprises the steps of firstly dissolving a rhenium source in a water-ethanol mixed solution, dispersing a carbon material in the mixed solution, and stirring for 10-12 hours at 75-85 ℃; washing and drying the reaction product to obtain a precursor material; then spreading the precursor material between two layers of carbon paper, fixing the precursor material in a flash furnace, and after introducing protective gas, setting the electrifying time to be 3-10 s, wherein the working current is 10-20 mA, and the target temperature is 800-1200 ℃; after the flash firing is finished, the carbon-supported small-particle nano metal rhenium catalyst is obtained; the rhenium source is rhenium pentachloride, ammonium perrhenate and rhenium disulfide, the carbon material is carbon nano tubes, carbon nano cages and graphene oxide, and the mass ratio of the rhenium source to the carbon material is 7:1-14:1.
2. The method for preparing the carbon-supported small-particle metal rhenium catalyst as claimed in claim 1, wherein: in the water-ethanol mixed solution, the volume percentage of ethanol is 89-91%.
3. The method for preparing the carbon-supported small-particle metal rhenium catalyst as claimed in claim 1, wherein: and freeze-drying or vacuum drying at 55-65 ℃ is adopted for drying.
4. The method for preparing the carbon-supported small-particle metal rhenium catalyst as claimed in claim 1, wherein: the shielding gas is argon or nitrogen.
5. The use of the carbon-supported small particle metal rhenium catalyst prepared by the method of claim 1 in a catalytic hydrolysis hydrogen production reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101248005A (en) * | 2005-06-23 | 2008-08-20 | Grdc有限责任公司 | Effective hydrogen production |
| CN108993483A (en) * | 2017-06-06 | 2018-12-14 | 神华集团有限责任公司 | A kind of support type catalyst with base of molybdenum and preparation method thereof |
| CN114210345A (en) * | 2021-11-19 | 2022-03-22 | 天津大学 | Homologous heterogeneous interface structure composite material and preparation method thereof |
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| KR101446116B1 (en) * | 2012-09-18 | 2014-10-06 | 한화케미칼 주식회사 | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101248005A (en) * | 2005-06-23 | 2008-08-20 | Grdc有限责任公司 | Effective hydrogen production |
| CN108993483A (en) * | 2017-06-06 | 2018-12-14 | 神华集团有限责任公司 | A kind of support type catalyst with base of molybdenum and preparation method thereof |
| CN114210345A (en) * | 2021-11-19 | 2022-03-22 | 天津大学 | Homologous heterogeneous interface structure composite material and preparation method thereof |
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