CN113353884A - Magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs, and preparation method and application thereof - Google Patents

Magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs, and preparation method and application thereof Download PDF

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CN113353884A
CN113353884A CN202110812958.0A CN202110812958A CN113353884A CN 113353884 A CN113353884 A CN 113353884A CN 202110812958 A CN202110812958 A CN 202110812958A CN 113353884 A CN113353884 A CN 113353884A
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CN113353884B (en
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孙立贤
林杰
徐芬
王涛
廖鹿敏
周天昊
张焕芝
邹勇进
曹子龙
刘博涛
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Guilin University of Electronic Technology
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract

The invention discloses a Bi-Mo-CNTs magnesium-based composite hydrogen production material, which is prepared from Mg powder and Bi2MoO6/CNTs mixed ball milling, the Bi2MoO6/CNTs preparation of Bi from soluble Bi salt and soluble Mo acid salt by hydrothermal method2MoO6Loading the CNTs to prepare the nano-carbon nanotubes; bi2MoO6The micro-morphology of the/CNTs is micron-sized microspheres, the microspheres are composed of floccule-loaded nano-scale crystals, wherein, Bi2MoO6CNTs microspheres of 10-30 μm size, Bi2MoO6Nano-scale crystals with the size of 100-200 nm. The preparation method comprises the following steps: 1) bi2MoO6Preparing CNTs; 2) preparing the Bi-Mo-CNTs magnesium-based composite hydrogen production material. As an application of a hydrolytic hydrogen production material, the Bi-Mo-CNTs magnesium-based composite hydrogen production material reacts with 3.5 percent NaCl solution to produce 826.7-860.9 mLg of hydrogen‑1The hydrogen production rate can reach 95.3-99.2%, and the apparent activation energy is 23-24 KJ.mol‑1。

Description

Magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs, and a preparation method and application thereof.
Background
Among many energy sources, hydrogen energy has been widely paid attention and researched as an ideal secondary energy carrier with the advantages of environmental friendliness, wide sources, high energy density and the like, and the preparation and storage of hydrogen energy have been the key points of hydrogen energy research. The method for preparing hydrogen by using magnesium water reaction is an efficient and clean hydrogen preparation method, and the magnesium-based hydrogen production material has the advantages of high theoretical hydrogen production amount, abundant and easily-obtained reserves, mild reaction conditions, no pollution of products and the like, so that the magnesium-based hydrogen production material has long-term application prospect.
The current Magnesium-based Hydrogen production material is mainly prepared by adopting a high-energy ball milling method, and a dense passivation layer generated by the reaction of Magnesium water through the physical or chemical reaction of a catalyst and Magnesium powder through high-energy ball milling cannot or is reduced to block the reaction of the Magnesium water, for example, related working reference 1 (DOI: 10.1039/x0xx00000x, Hydrogen generation of Magnesium with water using Mo, MoO)2, MoO3 and MoS2 as catalysts [J]) The high-energy ball milling method is adopted, the high activity is obtained by the compound of Mg powder and Mo in the high-energy ball milling process, the hydrogen production performance of the magnesium-based composite material is improved, and Mg-10 wt% x (x = Mo, MoO) is formed by ball milling2，MoS2And MoO3) When the conditions are that the ball-material ratio is 20:1, the ball milling speed is 1h, the rotation speed is 250rpm, the reaction is carried out for 10min at 25 ℃, the hydrogen production rate of 86.5 percent and the initial maximum hydrogen production rate of 751 mL-min can be obtained by Mg-10wt percent of Mo-1·g-1。Mg-10wt％MoO2Can obtain the hydrogen production rate of 88.0 percentAnd an initial maximum hydrogen production rate of 1933mL min-1·g-1。Mg-10wt％MoO391.7 percent of hydrogen production rate and 2423 mL-min of initial maximum hydrogen production rate can be obtained-1·g-1。Mg-10wt％MoS2Can obtain the hydrogen production rate of 89.8 percent and the initial maximum hydrogen production rate of 1376 mL-min-1·g-1. However, this technique has a problem that the hydrogen conversion rate is low at normal temperature.
However, in this hydrolysis technique, as the hydrolysis reaction proceeds, Mg (OH) is formed2The dense passivation layer blocks the contact of water with the Mg particles, thereby hindering further reactions, resulting in a large decrease in the kinetics of the hydrolysis reaction. Further, since magnesium metal powder is easily oxidized, an MgO oxide layer easily formed with oxygen in the air may hinder the hydrolysis reaction of water and Mg particles and also may cause a decrease in the hydrolysis reaction kinetics. In addition, because magnesium metal has good soft ductility and poor ball milling performance, the improvement of the hydrolysis performance of the magnesium metal by mechanical methods such as ball milling and the like is difficult, and the improvement of the hydrolysis performance can be started from the direction of reducing or destroying a compact passivation layer of the magnesium metal, the research on the high-efficiency clean hydrogen production material and the optimization of the process of the hydrogen production material have important research and practical significance.
In order to solve the problem of low hydrogen production rate, the inventors of the present invention have worked on the problem group, reference 2, chinese patent, application No.: 202110493380.7, a Bi and Mo-containing magnesium-based powder composite hydrogen production material, a preparation method and application thereof, and Bi prepared by the technology through a hydrothermal method2MoO6Bi powder is subjected to high-energy ball milling to ensure that Bi is added2MoO6The nano crystal is evenly attached to the magnesium powder, the active sites of the material reaction are increased, the hydrogen production performance of the magnesium-based material is improved, and when Bi is used2MoO6859.2 mLg can be obtained when the doping amount reaches 7 percent-1Hydrogen production amount and hydrogen production rate of 98.9%. Subsequent researches show that the technology has the following technical problems: the maximum hydrogen production rate of the prepared magnesium-based powder composite hydrogen production material is 756 mL-g when the magnesium-based powder composite hydrogen production material is not exposed in the air- 1min-1The maximum hydrogen production rate after 21 days of exposure in the air is 210mL g-1min-1Both of them have slower hydrogen production rate.
Disclosure of Invention
The invention aims to provide a Bi-Mo-CNTs magnesium-based composite hydrogen production material aiming at the defects of the prior art. In order to reduce the obstruction of a compact passivation layer generated in the hydrolysis process of the material and realize the effect of effectively catalyzing hydrogen production. The technical principle is as follows:
firstly, the Bi prepared by a hydrothermal method is induced by utilizing the active sites on CNTs2MoO6Uniformly dispersing the carbon nanotubes on the CNTs; then adding Bi2MoO6Ball milling is carried out on the/CNTs composite material and magnesium powder to realize Bi2MoO6The CNTs can be stripped into single-layer flexible carbon-coated Mg particles in the ball milling process, a more effective grinding effect is achieved, and the single-layer flexible carbon-coated Mg particles cover the surfaces of the Mg particles to protect the Mg particles and play a role in preventing the magnesium powder and air from carrying out oxidation reaction in the process of exposing the air.
According to the prior art, the Bi compound has better catalytic performance in the high-energy ball milling process, the carbon material can improve the ball milling performance in the high-energy ball milling preparation, the multi-component metal oxide has higher catalytic activity than metal or metal oxide, and the multi-component metal oxide has better chemical and physical stability and can be stored in outdoor environment for a long time.
The invention also aims to provide a method for preparing hydrogen by hydrolysis by using the magnesium-based powder composite hydrogen preparation material. The hydrogen production method is efficient and simple, does not need complex equipment and procedures in the preparation process, and is low in cost, safe and environment-friendly.
The technical scheme for realizing the purpose of the invention is as follows:
a magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs is prepared from Mg powder and Bi2MoO6CNTs mixturePrepared by ball milling, the Bi2MoO6/CNTs preparation of Bi from soluble Bi salt and soluble Mo acid salt by hydrothermal method2MoO6Loading the CNTs to prepare the nano-carbon nanotubes; the Bi2MoO6The micro-morphology of the/CNTs is micron-scale microspheres which are composed of floccule-loaded nano-scale crystals, wherein, Bi2MoO6CNTs microspheres of 10-30 μm size, Bi2MoO6Nano-scale crystals with the size of 100-200 nm.
The preparation method of the magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs comprises the following steps:
step 1) Bi2MoO6The preparation of CNTs comprises the steps of dissolving soluble Bi salt and soluble Mo salt in water according to a certain substance quantity ratio, adding CNTs subjected to ultrasonic dispersion according to a certain weight percentage, carrying out hydrothermal reaction under a certain condition, filtering, washing and drying the obtained product to obtain Bi2MoO6CNTs microspheres;
the soluble Bi salt in the step 1 is Bi (NO)3)3·5H2O, soluble Mo acid salt is Na2MoO4·2H2O, the mass ratio of the soluble Bi salt and the soluble Mo salt in the step 1 is 2:1, and the mass of the CNTs meets the requirement of Bi2MoO6The mass ratio of CNTs to CNTs is 6: 1;
the ultrasonic time of adding the CNTs into ultrapure water in the step 1) is 30min, the hydrothermal reaction conditions are that the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 16-24 h;
step 2) preparation of Bi-Mo-CNTs magnesium-based composite hydrogen production material, under the condition of protective gas, Bi obtained in step 1 is added2MoO6Ball milling the/CNTs and Mg powder in a certain mass ratio under certain conditions to obtain the uniformly mixed Bi-Mo-CNTs magnesium-based composite hydrogen production material;
the ball milling conditions in the step 2) are that the ball-material ratio of the ball milling is 20:1, and the rotating speed of the ball milling is 150--1The ball milling time is 30-120 min.
Application of magnesium-based composite hydrogen production material of Bi-Mo-CNTs as hydrolysis hydrogen production material, and Bi-Mo-CNTs magnesium-based composite hydrogen production materialThe hydrogen yield of the reaction with 3.5 percent NaCl solution is 826.7-860.9 mLg-1The hydrogen production rate can reach 95.3-99.2%, and the apparent activation energy is 23-24 KJ.mol-1。
Bi prepared by a hydrothermal method2MoO6The result of XRD analysis of the Bi-Mo-CNTs magnesium-based composite hydrogen production material prepared by ball milling shows that only Mg peak and Bi exist in the magnesium-based powder composite hydrogen production after ball milling2MoO6Peak of (b) indicates Bi in the ball milling process2MoO6Substantially no decomposition reaction takes place.
To Bi2MoO6SEM morphology analysis is respectively carried out on the/CNTs composite material and the ball-milled Bi-Mo-CNTs magnesium-based composite hydrogen production material, and the result shows that Bi prepared by a hydrothermal method2MoO6the/CNTs are microspheres with the diameter of 10-30 mu m; bi after ball milling process2MoO6Uniformly attached to the surface of Mg powder, and CNTs are mostly covered on magnesium powder particles.
For using different carbon materials and Bi respectively2MoO6The hydrogen production performance test of the material of the ball-milled magnesium powder shows that the Bi-Mo-CNTs ball-milled magnesium-based powder composite hydrogen production material prepared by a hydrothermal method has the best hydrogen production performance.
The ball-milled Bi-Mo-CNTs magnesium-based composite hydrogen production material is subjected to hydrogen production performance test at different reaction temperatures, and the apparent activation energy obtained by calculation according to the maximum reaction rate is 23.6 KJ.mol-1. 93 percent of Mg-7 percent of Bi in the reference (patent application number: 202110493380.7, a Mg-based powder composite hydrogen production material containing Bi and Mo, a preparation method and application thereof)2MoO6Apparent activation energy of 34.9 KJ. mol-1And the search for materials for hydrolytic hydrogen production with reference (Huangming hong. Mg/MgH _2 base [ D)]University of southern China, 2017.) the apparent activation energy of magnesium in reaction with seawater is 63.9KJ · mol-1The comparison shows that the magnesium-based powder composite hydrogen production material has excellent reaction activity.
The ball-milled magnesium-based composite hydrogen production material is subjected to hydrogen production performance test under different air exposure time, and the hydrogen production performance of the magnesium-based powder hydrogen production material is 823.7 mL/g after the magnesium-based composite hydrogen production material is exposed in normal temperature air for 28 days-1The corresponding hydrogen production rate and hydrogen production conversion rate are 562.7mL g-1min-1And 94.9%.
The experimental detection result of the hydrogen production performance of the invention is as follows: under the conditions of 3.5 percent NaCl solution and 25 ℃, the unit hydrogen production is 826.7-860.9 mL g-1The hydrogen production rate is 810.2-2046.5 mL g-1·min-1The conversion rate is 95.3-99.2%.
The hydrogen production performance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material is tested by adopting a drainage and gas collection method and weighing 0.1 g of prepared Mg- (Bi-Mo-CNTs) powder composite hydrogen production material; at 25 ℃, 10mL of 3.5% NaCl solution is added, and the generated gas is collected and the hydrogen production performance is measured.
The invention has the following advantages:
1. the preparation method is rapid, simple, energy-saving and environment-friendly;
2. bi prepared by hydrothermal method2MoO6The particle diameter of the/CNTs catalyst is small; ball milled nano-scale Bi2MoO6Can be uniformly attached to the surface of Mg particles to provide a plurality of reactive sites and improve the reaction rate of magnesium water;
3. the prepared Bi-Mo-CNTs magnesium-based composite hydrogen production material has good oxidation resistance.
Therefore, the invention has simple manufacturing process, low cost of raw materials, no pollution of products and high hydrogen production efficiency, and can be used as a hydrogen source of a fuel cell.
Description of the drawings:
FIG. 1 shows the composite hydrogen production material of ball-milled magnesium powder and magnesium-based powder prepared by ball milling in example 1 and Bi prepared by hydrothermal method2MoO6XRD pattern of/CNTs;
FIG. 2 shows Bi obtained after hydrothermal reaction in step 1 of example 12MoO6SEM picture of/CNTs;
FIG. 3 is an SEM image of the Mg- (Bi-Mo-CNTs) magnesium-based composite hydrogen production material prepared in step 2 of example 1;
FIG. 4 is an SEM photograph of the surface of the Mg- (Bi-Mo-CNTs) magnesium-based composite hydrogen production material in example 1
FIG. 5 shows examples 1 and Mg-Bi2MoO6-C magnesium base composite hydrogen production material hydrolyzed at 25 DEG CA hydrogen production rate curve;
FIG. 6 is a graph showing the hydrogen production curve of the Mg- (Bi-Mo-CNTs) magnesium-based composite hydrogen production material by hydrolysis reaction at 25 ℃ for different ball milling times, which is a hydrogen production curve and a hydrogen production rate curve respectively;
FIG. 7 is an apparent activation energy diagram of the Mg- (Bi-Mo-CNTs) magnesium-based powder composite hydrogen production material prepared in example 2;
FIG. 8 is a hydrogen production rate curve of hydrolysis of the Mg- (Bi-Mo-CNTs) powder composite hydrogen production material at 25 ℃ after exposure to air;
FIG. 9 is a hydrogen production rate curve of hydrolysis of the Mg- (Bi-Mo-CNTs) powder composite hydrogen production material at 25 ℃ after exposure to air at 60 ℃.
Detailed Description
The invention is further described in detail by the embodiments and the accompanying drawings, but the invention is not limited thereto.
Example 1
A preparation method of a magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs comprises the following steps:
step 1) hydrothermal reaction process according to Bi (NO)3)3·5H2O and Na2MoO4·2H2O satisfies the ratio of the amount of substance 2:1, weighing Bi (NO)3)3·5H2O and Na2MoO4·2H2Dissolving O in deionized water, adding CNTs into the deionized water, and ultrasonically dispersing for 30min, wherein the mass of the CNTs is Bi obtained by theoretical calculation2MoO6The mass ratio of the carbon nano tubes to the CNTs is 6:1, then the carbon nano tubes and the CNTs are transferred to a reaction kettle for hydrothermal reaction at the temperature of 180 ℃ for 20 hours, and the Bi is obtained by washing the reaction kettle for multiple times with deionized water2MoO6CNTs microspheres;
step 2) ball milling process, under the protection of argon atmosphere, according to Mg powder and Bi2MoO6the/CNTs microspheres meet the mass ratio of 93:7, and Mg powder and Bi are weighed2MoO6CNTs, the ball-material ratio is 20:1, the ball milling speed is 250 r.min-1And performing ball milling for 30min to obtain the uniformly mixed magnesium-based composite hydrogen production material.
In order to prove the respective functions of the hydrothermal process and the ball milling process in the technical scheme, Bi obtained in the step 1 before and after ball milling is subjected to2MoO6XRD analysis is carried out on the/CNTs and the magnesium-based powder composite hydrogen production material obtained in the step 2. The results are shown in FIG. 1, Bi obtained after hydrothermal process2MoO6In the/CNTs microspheres, only Bi is present2MoO6The experimental result shows that Bi is successfully synthesized in the hydrothermal method process2MoO6The particles are washed for many times by deionized water, most or all unreacted medicines are removed, namely the high-purity Bi is synthesized by a hydrothermal method2MoO6CNTs microspheres; the magnesium-based composite hydrogen production material obtained after the ball milling process only contains Mg and Bi2MoO6The experimental results show that no Bi occurs during the ball milling process2MoO6Self-decomposition of/CNTs or redox reaction with Mg, i.e. Bi in ball milling2MoO6the/CNTs function to increase ball milling performance.
To demonstrate that during the ball milling process, Bi2MoO6Influence of/CNTs on the micro morphology of the powder composite material, on Bi obtained in step 1 before and after ball milling2MoO6And performing SEM analysis on the/CNTs and the magnesium-based powder composite hydrogen production material obtained in the step 2. The results are shown in FIGS. 2 and 3 for Bi produced by hydrothermal method2MoO6The micro-morphology of the/CNTs microspheres is shown in FIG. 2, Bi2MoO6/CNTs microspheres composed of Bi2MoO6The composition is loaded on CNTs; the micro-morphology of the magnesium-based powder composite hydrogen production material is shown in figures 3 and 4, and figure 4 shows Bi2MoO6The nano-crystals are evenly attached to the magnesium powder, and the CNTs cover the surface of the magnesium powder.
In order to prove the hydrogen production performance of the magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs, a hydrogen production performance test is carried out. The results are shown in Table 1, and the hydrogen production amount reached 851.9 mL g-1Maximum hydrogen production rate of 1745.6 mL g-1·min-1The hydrogen production rate is 98.2 percent.
TABLE 1 carbon materials and Bi2MoO6Ball-milled magnesium powder and magnesium-based powder composite hydrogen production materialHydrogen generation performance of
Figure DEST_PATH_IMAGE002
To prove success, Bi2MoO6And (3) carrying out in-situ loading of the nano crystals on the CNTs for SEM test. The test results are shown in FIG. 2, Bi2MoO6The nano-crystal is successfully loaded on the CNTs floccule, and an in-situ hydrothermal method is adopted to lead Bi to be2MoO6The nano-crystals are uniformly loaded on the CNTs to enable the Bi2MoO6The nanocrystals are uniformly attached to the magnesium powder during ball milling, so that the active sites of the material reaction are increased, and as shown in fig. 3, CNTs cover the surface of the magnesium powder, so that the conductivity of the material is increased, and the hydrogen production performance of the material is improved.
In order to prove the effects of in-situ preparation of Bi-Mo-CNTs and different carbon materials on the performance of the magnesium-based composite hydrogen production material, a comparative example 1, a comparative example 2 and a comparative example 3 are provided, and the carbon materials are introduced by adopting an ex-situ method, namely the carbon materials are introduced in the ball milling process in the step 2; among these, carbon materials provide RGO and graphite in addition to CNTs.
Comparative example 1
The preparation method of the magnesium-based composite hydrogen production material for preparing Mg-Bi-Mo-CNTs in an ex-situ manner comprises the following steps which are not particularly described in the specific steps and are the same as those in the embodiment 1, and the difference is that: the step of adding the CNTs is not in the step 1, but in the step 2; the resulting material was named Mg-Bi-Mo-CNTs.
Comparative example 2
The preparation method of the magnesium-based composite hydrogen production material for preparing Mg-Bi-Mo-RGO in an ex-situ manner comprises the following steps which are not particularly described in the specific steps and are the same as those in the embodiment 1, except that: the link of RGO addition is not in step 1, but in step 2; the resulting material was named Mg-Bi-Mo-RGO.
Comparative example 3
The preparation method of the magnesium-based composite hydrogen production material for preparing Mg-Bi-Mo-Graphite ex situ has the same steps as example 1 except that the specific steps are not particularly described: the addition link of the Graphite is not in step 1, but in step 2; the resulting material was named Mg-Bi-Mo-Graphite.
The hydrogen production performance test results of the magnesium-based composite hydrogen production material for preparing Bi-Mo-C ex situ are shown in Table 1, and the following conclusions can be obtained:
1. by comparing the comparative examples 1, 2 and 3, the CNTs have better hydrogen production performance among different carbon materials;
2. as can be seen by comparing comparative example 1 with example 1, the performance of example 1 is significantly better than that of comparative example 1, i.e. in situ preparation of Bi is demonstrated2MoO6The method of/CNTs is superior to the ex situ preparation method.
In order to demonstrate the influence of different ball milling times on the hydrogen production performance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material, the Bi-Mo-CNTs magnesium-based composite hydrogen production material with the ball milling times of 30min, 60min, 90min and 120min is prepared in example 2, comparative example 4 and comparative example 5.
Example 2
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the ball milling time in the step 2 is 60min, and the obtained magnesium-based powder composite hydrogen production material is named as Mg- (Bi-Mo-CNTs) -60 min.
Comparative example 4
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the ball milling time in the step 2 is 90min, and the obtained magnesium-based powder composite hydrogen production material is named as Mg- (Bi-Mo-CNTs) -90 min.
Comparative example 5
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the ball milling time in the step 2 is 120min, and the obtained magnesium-based powder composite hydrogen production material is named as Mg- (Bi-Mo-CNTs) -120 min.
The hydrogen production performance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material for different ball milling times is shown in Table 2.
TABLE 2 Hydrogen production Performance of Bi-Mo-CNTs magnesium-based composite hydrogen production material at 25 ℃ and different ball milling times
Figure DEST_PATH_IMAGE004
The experimental result shows that the reaction rate can be effectively increased and the hydrogen production performance can be enhanced by properly increasing the ball milling time, wherein the Mg- (Bi-Mo-CNTs) -60min hydrogen production performance of the sample is optimal, and the hydrogen production amount reaches 860.8mL g-1The corresponding hydrogen production rate and hydrogen production conversion rate are 2172.4mL g-1min-1And 99.2%.
In order to prove the reaction kinetics performance of the magnesium-based powder composite hydrogen production material, the magnesium-based powder composite hydrogen production material is reacted with 3.5% NaCl solution at the temperature of 15 ℃, 25 ℃, 35 ℃, 45 ℃ and 55 ℃, the hydrogen production performance of the magnesium-based powder composite hydrogen production material is tested, the activation energy is calculated, and the hydrogen production performance is shown in Table 3.
TABLE 3 Hydrogen production Performance of Bi-Mo-CNTs magnesium-based composite Hydrogen production Material at different temperatures
Figure DEST_PATH_IMAGE006
Fitting was performed according to the arrhenitz equation and the experimental data in the table above, and the results are shown in fig. 6. The apparent activation energy of the reaction of the magnesium-based powder composite hydrogen production material and 3.5 percent NaCl solution is 23.6 KJ.mol-1. 93 percent of Mg-7 percent of Bi in the reference (patent application number: 202110493380.7, a Mg-based powder composite hydrogen production material containing Bi and Mo, a preparation method and application thereof)2MoO6Apparent activation energy of 34.9 KJ. mol-1And the search for materials for hydrolytic hydrogen production with reference (Huangming hong. Mg/MgH _2 base [ D)]University of southern China, 2017.) the apparent activation energy of magnesium in reaction with seawater is 63.9KJ · mol-1The comparison shows that the magnesium-based powder composite hydrogen production material has excellent reaction activity.
In order to prove the oxidation resistance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material, the invention is prepared by the following examples 3 and 34. Example 5, example 6, example 7 and example 8 Mg-Bi exposed to air for 7 days, 14 days, 21 days, 28 days and to air for 28 days at 60 ℃ were prepared2MoO6Powder composite hydrogen production material.
Example 3
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the magnesium-based powder composite hydrogen production material obtained after ball milling is exposed in the air for 7 days is named as Mg- (Bi-Mo-CNTs) -7D.
Example 4
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the magnesium-based powder composite hydrogen production material obtained after ball milling is exposed to the air for 14 days is named as Mg- (Bi-Mo-CNTs) -14D.
Example 5
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the magnesium-based powder composite hydrogen production material obtained after ball milling is exposed in the air for 21 days is named as Mg- (Bi-Mo-CNTs) -21D.
Example 6
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: and the magnesium-based powder is exposed in the air for 28 days after ball milling, and the obtained magnesium-based powder composite hydrogen production material is named as Mg- (Bi-Mo-CNTs) -28D.
Example 7
A preparation method of a Bi-Mo-CNTs magnesium-based composite hydrogen production material and a hydrogen production performance test are disclosed, and the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the magnesium-based powder composite hydrogen production material obtained after ball milling is exposed to air at 60 ℃ for 28 days is named as Mg- (Bi-Mo-CNTs) -28D at 60 ℃.
The hydrogen production performance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material with different air exposure time is shown in Table 4.
TABLE 4 Hydrogen production Performance of Bi-Mo-CNTs Mg-based composite Hydrogen production Material at 25 ℃ for different air-exposing times
Figure DEST_PATH_IMAGE008
FIG. 8 is a graph of hydrogen evolution of the Bi-Mo-CNTs magnesium-based composite hydrogen production material exposed to air for 0-28 days, and FIG. 9 is a graph of hydrogen evolution of Mg- (Bi-Mo-CNTs) exposed to air at 60 ℃ for 0-28 days.
The experimental result shows that the hydrogen production performance of the Bi-Mo-CNTs magnesium-based composite hydrogen production material exposed in the air for 28 days is 823.7mL g-1The corresponding hydrogen production rate and hydrogen production conversion rate are 528.5mL g-1min-194.9 percent of the Bi-Mo-CNTs magnesium-based composite hydrogen production material exposed in air at 60 ℃ for 28 days has the hydrogen production performance of 685.9mL g-1The corresponding hydrogen production rate and hydrogen production conversion rate are as follows. Has good oxidation resistance.

Claims (7)

1. The magnesium-based composite hydrogen production material based on in-situ preparation of Bi-Mo-CNTs is characterized by comprising the following components in parts by weight: prepared from Mg powder and Bi2MoO6/CNTs mixed ball milling, the Bi2MoO6/CNTs preparation of Bi from soluble Bi salt and soluble Mo acid salt by hydrothermal method2MoO6Prepared by loading CNTs.
2. The Bi-Mo-CNTs magnesium-based composite hydrogen production material of claim 1, wherein: the Bi2MoO6The micro-morphology of the/CNTs is micron-scale microspheres which are composed of floccule-loaded nano-scale crystals, wherein, Bi2MoO6CNTs microspheres of 10-30 μm size, Bi2MoO6Nano-scale crystals with the size of 100-200 nm.
3. The method for preparing the magnesium-based composite hydrogen production material based on the in-situ preparation of the Bi-Mo-CNTs according to the claim 1 is characterized by comprising the following steps:
step (ii) of1）Bi2MoO6The preparation of CNTs comprises the steps of dissolving soluble Bi salt and soluble Mo salt in water according to a certain substance quantity ratio, adding CNTs subjected to ultrasonic dispersion according to a certain weight percentage, carrying out hydrothermal reaction under a certain condition, filtering, washing and drying the obtained product to obtain Bi2MoO6CNTs microspheres;
step 2) preparation of Bi-Mo-CNTs magnesium-based composite hydrogen production material, under the condition of protective gas, Bi obtained in step 1 is added2MoO6And ball milling the/CNTs and the Mg powder in a certain mass ratio under certain conditions to obtain the uniformly mixed Bi-Mo-CNTs magnesium-based composite hydrogen production material.
4. The production method according to claim 3, characterized in that: the soluble Bi salt in the step 1 is Bi (NO)3)3·5H2O, soluble Mo acid salt is Na2MoO4·2H2O, the mass ratio of the soluble Bi salt and the soluble Mo salt in the step 1 is 2:1, and the mass of the CNTs meets the requirement of Bi2MoO6And CNTs in a mass ratio of 6: 1.
5. The production method according to claim 3, characterized in that: the ultrasonic time of adding the CNTs into the ultrapure water in the step 1) is 30min, the hydrothermal reaction conditions are that the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 16-24 h.
6. The production method according to claim 3, characterized in that: the ball milling conditions in the step 2) are that the ball-material ratio of the ball milling is 20:1, and the rotating speed of the ball milling is 150--1The ball milling time is 30-120 min.
7. The application of the magnesium-based composite hydrogen production material of Bi-Mo-CNTs as the hydrolysis hydrogen production material according to claim 1, wherein the magnesium-based composite hydrogen production material comprises the following components: the hydrogen production amount of the Bi-Mo-CNTs magnesium-based composite hydrogen production material is 826.7-860.9 mLg after the reaction with 3.5 percent NaCl solution-1The hydrogen production rate can reach 95.3-99.2%, and the apparent activation energy is 23-24 KJ.mol-1。
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