CN114682217A - Metal monatomic doped biomass carbon adsorption material, preparation method and application - Google Patents
Metal monatomic doped biomass carbon adsorption material, preparation method and application Download PDFInfo
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- CN114682217A CN114682217A CN202210358906.5A CN202210358906A CN114682217A CN 114682217 A CN114682217 A CN 114682217A CN 202210358906 A CN202210358906 A CN 202210358906A CN 114682217 A CN114682217 A CN 114682217A
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- biomass charcoal
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- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000002028 Biomass Substances 0.000 title claims abstract description 82
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 10
- 229910052799 carbon Inorganic materials 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003610 charcoal Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 42
- 125000004429 atom Chemical group 0.000 claims abstract description 29
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- 238000012360 testing method Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
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- 239000010431 corundum Substances 0.000 claims description 13
- 229910052573 porcelain Inorganic materials 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- -1 rare earth metal chloride Chemical class 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 8
- 235000020679 tap water Nutrition 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
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- 239000007789 gas Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229930182555 Penicillin Natural products 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229940124307 fluoroquinolone Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 150000002960 penicillins Chemical class 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims 1
- 125000005461 organic phosphorous group Chemical group 0.000 claims 1
- 235000020188 drinking water Nutrition 0.000 abstract description 10
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 11
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
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- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Organic Chemistry (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a metal monatomic doped biomass charcoal adsorption material, a preparation method and application thereof, and the invention can realize high-efficiency adsorption removal on refractory organic matters with environmental concentration (0.3 mu g/L < c <1 mu g/L) in drinking water. The material has an atomic level heterojunction interface which can form an effective interface electric field, and an effective electron migration channel is constructed by combining a monoatomic structure, so that the electron migration capability is enhanced. In the process of adsorbing the organic matters with the environmental concentration difficult to degrade in water, the metal monoatomic atoms generate stronger coulomb force and can attract the part with heterogeneous charges in a target object; the C atom in the second shell layer of the metal monoatomic atom can effectively activate the electrons in the outer electron orbit of the metal atom, and the strong interaction between the C atom and the electrons can further increase the adsorption performance and the adsorption stability of the C atom, thereby realizing the efficient removal of the refractory organic matters with environmental concentration in the drinking water. In addition, the adsorbing material has the advantages of simple preparation process, wide raw material source, low price and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, relates to the technical research on the preparation of transition metal and rare earth metal monatomic doped biomass charcoal materials, and particularly relates to the innovation of a method for efficiently adsorbing organic matters which are difficult to degrade in environmental concentration in drinking water by applying the materials.
Background
In recent years, organic substances that are difficult to degrade have been frequently detected in surface water and groundwater, and thus have been receiving much attention from researchers. The substance generally has the characteristics of genotoxicity, durability, bioaccumulation, long-distance migration and the like. The refractory organic pollutants are of a wide variety, including persistent organic pollutants, environmental endocrine disruptors, pharmaceuticals, personal care products, and the like. These contaminants pose high risks and hazards to the ecology and human beings in water even at environmental concentration levels (0.3 μ g/L < c <1 μ g/L). [1,2] because the substances have stable structures and generally have antibacterial performance or biological toxicity, the traditional sewage treatment process (comprising a biological method, an advanced oxidation method, a chemical method and the like) can not realize the effective degradation of target pollutants at the level of environmental concentration [3-6 ]. In 2022, in the new edition of drinking water quality standard (GB5749-2022) released in China, the safety limit of refractory organic matters is more strict, and especially the safety limit of organic matters with high toxicity, high carcinogenicity and high teratogenicity, such as perfluorinated compounds, pesticides, etc., reaches the ng/L level. [7] Therefore, the efficient and low-consumption removal of the refractory organics at the environmental concentration level in drinking water is an environmental problem which needs to be solved urgently.
The adsorption method has the advantages of simple operation, less secondary pollution, low operation cost and the like, and the method can adsorb and enrich the low-concentration pollutants in the water body so as to achieve the purpose of removing the refractory organic matters in the water body. The method has no secondary pollution to water body, and is suitable for drinking water treatment process. However, in past research, most of adsorbing materials generally have higher adsorption capacity for refractory organic matters, but cannot effectively remove the refractory organic matters with environmental concentration in a water body. [8] In recent years, researchers have conducted exploratory studies on the problem of environmental concentration level pollutant adsorption, and developed functional adsorbing materials, for example, Wang et al synthesized a magnetic nanoparticle adsorbing fluor-graphene-based adsorbent, which can reduce perfluorooctane sulfonic acid and perfluorooctane sulfonic acid in environmental water from 5 μ g/L to <50 ng/L. [9] However, the materials still have the problems of low adsorption capacity, low dissolution and adsorption rate of the adsorbent and the like.
Each single atom on the surface of the monatomic catalyst is an independent catalytic active center, and the atom utilization rate is close to 100 percent; meanwhile, the electronic structure of the catalyst can be effectively changed by the size effect of atomic level, so that the catalyst is endowed with unique catalytic performance and is widely concerned in the field of catalysis. In the catalytic reaction, the first step is mostly initiated by the adsorption of the monoatomic site and the target substance. Therefore, the monatomic catalytic material can be used as a potential adsorbent. For example, Gao et al have studied a series of iron and nickel monoatomic dispersion graphene substrates for selective adsorption of target gas components (e.g., toxic acid gases) by theoretical calculation methods. [10,11] at present, no study on the removal of refractory organic matters in liquid phase by using a single-atom reinforced adsorption material is available at home and abroad.
Reference documents:
[1]Richardson,S.D.；Ternes,T.A.,Water analysis:emerging contaminants and current issues.Anal.Chem.2014,86,2813-2848.
[2]Stuart,M.；Lapworth,D.；Crane,E.；Review of risk from potential emerging contaminants in UK groundwater.Sci.Total Environ.2012,416,1-21.
[3] the research on the existence and removal effect of perfluorinated compounds in municipal sewage treatment plants, such as Van Qing, Dengdibo, Zhouqin and the like, and the environmental pollution and control 2011,3330-35.
[4]Sui,Q.；Huang,J.；Deng,S.,Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in different biological wastewater treatment processes.Environ.Sci,Technol.2011,45,3341-3348.
[5]Sui,Q.；Huang,J.；Deng,S.,Occurrence and removal of pharmaceuticals,caffeine and DEET in wastewater treatment plants of Beijing,China.Water Res.2010,44,417-426.
[6]Sui,Q.；Huang.J.；Deng,S.,Rapid determination of pharmaceuticals from multiple therapeutic classes in wastewater by solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry.Chin.Sci.Bull.2009,54,4633-4643.
[7]SAC,Standards for drinking water quality(GB 5749-2022),2020.https://std.sacinfo.org.cn/home
[8]Xing,D.；Chen,Y.；Zhu,J.；Liu,T.；Fabrication of hydrolytically stable magnetic coreshell aminosilane nanocomposite for the adsorption of PFOS and PFOA.Chemosphere.2020,251,126384.
[9]Wang,W.；Xu,Z.；Zhang,X.；Wimmer,A.；Shi,E.；Qin,Y.；
Zhao,X.；Zhou,B.；Li,L.,Rapid and efficient removal of organic micropollutants from environmental water using a magnetic nanoparticles-attached fluorographene-based sorbent.Chem.Eng.J.2018,343,61-68.
[10]Gao,Z.；Li,L.；Huang,H.；Xu,S.；Yan,G.；Zhao,M.；Ding,Z.,Adsorption characteristics of acid gases(NO,NO2,SO2 and SO3)on different single-atom nickel adsorbent:a first-principles study.Appl.Surf.Sci.2020,527,146939.
[11]Yang,W.；Gao,Z.；Liu,X.；Ding,X.；Yan,W.,The adsorption characteristics of As2O3,Pb0,PbO and PbCl2 on single atom iron adsorbent with graphene-based substrates.Chem.Eng.J.2019,361,304-313.
Disclosure of Invention
In order to solve the problem that the prior art can not effectively remove the organic matters which are difficult to degrade in the environmental concentration in the drinking water, a transition metal or rare earth metal monoatomic atom is introduced into a carbon-based material structure to construct a metal monoatomic adsorption site; the C atom in the second shell layer of the metal monoatomic atom can effectively activate the outer electron orbit of the metal atom, and a strong interaction can be formed between the C atom and the outer electron orbit, so that the electron transfer capacity is enhanced, and the adsorption performance and the adsorption stability of the material to target pollutants can be further improved.
The invention discloses a preparation method and application of a metal monatomic doped biomass carbon adsorption material, wherein the technical scheme is as follows:
a metal monatomic doping biomass charcoal adsorption material, characterized by: the surface of the adsorbing material has metal monoatomic atoms, and the coordination structure is metal atom-oxygen atom; at the same time, strong interactions are formed between the metal monoatomic atoms and the adjacent C atoms.
Based on the metal monatomic doped biomass charcoal adsorption material, the invention also discloses a preparation method of the metal monatomic doped biomass charcoal adsorption material, which is characterized by comprising the following steps:
step 1: firstly, putting dry biomass into a sodium hydroxide solution with a certain molar concentration, stirring at room temperature, and then putting a reaction solution into an oven for pretreatment;
step 2: taking out the pretreated biomass, cleaning the residual alkaline solution on the surface, and then putting the pretreated biomass into a transition metal chloride or rare earth metal chloride aqueous solution with a certain molar concentration for stirring at room temperature;
and step 3: putting the reaction liquid obtained in the step (2) into an oven until the reaction liquid is completely dried, and then putting the reaction liquid into a corundum porcelain boat; uniformly scattering a proper amount of sodium hydroxide into the corundum porcelain boat, wherein the adding mass of the sodium hydroxide is 0.02-0.1 time of the mass of the dry biomass; then, with N2Putting the corundum porcelain boat into a tube furnace for protective gas, heating and calcining in a gradient manner, respectively maintaining the temperature at 300 ℃, 550, 750 and 950 ℃ for reaction for a period of time, and taking out the biomass charcoal material after the reaction is finished and the temperature is reduced to room temperature;
and 4, step 4: pouring the biomass charcoal material into a sodium hydroxide aqueous solution, standing, performing suction filtration, and leaching with deionized water; pouring the mixture into a hydrochloric acid aqueous solution, standing, performing suction filtration, and leaching with deionized water until the pH of effluent is more than 6; and (3) putting the material subjected to suction filtration into a drying oven for drying to obtain the metal monatomic doped biomass charcoal high-efficiency adsorbing material.
The invention also discloses an application method of the adsorbing material prepared by the preparation method of the metal monatomic doped biomass carbon efficient adsorbing material, the application method takes the metal monatomic doped biomass carbon as an adsorbent to remove the organic matters which are difficult to degrade and have the environmental concentration (0.3 mug/L < c <1 mug/L) in the water body, and the application method is characterized in that: the method comprises the following steps:
grinding the metal monatomic doped biomass carbon material, sieving the ground metal monatomic doped biomass carbon material by using a sieve of 40-80 meshes, adding the sieved powder into a filter column, filling the filter column, screwing a cock on the front and back of the filter column, placing the filter column into an adsorption test system, testing the temperature to be 25 ℃, configuring 0.3-1.0 mu g/L of refractory organic matter solution by using tap water, taking the refractory organic matter solution as inlet water, enabling the adsorption test system to maintain stable outlet water quality, enabling the content of the refractory organic matter in the outlet water to be between 10-50ng/L, and enabling the adsorption capacity of the adsorption material to the refractory organic matter with environmental concentration to be 500mg/g under a dynamic adsorption condition.
Advantageous effects
The invention can realize high-efficiency adsorption removal of refractory organic matters with environmental concentration (c is less than 1 mug/L and 0.3 mug/L) in drinking water. The material has an atomic level heterojunction interface which can form an effective interface electric field, and an effective electron migration channel is constructed by combining a monoatomic structure, so that the electron migration capability is enhanced. In the process of adsorbing the organic matters with the environmental concentration difficult to degrade in the water body, the metal monoatomic atoms can generate stronger coulomb force and can attract the part with heterogeneous charges in the target object; the C atom in the second shell layer of the metal monoatomic can effectively activate the electrons in the outer electron orbit of the metal atom, and the strong interaction between the C atom and the electrons can further increase the adsorption performance and the adsorption stability of the C atom, thereby realizing the efficient removal of the environmental concentration refractory organic matters in the drinking water. In addition, the adsorbing material has the advantages of simple preparation process, wide raw material source, low price and easy large-scale production.
Drawings
FIG. 1 is a schematic diagram of a dynamic adsorption system of the present invention;
in the figure: the device comprises a water inlet tank (1), a water inlet pump (2), a sealing cover (3), an adsorption column (4) and a water outlet tank (5).
Detailed Description
The following detailed description of the invention refers to the accompanying drawings.
A metal monatomic doped biomass charcoal adsorption material is characterized in that: the surface of the adsorbing material has metal monoatomic atoms, and the coordination structure is metal atom-oxygen atom; at the same time, strong interactions are formed between the metal monoatomic atoms and the adjacent C atoms.
Based on the metal monatomic doped biomass carbon adsorption material, the invention also discloses a preparation method of the metal monatomic doped biomass carbon adsorption material, which is characterized by comprising the following steps:
step 1: firstly, the dried biomass is put into a sodium hydroxide solution with the concentration of 4mol/L, the mass ratio of the dried biomass to the sodium hydroxide is 2:1-1:2, the pretreatment process is carried out, and the mixture is stirred for 12-36h at room temperature. After the reaction solution is put into an oven, the temperature is adjusted to 60-80 ℃ for reaction for 24-48 h. (wherein, when the reaction temperature is less than 60 ℃ or the reaction time is less than 24h, the pretreatment process is insufficient, the hydrolysis of lignin and other impurities is incomplete, and when the reaction temperature is more than 80 ℃ or the reaction time is more than 42h, the cellulose component in the biomass structure is hydrolyzed and damaged, and the subsequent metal monatomic load is influenced.) the pretreated biomass is taken out, and the alkaline solution remained on the surface is cleaned. Then the mixture is put into 0.03 to 0.12mol/L transition metal chloride (including but not limited to iron, copper, nickel, scandium, manganese, vanadium and titanium) or rare earth metal chloride (including but not limited to samarium, erbium, cerium, europium and neodymium) aqueous solution, the adding molar quantity of the metal chloride is 0.01 to 0.05 time of that of sodium hydroxide, and the mixture is stirred for 12 to 24 hours at room temperature. (wherein, when the amount of the transition metal chloride or the rare earth metal chloride added is too large, metal nanoparticles are formed during the biomass calcination process, and monoatomic species cannot be formedStructure; when the addition amount of the transition metal chloride or the rare earth metal chloride is too small, the loading amount of single atoms on the surface of the biomass charcoal can be reduced, and the adsorption performance is influenced. ) Then, the reaction liquid is put into a 60 ℃ oven until the reaction liquid is completely dried, and then the reaction liquid is put into a corundum porcelain boat. And uniformly scattering a proper amount of sodium hydroxide into the corundum porcelain boat, wherein the adding mass of the sodium hydroxide is 0.02-0.1 time of the mass of the dried coconut shells. (in the step, sodium hydroxide added before calcination can be melted at high temperature to provide a reaction atmosphere of molten alkali and promote the formation of a monoatomic structure and the rearrangement of a carbonized structure; if the adding amount of the sodium hydroxide before calcination is too large, the micro morphology of the biomass charcoal in the calcination stage can be damaged and the monoatomic load can be inhibited; if the adding amount of the sodium hydroxide before calcination is too small, the reaction atmosphere of sufficient molten alkali cannot be provided, and the monoatomic load can be too small.) then, N is used2And (3) putting the corundum porcelain boat into a tube furnace for shielding gas, heating up and calcining in a gradient manner at a heating rate of 3-5 ℃/min, respectively maintaining the temperature at 300 ℃, 550, 750 and 950 ℃ for reaction for 0.5-1h, and after the reaction is finished, cooling to room temperature, and taking out the biomass charcoal material. (the gradient temperature rise in the calcining process is to fully carry out the reaction in each stage, wherein 300 ℃ is the full cracking of oxygen-containing functional groups in the biomass, 550 ℃ is the primary carbonization process of the biomass material, 750 ℃ is the loading stage of the single atom of the molten alkali auxiliary metal, and the final 950 ℃ is the structural rearrangement and morphology regulation stage after carbonization.)
Step 2: the biomass charcoal material is poured into 0.5mol/L sodium hydroxide aqueous solution, and the using amount of the sodium hydroxide aqueous solution is 200ml for every 1g of the biomass charcoal material. (the function of adding the alkaline solution is to effectively dissolve the by-products containing the metal components generated in the high-temperature process, such as metal complexes, etc.) standing for 24h, filtering, and rinsing with deionized water for 3 times. Then pouring the mixture into 0.5mol/L hydrochloric acid aqueous solution, wherein the dosage of the hydrochloric acid aqueous solution is 3-10 times of that of the sodium hydroxide aqueous solution. Standing for 24h, filtering, and leaching with deionized water until the pH of effluent is more than 6. And (3) drying the material subjected to suction filtration in a drying oven at 60 ℃ to obtain the metal monoatomic-doped biomass charcoal. (in the step, too low concentration of HCl aqueous solution can cause incomplete removal of alkaline substance residues in the structure of the biomass charcoal material, and too high HCl can cause water consumption in the subsequent water washing step.)
The invention also discloses an application method of the adsorbing material prepared by the preparation method of the monatomic doped biomass carbon efficient adsorbing material, the application method takes the metal monatomic doped biomass carbon as an adsorbent to remove the organic matters which are difficult to degrade and have the environmental concentration (0.3 mug/L < c <1 mug/L) in the water body, and the preparation method is characterized in that: the method comprises the following steps: grinding a metal monatomic doped biomass carbon material, sieving the ground material by using a sieve (40-80 meshes), adding the sieved powder into a filter column, filling the filter column, screwing cocks on the front and back of the filter column, putting the filter column into an adsorption test system, testing the temperature at 25 ℃, using tap water to prepare 0.3-1.0 mu g/L of a refractory organic matter (including but not limited to perfluorinated compounds, fluoroquinolones, penicillins and organic phosphorus flame retardants) solution as water inlet, putting the water inlet into a water inlet tank (1) as shown in figure 1, pumping the water into an adsorption column (4) with a sealing cover (3) by using a water inlet pump (2), and finally flowing into a water outlet tank (5). The adsorption test system can maintain stable effluent quality, the content of refractory organics in the effluent is between 10 and 50ng/L, and the adsorption capacity of the adsorption material on the refractory organics with environmental concentration is 500mg/g under the condition of dynamic adsorption.
Example 1
Preparing a metal monatomic doped biomass charcoal adsorption material:
preferably, 10g of dried coconut shell is put into a 4mol/L sodium hydroxide solution, the mass ratio of the dried coconut shell to the sodium hydroxide is 1:1, the pretreatment process is carried out, the mixture is stirred for 36 hours at room temperature, and then the reaction solution is put into an oven and the temperature is adjusted to 60 ℃ for reaction for 24 hours. And taking out the pretreated coconut shell, and cleaning the surface of the coconut shell with residual alkaline solution. Then the mixture is put into 0.03mol/L ferric chloride aqueous solution, the adding molar weight of ferric chloride is 0.02 time of that of sodium hydroxide, and the mixture is stirred for 24 hours at room temperature. Then, the reaction liquid is put into a 60 ℃ oven until the reaction liquid is completely dried, and then the reaction liquid is put into a corundum porcelain boat. 1g of sodium hydroxide is uniformly scattered into a corundum porcelain boat, and then N is added2Putting the corundum porcelain boat into a tube furnace for protective gas, and carrying out gradient temperature rise calcination at the temperature rise rate of 5 ℃/min at 300 DEG, respectively,550. And (3) keeping the temperature of 750 ℃ and 950 ℃ respectively for reaction for 1h, cooling to room temperature after the reaction is finished, and taking out the biomass charcoal material. Thereafter, the calcined material was poured into a 0.5mol/L aqueous sodium hydroxide solution in an amount of 200ml per 1g of the biomass charcoal material. Standing for 24h, filtering, and rinsing with deionized water for 3 times. Then the mixture is poured into 0.5mol/L hydrochloric acid aqueous solution, and the dosage of the hydrochloric acid aqueous solution is 3 times of that of the sodium hydroxide aqueous solution. Standing for 24h, filtering, and leaching with deionized water until the pH of effluent is more than 6. Drying the material after suction filtration in a drying oven at 60 ℃ to obtain Fe monatomic doped biomass charcoal (BC-Fe)1)。
In the same way, only copper chloride, nickel chloride, scandium chloride, manganese chloride, vanadium chloride, titanium chloride, samarium chloride, erbium chloride, cerium chloride, europium chloride and neodymium are substituted for ferric chloride. Preparation of a series of metal monoatomic-doped biomass charcoal (BC-Cu)1、BC-Ni1、BC-Sc1、BC-Mn1、BC-V1、BC-Ti1、BC-Sm1、BC-Er1、BC-Ce1、BC-Eu1And BC-Nd1). The surface of the biomass carbon material is confirmed to be of a metal monoatomic structure without metal nanoparticles by means of transmission electron microscopy, EXAFS, X-ray photoelectron spectroscopy, in-situ Raman spectroscopy, elemental analysis, electron spin resonance spectroscopy and other characterization means.
Example 2
The adsorption performance ratios of different metal monatomic doped biomass carbon materials are as follows: respectively taking perfluorooctanoic acid (PFOA), Ciprofloxacin (CIP) and tris (2-chloroethyl) phosphate (TCEP) as target pollutants, preparing 1 mu g/L concentration aqueous solution from tap water as inlet water, and respectively taking BC-Fe1、BC-Cu1、BC-Ni1、BC-Sc1、BC-Mn1、BC-V1、BC-Ti1、BC-Sm1、BC-Er1、BC-Ce1、BC-Eu1And BC-Nd1Grinding the materials, sieving with 40 mesh sieve, filling filter column, placing into dynamic adsorption test system, testing at 25 deg.C for 48 hr, collecting 50ml of effluent per hour as test sample, filtering with 0.22 μm filter membrane, and placing into plastic sample bottleEvaporating the dry water at 60 ℃, eluting the sample bottle by using 2mL of ultrapure water, repeatedly washing for 3 times, and extracting the organic matters in the sample bottle by using a solid phase extraction method for testing.
The PFOA in the sample is determined by the ultra-high performance liquid chromatography-mass spectrometry combined technology, and the result shows that the adsorption performance of the transition metal single-atom doped biomass charcoal material is superior to that of the rare earth metal single-atom doped biomass charcoal material, BC-Fe1The adsorption performance of the adsorption material is optimal, and the adsorption rate is over 96 percent. Therefore, BC-Fe is adopted in the subsequent adsorption test1。
Example 3
The metal monatomic doped biomass charcoal material is used for continuous adsorption test of the refractory pollutants in tap water: respectively taking perfluorooctanoic acid (PFOA), Ciprofloxacin (CIP) and tris (2-chloroethyl) phosphate (TCEP) as target pollutants, preparing 1 mu g/L concentration aqueous solution from tap water as inlet water, and mixing BC-Fe1Grinding the materials, sieving by a 40-mesh sieve, filling a filter column after sieving, putting the filter column into a dynamic adsorption test system, continuously operating for 14 days at the test temperature of 25 ℃, taking 50mL of effluent water per hour as a test sample, filtering the test sample by a 0.22-micron filter membrane, putting the test sample in a plastic sample bottle, evaporating dry water at 60 ℃, eluting the sample bottle by 2mL of ultrapure water, repeatedly washing for 3 times, and extracting organic matters by a solid phase extraction method for testing.
The concentrations of PFOA, CIP and TCEP are measured by the ultra-performance liquid chromatography-mass spectrometry combined technology, and the result shows that BC-Fe is used in the continuous operation process1The adsorption rate of the material to the environmental concentration PFOA, CIP and TCEP can be kept above 96%, and the material has no attenuation phenomenon.
Example 4
And (3) impact load resistance test in the adsorption process of the metal monatomic doped biomass carbon material: respectively taking perfluorooctanoic acid (PFOA), Ciprofloxacin (CIP) and tris (2-chloroethyl) phosphate (TCEP) as target pollutants, preparing 1 mu g/L and 1mg/L aqueous solutions from tap water as inlet water, and taking BC-Fe1Grinding the materials, sieving with 40 mesh sieve, filling filter column, placing into dynamic adsorption test system, testing at 25 deg.C, feeding water at 1mg/L concentration for 1 hr, draining water, and concentrating at 1 μ g/LAnd (3) running for 5h while repeatedly carrying out water inflow for 10 times, taking 50mL of effluent water per hour as a test sample, filtering the test sample by using a 0.22-micron filter membrane, putting the test sample in a plastic sample bottle to evaporate dry water at 60 ℃, eluting the sample bottle by using 2mL of ultrapure water, repeatedly washing the sample bottle for 3 times, and extracting organic matters in the test sample by using a solid phase extraction method to reserve the test sample.
PFOA, CIP and TCEP concentrations are measured by an ultra-performance liquid chromatography-mass spectrometry combined technology, and the result shows that BC-Fe1The adsorption capacity of the material to PFOA, CIP and TCEP reaches 250mg/gBC-Fe1The above.
The invention realizes the removal of the organic matters with the environmental concentration difficult to degrade in the water body by doping the transition metal and rare earth metal monoatomic material with the biomass charcoal adsorbing material for the first time. The alkaline solution is used for pretreating the biomass in the step 1 to promote the decomposition of lignin in the structure of the biomass, and a cellulose part is reserved to achieve the effect of regulating and controlling the structural components and the morphology. This process can also increase the loading of subsequent metal monoatomic precursors. In the calcining process, the added sodium hydroxide is molten at high temperature, and can provide a liquid reaction environment for pyrolysis and monatomic doping. In addition, under the high-temperature condition, the sodium hydroxide can effectively increase the number of oxygen-containing functional groups on the surface of the biomass charcoal, and is beneficial to single-atom capture and formation of a stable coordination structure. In the step 2, the calcined biomass carbon material is soaked by the alkali solution, so that byproducts (such as metal complexes and the like) containing metal components generated in the high-temperature process can be effectively dissolved, the surface charge of the adsorption material can be adjusted in the subsequent pickling process, and unreacted metal precursors on the surface of the adsorption material can be removed. The method for doping the single atom on the surface of the biomass charcoal material has universality for transition metals and rare earth metals, and the formation of an isolated metal single atom structure on the surface of the biomass charcoal substrate is confirmed by structural characterization means such as X-ray absorption fine structure spectrum (EXAFS), X-ray photoelectron spectroscopy, spherical aberration correction scanning electron microscope (STEM), in-situ Raman spectroscopy and the like. The monoatomic structure of the material is metal atom-oxygen atom (M-O)nThe number of coordination bonds varies depending on the kind of metal). Taking Fe single atom as an example, the results of the atomic-level structural characterization tests such as EXAFS and STEM show that the coordination environment of Fe atom is Fe-O4The valence state of Fe is between 2+ and 3+, and an atomic-scale heterogeneous interface is formed between the Fe and the substrate, so that an interface electric field can be formed, and the electron transfer is promoted. According to the calculation of the density functional theory, the structure can effectively regulate and control the local electron density of the material, construct an effective electron migration channel and strengthen the electron migration capability. In the process of adsorbing the organic matter with the environmental concentration difficult to degrade in the water body, Fe single atoms can generate stronger coulomb force and can effectively attract the part with heterogeneous charges in target pollutants; the EXAFS result shows that strong interaction exists between the Fe monoatomic atom and the C atom in the second shell layer, and the DFT calculation shows that the part of the C atoms can provide electrons for the Fe monoatomic atom due to the existence of an electron migration channel, effectively activate the electrons in the outer-layer orbit, strengthen the interaction between the Fe monoatomic atom and the C atom in the second shell layer, further increase the adsorption capacity and the adsorption stability of the material on target pollutants, and realize the efficient removal of the refractory organic matters with environmental concentration in the water body. In addition, the coordination numbers of different metal monoatomic atoms are different from each other due to the difference of valence electron orbital structures, and the charges of the metal monoatomic atoms are different. In the comparison of adsorption performance, the adsorption performance of the transition metal monatomic biomass charcoal material is generally higher than that of rare earth metals, which is caused by the fact that the existence of the sub-electron outer layer orbit in the transition metal can further improve the electron transfer performance. The preparation method of the metal monatomic doped biomass charcoal adsorbing material provided by the invention has the advantages of simple process, low cost, wide raw material source, excellent adsorption performance and the like, is a monatomic adsorbing material method easy for industrial production, and can realize the high-efficiency and low-consumption removal of pollutants with difficult degradation of environmental concentration in drinking water.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The metal monatomic doping biomass charcoal adsorption material, characterized by: the surface of the adsorbing material has metal monoatomic atoms, and the coordination structure is metal atom-oxygen atom; at the same time, strong interactions are formed between the metal monoatomic atoms and the adjacent C atoms.
2. A preparation method of a metal monatomic doped biomass charcoal adsorbing material, which comprises the metal monatomic doped biomass charcoal adsorbing material of claim 1, and is characterized by comprising the following steps:
step 1: firstly, putting dry biomass into a sodium hydroxide solution with a certain molar concentration, stirring at room temperature, and then putting a reaction solution into an oven for pretreatment;
step 2: taking out the pretreated biomass, cleaning the residual alkaline solution on the surface, and then putting the pretreated biomass into a transition metal chloride or rare earth metal chloride aqueous solution with a certain molar concentration for stirring at room temperature;
and step 3: putting the reaction liquid obtained in the step (2) into an oven until the reaction liquid is completely dried, and then putting the reaction liquid into a corundum porcelain boat; uniformly scattering a proper amount of sodium hydroxide into the corundum porcelain boat, wherein the adding mass of the sodium hydroxide is 0.02-0.1 time of the mass of the dried biomass; then, with N2Putting the corundum porcelain boat into a tube furnace for protective gas, heating and calcining in a gradient manner, respectively maintaining the temperature at 300 ℃, 550, 750 and 950 ℃ for reaction for a period of time, and taking out the biomass charcoal material after the reaction is finished and the temperature is reduced to room temperature;
and 4, step 4: pouring the biomass charcoal material into a sodium hydroxide aqueous solution, standing, performing suction filtration, and leaching with deionized water; pouring the mixture into a hydrochloric acid aqueous solution, standing, performing suction filtration, and leaching with deionized water until the pH of effluent is more than 6; and (3) putting the material subjected to suction filtration into a drying oven for drying to obtain the metal monatomic doped biomass charcoal high-efficiency adsorbing material.
3. The preparation method of the metal monatomic doped biomass charcoal adsorbing material according to claim 2, characterized by comprising the following steps: the step 1 further comprises the following steps: putting the dried biomass into a 4mol/L sodium hydroxide solution, wherein the mass ratio of the dried biomass to the sodium hydroxide is 2:1-1:2, carrying out a pretreatment process, stirring at room temperature for 12-36h, then putting the reaction solution into an oven, and adjusting the temperature to 60-80 ℃ to react for 24-48 h.
4. The preparation method of the metal monatomic doped biomass charcoal adsorbing material according to claim 2, characterized by comprising the following steps: the step 2 further comprises the following steps: putting the mixture into 0.03-0.12mol/L transition metal chloride or rare earth metal chloride aqueous solution, wherein the adding molar weight of the metal chloride is 0.01-0.05 times of that of sodium hydroxide, and stirring at room temperature for 12-24 h.
5. The preparation method of the metal monatomic doped biomass charcoal adsorbing material according to claim 2, characterized by comprising the following steps: the step 3 further comprises the following steps: putting the reaction solution into a 60 ℃ oven until the reaction solution is completely dried; putting the corundum porcelain boat into a tube furnace, heating up and calcining in a gradient way, wherein the heating up rate is 3-5 ℃/min, the temperature is respectively maintained at 300 ℃, 550, 750 and 950 ℃ for reaction for 0.5-1h, and the temperature is cooled to room temperature after the reaction is finished.
6. The preparation method of the biomass charcoal adsorbing material doped with the metal monoatomic atom according to claim 2, wherein the preparation method comprises the following steps: the step 4 further comprises the following steps: the biomass charcoal material is poured into 0.5mol/L sodium hydroxide aqueous solution, and the using amount of the sodium hydroxide aqueous solution is 200ml for every 1g of the biomass charcoal material. Standing for 24h, filtering, and rinsing with deionized water for 3 times. Then pouring the mixture into 0.5mol/L hydrochloric acid aqueous solution, wherein the dosage of the hydrochloric acid aqueous solution is 3-10 times of that of the sodium hydroxide aqueous solution. Standing for 24h, filtering, and leaching with deionized water until the pH of effluent is more than 6. And (4) putting the filtered material into a drying oven for drying at 60 ℃.
7. The preparation method of the metal monatomic doped biomass charcoal adsorbing material according to claim 4, characterized by comprising the following steps: the transition metal chloride comprises ferric chloride, cupric chloride, nickel chloride, scandium chloride, manganese chloride, vanadium chloride and titanium chloride; the rare earth metal chloride comprises samarium chloride, erbium chloride, cerium chloride, europium chloride and neodymium chloride.
8. An application method of the adsorption material prepared by the preparation method of the metal monatomic doped biomass charcoal adsorption material according to any one of claims 2 to 7, which uses the metal monatomic doped biomass charcoal as an adsorbent to remove the refractory organics with the environmental concentration (0.3 μ g/L < c <1 μ g/L) in the water body, and is characterized in that: the method comprises the following steps:
grinding the metal monatomic doped biomass carbon material, sieving the ground metal monatomic doped biomass carbon material by using a sieve of 40-80 meshes, adding the sieved powder into a filter column, filling the filter column, screwing a cock on the front and back of the filter column, placing the filter column into an adsorption test system, testing the temperature to be 25 ℃, configuring 0.3-1.0 mu g/L of refractory organic matter solution by using tap water, taking the refractory organic matter solution as inlet water, enabling the adsorption test system to maintain stable outlet water quality, enabling the content of the refractory organic matter in the outlet water to be between 10-50ng/L, and enabling the adsorption capacity of the adsorption material to the refractory organic matter with environmental concentration to be 500mg/g under a dynamic adsorption condition.
9. The method for applying the adsorbing material according to claim 8, wherein the refractory organics include, but are not limited to, perfluor compounds, fluoroquinolones, penicillins, and organic phosphorous flame retardants.
10. The method of using the adsorbent material according to claim 8, wherein: the source of the inlet water comprises deionized water, surface water and underground water besides tap water.
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| CN116159549A (en) * | 2023-04-26 | 2023-05-26 | 西安博探石油工程有限公司 | Hydrogen sulfide gas adsorption material and preparation method and application thereof |
| CN116159537A (en) * | 2023-01-17 | 2023-05-26 | 南京邮电大学 | Magnetic adsorbent and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8900528D0 (en) * | 1988-06-17 | 1989-03-08 | Ca Minister Energy | Catalytic metal clusters and processes for their preparation |
| CA2363456A1 (en) * | 2000-11-22 | 2002-05-22 | Air Products And Chemicals, Inc. | Hydrogen storage using carbon-metal hybrid compositions |
| CN106064051A (en) * | 2016-06-10 | 2016-11-02 | 苏州巨联环保科研有限公司 | A kind of preparation method of the graphene-based composite adsorbing material of loading nano silvery |
| CN108236919A (en) * | 2016-12-27 | 2018-07-03 | 海门市源美美术图案设计有限公司 | A kind of graphene oxide of surface modification and its application in pharmaceutical wastewater processing |
| WO2018205610A1 (en) * | 2017-05-12 | 2018-11-15 | 华南理工大学 | Porous biogold-doped zero-valent iron catalyst, preparation method therefor and use thereof |
| US20190276943A1 (en) * | 2018-03-08 | 2019-09-12 | Uchicago Argonne, Llc | Carbon supported single atom carbon dioxide reduction electro catalysts |
| AU2020101584A4 (en) * | 2019-07-31 | 2020-09-10 | Hefei University Of Technology | Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton |
| CN112028052A (en) * | 2020-09-18 | 2020-12-04 | 西北大学 | Preparation method and application of biomass carbon-based Fe monatomic-N doped porous carbon material |
| CN112121771A (en) * | 2020-09-25 | 2020-12-25 | 江苏省环境科学研究院 | Biomass adsorbent for removing refractory organic pollutants, preparation method and application method thereof |
| CN113070036A (en) * | 2021-03-29 | 2021-07-06 | 浙江科技学院 | Biomass-based functional carbon, preparation method thereof and application of biomass-based functional carbon in removal of micro-plastics in water body |
| CN113441157A (en) * | 2021-07-02 | 2021-09-28 | 南昌大学 | Photoreduction synthesis method of supported high-dispersion metal monatomic catalyst |
| CN113731416A (en) * | 2021-07-30 | 2021-12-03 | 联科华技术有限公司 | Local acid site modified monatomic catalyst, preparation method and application thereof |
| US20220062864A1 (en) * | 2020-09-01 | 2022-03-03 | Uchicago Argonne, Llc | Method of preparing electrocatalysts for converting carbon dioxide to chemicals |
-
2022
- 2022-04-07 CN CN202210358906.5A patent/CN114682217B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8900528D0 (en) * | 1988-06-17 | 1989-03-08 | Ca Minister Energy | Catalytic metal clusters and processes for their preparation |
| CA2363456A1 (en) * | 2000-11-22 | 2002-05-22 | Air Products And Chemicals, Inc. | Hydrogen storage using carbon-metal hybrid compositions |
| CN106064051A (en) * | 2016-06-10 | 2016-11-02 | 苏州巨联环保科研有限公司 | A kind of preparation method of the graphene-based composite adsorbing material of loading nano silvery |
| CN108236919A (en) * | 2016-12-27 | 2018-07-03 | 海门市源美美术图案设计有限公司 | A kind of graphene oxide of surface modification and its application in pharmaceutical wastewater processing |
| WO2018205610A1 (en) * | 2017-05-12 | 2018-11-15 | 华南理工大学 | Porous biogold-doped zero-valent iron catalyst, preparation method therefor and use thereof |
| US20190276943A1 (en) * | 2018-03-08 | 2019-09-12 | Uchicago Argonne, Llc | Carbon supported single atom carbon dioxide reduction electro catalysts |
| AU2020101584A4 (en) * | 2019-07-31 | 2020-09-10 | Hefei University Of Technology | Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton |
| US20220062864A1 (en) * | 2020-09-01 | 2022-03-03 | Uchicago Argonne, Llc | Method of preparing electrocatalysts for converting carbon dioxide to chemicals |
| CN112028052A (en) * | 2020-09-18 | 2020-12-04 | 西北大学 | Preparation method and application of biomass carbon-based Fe monatomic-N doped porous carbon material |
| CN112121771A (en) * | 2020-09-25 | 2020-12-25 | 江苏省环境科学研究院 | Biomass adsorbent for removing refractory organic pollutants, preparation method and application method thereof |
| CN113070036A (en) * | 2021-03-29 | 2021-07-06 | 浙江科技学院 | Biomass-based functional carbon, preparation method thereof and application of biomass-based functional carbon in removal of micro-plastics in water body |
| CN113441157A (en) * | 2021-07-02 | 2021-09-28 | 南昌大学 | Photoreduction synthesis method of supported high-dispersion metal monatomic catalyst |
| CN113731416A (en) * | 2021-07-30 | 2021-12-03 | 联科华技术有限公司 | Local acid site modified monatomic catalyst, preparation method and application thereof |
Non-Patent Citations (9)
| Title |
|---|
| NANNAN LI ET AL: "Molten salt as ultrastrong polar solvent enables the most straightforward pyrolysis towards highly efficient and stable single-atom electrocatalyst", 《JOURNAL OF ENERGY CHEMISTRY》, vol. 54, pages 519 - 527, XP086432997, DOI: 10.1016/j.jechem.2020.06.021 * |
| YUFEI ZHOU ET AL: "Modulating hierarchically microporous biochar via molten alkali treatment for efficient adsorption removal of perfluorinated carboxylic acids from wastewater", 《SCIENCE OF THE TOTAL ENVIRONMENT》, vol. 757, 25 February 2021 (2021-02-25), pages 2 * |
| 刘自若: "氮掺杂碳基单原子催化剂的制备及电催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 刘自若: "氮掺杂碳基单原子催化剂的制备及电催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 1 January 2022 (2022-01-01), pages 1 * |
| 刘自若等: "蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究", 《无机材料学报》, vol. 36, no. 9, pages 943 - 949 * |
| 刘龙飞: "表面修饰的碳纳米管对全氟辛酸的吸附研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 刘龙飞: "表面修饰的碳纳米管对全氟辛酸的吸附研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 September 2018 (2018-09-15), pages 2 * |
| 吴志杰: "《能源转化催化原理》", 中国石油大学出版社, pages: 121 * |
| 杨维结: "碳基单原子铁催化剂催化氧化燃煤烟气NO和Hg0的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, pages 016 - 103 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020413A (en) * | 2022-12-26 | 2023-04-28 | 清华大学深圳国际研究生院 | Adsorption material for removing perfluorinated compounds in water, and preparation method and application thereof |
| CN116020413B (en) * | 2022-12-26 | 2023-10-13 | 清华大学深圳国际研究生院 | Adsorption material for removing perfluorinated compounds in water, and preparation method and application thereof |
| CN116159537A (en) * | 2023-01-17 | 2023-05-26 | 南京邮电大学 | Magnetic adsorbent and preparation method thereof |
| CN116159549A (en) * | 2023-04-26 | 2023-05-26 | 西安博探石油工程有限公司 | Hydrogen sulfide gas adsorption material and preparation method and application thereof |
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