CN115520865A - Ultrahigh-specific-surface-area hydrogen storage activated carbon, preparation method and application - Google Patents

Ultrahigh-specific-surface-area hydrogen storage activated carbon, preparation method and application Download PDF

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CN115520865A
CN115520865A CN202211239072.2A CN202211239072A CN115520865A CN 115520865 A CN115520865 A CN 115520865A CN 202211239072 A CN202211239072 A CN 202211239072A CN 115520865 A CN115520865 A CN 115520865A
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activated carbon
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张慧
李娴
白红存
田虎
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Ningxia University
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    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract

The invention provides hydrogen storage activated carbon with ultrahigh specific surface area, a preparation method and application thereof: the carbon precursor is activated at high temperature by using a confined space method, so that the chemical activating agent is effectively prevented from corroding equipment, and the formed closed system can fully utilize gas generated by activation to realize 'integrated' double repeated activation, so that the specific surface area of the activated carbon is larger than or equal to 4090m 2 g ‑1 And the hydrogen storage capacity of the activated carbon is not less than 7.40wt% at the temperature of 77K and the pressure of 80 bar. The method comprises the following steps: pre-carbonizing biomass in an inert atmosphere to obtain a carbon precursor; grinding and mixing the precursor and the activating agent, and then filling the mixture into a reactor with a limited range; heating the reactor at high temperature under inert atmosphere, and taking outAnd (3) carrying out acid washing, water washing and drying on the product to obtain the activated carbon. The method improves the specific surface area, the pore volume and the physical and chemical properties of the carbon material by using a confined space activation method, has simple process, controllable cost and easy industrialization, and provides reference for exploring the carbon material with the optimal hydrogen storage capacity.

Description

Ultrahigh-specific-surface-area hydrogen storage activated carbon, preparation method and application
Technical Field
The invention relates to a preparation method of activated carbon, in particular to hydrogen storage activated carbon with ultrahigh specific surface area, a preparation method and application.
Background
Because fossil fuels are about to be exhausted and cause serious harm to the environment, the global energy crisis is increasing day by day, hydrogen energy is one of six prospective future industries, and hydrogen energy becomes an ideal energy source capable of replacing fossil fuels due to high combustion efficiency, reproducibility and environmental friendliness and the realization of the goals of promoting carbon peak reaching and carbon neutralization. However, due to the very low density of hydrogen, storage is the most important bottleneck for the development of hydrogen energy. The activated carbon has the advantages of high storage capacity, reversibility, rapid kinetics and the like, so that the activated carbon is one of materials widely and commercially applied to hydrogen storage at present.
The biomass not only has rich carbon sources, high specific surface area and porosity which is easy to regulate and control, but also has the advantages of large quantity, wide sources, low price, renewability and the like, so the biomass is a high-quality material for preparing the active carbon at present, and the preparation process takes the biomass as a precursor and leads the biomass to have high specific surface area and rich pore structures through physical activation or chemical activation. Due to chemical activators of KOH, naOH and H 2 PO 4 The activation is carried out in a limited space, so that physical and chemical activation can be simultaneously carried out in one step, gas generated by activation can be fully and repeatedly utilized, namely integral double repeated activation is achieved, and tail gas pollution is not caused in the activation process. Therefore, the development of preparing activated carbon materials in a confined space becomes important.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the hydrogen storage activated carbon with the ultrahigh specific surface area, the preparation method and the application.
An ultrahigh specific surface area hydrogen storage activated carbon, which is characterized in that: the active carbon has a three-dimensional hierarchical pore structure, and the specific surface area of the active carbon is more than or equal to 4090m 2 g -1 The pore volume of the micropores is 0.3-1.69cm 3 g -1 The hydrogen storage capacity of the activated carbon is more than or equal to 7.40wt% at the temperature of 77K and the pressure of 80 bar.
The preparation method of the hydrogen storage activated carbon with the ultrahigh specific surface area comprises the following steps:
(1) Heating and acid-washing the biomass, then washing the biomass to be neutral, and drying the biomass for later use;
(2) Under inert protective atmosphere, pre-carbonizing the biomass obtained in the step (1) to obtain a carbon precursor;
(3) Fully grinding and mixing the carbon precursor obtained in the step (2) and a chemical activating agent, then filling the mixture into a limited reactor, sealing the limited reactor after all air in the limited reactor is discharged, and carrying out physical activation and chemical activation double activation reaction;
(4) And (3) heating the limited-area reactor at high temperature under the inert protective atmosphere, taking out a product, and carrying out acid washing, water washing and drying on the product to obtain the activated carbon.
In the step (1), the biomass is one of wood chips, peanut shells and waste paper scraps.
In the step (2), the pre-carbonization temperature is 350-500 ℃, and the pre-carbonization heat preservation time is 100-140 min.
In step (3), the chemical activator is one of KOH and NaOH, and the mass ratio of the chemical activator to the carbon precursor is 2.
In the step (3), the activation reaction is carried out in a confined space, and the formed closed system can fully utilize the gas generated by activation, so that the double repetition of physical activation and chemical activation in one system is realized.
In the step (4), the high-temperature heating temperature is 600-800 ℃, and the high-temperature heating heat preservation time is 90-150 min.
In the step (2) and the step (4), the inert protective atmosphere is one of nitrogen, argon and helium.
The activated carbon material is applied to the field of hydrogen storage.
Compared with the prior art, the invention has at least the following advantages:
the activated carbon material has rich functional groups, adjustable specific surface area and pore channel structure, the hydrogen storage capacity of the activated carbon is not less than 7.40wt% at the temperature of 77K and the pressure of 80bar, the hydrogen storage quality standard of the hydrogen storage material specified by the U.S. department of energy is higher, the used raw materials are rich in sources, the process is simple, the cost is low, the industrial application is easy to realize, and a new idea is provided for promoting the scale of the carbon material hydrogen storage industry technology.
The carbon precursor is activated at high temperature by adopting a confined space method, so that the activation process of the carbon precursor is carried out in a closed space, the activated carbon with the ultrahigh specific surface area is prepared, the activation in the confined space can not only prevent the activating agent from corroding equipment, but also can fully utilize the steam and CO generated in the activation process 2 And the chemical activation and the physical activation are carried out simultaneously and repeatedly by the aid of the gases, so that the specific surface area and the pore structure of the carbon material can be regulated and controlled.
Drawings
FIG. 1 is the results of a nitrogen isothermal adsorption/desorption test of an activated carbon material prepared in example 1 of the present invention;
FIG. 2 shows the results of pore size distribution tests of the activated carbon material prepared in example 1 of the present invention;
fig. 3 is a XRD test result of the activated carbon material prepared in example 1 of the present invention;
FIGS. 4a and 4b are 10 μm and 100 μm SEM images, respectively, of the activated carbon material prepared in example 1 of the present invention;
FIG. 5a, FIG. 5b, FIG. 5C and FIG. 5d are XPS total spectrum, C1 s spectrum, O1 s spectrum and N1s spectrum of the activated carbon material prepared in example 1 of the present invention, respectively;
FIG. 6 shows the results of hydrogen sorption tests at 77K at 0-80bar for the activated carbon material prepared in example 1 of the present invention.
FIG. 7 is the results of the nitrogen isothermal adsorption/desorption test of the activated carbon material prepared in example 2 of the present invention;
FIG. 8 shows the results of pore size distribution tests of the activated carbon material prepared in example 2 of the present invention;
FIG. 9 shows the XRD test results of the activated carbon material prepared in example 2 of the present invention;
FIG. 10 is the results of the nitrogen isothermal adsorption/desorption test of the activated carbon material prepared in example 3 of the present invention;
FIG. 11 shows the results of pore size distribution tests of the activated carbon material prepared in example 3 of the present invention;
FIG. 12 shows the XRD test results of the activated carbon material prepared in example 3 of the present invention;
FIG. 13 shows the results of the nitrogen isothermal adsorption/desorption test of the activated carbon material prepared in example 4 of the present invention;
FIG. 14 shows the results of pore size distribution tests on the activated carbon material prepared in example 4 of the present invention;
fig. 15 is a XRD test result of the activated carbon material prepared in example 4 of the present invention.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples. It is to be understood, however, that the following examples are for the purpose of illustrating the present invention only and are not intended to limit the scope of the present invention.
Example 1
Pickling the wood chips, namely adding hydrochloric acid, performing water bath constant-temperature magnetic stirring, washing with water until the pH value is neutral, drying, weighing 5g of pickled sample, performing pre-carbonization, heating to 350 ℃, 400 ℃ and 500 ℃ respectively under the protection of nitrogen, preserving heat for 120min, and naturally cooling to room temperature to obtain a carbon precursor, namely PSC; fully grinding and mixing potassium hydroxide and PSC according to a mass ratio of 4 to obtain a mixture, then loading the mixture into a self-made limited-range reactor, then placing the limited-range reactor into a glove box, and sealing after all air in the limited-range reactor is exhausted; heating the reactor to 700 ℃ in nitrogen atmosphere, preserving heat for 120min, taking out the product after the reactor is naturally cooled to room temperature, and carrying out acid washing on the product by hydrochloric acid to removeAnd washing the mixture with distilled water until the pH value is neutral, and drying the washed mixture to obtain the sawdust-derived activated carbon, wherein a sample is named PSACT-XY, T represents the pre-carbonization temperature, X represents the mass ratio of the carbon precursor to KOH, and Y represents the activation temperature. In all examples, the specific surface area of the sample was calculated by the Brunauer-Emmett-Teller (abbreviated as BET) method, and the non-local density functional theory (abbreviated as NLDFT) was used to analyze the pore size distribution, and the total pore volume was determined by the relative pressure P/P 0 The nitrogen absorption amount at the time of =0.99 was determined, and the specific surface area and pore volume of the micropores were determined by the t-Plot method. Fig. 1 is a nitrogen isothermal adsorption/desorption graph of the activated carbon material prepared above, and it can be seen from the graph that all the sample isotherm types are i type, and as the temperature rises, the nitrogen adsorption amount increases first and then decreases. As shown in Table 1, for the specific surface area and pore size parameters of the activated carbon material prepared in example 1, the specific surface area was as high as 4097.49m at a pre-carbonization temperature of 400 deg.C 2 The specific surface area of the micropores reaches 3474.18m 2 And/g, accounting for 84.79 percent of the total specific surface area. Fig. 2 is a diagram showing the pore size distribution of the activated carbon material prepared as described above, all samples have pore size distribution mainly below 5nm, wide pore distribution range, multi-level pore distribution, a large number of microporous structures in the range of 0.4 to 2nm, and many mesopores with smaller diameters at 400 ℃. Fig. 3 is an XRD pattern of the activated carbon material prepared as described above, all samples having diffraction peaks at 2 θ =28 ° and 44 ° corresponding to (002) diffraction peak and (100) diffraction peak, respectively, the (002) diffraction peak being due to the interconnection and parallel stacking of the flake graphite layers; (100) The diffraction intensity of the diffraction peak is weaker, which indicates that the graphitization degree of the sample is lower; FIGS. 4a and 4b are SEM images of PSAC400-4700 at different magnifications, and it can be seen that the prepared activated carbon material has a three-dimensional cubic structure and a more developed pore structure, which is one of the reasons for the higher specific surface area; FIG. 5a, FIG. 5b, FIG. 5C and FIG. 5d are the XPS total spectrum, C1 s spectrum, O1 s spectrum and N1s spectrum of PSAC400-4700 sample, respectively, and from FIG. 5a, the sample contains three kinds of C, N and O, and is mainly composed of C element, C1 s spectrum is convoluted into three features corresponding to C = C (284.8 eV), C-O (286.2 eV), C = O (288.7 eV), O1 s spectrum is convoluted into three features corresponding to C = O (532.2 eV), C-O (533.5 eV), O-C = O (535.3 eV), N1s spectrum, respectivelyThe spectrum is convoluted into three characteristics which respectively correspond to N-6 (397.7 eV), N-5 (400.4 eV) and N-Q (401.7 eV), so that the prepared activated carbon material has rich functional groups; fig. 6 is a graph of hydrogen absorption test curves of 77K and 0-80bar of the activated carbon materials prepared at the pre-carbonization temperatures of 400 ℃ and 500 ℃, respectively, and it can be seen from the graph that the hydrogen absorption amount of the PSAC400-4700 and the PSAC500-4700 is gradually increased with the increase of the pressure at 77K, when the pressure is 80bar, the hydrogen storage amount can reach 7.50wt%, and when the carbonization temperature is increased, the hydrogen absorption amount is decreased, and the hydrogen storage amount of the PSAC500-4700 is 6.71wt%, because the micro-pores and the narrow meso-pores are damaged by the over-high temperature to collapse to form pores with larger diameters, and the pores do not contribute to the hydrogen storage. In view of the above, 400 ℃ is preferred as the optimum pre-carbonization temperature.
TABLE 1
Figure BDA0003884302840000051
Example 2
Crushing and pickling peanut shells, namely adding hydrochloric acid, performing water bath constant-temperature magnetic stirring, washing with water until the pH value is neutral, and drying; weighing 5g of a sample subjected to acid pickling, pre-carbonizing, heating to 400 ℃ under the protection of argon, preserving heat for 100min, and naturally cooling to room temperature to obtain a carbon precursor named as PWC; fully grinding and mixing sodium hydroxide and PWC according to the mass ratio of 2 to 1 to 3 to 1 to 4 to 1 to 5, then loading the mixture into a confinement reactor, placing the confinement reactor into a glove box, and sealing after all air in the confinement reactor is exhausted; heating the reactor to 700 ℃ under the argon atmosphere, preserving heat for 90min, taking out a product after the reactor is naturally cooled to room temperature, carrying out acid cleaning and impurity removal on the product by hydrochloric acid, washing the product by distilled water until the pH value is neutral, and drying the product to obtain the peanut shell-derived activated carbon, wherein the sample is named as PWACT-XY, T represents the pre-carbonization temperature, X represents the mass ratio of a carbon precursor to NaOH, and Y represents the activation temperature. Fig. 7 is a nitrogen isothermal adsorption/desorption graph of the activated carbon material prepared above, wherein all the sample isothermal lines are type i, the nitrogen adsorption amount of the unactivated samples PWAC400-0700 is very low, and the nitrogen adsorption amount is increased along with the alkali-carbon ratioThe nitrogen adsorption amount gradually increased with increasing, and the specific surface area was the largest when the alkali-carbon ratio was 4 (as shown in table 2), and when the alkali-carbon ratio continued to increase to 5 0 <The nitrogen adsorption amount is decreased in the interval of 0.4 because too high alkali content causes excessive activation of the carbon substrate, collapsing the micropores into mesopores, resulting in a specific surface area less than PWAC400-4700. FIG. 8 is a graph showing the pore size distribution of the activated carbon material prepared as described above, except PWAC400-0700, the pore distribution of the samples is wide. As shown in table 2, for the specific surface area and the pore size parameters of the activated carbon material prepared in example 2, the pore volume of the micropores gradually increased with the increase of the alkali carbon ratio, and the pore volume of the micropores was maximum and 1.34cm when the alkali carbon ratio was 3 3 As the alkali carbon ratio further increased to 5 3 (iv) g. FIG. 9 is an XRD pattern of the activated carbon material prepared as described above, showing that PWAC400-0700 has a more pronounced SiO at 2 θ =27 ° compared to the other samples 2 Characteristic peaks, siO after alkali activation 2 The characteristic peak disappeared, and the (002) diffraction peak was shifted, which is probably due to the larger change in the carbon layer spacing caused by the alkali activation, and as the alkali-carbon ratio increased, the intensity of the (100) diffraction peak gradually decreased, indicating that the degree of graphitization gradually decreased. Therefore, the binding specific surface area and the micropore volume may preferably be an alkali carbon ratio of 3.
TABLE 2
Figure BDA0003884302840000061
Example 3
Pickling the waste paper scraps, namely adding hydrochloric acid, performing water bath constant-temperature magnetic stirring, washing with water until the pH value is neutral, and drying; weighing 5g of the sample subjected to acid pickling, pre-carbonizing, heating to 400 ℃ under the protection of helium, preserving heat for 140min, and naturally cooling to room temperature to obtain a carbon precursor, namely WSC; fully grinding and mixing potassium hydroxide and WSC according to a mass ratio of 4 to obtain a mixture, then loading the mixture into a confinement reactor, then placing the confinement reactor into a glove box, and sealing after all air in the confinement reactor is exhausted; heating the reactor to 600 ℃, 700 ℃ and 800 ℃ respectively in a helium atmosphere, preserving heat for 150min, naturally cooling the reactor to room temperature, taking out a product, carrying out acid cleaning and impurity removal on the product by hydrochloric acid, washing the product by distilled water until the pH value is neutral, and drying the product to obtain the waste paper scrap derived activated carbon, wherein WSACT-XY, T represents the pre-carbonization temperature, X represents the mass ratio of a carbon precursor to KOH, and Y represents the activation temperature. Fig. 10 is a graph of nitrogen isothermal adsorption/desorption curves of the activated carbon materials prepared as described above, where adsorption and desorption isotherms of the WSAC400-4600 and WSAC400-4700 samples are type i, and when the activation temperature is increased from 600 ℃ to 700 ℃, a large number of carbon atoms are continuously activated due to heat absorption, so as to promote the reaction with KOH to form rich pores, generate a large number of micropores, and partially further expand to narrow mesopores, thereby greatly increasing the specific surface area of the activated carbon (as shown in table 3, the specific surface area and pore size parameters of the activated carbon material prepared in example 1), but when the activation temperature is increased to 800 ℃, the nitrogen adsorption and desorption isotherm is type iii and the specific surface area is decreased, because the reaction rate of the precursor with KOH is too high, the pore structure in the carbon matrix is excessively ablated, and the micropore volume is decreased, so that the specific surface area is decreased. Fig. 11 is a pore size distribution diagram of the activated carbon material prepared as described above, when the activation temperature is raised to 800 ℃, the pore structure is destroyed due to over activation, and micropores and narrow mesopores form mesopores with larger diameter under the action of severe pore expansion, thereby resulting in the decrease of the micropore volume of the activated carbon. Fig. 12 is an XRD pattern of the activated carbon material prepared as described above, and all samples had diffraction peaks at 2 θ =28 ° and 44 °, corresponding to (002) and (100) diffraction peaks, respectively.
TABLE 3
Figure BDA0003884302840000071
Example 4
Pickling the wood chips, namely adding hydrochloric acid, performing water bath constant-temperature magnetic stirring, washing with water until the pH value is neutral, and drying; 5g of the pickled sample were weighed for pre-carbonization in N 2 Heating to 400 deg.C at a heating rate of 5 deg.C/min under protective atmosphere, maintaining for 120min, and heating to room temperatureNaturally cooling to room temperature to obtain a carbon precursor, which is named as PSC; potassium hydroxide and PSC were sufficiently ground and mixed at a mass ratio of 4 2 Heating to 700 ℃ in the atmosphere, preserving the heat for 120min, naturally cooling to room temperature, taking out the product, carrying out acid cleaning and impurity removal on the product by hydrochloric acid, washing by distilled water until the pH value is neutral, and drying to obtain the sawdust-derived activated carbon. FIG. 13 is a graph showing the adsorption/desorption isotherms of nitrogen for the activated carbon material prepared as described above and for the activated carbon material prepared using a confined reactor under the same conditions, and it can be seen that the isotherms satisfy the type I curve, and that the two materials differ in that the adsorption curve for the PSAC400-4700 sample is at a relative pressure P/P 0 The sharp diagonal line segment appears in the interval of 0.05-0.4, which indicates that a large amount of mesopores exist in the material, and from the viewpoint of adsorption capacity, PSAC400-4700 is higher than that of a sample without using a limited-domain reactor, which proves that the limited-domain space method of the invention is favorable for improving the specific surface area and the total pore volume of the material (as shown in Table 4, the specific surface area and the pore diameter parameter of the activated carbon material prepared for example 4). Fig. 14 is a graph of pore size distribution of two materials with similar trends, except that the number of narrow mesopores of the sample is significantly increased after using the confinement reactor, and the analysis reason may be that in a closed system, KOH and the gas generated by the reaction thereof repeatedly activates the carbon matrix, resulting in an increase of defect levels, thereby collapsing a portion of micropores into mesopores. FIG. 15 is an XRD pattern for both materials, showing (002) and (100) diffraction peaks, but the intensity of the (100) diffraction peak is weaker for the PSAC400-4700 sample compared to the sample without the use of a confined zone reactor, indicating a lower degree of graphitization. In conclusion, the limited space method can not only prevent the activator from corroding equipment, but also fully utilize the gas generated by activation to realize 'integrated' double repeated activation, thereby greatly improving the specific surface area and the total pore volume of the material and reducing the tail gas pollution.
TABLE 4
Figure BDA0003884302840000081
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (9)

1. An ultrahigh specific surface area hydrogen storage activated carbon, which is characterized in that: the active carbon has a three-dimensional hierarchical pore structure, and the specific surface area of the active carbon is more than or equal to 4090m 2 g -1 The pore volume of the micropores is 0.3-1.69cm 3 g -1 And the hydrogen storage capacity of the activated carbon is more than or equal to 7.40wt% at the temperature of 77K and the pressure of 80 bar.
2. The method for preparing hydrogen storage activated carbon with ultra-high specific surface area as claimed in claim 1, which is characterized by comprising the following steps:
(1) Heating and acid-washing the biomass, then washing the biomass to be neutral, and drying the biomass for later use;
(2) Under inert protective atmosphere, pre-carbonizing the biomass obtained in the step (1) to obtain a carbon precursor;
(3) Fully grinding and mixing the carbon precursor obtained in the step (2) and a chemical activating agent, then filling the mixture into a limited-area reactor, sealing the limited-area reactor after all air in the limited-area reactor is discharged, and carrying out physical activation and chemical activation double activation reaction;
(4) And (3) heating the limited-area reactor at high temperature under the inert protective atmosphere, taking out a product, and carrying out acid washing, water washing and drying on the product to obtain the activated carbon.
3. The method of claim 2, wherein: in the step (1), the biomass is one of wood chips, peanut shells and waste paper scraps.
4. The method of claim 2, wherein: in the step (2), the pre-carbonization temperature is 350-500 ℃, and the pre-carbonization heat preservation time is 100-140 min.
5. The method of claim 2, wherein: in step (3), the chemical activator is one of KOH and NaOH, and the mass ratio of the chemical activator to the carbon precursor is 2.
6. The production method according to claim 2, characterized in that: in the step (3), the activation reaction is carried out in a confined space, and the formed closed system can fully utilize the gas generated by activation, so that the double repetition of physical activation and chemical activation in one system is realized.
7. The method of claim 2, wherein: in the step (4), the high-temperature heating temperature is 600-800 ℃, and the high-temperature heating heat preservation time is 90-150 min.
8. The method of claim 1, wherein: in the step (2) and the step (4), the inert protective atmosphere is one of nitrogen, argon and helium.
9. Use of the activated carbon material of claim 1 in the field of hydrogen storage.
CN202211239072.2A 2022-10-11 2022-10-11 Ultrahigh-specific-surface-area hydrogen storage activated carbon, preparation method and application Pending CN115520865A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496698A (en) * 2013-10-14 2014-01-08 中国林业科学研究院林产化学工业研究所 Method for preparing activated carbon high in specific surface area by activation in self-generated pressure
CN106335900A (en) * 2015-07-07 2017-01-18 云南民族大学 Method for preparation of activated carbon hydrogen storage material by microwave modification of mangosteen shell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496698A (en) * 2013-10-14 2014-01-08 中国林业科学研究院林产化学工业研究所 Method for preparing activated carbon high in specific surface area by activation in self-generated pressure
CN106335900A (en) * 2015-07-07 2017-01-18 云南民族大学 Method for preparation of activated carbon hydrogen storage material by microwave modification of mangosteen shell

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