CN110681359A - Preparation method and application of multistep modified nano porous silicon adsorbent for Hg - Google Patents

Preparation method and application of multistep modified nano porous silicon adsorbent for Hg Download PDF

Info

Publication number
CN110681359A
CN110681359A CN201911151300.9A CN201911151300A CN110681359A CN 110681359 A CN110681359 A CN 110681359A CN 201911151300 A CN201911151300 A CN 201911151300A CN 110681359 A CN110681359 A CN 110681359A
Authority
CN
China
Prior art keywords
silicon
porous silicon
nano porous
modified nano
adsorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911151300.9A
Other languages
Chinese (zh)
Inventor
陈秀华
李毅
刘家森
胡焕然
马壮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan University YNU
Original Assignee
Yunnan University YNU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yunnan University YNU filed Critical Yunnan University YNU
Priority to CN201911151300.9A priority Critical patent/CN110681359A/en
Publication of CN110681359A publication Critical patent/CN110681359A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (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)
  • Silicon Compounds (AREA)

Abstract

The invention takes diamond wire-electrode cutting silicon waste as a raw material, adopts a metal-assisted chemical etching method to prepare a multi-step modified nano porous silicon adsorbent for Hg, and has a structural formulaThe nano porous silicon has larger porosity, more active sites, active surface chemical activity, high specific surface area and controllable morphology, and is easy to modify; the invention obtains modified nano-poly by organically modifying nano-porous siliconThe porous silicon material can realize Hg in wastewater2+The rapid and efficient enrichment and removal are realized; the modified nano porous silicon material has the mercury ion adsorption capacity of more than 110mg/g and the adsorption efficiency of more than 90 percent, can reach adsorption balance within 30min of adsorption time, and can be used for quickly and efficiently removing and separating mercury ions in industrial wastewater.

Description

Preparation method and application of multistep modified nano porous silicon adsorbent for Hg
Technical Field
The invention relates to the field of modification of a nano porous silicon adsorbent, in particular to a preparation method and application of a multi-step modified nano porous silicon adsorbent for Hg.
Background
Heavy metal water pollution is a serious social and environmental problem. Mercury, commonly known as "mercury," is a relatively rare element in the earth's crust. Very little mercury is naturally present as a pure metal and is the only liquid metal. Cinnabar, chlorothiomercury ore, stibium mercuric ore and other minerals with cinnabar are the most common deposits of mercury. The world has 50% mercury from spain and italy, the others being predominantly silovinia, russia and north america. The mercury can be reduced after cinnabar is heated in flowing air, and the mercury is condensed after the temperature is reduced, which is the most main mode for producing mercury. Mercury is the only metal element that is liquid at ambient temperature. In nature, most of mercury and sulfur combine into mercury sulfide (HgS), also known as cinnabar or cinnabar, which is widely distributed on the surface of the earth crust. Cinnabar and its polycrystal meta-cinnabar are the main mercury-containing mineral sources. With the natural evolution, various factors of the environment may contain mercury, and the natural background of mercury is formed. The toxicity of various mercury compounds varies widely. Mercuric chloride in the inorganic mercury is a highly toxic substance; phenyl mercury in organic mercury is decomposed quickly and has low toxicity, and methyl mercury is absorbed easily in human body, is not easy to degrade and excrete slowly, and is easy to accumulate in brain and has maximum toxicity. Therefore, how to scientifically and effectively solve Hg2+The polluted water body is increasingly important, and meanwhile, the polluted water body also becomes one of the hot spots of research and attention of countries in the world and vast environmental protection scientific research workers.
At present, the traditional methods for treating heavy metal ions mainly comprise ion exchange, reverse osmosis, electrochemical treatment, chemical precipitation and membrane separation, which can not effectively remove Hg2+And high cost, poor selectivity, and secondary waste generation.The adsorption process, because of its low cost, high efficiency, simple process, high selectivity, and recyclability, has been considered to treat Hg-containing2+Wastewater is one of the most promising methods. The existing common adsorbents, such as zeolite, activated carbon, biological adsorbent, clay and industrial and agricultural wastes, have greatly limited adsorption effect due to low specific surface area, poor porosity and lack of organic functional groups on the surface.
In recent years, with the vigorous development of the photovoltaic industry, the yield of solar grade silicon materials is also rapidly increased, and according to statistics, the global silicon wafer yield reaches 109.2GW in 2018 (the yield is about 230 hundred million silicon wafers, and the silicon quantity reaches 58 million tons). As the first major photovoltaic product-making country worldwide, china produces over 40 million tons of high purity solar grade silicon per year. Generally, a solar silicon wafer is obtained by cutting a solar-grade silicon ingot (purity 99.9999%) in multiple lines. In both the traditional mortar silicon carbide cutting mode and the current diamond wire cutting mode, the difference between the diameter of a cutting steel wire (d-110 microns) and the thickness of a silicon wafer is not large, so that 40% of high-purity silicon materials enter cutting liquid in the form of submicron-grade cutting sawdust in the silicon ingot cutting process, and only in 2018, for example, when the silicon wafer cutting of 109.2GW is realized, 38 ten thousand tons of cutting waste materials are generated. The preparation of the solar-grade high-purity silicon material is a long-flow and high-energy-consumption process, and the direct discharge of a large amount of fine cutting waste materials brings serious environmental damage and resource waste, so that an effective technical route or process is sought to realize the comprehensive recovery and efficient utilization of the cutting waste materials, the treatment problem of the silicon waste materials in the photovoltaic industry can be greatly solved, and huge economic and environmental benefits are brought. If the silicon waste can be used as a silicon-based material to be modified and applied to the research of treating toxic heavy metal ions, good recycling performance and selectivity can be realized, the large-scale preparation and the commercial application of the silicon material can be effectively promoted, the treatment problem of the silicon waste cut in the photovoltaic industry can be effectively solved, and great economic and environmental benefits can be brought.
Disclosure of Invention
Aiming at the technical problems of utilization of silicon waste and adsorption of heavy metal ions in the prior art, the invention provides a modified nano porous silicon adsorbent and a preparation method and application thereof. In order to achieve the purpose, the invention adopts the technical scheme that:
a multi-step modified nanoporous silicon adsorbent for Hg, the modified nanoporous silicon having the structural formula:
Figure BDA0002283613860000031
further, the preparation method of the multi-step modified nano porous silicon adsorbent for Hg at least comprises the following steps: reacting porous silicon with a raw material containing 3-ethylenedioxy propyl trimethoxy silane to carry out primary modification to obtain modified nano-porous silicon A; reacting the modified nano porous silicon A with a raw material containing tetraethylenepentamine, and performing secondary modification to obtain modified nano porous silicon B; and reacting the modified nano porous silicon B with a mixed solution of hypophosphorous acid, formaldehyde and ethanol to obtain the modified nano porous silicon adsorbent.
Further, the preparation method of the multi-step modified nano porous silicon adsorbent for Hg comprises the following specific steps:
(1) chemically purifying silicon waste obtained by cutting a silicon wafer by a diamond wire to remove most of organic cutting liquid and other metal particle impurities remained on the silicon powder to obtain purified silicon powder;
(2) etching the silicon powder obtained by purifying in the step (1) at room temperature by a two-step metal nanoparticle assisted chemical etching method to obtain silicon fine powder with pores of 50-200 nm;
(3) placing the silicon fine powder with the nanoscale pore channels in the step (2) in a nitric acid solution, stirring for 5-120 min, performing solid-liquid separation to obtain silicon powder, washing with deionized water until the washing liquid is neutral, filtering, and drying to obtain porous silicon fine powder;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 10-120 min to obtain activated nano porous silicon;
(5) dissolving the activated nano porous silicon obtained in the step (4) and 3-ethylenedioxy propyl trimethoxy silane in anhydrous toluene, carrying out reflux reaction for 12-48 h at the temperature of 50-70 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol and deionized water, and carrying out vacuum drying at the temperature of 50-70 ℃ to obtain modified nano porous silicon A;
(6) and (3) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, heating and refluxing for 12-24 h, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain modified nano porous silicon B.
(7) And (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by adopting absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent.
Further, the purification treatment in the step (1) is characterized by comprising the following specific steps:
1) crushing and grinding the diamond wire cutting waste until the particle size is 1-50 mu m to obtain waste silicon powder;
2) placing the waste silicon powder obtained in the step 1) at room temperature in a NH3 & H manner2O、H2O2、H2Soaking and stirring the O mixed solution for 2-6 h, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and deionized water respectively, and drying the O mixed solution to obtain primarily purified silicon powder;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperature in HCl and H2O2、H2Soaking and stirring the O mixed solution for 2-6 h, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and deionized water respectively, and drying the O mixed solution to obtain secondary purified silicon powder;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring at room temperature for 1-120 min to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.05-5 mol/L.
Further, the step (2) of metal nanoparticle assisted chemical etching specifically comprises the following steps:
1) adding the purified silicon powder into a HF-metal ion salt mixed solution to perform chemical deposition reaction for 10-180 s to obtain silicon powder with metal nanoparticles deposited on the surface; wherein the metal nanoparticles are Au, Ag, Cu or Pt;
2) under the stirring condition, the silicon powder with the metal nanoparticles deposited on the surface in the step 1) is placed in an HF-oxidant mixed solution for chemical etching for 1-240 min to obtain silicon particles with nanoscale pore channels, wherein in the HF-oxidant mixed solution, the concentration of HF is 0.1-10 mol/L, the concentration of an oxidant is 0.01-5 mol/L, and the oxidant is H2O2One or more of nitric acid, ferric nitrate, potassium permanganate, potassium chromate and potassium iodate.
Further, the mass concentration of the nitric acid solution in the step (3) is 20-60%.
Further, H in the step (4)2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3-3.5: 1, and the activation temperature is room temperature-95 ℃; and (4) adding the porous silicon obtained in the step (3) into a methanesulfonic acid solution, and treating the solution at room temperature to 60 ℃ for 30-180 min to obtain activated nano porous silicon, or placing the porous silicon obtained in the step (3) under low-pressure mercury arc light for oxidation treatment for 30-180 min to obtain the activated nano porous silicon.
Further, the liquid-solid ratio mL of anhydrous toluene to activated nanoporous silicon in the step (5) is 20-30: 1, and the liquid-solid ratio mL of activated nanoporous silicon to 3-ethylenedioxypropyltrimethoxysilane is 1-3: 1.
Further, the reaction temperature in the step (6) is 40-60 ℃; the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 20-30: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5-10: 1.
Further, the reaction temperature in the step (7) is 40-60 ℃; the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 1-3; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 1-5: 1.
further, the invention can be prepared by any of the methods described above.
Further, the multi-step modified nano porous silicon adsorbent is used as Hg2+But not limited to Hg2+The application of selective adsorbent.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the nano porous silicon prepared by using the diamond wire-electrode cutting silicon waste as the raw material and adopting the metal-assisted chemical etching method has higher porosity, more active sites, active surface chemical activity, high specific surface area and controllable morphology, and is easy to modify;
(2) the modified nano porous silicon material obtained by organically modifying the nano porous silicon can realize Hg in wastewater2+The rapid and efficient enrichment and removal are realized;
(3) the modified nano porous silicon material has the mercury ion adsorption capacity of more than 110mg/g and the adsorption efficiency of more than 90 percent, can reach adsorption balance within 30min of adsorption time, and can be used for quickly and efficiently removing and separating mercury ions in industrial wastewater.
Drawings
FIG. 1 is a flow diagram of the organic modification of nanoporous silicon;
FIG. 2 is an FE-SEM photograph of nanoporous silicon of example 1;
FIG. 3 is FT-IR diagram of modified nanoporous silicon of example 1
FIG. 4 shows example 1Hg2+Initial concentration vs. Hg of modified nanoporous silicon adsorbents2+Removing the influence of efficiency and adsorption capacity;
FIG. 5 is Hg for adsorption time vs. modified nanoporous silica adsorbent of example 12+The effect of efficiency is removed.
Detailed Description
As shown in fig. 1-5:
example 1: the structural formula of the modified nanoporous silicon of this example is:
Figure BDA0002283613860000061
the preparation method of the modified nano porous silicon adsorbent comprises the following specific steps:
(1) purifying the diamond wire-electrode cutting silicon waste to obtain purified silicon powder; wherein the purification treatment comprises the following specific steps
1) Crushing and grinding the diamond wire cutting waste material until the particle size is 10 mu m to obtain waste silicon powder;
2) putting the waste silicon powder obtained in the step 1) at room temperature into NH3·H2O、H2O2、H2Soaking and stirring the O mixed solution for 2 hours, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and water respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein NH3·H2O、H2O2、H2The ratio of O is 2: 2: 5;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperature in HCl and H2O2、H2Soaking and stirring the O mixed solution for 2 hours, then washing the O mixed solution with absolute ethyl alcohol and water for 2-3 hours respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein HCl and H2O2、H2The ratio of O is 2: 2: 5;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring for 30min at room temperature to completely remove an oxide layer on the surface of the cut silicon waste to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.1 mol/L;
(2) at room temperature, carrying out metal nanoparticle assisted chemical etching on the purified silicon powder obtained in the step (1) to obtain silicon particles containing nanoscale pore channels; the specific steps of the metal nano-particles assisted chemical etching are
1) Adding the purified silicon powder into a HF-metal ion salt mixed solution for chemical deposition reaction to obtain silicon powder with metal nano particles (nano copper particles) deposited on the surface; wherein the metal nanoparticles are copper;
2) under the condition of stirring, the silicon powder with the metal nano particles deposited on the surface in the step 1) is placed in an HF-oxidant (H)2O2) Chemically etching in the mixed solution for 60min to obtain silicon particles containing nanometer-scale pore canals, wherein HF-oxidant (H)2O2) The concentration of HF in the mixed solution was 4.5mol/L, and an oxidizing agent (H)2O2) The concentration of (A) is 0.5 mol/L;
(3) soaking the silicon particles containing the nanoscale pore channels in the step (2) in a nitric acid solution for 30min, taking out the silicon particles, washing the silicon particles by using deionized water until the washing liquid is neutral, filtering and drying to obtain porous silicon; wherein the mass concentration of the nitric acid solution is 60 percent;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 3 hours at the activation temperature of 90 ℃ to increase the silicon hydroxyl bonds on the surface of the porous silicon to obtain activated nano porous silicon; wherein H2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3: 1; the specific surface area of the nano-porous silicon in the embodiment is 84.2m2/g；
(5) Dissolving the activated nano porous silicon obtained in the step (4) and 3-ethylenedioxypropyltrimethoxysilane in anhydrous toluene, carrying out reflux reaction for 48 hours at the temperature of 65 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol and deionized water, and carrying out vacuum drying to obtain modified nano porous silicon A, which is marked as GTS-NPSi; wherein the liquid-solid ratio mL of the anhydrous toluene to the activated nano porous silicon is 20:1, and the liquid-solid ratio mL of the activated nano porous silicon to the 3-aminopropyltriethoxysilane is 2: 1;
(6) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, reacting for 24h at 60 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain a modified nano porous silicon adsorbent, which is marked as TEPA-GTS-NPSi; wherein the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 20: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5: 1.
(7) And (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent, which is marked as PA-TEPA-GTS-NPSi. Wherein the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 3; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 2: 1.
In this example, steps (5) to (7) are the method for organically modifying nanoporous silicon, and the modification flow chart is shown in fig. 1;
the FE-SEM image of the nanoporous silicon of this example is shown in fig. 2, and it can be seen from fig. 2 that the etched diamond wire-cut silicon waste material has a rough surface and a certain pore structure on the surface.
The FT-IR chart of the modified nanoporous silicon of this example is shown in FIG. 3, and it can be seen from FIG. 3 that 461, 805, 1108cm-1The peak values are respectively Si-O-Si bending vibration, symmetrical stretching vibration and stretching vibration. 950cm-1The peak at (a) is due to the oscillation of the Si-OH groups. 3440 and 1630cm under the action of water and silanol groups-1The peak values at the points are O-H stretching vibration and deformation vibration, respectively. In the spectrum of GTS-NPSi, 2934 and 2834cm-1The peaks are all C-H tensile vibration, which indicates that the organosilane is successfully grafted to the surface of the silicon nano-particle. 1384cm in the spectrum of TEPA-GTS-NPSi-1The band of (C) is due to-NH2and-NH flexural vibration. For PA-TEPA-GTS-NPSi, -NH2and-NH flexural vibration at 1384cm-1The peak at (a) disappears due to phosphonic acid groups with-NH2and-NH. Furthermore, the peak of phosphate group (1185 cm inclusive)-1Adsorption peak at position P ═ O bond, 10541185cm-1PO of2Peak sum of stretching vibration 1185cm-1PO of2Stretching vibration peaks) are not clearly indicated in the FT-IR spectrum of PA-TEPA-GTS-NPSi, since they are at 1101cm from the FT-IR spectrum-1With wide key overlap in between.
The above analysis shows that the preparation of modified nanoporous silicon is successful.
Adsorption experiment: the modified nanoporous silica adsorbent TEPA-GTS-NPSi of the example was added to the Hg-containing solution2+In the waste water solution of (1), Hg in this example2+Initial concentration vs. Hg of modified nanoporous silicon adsorbents2+The effects of removal efficiency and adsorption capacity are shown in FIG. 4, and it can be seen from FIG. 4 that PA-TEPA-GTS-NPSi adsorbs Hg2+Equilibrium adsorption capacity of (2) with Hg2+The concentration of (B) was increased, but the tendency of the increase was gradually decreased, and when the initial ion concentration was 600mg/L, the saturated adsorption amount (116.8mg/g) was reached. Example adsorption time vs. Hg of modified nanoporous silica adsorbent2+The effect of removal efficiency is shown in FIG. 5, and it can be seen from FIG. 5 that the adsorbent PA was adsorbed in the first 10min-TEPA-GTS-NPSi vs Hg2+The adsorption rate of (A) is very fast, and as the adsorption proceeds, the adsorbent works against Hg2+The adsorption rate of (A) gradually becomes slow, and the dynamic equilibrium of adsorption is gradually reached after 60 min; the modified nano porous silicon adsorbent PA-TEPA-GTS-NPSi can realize the effect of Hg in water through comprehensive analysis2+High efficiency and quick adsorption.
Example 2: the structural formula of the modified nanoporous silicon of this example is:
the preparation method of the modified nano porous silicon adsorbent comprises the following specific steps:
(1) purifying the diamond wire-electrode cutting silicon waste to obtain purified silicon powder; wherein the purification treatment comprises the following specific steps
1) Crushing and grinding the diamond wire cutting waste material until the particle size is 10 mu m to obtain waste silicon powder;
2) putting the waste silicon powder obtained in the step 1) at room temperature into NH3·H2O、H2O2、H2Soaking and stirring the O mixed solution for 2 hours, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and water respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein NH3·H2O、H2O2、H2The ratio of O is 2: 2: 5;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperature in HCl and H2O2、H2Soaking and stirring the O mixed solution for 2 hours, then washing the O mixed solution with absolute ethyl alcohol and water for 2-3 hours respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein HCl and H2O2、H2The ratio of O is 2: 2: 5;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring for 30min at room temperature to completely remove an oxide layer on the surface of the cut silicon waste to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.1 mol/L;
(2) at room temperature, carrying out metal nanoparticle assisted chemical etching on the purified silicon powder obtained in the step (1) to obtain silicon particles containing nanoscale pore channels; the specific steps of the metal nano-particles assisted chemical etching are
1) Adding the purified silicon powder into a HF-metal ion salt mixed solution for chemical deposition reaction to obtain silicon powder with metal nano particles (nano Ag particles) deposited on the surface; wherein the metal nanoparticles are silver;
2) under the condition of stirring, the silicon powder with the metal nano particles deposited on the surface in the step 1) is placed in an HF-oxidant (H)2O2) Chemically etching in the mixed solution for 60min to obtain silicon particles containing nanometer-scale pore canals, wherein HF-oxidant (H)2O2) The concentration of HF in the mixed solution was 4.6mol/L, and an oxidizing agent (H)2O2) The concentration of (A) is 0.5 mol/L;
(3) soaking the silicon particles containing the nanoscale pore channels in the step (2) in a nitric acid solution for 30min, taking out the silicon particles, washing the silicon particles by using deionized water until the washing liquid is neutral, filtering and drying to obtain porous silicon; wherein the mass concentration of the nitric acid solution is 60 percent;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 3 hours at the activation temperature of 90 ℃ to increase the silicon hydroxyl bonds on the surface of the porous silicon to obtain activated nano porous silicon; wherein H2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3: 1; the specific surface area of the nano-porous silicon in the embodiment is 86.3m2/g；
(5) Dissolving the activated nano porous silicon obtained in the step (4) and 3-ethylenedioxypropyltrimethoxysilane in anhydrous toluene, carrying out reflux reaction for 48 hours at the temperature of 65 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol and deionized water, and carrying out vacuum drying to obtain modified nano porous silicon A, which is marked as GTS-NPSi; wherein the liquid-solid ratio mL of the anhydrous toluene to the activated nano porous silicon is 20:1, and the liquid-solid ratio mL of the activated nano porous silicon to the 3-aminopropyltriethoxysilane is 2: 1;
(6) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, reacting for 24h at 60 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain a modified nano porous silicon adsorbent, which is marked as TEPA-GTS-NPSi; wherein the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 20: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5: 1.
(7) And (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent, which is marked as PA-TEPA-GTS-NPSi. Wherein the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 2; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 2: 1.
adsorption experiment: the modified nanoporous silica adsorbent TEPA-GTS-NPSi of the example was added to the Hg-containing solution2+Is adsorbed in the waste water solution, and PA-TEPA-GTS-NPSi is used for treating Hg-containing2+The adsorption efficiency is more than 95 percent, the adsorption capacity reaches 114.6mg/g, the adsorption balance is achieved in 60min, and the Hg in water can be adsorbed2+The adsorption is fast and efficient.
Example 3: the structural formula of the modified nanoporous silicon of this example is:
the preparation method of the modified nano porous silicon adsorbent comprises the following specific steps:
(1) purifying the diamond wire-electrode cutting silicon waste to obtain purified silicon powder; wherein the purification treatment comprises the following specific steps
1) Crushing and grinding the diamond wire cutting waste material until the particle size is 10 mu m to obtain waste silicon powder;
2) putting the waste silicon powder obtained in the step 1) at room temperature into NH3·H2O、H2O2、H2Soaking and stirring the O mixed solution for 2 hours, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and water respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein NH3·H2O、H2O2、H2The ratio of O is 2: 2: 5;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperature in HCl and H2O2、H2Soaking and stirring the O mixed solution for 2 hours, then washing the O mixed solution with absolute ethyl alcohol and water for 2-3 hours respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein HCl and H2O2、H2The ratio of O is 2: 2: 5;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring and treating for 30min at room temperature to completely remove an oxide layer on the surface of the cut silicon waste to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.5 mol/L;
(2) at room temperature, carrying out metal nanoparticle assisted chemical etching on the purified silicon powder obtained in the step (1) to obtain silicon particles containing nanoscale pore channels; the specific steps of the metal nano-particles assisted chemical etching are
1) Adding the purified silicon powder into a HF-metal ion salt mixed solution for chemical deposition reaction to obtain silicon powder with metal nano particles (nano Ag particles) deposited on the surface; wherein the metal nanoparticles are silver;
2) under the condition of stirring, the silicon powder with the metal nano particles deposited on the surface in the step 1) is placed in an HF-oxidant (H)2O2) Chemically etching in the mixed solution for 60min to obtain silicon particles containing nanometer-scale pore canals, wherein HF-oxidant (H)2O2) The concentration of HF in the mixed solution was 4.6mol/L, and an oxidizing agent (H)2O2) The concentration of (A) is 1 mol/L;
(3) soaking the silicon particles containing the nanoscale pore channels in the step (2) in a nitric acid solution for 30min, taking out the silicon particles, washing the silicon particles by using deionized water until the washing liquid is neutral, filtering and drying to obtain porous silicon; wherein the mass concentration of the nitric acid solution is 60 percent;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 3 hours at the activation temperature of 90 ℃ to increase the silicon hydroxyl bonds on the surface of the porous silicon to obtain activated nano porous silicon; wherein H2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3: 1; the specific surface area of the nano-porous silicon in the embodiment is 86.3m2/g；
(5) Dissolving the activated nano porous silicon obtained in the step (4) and 3-ethylenedioxypropyltrimethoxysilane in anhydrous toluene, carrying out reflux reaction for 48 hours at the temperature of 65 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol and deionized water, and carrying out vacuum drying to obtain modified nano porous silicon A, which is marked as GTS-NPSi; wherein the liquid-solid ratio mL of the anhydrous toluene to the activated nano porous silicon is 20:1, and the liquid-solid ratio mL of the activated nano porous silicon to the 3-aminopropyltriethoxysilane is 2: 1;
(6) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, reacting for 24h at 60 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain a modified nano porous silicon adsorbent, which is marked as TEPA-GTS-NPSi; wherein the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 20: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5: 1.
(7) And (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent, which is marked as PA-TEPA-GTS-NPSi. Wherein the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 2; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 5: 1.
adsorption experiment: the modified nanoporous silica adsorbent TEPA-GTS-NPSi of the example was added to the Hg-containing solution2+Is adsorbed in the waste water solution, and PA-TEPA-GTS-NPSi is used for treating Hg-containing2+The adsorption efficiency is more than 95 percent, the adsorption capacity reaches 116.4mg/g, the adsorption balance is achieved in 60min, and the Hg in water can be adsorbed2+The adsorption is fast and efficient.
Example 4: the structural formula of the modified nanoporous silicon of this example is:
Figure BDA0002283613860000131
the preparation method of the modified nano porous silicon adsorbent comprises the following specific steps:
(1) purifying the diamond wire-electrode cutting silicon waste to obtain purified silicon powder; wherein the purification treatment comprises the following specific steps
1) Crushing and grinding the diamond wire cutting waste material until the particle size is 10 mu m to obtain waste silicon powder;
2) putting the waste silicon powder obtained in the step 1) at room temperature into NH3·H2O、H2O2、H2Soaking and stirring the O mixed solution for 2 hours, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and water respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein NH3·H2O、H2O2、H2The ratio of O is 2: 2: 5;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperature in HCl and H2O2、H2Soaking and stirring the O mixed solution for 2 hours, then washing the O mixed solution with absolute ethyl alcohol and water for 2-3 hours respectively, and drying the O mixed solution to obtain primarily purified silicon powder; wherein HCl and H2O2、H2The ratio of O is 2: 2: 5;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring for 30min at room temperature to completely remove an oxide layer on the surface of the cut silicon waste to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.1 mol/L;
(2) at room temperature, carrying out metal nanoparticle assisted chemical etching on the purified silicon powder obtained in the step (1) to obtain silicon particles containing nanoscale pore channels; the specific steps of the metal nano-particles assisted chemical etching are
1) Adding the purified silicon powder into a HF-metal ion salt mixed solution for chemical deposition reaction to obtain silicon powder with metal nano particles (nano Cu particles) deposited on the surface; wherein the metal nanoparticles are copper;
2) under the condition of stirring, the silicon powder with the metal nano particles deposited on the surface in the step 1) is placed in an HF-oxidant (H)2O2) Chemically etching in the mixed solution for 60min to obtain silicon particles containing nanometer-scale pore canals, wherein HF-oxidant (H)2O2) The concentration of HF in the mixed solution was 4.6mol/L, and an oxidizing agent (H)2O2) The concentration of (A) is 0.5 mol/L;
(3) soaking the silicon particles containing the nanoscale pore channels in the step (2) in a nitric acid solution for 30min, taking out the silicon particles, washing the silicon particles by using deionized water until the washing liquid is neutral, filtering and drying to obtain porous silicon; wherein the mass concentration of the nitric acid solution is 60 percent;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 3 hours at the activation temperature of 90 ℃ to increase the silicon hydroxyl bonds on the surface of the porous silicon to obtain activated nano porous silicon; wherein H2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3: 1; the specific surface area of the nano-porous silicon in the embodiment is 87.1m2/g；
(5) Dissolving the activated nano porous silicon obtained in the step (4) and 3-ethylenedioxypropyltrimethoxysilane in anhydrous toluene, carrying out reflux reaction for 24 hours at the temperature of 65 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol and deionized water, and carrying out vacuum drying to obtain modified nano porous silicon A, which is marked as GTS-NPSi; wherein the liquid-solid ratio mL of the anhydrous toluene to the activated nano porous silicon is 20:1, and the liquid-solid ratio mL of the activated nano porous silicon to the 3-aminopropyltriethoxysilane is 2: 1;
(6) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, reacting for 24h at 60 ℃, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain a modified nano porous silicon adsorbent, which is marked as TEPA-GTS-NPSi; wherein the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 30: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5: 1.
(7) And (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent, which is marked as PA-TEPA-GTS-NPSi. Wherein the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 1; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 1: 1.
adsorption experiment: the modified nanoporous silica adsorbent TEPA-GTS-NPSi of the example was added to the Hg-containing solution2+The wastewater solution is adsorbed, PA-TEPA-GTS-Use of NPSi for the treatment of Hg-containing2+The adsorption efficiency is more than 95 percent, the adsorption capacity reaches 110.8mg/g, the adsorption balance is achieved in 60min, and the Hg in water can be adsorbed2+The adsorption is fast and efficient.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A multi-step modified nanoporous silicon adsorbent for Hg, wherein the modified nanoporous silicon has the structural formula:
Figure FDA0002283613850000011
2. the preparation method of the multi-step modified nanoporous silicon adsorbent for Hg according to claim 1, wherein the preparation method comprises at least the following steps:
reacting porous silicon with a raw material containing 3-ethylenedioxy propyl trimethoxy silane to carry out primary modification to obtain modified nano-porous silicon A; reacting the modified nano porous silicon A with a raw material containing tetraethylenepentamine, and performing secondary modification to obtain modified nano porous silicon B; and reacting the modified nano porous silicon B with a mixed solution of hypophosphorous acid, formaldehyde and ethanol to obtain the modified nano porous silicon adsorbent.
3. The preparation method of the multi-step modified nano-porous silicon adsorbent for Hg according to claim 2, which is characterized by comprising the following specific preparation steps:
(1) chemically purifying silicon waste obtained by cutting a silicon wafer by a diamond wire to remove organic cutting fluid and other metal particle impurities remained on the silicon powder to obtain purified silicon powder;
(2) etching the purified silicon powder obtained in the step (1) by a two-step metal nanoparticle assisted chemical etching method at room temperature to obtain silicon fine powder with nanometer-scale pore passages of 50-200 nm;
(3) placing the silicon fine powder with the nanoscale pore channels in the step (2) in a nitric acid solution, stirring for 5-120 min, performing solid-liquid separation to obtain silicon powder, washing with deionized water until the washing liquid is neutral, filtering, and drying to obtain porous silicon fine powder;
(4) placing the porous silicon obtained in the step (3) in H2SO4/H2O2Activating the mixed solution for 10-120 min to obtain activated nano porous silicon powder;
(5) dissolving the activated nano porous silicon powder obtained in the step (4) and 3-ethylenedioxy propyl trimethoxy silane in anhydrous toluene, carrying out reflux reaction for 12-48 h at the temperature of 50-70 ℃, carrying out solid-liquid separation, washing, and carrying out vacuum drying at the temperature of 50-70 ℃ to obtain modified nano porous silicon A;
(6) adding the modified nano porous silicon A and tetraethylenepentamine obtained in the step (5) into anhydrous toluene, heating and refluxing for 12-24 h, carrying out solid-liquid separation, repeatedly washing the solid by using anhydrous ethanol, and carrying out vacuum drying to obtain modified nano porous silicon B;
(7) and (3) adding the modified nano porous silicon B obtained in the step (6) into a mixed solution of hypophosphorous acid, formaldehyde and ethanol, heating and refluxing for 12-48 h at 50-70 ℃ in a nitrogen atmosphere, carrying out solid-liquid separation, repeatedly washing the solid by adopting absolute ethyl alcohol and deionized water, and carrying out vacuum drying at 50-70 ℃ to obtain the modified nano porous silicon adsorbent.
4. The method for preparing the multi-step modified nanoporous silicon adsorbent for Hg according to claim 3, further comprising: the purification treatment in the step (1) comprises the following specific steps:
1) crushing and grinding the diamond wire cutting waste to waste silicon powder with the particle size of 1-50 mu m;
2) placing the waste silicon powder obtained in the step 1) at room temperature under NH3·H2O、H2O2And H2Soaking and stirring the mixed solution of O for 2-6 h, repeatedly washing the mixed solution for 2-3 times by adopting absolute ethyl alcohol and deionized water respectively, and drying to obtain primary purified silicon powder;
3) placing the primarily purified silicon powder obtained in the step 2) at room temperatureHCl and H2O2、H2Soaking and stirring the O mixed solution for 2-6 h, washing the O mixed solution for 2-3 times by adopting absolute ethyl alcohol and deionized water respectively, and drying to obtain primary purified silicon powder;
4) adding the silicon powder treated in the step 3) into a hydrofluoric acid solution, and stirring for 1-120 min at room temperature to obtain purified silicon powder, wherein the concentration of the hydrofluoric acid solution is 0.05-5 mol/L.
5. The method for preparing the multi-step modified nano-porous silicon adsorbent for Hg according to claim 3, wherein H in the step (4)2SO4/H2O2The volume ratio of sulfuric acid to hydrogen peroxide in the mixed solution is 3-3.5: 1, and the activation temperature is room temperature-95 ℃; and (4) adding the porous silicon obtained in the step (3) into a methanesulfonic acid solution, and treating the solution at room temperature to 60 ℃ for 30-180 min to obtain activated nano porous silicon, or placing the porous silicon obtained in the step (3) under low-pressure mercury arc light for oxidation treatment for 30-180 min to obtain the activated nano porous silicon.
6. The preparation method of the multi-step modified nanoporous silicon adsorbent for Hg according to claim 3, wherein the liquid-solid ratio mL/g of the anhydrous toluene to the activated nanoporous silicon in the step (5) is 20-30: 1, and the liquid-solid ratio mL/g of the activated nanoporous silicon to 3-ethylenedioxypropyltrimethoxysilane is 1-3: 1.
7. The preparation method of the multi-step modified nano porous silicon adsorbent for Hg according to claim 3, wherein the reaction temperature in the step (6) is 40-60 ℃; the liquid-solid ratio mL/g of the anhydrous toluene to the activated nano porous silicon is 20-30: 1; the volume ratio of the anhydrous toluene to the tetraethylenepentamine is 5-10: 1.
8. The preparation method of the multi-step modified nano-porous silicon adsorbent for Hg according to claim 3, wherein the reaction temperature in the step (7) is 40-60 ℃; the volume ratio of hypophosphorous acid to formaldehyde to ethanol is 1: 1: 1-3; liquid-solid ratio ml of hypophosphorous acid to activated nanoporous silicon mobile: g is 1-5: 1.
9. a multi-step modified nanoporous silicon adsorbent for Hg, characterized in that it is prepared by the method of any of claims 2-8.
10. Use of the multi-step modified nanoporous silicon adsorbent for Hg according to claim 1 as Hg2+But not limited to Hg2+The selective adsorbent of (1).
CN201911151300.9A 2019-11-21 2019-11-21 Preparation method and application of multistep modified nano porous silicon adsorbent for Hg Pending CN110681359A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911151300.9A CN110681359A (en) 2019-11-21 2019-11-21 Preparation method and application of multistep modified nano porous silicon adsorbent for Hg

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911151300.9A CN110681359A (en) 2019-11-21 2019-11-21 Preparation method and application of multistep modified nano porous silicon adsorbent for Hg

Publications (1)

Publication Number Publication Date
CN110681359A true CN110681359A (en) 2020-01-14

Family

ID=69117308

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911151300.9A Pending CN110681359A (en) 2019-11-21 2019-11-21 Preparation method and application of multistep modified nano porous silicon adsorbent for Hg

Country Status (1)

Country Link
CN (1) CN110681359A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114164456A (en) * 2021-12-08 2022-03-11 昆明理工大学 Method for preparing composite silicon nano-structure catalyst by using industrial waste silicon powder and application
CN118005006A (en) * 2024-01-16 2024-05-10 广东稳泰新能源有限公司 Preparation method of graphite-phase carbon nitride composite nano silicon anode material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038071A (en) * 1976-07-14 1977-07-26 Tenneco Chemicals, Inc. Process for the removal of mercury from aqueous solutions
CN105293783A (en) * 2015-11-26 2016-02-03 昆明理工大学 Method for processing heavy metal in sewage
CN108568285A (en) * 2017-03-08 2018-09-25 武汉中地金盾环境科技有限公司 A kind of preparation method of novel magnetic arsenic removal solid chelant
CN109231215A (en) * 2018-10-31 2019-01-18 大连颐和顺新材料科技有限公司 A method of porous silicon is prepared with silicon wafer cut by diamond wire waste silicon powder
CN110075806A (en) * 2019-05-20 2019-08-02 云南大学 A kind of amino modified nano-structure porous silicon adsorbent and the preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038071A (en) * 1976-07-14 1977-07-26 Tenneco Chemicals, Inc. Process for the removal of mercury from aqueous solutions
CN105293783A (en) * 2015-11-26 2016-02-03 昆明理工大学 Method for processing heavy metal in sewage
CN108568285A (en) * 2017-03-08 2018-09-25 武汉中地金盾环境科技有限公司 A kind of preparation method of novel magnetic arsenic removal solid chelant
CN109231215A (en) * 2018-10-31 2019-01-18 大连颐和顺新材料科技有限公司 A method of porous silicon is prepared with silicon wafer cut by diamond wire waste silicon powder
CN110075806A (en) * 2019-05-20 2019-08-02 云南大学 A kind of amino modified nano-structure porous silicon adsorbent and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHAO XIONG ET AL.: ""Preparation and application of phosphinic acid functionalized nanosilica for the effective removal of mercury (II) in aqueous solutions"", 《JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114164456A (en) * 2021-12-08 2022-03-11 昆明理工大学 Method for preparing composite silicon nano-structure catalyst by using industrial waste silicon powder and application
CN114164456B (en) * 2021-12-08 2023-08-08 昆明理工大学 Method for preparing composite silicon nanostructure catalyst by utilizing industrial waste silicon powder and application
CN118005006A (en) * 2024-01-16 2024-05-10 广东稳泰新能源有限公司 Preparation method of graphite-phase carbon nitride composite nano silicon anode material

Similar Documents

Publication Publication Date Title
CN104826582A (en) Preparation method of graphene-mesoporous silica aerogel
CN103706326B (en) A kind of preparation method of natural minerals loaded nano defluorinating agent
CN110681359A (en) Preparation method and application of multistep modified nano porous silicon adsorbent for Hg
CN110775979B (en) Method for recovering high-purity silicon and silicon carbide from crystalline silicon cutting waste
CN107551829A (en) A kind of graphene/carbon titanium water body purification composite film material
CN110368894B (en) Efficient fluorine removal agent for removing fluorine ions in wastewater and preparation method thereof
CN109052543B (en) Method for recovering precious metal silver in wastewater
Yang et al. Effective removal of Cr (VI) from aqueous solution based on APTES modified nanoporous silicon prepared from kerf loss silicon waste
CN111018037B (en) Method for removing heavy metal mercury ions in water based on polyacrylonitrile nano-film compound
CN114797783A (en) Adsorbent for selectively removing Cr (VI), preparation method and application thereof
CN110075806B (en) Amino modified nano porous silicon adsorbent and preparation method and application thereof
CN108218039A (en) A kind of method of resin adsorption desorption-diffusion dialysis processing VA races element oxo-anions waste water
CN114262034A (en) Method for separating rubidium from salt lake brine by using polyvinyl alcohol/chitosan/graphene/nickel copper hexacyanide complex
CN110038537A (en) A kind of modified Nano porous silicon adsorbent and the preparation method and application thereof
CN112410579B (en) Method for extracting rubidium and co-producing As (III) adsorption material from rubidium-containing biotite, As (III) adsorption material and application
CN103272563A (en) Preparation method of aluminum hydroxide film
CN110711557A (en) Preparation method and application of multi-step modified nano porous silicon adsorbent for As
CN103540755A (en) Method for enriching germanium from low-concentration germanium-containing solution
CN108341410B (en) Preparation method and application of graphene aerogel
CN110075807B (en) Modified nano porous silicon adsorbent and preparation method and application thereof
Jianglong et al. Adsorption and mechanism of copper ions in water by red mud modified with FeCl3 and hexadecyl trimethyl ammonium bromide (CTAB)
CN106179231A (en) A kind of hollow cube ferrum aluminum is combined preparation and the application process of oxyhydroxide de-fluoridation adsorbent
Fu et al. Multiple modification on nanoporous silicon derived from photovoltaic silicon cutting waste for extraction of PbⅡ in industrial effluents
CN113277591A (en) Method for removing heavy metal ions in water by using magadiite/graphene oxide nanosheet compound
CN110980865A (en) Graphene composite filter element for purifying water and improving taste and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200114

RJ01 Rejection of invention patent application after publication