CN109453742B - Preparation method of dehydrogenation material - Google Patents
Preparation method of dehydrogenation material Download PDFInfo
- Publication number
- CN109453742B CN109453742B CN201811406598.9A CN201811406598A CN109453742B CN 109453742 B CN109453742 B CN 109453742B CN 201811406598 A CN201811406598 A CN 201811406598A CN 109453742 B CN109453742 B CN 109453742B
- Authority
- CN
- China
- Prior art keywords
- parts
- temperature
- solution
- alkynyl
- weight
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a dehydrogenation material, which comprises the following steps: oxidizing a carbon nano material, and then activating and alkynylating to prepare an alkynylated carbon nano material with a hydrogen storage function; dispersing the alkynyl carbon nano material in a solvent, adding a noble metal salt solution, heating and stirring; and adding a reducing agent solution, and continuously stirring to obtain the alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material. The preparation method comprises the steps of oxidizing a carbon nano material with a hydrogen storage function, activating and alkynylating to prepare an alkynylated carbon nano material with the hydrogen storage function, and preparing the alkynylated carbon nano material loaded with the nano noble metal dehydrogenation material by an in-situ reduction method. In the alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material, the carbon nanomaterial has a hydrogen storage function, and the nano noble metal is used as a catalyst, so that unsaturated alkynyl can react with hydrogen at normal temperature to achieve the dehydrogenation function.
Description
Technical Field
The invention belongs to the technical field of hydrogen absorption material preparation, and particularly relates to a preparation method of a nanometer noble metal dehydrogenation material loaded on an alkynyl carbon nanometer material.
Background
With the increasing scarcity of fossil fuels and the continuous deterioration of the ecological environment, the search and development of a clean and renewable new energy source is attracting attention all over the world. Under the dual requirements of environmental pressure and energy crisis, hydrogen energy is emerging as a green energy source and energy carrier with abundant reserves, wide sources and high energy density. However, the lack of economical, efficient and safe hydrogen storage technology has become a major bottleneck limiting the scale application of hydrogen energy. For the research of the hydrogen storage technology at the present stage, the existing hydrogen storage materials have advantages and disadvantages, and must be reasonably utilized by combining with a specific use mode, and meanwhile, the diversified co-development is focused.
Hydrogen has extremely strong permeability, and is easy to generate hydrogenation with a material body when entering a metal material to generate a hydride with brittleness, so that the plastic loss and the hysteresis cracking of the material are caused. The accumulation of hydrogen in a closed environment also presents a risk of combustion and explosion, and the american nuclear regulatory commission has mandated that the concentration of hydrogen in the nuclear waste storage vessel cannot be higher than 5 vol%. For radionuclide tritium in hydrogen isotopes, the leakage thereof into the environment also causes serious harm to human health. Therefore, hydrogen elimination and hydrogen control have important significance for maintaining the stability of the structure and performance of the material in a closed environment and ensuring the safety of hydrogen-involved isotopes, particularly tritium-involved production. In addition to trying to control the generation of hydrogen, the absorption and elimination of hydrogen and its isotopes present in the environment by hydrogen-absorbing materials is also a feasible and common method. The hydrogen absorption material prepared in the prior art has low hydrogen absorption capacity and poor hydrogen elimination effect.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the invention, there is provided a method for preparing a hydrogen scavenging material, comprising the steps of:
oxidizing a carbon nano material, and then activating and alkynylating to prepare an alkynylated carbon nano material with a hydrogen storage function;
dispersing the alkynyl carbon nano material in a solvent, adding a noble metal salt solution, heating and stirring; and adding a reducing agent solution, and continuously stirring to obtain the alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material.
Preferably, the process of the first step is as follows: adding 1 part of carbon nano material into 100-1000 parts of fuming nitric acid or fuming sulfuric acid by weight, stirring and reacting at 25-80 ℃ for 0.5-20 hours, then adding 10-70 parts of alkynylamine, 10-100 parts of nitrite and 0.3-6 parts of initiator, stirring at 30-250 ℃, condensing and refluxing for 2-10 hours, diluting with distilled water, centrifugally separating and purifying, washing with an organic solvent for 3-10 times, and drying in vacuum to obtain an alkynylated carbon nano material; the rotation speed of the centrifugal separation and purification is 3000-12000 r/min, the temperature is 3-30 ℃, and the time is 3-20 min; the organic solvent for washing the organic solvent is one or more of toluene, xylene, acetone or tetrahydrofuran; the vacuum drying conditions are as follows: the temperature is 10-120 ℃, the vacuum degree is-0.05-0.1 MPa, and the drying time is 3-60 hours.
Preferably, the carbon nano material is one or more of carbon nano tube, carbon nano fiber and fullerene.
Preferably, the alkynylamine is one or more of 4-ethynylaniline, 4-propynylaniline, dimethyl propynylamine and propargylamine; the nitrite is one or more of barium nitrite, sodium nitrite and magnesium nitrite; the initiator is one or more of azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, azodiisoheptonitrile, potassium persulfate and sodium persulfate.
Preferably, the process of step two is as follows: dispersing 0.1-1 parts by weight of alkynyl carbon nano material in a solvent, adding 0.5-5 parts by weight of noble metal salt solution, and stirring at the temperature of 40-130 ℃ for 1-10 min; then adding 0.2-3 parts of reducing agent solution, and continuously stirring for 3-25 min to obtain an alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material; the solvent is one of N, N-dimethylformamide, toluene and tetrahydrofuran; the amount of solvent used is 5-50 parts.
Preferably, the noble metal salt solution is one or more of a platinum salt solution and a rhodium salt solution; the preparation method of the noble metal salt solution comprises the following steps: according to the parts by weight, 0.01-0.1 part of noble metal salt is dissolved in 0.3-5 parts of distilled water to prepare the catalyst; the preparation method of the reducing agent solution comprises the following steps: dissolving 0.005-0.10 part of reducing agent in 0.1-3.0 parts of distilled water according to parts by weight; the reducing agent is any one of diethylenetriamine, ethylenediamine, diethylamine, 1, 4-butanediamine, ethanol, oxalic acid, stannous chloride and magnesium borohydride.
Preferably, the platinum salt solution is any one of a sodium chloroplatinate solution, a platinum chloride solution, a potassium chloroplatinate solution, an ammonium chloroplatinate solution and a dichlorodiammineplatinum solution, and the rhodium salt solution is any one of a sodium chloroplatinate solution and a rhodium sulfate solution.
Preferably, the carbon nanomaterial is a pretreated fullerene, and the pretreatment method comprises the following steps: putting 1 part of fullerene and 100-200 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 370-400 ℃, adjusting the pressure in the high-pressure reaction kettle to 20-30 MPa, reacting for 30-60 min, and naturally cooling to room temperature to obtain the pretreated fullerene.
Preferably, the following process is further included between the first step and the second step: putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 30-60 min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma treatment instrument is 30-50 KHz, the power is 30-50W, and the pressure of argon is 30-80 Pa.
Preferably, the process of the first step is as follows: adding 1 part of carbon nano material into 100-1000 parts of fuming nitric acid or fuming sulfuric acid according to parts by weight, stirring and reacting for 0.5-20 hours at the temperature of 25-80 ℃, then adding the reacted mixed solution into a supercritical reaction device, then adding 10-70 parts of alkynylamine, 10-100 parts of nitrite and 0.3-6 parts of initiator, sealing the system, introducing carbon dioxide to 25-35 MPa, stirring and reacting for 2-5 hours at the temperature of 50-150 ℃, releasing pressure, then diluting with distilled water, centrifugally separating and purifying, washing with an organic solvent for 3-10 times, and drying in vacuum to obtain an alkynylated carbon nano material; the rotation speed of the centrifugal separation and purification is 3000-12000 r/min, the temperature is 3-30 ℃, and the time is 3-20 min; the organic solvent for washing the organic solvent is one or more of toluene, xylene, acetone or tetrahydrofuran; the vacuum drying conditions are as follows: the temperature is 10-120 ℃, the vacuum degree is-0.05-0.1 MPa, and the drying time is 3-60 hours.
The invention at least comprises the following beneficial effects: the preparation method comprises the steps of oxidizing a carbon nano material with a hydrogen storage function, activating and alkynylating to prepare an alkynylated carbon nano material with the hydrogen storage function, and preparing the alkynylated carbon nano material loaded with the nano noble metal dehydrogenation material by an in-situ reduction method. In the alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material, the carbon nanomaterial has a hydrogen storage function, and the nano noble metal is used as a catalyst, so that unsaturated alkynyl can react with hydrogen at normal temperature to achieve the dehydrogenation function. Meanwhile, the alkynyl carbon nanomaterial loaded nano noble metal dehydrogenation material is prepared by an in-situ reduction method, so that the agglomeration of nano noble metal catalyst particles can be reduced, the contact probability of reactants and the catalyst is increased, and the dehydrogenation reaction rate is effectively improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of carbon nano tube into 200 parts of fuming nitric acid according to parts by weight, stirring and reacting for 3 hours at the temperature of 50 ℃, then adding 30 parts of 4-ethynylaniline, 50 parts of barium nitrite and 2 parts of azodiisobutyronitrile, stirring at the temperature of 150 ℃, condensing, refluxing and reacting for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain an alkynylated carbon nano tube; the rotational speed of the centrifugal separation and purification is 10000r/min, the temperature is 15 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is toluene; the vacuum drying conditions are as follows: the temperature is 120 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl carbon nano tube in 20 parts of N, N-dimethylformamide according to parts by weight, adding 5 parts of sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 3 parts of diethylenetriamine solution, and continuously stirring for 20min to obtain an alkynylated carbon nanotube loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 5 parts of distilled water according to parts by weight; the preparation method of the diethylenetriamine solution comprises the following steps: dissolving 0.1 part of diethylenetriamine in 3.0 parts of distilled water by weight;
the hydrogen absorption performance test of the alkynyl carbon nanotube loaded nano platinum dehydrogenation material prepared in the embodiment is carried out, and the hydrogen absorption capacity is 8.5 mol/kg.
Example 2:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of carbon nano tube into 500 parts of fuming nitric acid according to parts by weight, stirring and reacting for 3 hours at the temperature of 50 ℃, then adding 50 parts of dimethyl propynylamine, 30 parts of sodium nitrite and 3 parts of cumene hydroperoxide, stirring at the temperature of 150 ℃, condensing and refluxing for reacting for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain an alkynylated carbon nano tube; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 15 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 120 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl carbon nano tube in 30 parts of toluene according to parts by weight, adding 4 parts of sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; then adding 2 parts of 1, 4-butanediamine solution, and continuously stirring for 20min to obtain an alkynylated carbon nanotube loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the 1, 4-butanediamine solution comprises the following steps: according to the weight portion, 0.1 portion of 1, 4-butanediamine is dissolved in 2 portions of distilled water to prepare the product;
the hydrogen absorption performance test of the alkynyl carbon nanotube loaded nano platinum dehydrogenation material prepared in the embodiment is carried out, and the hydrogen absorption capacity is 8.6 mol/kg.
Example 3:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding 50 parts of dimethyl propynylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptanonitrile, stirring at the temperature of 150 ℃, condensing and refluxing for reacting for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 8.8 mol/kg.
Example 4:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 600 parts of fuming sulfuric acid by weight, stirring and reacting for 5 hours at the temperature of 80 ℃, then adding 50 parts of 4-ethynylaniline, 30 parts of magnesium nitrite and 3 parts of benzoyl peroxide, stirring at the temperature of 120 ℃, condensing and refluxing for reaction for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of N, N-dimethylformamide, adding 5 parts of sodium chlororhodate solution, and stirring at 100 ℃ for 10 min; adding 2 parts of ethylenediamine solution, and continuously stirring for 20min to obtain an alkynylated fullerene loaded nano rhodium dehydrogenation material; the preparation method of the sodium chlororhodate solution comprises the following steps: dissolving 0.1 part of sodium chlororhodate in 3 parts of distilled water according to parts by weight; the preparation method of the ethylenediamine solution comprises the following steps: according to the weight portion, 0.1 portion of ethylenediamine is dissolved in 2 portions of distilled water to obtain the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano rhodium dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 8.9 mol/kg.
Example 5:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding 50 parts of dimethyl propynylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptanonitrile, stirring at the temperature of 150 ℃, condensing and refluxing for reacting for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: dissolving 0.1 part of stannous chloride in 2 parts of distilled water by weight;
the fullerene in the step one is pretreated fullerene, and the pretreatment method comprises the following steps: putting 1 part of fullerene and 200 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 385 ℃, adjusting the pressure in the high-pressure reaction kettle to 22.1MPa, reacting for 60min, and naturally cooling to room temperature to obtain the pretreated fullerene.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.3 mol/kg.
Example 6:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 600 parts of fuming sulfuric acid by weight, stirring and reacting for 5 hours at the temperature of 80 ℃, then adding 50 parts of 4-ethynylaniline, 30 parts of magnesium nitrite and 3 parts of benzoyl peroxide, stirring at the temperature of 120 ℃, condensing and refluxing for reaction for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of N, N-dimethylformamide, adding 5 parts of sodium chlororhodate solution, and stirring at 100 ℃ for 10 min; adding 2 parts of ethylenediamine solution, and continuously stirring for 20min to obtain an alkynylated fullerene loaded nano rhodium dehydrogenation material; the preparation method of the sodium chlororhodate solution comprises the following steps: dissolving 0.1 part of sodium chlororhodate in 3 parts of distilled water according to parts by weight; the preparation method of the ethylenediamine solution comprises the following steps: dissolving 0.1 part of ethylenediamine in 2 parts of distilled water according to parts by weight to obtain the product;
the fullerene in the step one is pretreated fullerene, and the pretreatment method comprises the following steps: putting 1 part of fullerene and 150 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 400 ℃, adjusting the pressure in the high-pressure reaction kettle to 22.1MPa, reacting for 45min, and naturally cooling to room temperature to obtain the pretreated fullerene.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano rhodium dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.4 mol/kg.
Example 7:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding 50 parts of dimethyl propynylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptanonitrile, stirring at the temperature of 150 ℃, condensing and refluxing for reacting for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours; putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 60min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 50KHz, the power is 50W, and the pressure of argon is 30 Pa;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.6 mol/kg.
Example 8:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 600 parts of fuming sulfuric acid by weight, stirring and reacting for 5 hours at the temperature of 80 ℃, then adding 50 parts of 4-ethynylaniline, 30 parts of magnesium nitrite and 3 parts of benzoyl peroxide, stirring at the temperature of 120 ℃, condensing and refluxing for reaction for 5 hours, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours; putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 45min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 45KHz, the power is 40W, and the pressure of argon is 50 Pa;
dispersing 1 part of alkynyl fullerene in 50 parts of N, N-dimethylformamide, adding 5 parts of sodium chlororhodate solution, and stirring at 100 ℃ for 10 min; adding 2 parts of ethylenediamine solution, and continuously stirring for 20min to obtain an alkynylated fullerene loaded nano rhodium dehydrogenation material; the preparation method of the sodium chlororhodate solution comprises the following steps: dissolving 0.1 part of sodium chlororhodate in 3 parts of distilled water according to parts by weight; the preparation method of the ethylenediamine solution comprises the following steps: according to the weight portion, 0.1 portion of ethylenediamine is dissolved in 2 portions of distilled water to obtain the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano rhodium dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.7 mol/kg.
Example 9:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 50 parts of dimethylpropargylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptonitrile, sealing the system, introducing carbon dioxide to 28MPa, stirring and reacting for 5 hours at the temperature of 150 ℃, relieving pressure, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.5 mol/kg.
Example 10:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 600 parts of fuming sulfuric acid by weight, stirring and reacting for 5 hours at the temperature of 80 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 50 parts of 4-ethynylaniline, 30 parts of magnesium nitrite and 3 parts of benzoyl peroxide, sealing the system, introducing carbon dioxide to 28MPa, stirring and reacting for 5 hours at the temperature of 120 ℃, relieving pressure, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of N, N-dimethylformamide, adding 5 parts of sodium chlororhodate solution, and stirring at 100 ℃ for 10 min; adding 2 parts of ethylenediamine solution, and continuously stirring for 20min to obtain an alkynylated fullerene loaded nano rhodium dehydrogenation material; the preparation method of the sodium chlororhodate solution comprises the following steps: dissolving 0.1 part of sodium chlororhodate in 3 parts of distilled water according to parts by weight; the preparation method of the ethylenediamine solution comprises the following steps: according to the weight portion, 0.1 portion of ethylenediamine is dissolved in 2 portions of distilled water to obtain the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano rhodium dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 9.6 mol/kg.
Example 11:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 50 parts of dimethylpropargylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptonitrile, sealing the system, introducing carbon dioxide to 28MPa, stirring and reacting for 5 hours at the temperature of 150 ℃, relieving pressure, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The fullerene in the step one is pretreated fullerene, and the pretreatment method comprises the following steps: putting 1 part of fullerene and 200 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 385 ℃, adjusting the pressure in the high-pressure reaction kettle to 22.1MPa, reacting for 60min, and naturally cooling to room temperature to obtain the pretreated fullerene.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 10.5 mol/kg.
Example 12:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 50 parts of dimethylpropargylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptonitrile, sealing the system, introducing carbon dioxide to 28MPa, stirring and reacting for 5 hours at the temperature of 150 ℃, relieving pressure, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours; putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 60min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 50KHz, the power is 50W, and the pressure of argon is 30 Pa;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano platinum dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 10.6 mol/kg.
Example 13:
a preparation method of a hydrogen-eliminating material comprises the following steps:
step one, adding 1 part of fullerene into 300 parts of fuming sulfuric acid according to parts by weight, stirring and reacting for 5 hours at the temperature of 60 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 50 parts of dimethylpropargylamine, 30 parts of magnesium nitrite and 3 parts of azodiisoheptonitrile, sealing the system, introducing carbon dioxide to 28MPa, stirring and reacting for 5 hours at the temperature of 150 ℃, relieving pressure, then diluting with distilled water, centrifugally separating and purifying, washing for 5 times with an organic solvent, and drying in vacuum to obtain alkynyl fullerene; the rotational speed of the centrifugal separation and purification is 12000r/min, the temperature is 25 ℃, and the time is 10 min; the organic solvent for washing the organic solvent is xylene; the vacuum drying conditions are as follows: the temperature is 100 ℃, the vacuum degree is-0.05 MPa, and the drying time is 24 hours; putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 60min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon; the frequency of the low-temperature plasma processor is 50KHz, the power is 50W, and the pressure of argon is 30 Pa;
dispersing 1 part of alkynyl fullerene in 50 parts of tetrahydrofuran by weight, adding 5 parts of a sodium chloroplatinate solution, and stirring at the temperature of 100 ℃ for 10 min; adding 2 parts of stannous chloride solution, and continuously stirring for 20min to obtain an alkynyl fullerene loaded nano noble metal dehydrogenation material; the preparation method of the sodium chloroplatinate solution comprises the following steps: dissolving 0.1 part of sodium chloroplatinate in 3 parts of distilled water according to parts by weight; the preparation method of the stannous chloride solution comprises the following steps: according to the weight portion, 0.1 portion of stannous chloride is dissolved in 2 portions of distilled water to prepare the product.
The fullerene in the step one is pretreated fullerene, and the pretreatment method comprises the following steps: putting 1 part of fullerene and 200 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 385 ℃, adjusting the pressure in the high-pressure reaction kettle to 22.1MPa, reacting for 60min, and naturally cooling to room temperature to obtain the pretreated fullerene.
The hydrogen absorption performance test is carried out on the alkynyl fullerene loaded nano platinum dehydrogenation material prepared in the embodiment, and the hydrogen absorption capacity is 11.8 mol/kg.
The hydrogen absorption performance test method adopted in the invention adopts a test method in the prior art, namely a test method given in Shuoshi's paper preparation of alkynyl polyvinyl alcohol/nano palladium composite material and normal temperature hydrogen absorption performance thereof (Heifeng Wen, 2014).
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (6)
1. The preparation method of the hydrogen-eliminating material is characterized by comprising the following steps:
step one, adding 1 part of carbon nano material into 100-1000 parts of fuming nitric acid or fuming sulfuric acid by weight, stirring and reacting for 0.5-20 hours at the temperature of 25-80 ℃, then adding a mixed solution after reaction into a supercritical reaction device, then adding 10-70 parts of alkynylamine, 10-100 parts of nitrite and 0.3-6 parts of initiator, sealing the system, introducing carbon dioxide to 25-35 MPa, stirring and reacting for 2-5 hours at the temperature of 50-150 ℃, releasing pressure, diluting with distilled water, centrifugally separating and purifying, washing with an organic solvent for 3-10 times, and drying in vacuum to obtain an alkynylated carbon nano material; the rotation speed of the centrifugal separation and purification is 3000-12000 r/min, the temperature is 3-30 ℃, and the time is 3-20 min; the organic solvent for washing the organic solvent is one or more of toluene, xylene, acetone or tetrahydrofuran; the vacuum drying conditions are as follows: the temperature is 10-120 ℃, the vacuum degree is-0.05 to-0.1 MPa, and the drying time is 3-60 hours;
dispersing 0.1-1 parts by weight of alkynyl carbon nano material in a solvent, adding 0.5-5 parts by weight of noble metal salt solution, and stirring at the temperature of 40-130 ℃ for 1-10 min; then adding 0.2-3 parts of reducing agent solution, and continuously stirring for 3-25 min to obtain an alkynyl carbon nanomaterial-loaded nano noble metal dehydrogenation material; the solvent is one of N, N-dimethylformamide, toluene and tetrahydrofuran; the solvent is used in an amount of 5-50 parts;
the carbon nano material is a pretreated carbon nano material, and the pretreatment method comprises the following steps: putting 1 part of carbon nano material and 100-200 parts of water in parts by weight into a high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 370-400 ℃, adjusting the pressure in the high-pressure reaction kettle to 20-30 MPa, reacting for 30-60 min, and naturally cooling to room temperature to obtain the pretreated carbon nano material.
2. The method for preparing a dehydrogenation material according to claim 1, wherein the carbon nanomaterial is one or more of carbon nanotubes, carbon nanofibers, and fullerenes.
3. The method for preparing a dehydrogenation material according to claim 1, wherein the alkynylamine is one or more selected from the group consisting of 4-ethynylaniline, 4-propynylaniline, dimethylpropynylamine and propargylamine; the nitrite is one or more of barium nitrite, sodium nitrite and magnesium nitrite; the initiator is one or more of azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, azodiisoheptonitrile, potassium persulfate and sodium persulfate.
4. The preparation method of the dehydrogenation material as claimed in claim 1, wherein the noble metal salt solution is one or more of a platinum salt solution and a rhodium salt solution; the preparation method of the noble metal salt solution comprises the following steps: according to the parts by weight, 0.01-0.1 part of noble metal salt is dissolved in 0.3-5 parts of distilled water to prepare the catalyst; the preparation method of the reducing agent solution comprises the following steps: dissolving 0.005-0.10 part of reducing agent in 0.1-3.0 parts of distilled water according to parts by weight; the reducing agent is any one of diethylenetriamine, ethylenediamine, diethylamine, 1, 4-butanediamine, ethanol, oxalic acid, stannous chloride and magnesium borohydride.
5. The method for preparing the dehydrogenation material according to claim 4, wherein the platinum salt solution is any one of a sodium chloroplatinate solution, a platinum chloride solution, a potassium chloroplatinate solution, an ammonium chloroplatinate solution and a dichlorodiammineplatinum solution, and the rhodium salt solution is any one of a sodium chloroplatinate solution and a rhodium sulfate solution.
6. The method for preparing a dehydrogenating material as claimed in claim 1, further comprising the following steps between the first step and the second step: putting the alkynyl carbon nano material into a low-temperature plasma treatment instrument for treatment for 30-60 min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma treatment instrument is 30-50 KHz, the power is 30-50W, and the pressure of argon is 30-80 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811406598.9A CN109453742B (en) | 2018-11-23 | 2018-11-23 | Preparation method of dehydrogenation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811406598.9A CN109453742B (en) | 2018-11-23 | 2018-11-23 | Preparation method of dehydrogenation material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109453742A CN109453742A (en) | 2019-03-12 |
| CN109453742B true CN109453742B (en) | 2021-05-28 |
Family
ID=65611481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811406598.9A Active CN109453742B (en) | 2018-11-23 | 2018-11-23 | Preparation method of dehydrogenation material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109453742B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177257A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Method for preparing hydrophilic carbon nano tube |
| CN103663369A (en) * | 2012-09-12 | 2014-03-26 | 财团法人工业技术研究院 | Hydrogen storage composite and method of forming same |
| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
| CN108636449A (en) * | 2018-04-26 | 2018-10-12 | 西南科技大学 | The preparation method of the compound hydrogen-absorbing material of the graphene-supported nano Pd catalyst of alkynyl |
-
2018
- 2018-11-23 CN CN201811406598.9A patent/CN109453742B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177257A (en) * | 2006-11-10 | 2008-05-14 | 同济大学 | Method for preparing hydrophilic carbon nano tube |
| CN103663369A (en) * | 2012-09-12 | 2014-03-26 | 财团法人工业技术研究院 | Hydrogen storage composite and method of forming same |
| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
| CN108636449A (en) * | 2018-04-26 | 2018-10-12 | 西南科技大学 | The preparation method of the compound hydrogen-absorbing material of the graphene-supported nano Pd catalyst of alkynyl |
Non-Patent Citations (1)
| Title |
|---|
| "Pt修饰多壁碳纳米管的储氢性能初步研究";木士春等;《第四届全国氢能学术会议论文集》;20040426;1.1 MWNTS的提纯及改性，1.2Pt修饰MWNTS的制备 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109453742A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113150337B (en) | Regenerated cellulose membrane based on phosphoric acid solution and preparation method thereof | |
| CN105152137B (en) | A kind of anthraquinone recycling agent for hydrogen peroxide solution prepared in hydrogen peroxide process and preparation method thereof | |
| WO2021120800A1 (en) | Lignin-based graphene quantum dot, preparation method therefor and use thereof | |
| CN109225276B (en) | Flower-like molybdenum diselenide/carbon nanotube composite material and synthesis method and application thereof | |
| CN109384976B (en) | Preparation method of flexible dehydrogenation film material | |
| CN109453742B (en) | Preparation method of dehydrogenation material | |
| CN109232993A (en) | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball | |
| CN116726970A (en) | Sulfur-nitrogen doped MXene hydrogen storage material catalyst, hydrogen storage material containing catalyst and preparation method | |
| CN110902654A (en) | Method for preparing deuterium gas by photocatalytic heavy water | |
| CN101698479B (en) | Preparation method of carbon ball with big size | |
| CN108163845B (en) | Preparation method of porous graphene material | |
| CN111422853A (en) | Preparation method of carbon aerogel | |
| CN108993566A (en) | A kind of carbon nano-tube catalyst being used to prepare fuel cell hydrogen and preparation method | |
| CN107754807A (en) | A kind of method that estrogen in water removal is removed using sodium peroxydisulfate and magnetic photocatalyst | |
| CN113522309A (en) | Palladium-gold-nickel/graphene catalyst for dehydrogenation of dodecahydroethylcarbazole and preparation method thereof | |
| CN110590964B (en) | Kelp cellulose nanofiber and preparation method thereof | |
| CN113042067A (en) | Method for preparing hydrogen transfer catalyst based on waste lithium battery cathode carbon material | |
| CN104128093B (en) | A kind of hydrogen isotope method for gas purification | |
| CN108554371B (en) | Method for preparing silicon-magnesium-based nano water treatment agent | |
| CN110215903A (en) | A kind of POSS base weight metal ion adsorbent and mercapto alkene clicking chemistry preparation method | |
| CN110294460A (en) | A kind of dicyandiamide solution of the complete acid hydrogen-peroxide working solution of anthraquinone production | |
| CN101857220A (en) | Method for preparing rope-shaped carbon nano-tube | |
| CN109319761A (en) | A kind of microwave heating hydrazine hydrate reduction carbon aerogels and preparation method thereof | |
| CN115246954B (en) | High-efficiency recovery method of polyvinyl alcohol in waste polyvinyl formal product | |
| CN114920952B (en) | Lignin nanowire and 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 |