CN115092925A - Preparation method and application of nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores - Google Patents

Preparation method and application of nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores Download PDF

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CN115092925A
CN115092925A CN202210809255.7A CN202210809255A CN115092925A CN 115092925 A CN115092925 A CN 115092925A CN 202210809255 A CN202210809255 A CN 202210809255A CN 115092925 A CN115092925 A CN 115092925A
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nitrogen
sulfur
carbon material
doped carbon
sulfur content
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徐群杰
石珊珊
时鹏辉
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Shanghai Electric Power University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a preparation method and application of a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores. Mixing biomass and an activating agent, then carrying out pyrolysis in an inert gas atmosphere, and then carrying out acid washing and water washing to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores. The nitrogen and sulfur co-doped carbon material prepared by the preparation method provided by the invention has the advantages of high nitrogen and sulfur content, small particle size, large specific surface area and developed micropores. Compared with the conventional carbon material, the nitrogen and sulfur co-doped carbon material prepared by the method disclosed by the invention has the advantage that the removal efficiency of organic pollutants and heavy metals in a water body is greatly improved. In addition, the preparation method provides a new way for treating the biomass waste, thereby saving the cost and realizing the resource utilization of the biomass waste.

Description

Preparation method and application of nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores
Technical Field
The invention belongs to the field of carbon material preparation technology and environmental remediation, and particularly relates to a preparation method and application of a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
Background
In recent years, the discharge amount of urban domestic sewage and industrial wastewater is increased year by year, and according to statistics, in 2020, the discharge amount of volatile phenol in the wastewater discharged in China is as high as 59.8 tons, and the discharge amount of heavy metal is as high as 73.1 tons, which seriously threatens the water environment, and the removal of the volatile phenol is more and more paid attention by people.
The biochar has excellent physical and chemical characteristics of high carbon content, high cation exchange capacity, stable structure, large specific surface area and the like, so that the biochar is widely applied to the field of water body purification. However, the pore structure of the biochar is not developed, and the surface functional groups are fewer, so that the direct application of the biochar is limited. The good porous structure and rich heteroatom modification are two important factors for improving the adsorption performance of the carbon adsorbent, the pore structure of the carbon material can be improved through the modification, and substances with specific chemical activity are added.
Among the numerous modifications, heteroatom doping is of great interest. Nitrogen and sulfur doped microporous carbon is considered to be a very effective adsorbent due to its developed porosity and variable surface chemical characteristics, and in recent years, the preparation methods of nitrogen and sulfur doped carbon materials are mainly divided into two types: (i) direct pyrolysis of N and S rich organic precursors without the use of an activator and (ii) combining an inorganic pore former with an organic dopant (such as urea, melamine, or thiourea) to produce a carbon material. However, both methods have some disadvantages, such as low efficiency of doping heteroatoms, the need to add excessive dopant, and high cost and energy consumption.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
The specific technical scheme of the invention is as follows:
the invention provides a preparation method of a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, which is characterized by comprising the following steps: step S1, mixing the biomass with an activating agent to obtain a mixture; step S2, pyrolyzing the mixture in an inert gas atmosphere to obtain a pyrolyzed mixture; and step S3, acid washing and water washing the pyrolyzed mixture to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
The preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores provided by the invention is also characterized in that in the step S1, the biomass comprises any one of wood chips, walnut shells, corn straws, wheat straws, shaddock peels, kitchen waste and peanut shells, and the activating agent comprises NaSCN, KSCN and Fe (SCN) 3 Any one or a mixture of several of them.
The preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, provided by the invention, also has the technical characteristic that the mass ratio of the biomass to the activating agent in the step S1 is 1: 0.4-1.2.
The preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores also has the technical characteristics that the pyrolysis temperature in the step S2 is 800 ℃ plus 300 ℃, the time is 1-4h, and the flow of inert gas is 0.05-1.0L/min.
The preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, provided by the invention, also has the technical characteristic that the lotion for acid washing in the step S3 is hydrochloric acid or nitric acid, and the concentration is 1-2 mol/L.
The invention also provides a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, which is characterized by being prepared by adopting the preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
The invention also provides application of the nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores in adsorption removal of organic pollutants and heavy metals in water.
Action and Effect of the invention
According to the invention, biomass and an activating agent are mixed and then pyrolyzed in an inert gas atmosphere, and then acid washing and water washing are carried out to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
According to the invention, thiocyanate containing nitrogen and sulfur elements is used as an activating agent to prepare the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed microporous structure, and in the process of pyrolyzing biomass and thiocyanate, the nitrogen and sulfur content and pore structure of the nitrogen and sulfur co-doped carbon material are regulated and controlled by the properties of raw materials through influencing the degree of oxygen replacement reaction and thermal stability effect. The above reaction is more likely to occur with a raw material having a high oxygen content and a strong heat resistance, thereby doping more nitrogen and sulfur and forming more abundant micropores.
Therefore, compared with the prior art, the nitrogen and sulfur co-doped carbon material prepared by the preparation method of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores has the following advantages:
(1) the nitrogen and sulfur content is high, the nitrogen content is as high as 5.28 percent, and the sulfur content is as high as 14.4 percent;
(2) small particle size and high specific surface area (up to 1532 cm) 2 Per gram), developed micropores (microporosity of 63-88%);
(3) compared with the conventional carbon material prepared by the traditional preparation method, the removal efficiency of the carbon material to organic pollutants and heavy metals in water is greatly improved.
In addition, the preparation method of the nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores, provided by the invention, adopts the agricultural and forestry waste as the raw material for preparing the biochar, so that the preparation method provides a new way for treating the biomass waste, saves the cost and realizes the resource utilization of the biomass waste.
Drawings
FIG. 1 is a nitrogen adsorption and desorption curve of a nitrogen and sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores, which is prepared in example 1 of the present invention.
FIG. 2 is a pore size distribution diagram of a nitrogen and sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores, which is prepared in example 1 of the present invention.
FIG. 3 is a graph showing the effect of the carbon materials prepared in examples 1 to 3 of the present invention and comparative example on the adsorption and removal of organic pollutants and heavy metals in water.
Detailed Description
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
The reagents used in the following examples are commercially available and the experimental procedures and experimental conditions not specified are those conventional in the art.
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings.
< example 1>
The embodiment provides a preparation method for preparing a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores by using wood chips and KSCN, which comprises the following steps:
step S1, mixing the biomass with an activating agent to obtain a mixture, wherein the specific process is as follows:
vibrating and mixing the wood chips and the KSCN in an aqueous solution according to a mass ratio of 1:1 for 12 hours, and drying to obtain a mixture;
step S2, pyrolyzing the mixture under the atmosphere of inert gas to obtain a pyrolyzed mixture, which comprises the following specific steps:
putting the mixture into a tubular furnace for pyrolysis, heating to 700 ℃ at a heating rate of 10 ℃/min under the nitrogen flow of 0.1L/min for pyrolysis for 1.5h, and cooling to room temperature in a nitrogen atmosphere to obtain a pyrolyzed mixture;
step S3, acid washing and water washing the pyrolyzed mixture to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, wherein the specific process comprises the following steps:
and washing the pyrolyzed mixture with 2mol/L hydrochloric acid for 2 times to remove inorganic impurities and the like, washing with ultrapure water to be neutral, drying in an oven at 80 ℃ to constant weight, and sieving with a 100-mesh sieve to obtain the nitrogen-sulfur co-doped carbon material (NSC-1) with high nitrogen-sulfur content and developed micropores.
< example 2>
The embodiment provides a preparation method for preparing a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores by using walnut shells and KSCN, which comprises the following steps:
step S1, mixing the biomass with an activating agent to obtain a mixture, wherein the specific process is as follows:
the walnut shell and the KSCN are shaken and mixed in an aqueous solution for 12 hours according to the mass ratio of 1:1, and a mixture is obtained after drying;
step S2, pyrolyzing the mixture under the atmosphere of inert gas to obtain a pyrolyzed mixture, which comprises the following specific steps:
putting the mixture into a tubular furnace for pyrolysis, heating to 800 ℃ at a heating rate of 10 ℃/min under the nitrogen flow of 0.1L/min for pyrolysis for 1.5h, and cooling to room temperature in a nitrogen atmosphere to obtain a pyrolyzed mixture;
step S3, acid washing and water washing the pyrolyzed mixture to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, wherein the specific process comprises the following steps:
and washing the pyrolyzed mixture for 2 times by using 2mol/L hydrochloric acid to remove inorganic impurities and the like, washing the mixture to be neutral by using ultrapure water, drying the mixture in an oven at the temperature of 80 ℃ to be constant in weight, and sieving the dried mixture by using a 100-mesh sieve to obtain the nitrogen and sulfur co-doped carbon material (NSC-2) with high nitrogen and sulfur content and developed micropores.
< example 3>
The embodiment provides a preparation method for preparing a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores by adopting cellulose and KSCN, which comprises the following steps:
step S1, mixing the biomass with an activating agent to obtain a mixture, wherein the specific process comprises the following steps:
oscillating and mixing cellulose and KSCN in an aqueous solution according to a mass ratio of 1:0.5 for 12 hours, and drying to obtain a mixture;
step S2, pyrolyzing the mixture under the atmosphere of inert gas to obtain a pyrolyzed mixture, which comprises the following specific steps:
putting the mixture into a tubular furnace for pyrolysis, heating to 500 ℃ at a heating rate of 10 ℃/min under the nitrogen flow of 0.1L/min for pyrolysis for 2h, and cooling to room temperature in a nitrogen atmosphere to obtain a pyrolyzed mixture;
step S3, acid washing and water washing the pyrolyzed mixture to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores, wherein the specific process comprises the following steps:
and washing the pyrolyzed mixture for 2 times by using 2mol/L hydrochloric acid to remove inorganic impurities and the like, washing the mixture to be neutral by using ultrapure water, drying the mixture in an oven at the temperature of 80 ℃ to be constant in weight, and sieving the dried mixture by using a 100-mesh sieve to obtain the nitrogen-sulfur co-doped carbon material (NSC-3) with high nitrogen-sulfur content and developed micropores.
< comparative example >
The embodiment provides a preparation method of a conventional carbon material, which comprises the following steps:
step S1, pyrolyzing the wood chips in an inert gas atmosphere to obtain pyrolyzed wood chips, wherein the specific process comprises the following steps:
putting the dried wood chips into a tubular furnace for pyrolysis, heating to 800 ℃ at a heating rate of 10 ℃/min under the nitrogen flow of 0.1L/min for pyrolysis for 1.5h, and cooling to room temperature in a nitrogen atmosphere to obtain pyrolyzed wood chips;
step S3, pickling, washing with water, and pyrolyzing the wood chips to obtain the conventional carbon material, wherein the specific process comprises the following steps:
washing the pyrolyzed wood chips with 2mol/L hydrochloric acid for 2 times to remove inorganic impurities and the like, washing with ultrapure water to be neutral, drying in an oven at 80 ℃ to constant weight, and sieving with a 100-mesh sieve to obtain the conventional carbon material (BC).
< test example >
Elemental analysis and nitrogen adsorption and desorption test characterization are carried out on the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores prepared in the embodiment and the conventional carbon material prepared in the comparative example, and the adsorption and removal performance test of organic pollutants (bisphenol A) and heavy metals (lead ions) in water is carried out on the carbon material.
The elemental analysis measurement results are: the nitrogen content and the sulfur content of the nitrogen-sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores prepared in the embodiment 1 are 4.87% and 13.2%; the nitrogen content of the nitrogen-sulfur co-doped carbon material (NSC-2) with high nitrogen-sulfur content and developed micropores prepared in the example 2 is 5.25%, and the sulfur content is 13.0%; the nitrogen content of the nitrogen-sulfur co-doped carbon material (NSC-3) with high nitrogen-sulfur content and developed micropores prepared in the example 3 is 5.28%, and the sulfur content is 14.4%; the nitrogen content of the conventional carbon material (BC) prepared in the comparative example was 0.10%, and the sulfur content was 0.26%.
FIG. 1 is a nitrogen adsorption and desorption curve of a nitrogen and sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores, which is prepared in example 1 of the present invention. FIG. 2 is a pore size distribution diagram of a nitrogen and sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores, which is prepared in example 1 of the present invention.
As can be seen from FIGS. 1 and 2, the nitrogen and sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur contents and developed micropores prepared in example 1 has a specific surface area of 1532m 2 The microporosity was 88%.
The specific surface area of the nitrogen-sulfur co-doped carbon material (NSC-2) with high nitrogen-sulfur content and developed micropores prepared in example 2 is 1485m 2 (iv)/g, microporosity of 69%; the specific surface area of the nitrogen and sulfur co-doped carbon material (NSC-3) with high nitrogen and sulfur content and developed micropores prepared in example 3 is 832m 2 (iv)/g, microporosity of 63%; the conventional carbon material (BC) prepared by the comparative example had a specific surface area of 577m 2 The microporosity was 49%.
FIG. 3 is a graph showing the effect of the carbon materials prepared in examples 1 to 3 of the present invention and comparative example on the adsorption and removal of organic pollutants and heavy metals in water.
As can be seen from fig. 3, the nitrogen-sulfur co-doped carbon material (NSC-1) with high nitrogen and sulfur content and developed micropores prepared in example 1 has a maximum adsorption capacity of 416mg/g for bisphenol a in water and a maximum adsorption capacity of 345mg/g for lead ions in water; the nitrogen and sulfur co-doped carbon material (NSC-2) with high nitrogen and sulfur content and developed micropores prepared in the embodiment 2 has the highest adsorption capacity of 556mg/g for bisphenol A in water and 333mg/g for lead ions in water; the nitrogen and sulfur co-doped carbon material (NSC-3) with high nitrogen and sulfur content and developed micropores prepared in the embodiment 3 has the highest adsorption capacity of 303 mg/g for bisphenol A in water and 357mg/g for lead ions in water; the maximum adsorption capacity of the conventional carbon material (BC) prepared by the comparative example on bisphenol A in water reaches 117mg/g, and the maximum adsorption capacity on lead ions in water reaches 59 mg/g. Compared with the conventional carbon material prepared by the traditional method, the nitrogen-sulfur doped carbon material prepared by the invention has greatly improved removal efficiency of organic pollutants and heavy metals in water.
The foregoing is a detailed description of embodiments that will enable those skilled in the art to make and use the invention. The technical solutions of the present invention, which can be improved or modified only by analysis, analogy or limited enumeration, should be within the scope of protection determined by the claims.

Claims (7)

1. A preparation method of a nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores is characterized by comprising the following steps:
step S1, mixing the biomass with an activating agent to obtain a mixture;
step S2, pyrolyzing the mixture under the atmosphere of inert gas to obtain a pyrolyzed mixture;
and step S3, acid washing and water washing the pyrolyzed mixture to obtain the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores.
2. The method for preparing nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores according to claim 1,
wherein the biomass in the step S1 comprises any one of wood chips, walnut shells, corn stalks, wheat stalks, shaddock peels, kitchen waste and peanut shells,
the activators include NaSCN, KSCN and Fe (SCN) 3 Any one or a mixture of several of them.
3. The method for preparing nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores according to claim 1,
wherein the mass ratio of the biomass to the activator in step S1 is 1: 0.4-1.2.
4. The method for preparing nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores according to claim 1,
wherein the pyrolysis temperature in the step S2 is 300-800 ℃, the time is 1-4h,
the flow rate of the inert gas is 0.05-1.0L/min.
5. The method for preparing nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores according to claim 1,
wherein, the washing agent for acid washing in the step S3 is hydrochloric acid or nitric acid, and the concentration is 1-2 mol/L.
6. The nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores is characterized by being prepared by the preparation method of the nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores according to any one of claims 1 to 5.
7. The application of the nitrogen and sulfur co-doped carbon material with high nitrogen and sulfur content and developed micropores in claim 6 in adsorption removal of organic pollutants and heavy metals in water.
CN202210809255.7A 2022-07-11 2022-07-11 Preparation method and application of nitrogen-sulfur co-doped carbon material with high nitrogen-sulfur content and developed micropores Pending CN115092925A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115445574A (en) * 2022-10-11 2022-12-09 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water

Citations (2)

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Publication number Priority date Publication date Assignee Title
RU2008143817A (en) * 2008-11-05 2010-05-10 Государственное образовательное учреждение высшего профессионального образования "Северо-Кавказский государственный техническтй ун METHOD FOR PRODUCING CARBON ADSORBENT FROM SUNFLOWER POD
CN112938969A (en) * 2021-03-23 2021-06-11 复旦大学 Method for preparing nitrogen-sulfur co-doped activated carbon by pore-forming/doping integrated activating agent and application of method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2008143817A (en) * 2008-11-05 2010-05-10 Государственное образовательное учреждение высшего профессионального образования "Северо-Кавказский государственный техническтй ун METHOD FOR PRODUCING CARBON ADSORBENT FROM SUNFLOWER POD
CN112938969A (en) * 2021-03-23 2021-06-11 复旦大学 Method for preparing nitrogen-sulfur co-doped activated carbon by pore-forming/doping integrated activating agent and application of method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115445574A (en) * 2022-10-11 2022-12-09 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water
CN115445574B (en) * 2022-10-11 2024-01-16 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water

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