CN111777056B - Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof - Google Patents
Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111777056B CN111777056B CN202010667500.6A CN202010667500A CN111777056B CN 111777056 B CN111777056 B CN 111777056B CN 202010667500 A CN202010667500 A CN 202010667500A CN 111777056 B CN111777056 B CN 111777056B
- Authority
- CN
- China
- Prior art keywords
- hydrated carbon
- molybdenum selenide
- carbon
- amorphous molybdenum
- composite material
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
- B01J20/0266—Compounds of S
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Inorganic Chemistry (AREA)
- 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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a hydrated carbon/amorphous molybdenum selenide composite material and a preparation method and application thereof, belonging to the technical field of palladium adsorbents. The invention provides a hydrated carbon/amorphous molybdenum selenide composite material, which comprises hydrated carbon and amorphous molybdenum selenide dispersed on the surface of the hydrated carbon; the surface of the hydrated carbon has oxygen-containing functional groups; the molar ratio of selenium to molybdenum in the amorphous molybdenum selenide is 2.3-2.6: 1. In the hydrated carbon/amorphous molybdenum selenide composite material provided by the invention, compared with crystalline molybdenum selenide, amorphous molybdenum selenide has more effective selenium sites, and the removal effect on palladium ions is better; the oxygen-containing functional groups on the surface of the hydrated carbon provide more growth sites for amorphous molybdenum selenide, and the existence of the hydrated carbon carrier ensures that the amorphous molybdenum selenide has good dispersibility and can not agglomerate, so that more effective selenium sites are exposed, and the adsorption effect of the hydrated carbon/amorphous molybdenum selenide composite material on palladium ions is further improved.
Description
Technical Field
The invention relates to the technical field of palladium adsorbents, in particular to a hydrated carbon/amorphous molybdenum selenide composite material and a preparation method and application thereof.
Background
Palladium is an indispensable key material in the high-tech fields such as aerospace, aviation, navigation, weapons and nuclear energy and the automobile manufacturing industry, and is also commonly used as a catalyst for organic synthesis, and particularly in the manufacture of chemical products such as pesticides, pharmaceuticals, perfumes and dyes, the palladium catalyst can be used in a wide range of reactions such as hydrogenation of olefins, ketones, aldehydes and the like, and hydrogenation decomposition of halogen compounds, allyl compounds and the like; in addition, palladium is widely used in the field of electroplating. Since palladium is contained in the earth's crust in a low content and is expensive, it is important to recover palladium from a palladium-containing waste liquid in view of reuse and stable supply of palladium.
Chinese patent CN104988315A discloses an acid palladium recovery process, which comprises the following process steps: a. dissolving: dissolving a palladium-containing material in aqua regia, heating to 55-65 ℃, and continuing heating for denitration after the reaction is finished; b. and (3) filtering: filtering after the dissolution is finished, adding hydrochloric acid, and adjusting the pH value of the solution to 1-1.5; c. adsorption: adsorbing with basic anion resin under water pressure of 0.5kg/cm2The flow rate is 15-20 times of the loading amount of the basic anion resin until the adsorption is finished; d. and (3) precipitation: adding ammonia water and ammonium chloride at normal temperature for elution for 2.5-3.5 hours, and then adding hydrochloric acid for precipitation until the precipitation is complete; e. reduction: after ammonia water is added for dissolution, hydrazine hydrate is reduced, and the recovery of palladium is completed. However, the basic anion resin adsorbent is expensive and the above-mentioned palladium adsorption method is complicated in operation.
The molybdenum selenide has a typical Se-Mo-Se layered sandwich structure, the layers are connected through weak van der Waals force, and Se sites in the molybdenum selenide are paired with Pd2+Has strong affinity and is a common palladium adsorbent. However, the interlayer spacing of the crystalline molybdenum diselenide is small, the water and the radius of palladium ions are large, and the palladium ions cannot be effectively diffused into the molybdenum diselenide, and the molybdenum diselenide is easy to agglomerate, so that the adsorption sites of the crystalline molybdenum diselenide cannot be completely exposed, and the palladium adsorption effect of the crystalline molybdenum diselenide is not ideal.
Disclosure of Invention
In view of the above, the present invention aims to provide a hydrated carbon/amorphous molybdenum selenide composite material, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a hydrated carbon/amorphous molybdenum selenide composite material, which comprises hydrated carbon and amorphous molybdenum selenide dispersed on the surface of the hydrated carbon;
the surface of the hydrated carbon has oxygen-containing functional groups;
the molar ratio of selenium to molybdenum in the amorphous molybdenum selenide is (2.3-2.6): 1.
Preferably, the loading amount of the amorphous molybdenum selenide is 45-65 wt%.
Preferably, the particle size of the amorphous molybdenum selenide is 20-50 nm.
The invention provides a preparation method of a hydrated carbon/amorphous molybdenum selenide composite material in the technical scheme, which comprises the following steps:
(1) mixing a carbon-containing material with water, and carrying out hydrothermal carbonization reaction to obtain hydrated carbon;
(2) mixing selenium and hydrazine hydrate solution, and carrying out oxidation-reduction reaction to obtain selenium anion solution;
(3) mixing the hydrated carbon, the selenium anion solution, ammonium molybdate and an organic solvent, and carrying out a solvothermal reaction to obtain a hydrated carbon/amorphous molybdenum selenide composite material; the temperature of the solvothermal reaction is not lower than 140 ℃.
The step (1) and the step (2) have no chronological order.
Preferably, the temperature of the hydrothermal carbonization reaction is 180-220 ℃, and the time is 2-6 h.
Preferably, the mass ratio of the selenium to the hydrazine hydrate in the hydrazine hydrate solution is 1: (0.12-0.13).
Preferably, the dosage of the selenium anion solution is calculated by the mass of selenium, and the mass ratio of the hydrated carbon to the selenium to the ammonium molybdate is 1: (4-8): (5-10).
Preferably, the organic solvent includes methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, or acetone.
Preferably, the temperature of the solvothermal reaction is 140-210 ℃ and the time is 10-15 h.
The invention also provides the application of the hydrated carbon/amorphous molybdenum selenide composite material or the hydrated carbon/amorphous molybdenum selenide composite material prepared by the preparation method in the technical scheme in palladium recovery.
The invention provides a hydrated carbon/amorphous molybdenum selenide composite material, which comprises hydrated carbon and amorphous molybdenum selenide dispersed on the surface of the hydrated carbon; the surface of the hydrated carbon has oxygen-containing functional groups; the molar ratio of selenium to molybdenum in the amorphous molybdenum selenide is (2.3-2.6): 1. In the hydrated carbon/amorphous molybdenum selenide composite material provided by the invention, compared with crystalline molybdenum selenide, amorphous molybdenum selenide has more effective selenium sites, and the removal effect on palladium ions is better; oxygen-containing functional groups (hydroxyl, carboxyl and carbonyl) on the surface of the hydrated carbon are combined with molybdenum selenide through interaction, more growth sites are provided for amorphous molybdenum selenide, the amorphous molybdenum selenide has good dispersibility and can not agglomerate due to the existence of the hydrated carbon carrier, more effective selenium sites are exposed, the adsorption effect of the hydrated carbon/amorphous molybdenum selenide composite material on palladium ions is further improved, and the hydrophilic property is good.
The preparation method provided by the invention is simple to operate, low in cost and suitable for industrial production.
Drawings
FIG. 1 hydrated charcoal prepared in example 1, MoSe prepared in comparative example 2x-140 and MoSe prepared in examples 1-4xThe scanning electron microscope picture of/hydrochar, wherein a is hydrated carbon, b is MoSex-140, c is MoSex(hydrogen-140, d is MoSe)x(hydrogen-160) e is MoSex(hydrogen-180, f is MoSe)x/hydrochar-200；
FIG. 2 shows MoSe prepared in example 1x/Hydrogen-140 MoSe prepared in comparative example 2x-140 and MoSe prepared in comparative example 32X-ray diffraction patterns of (a);
FIG. 3 is an infrared spectrum of a hydrated carbon prepared in example 1;
FIG. 4 shows MoSe prepared in example 1xMoSe prepared by/hydrogen-140 and comparative example 2x-an edsmaping result graph of 140;
FIG. 5 shows MoSe prepared in example 1x/Hydrogen-140 MoSe prepared in comparative example 2x-140 and MoSe prepared in comparative example 32A graph of the adsorption capacity for Pd (II);
FIG. 6 is a Langmuir isothermal adsorption model of Pd (II);
FIG. 7 is a Freundlich isothermal adsorption model of Pd (II);
FIG. 8 shows MoSe prepared in example 1xThe adsorption capacity diagram of the hydrogen-140 to Pd (II) in the water body containing palladium (II) ions with different pH values;
FIG. 9 shows MoSe prepared in example 1xMoSe prepared by/hydrogen-180 and comparative example 4xThe adsorption capacity of the Pd (II) under different adsorption times is plotted for the AC-180.
Detailed Description
The invention provides a hydrated carbon/amorphous molybdenum selenide composite material, which comprises hydrated carbon and amorphous molybdenum selenide dispersed on the surface of the hydrated carbon;
the surface of the hydrated carbon has oxygen-containing functional groups;
the molar ratio of selenium to molybdenum in the amorphous molybdenum selenide is (2.3-2.6): 1.
In the invention, the amorphous molybdenum selenide is granular and has a nanometer flower-shaped structure. In the invention, the load capacity of the amorphous molybdenum selenide is preferably 45-65 wt%, and more preferably 50-60 wt%; the particle size of the amorphous molybdenum selenide is preferably 20-50 nm, and more preferably 30-40 nm. In the present invention, the amorphous molybdenum selenide (abbreviated as MoSe)x) The molar ratio of selenium to molybdenum (i.e., x) is preferably (2.3-2.6): 1, and more preferably (2.33-2.52): 1. Compared with crystalline molybdenum selenide, the amorphous molybdenum selenide provided by the invention has more effective selenium sites and better removal effect on palladium ions.
In the invention, the hydrated carbon has a spherical structure, and the particle size of the hydrated carbon is preferably 100-800 nm, more preferably 300-500 nm; the hydrated carbon surface has oxygen-containing functional groups, which preferably include carboxyl, hydroxyl, carbonyl. In the invention, the oxygen-containing functional group on the surface of the hydrated carbon can provide more growth sites for amorphous molybdenum selenide, and the hydrated carbon can improve the dispersion uniformity of the amorphous molybdenum selenide, expose more effective selenium sites and further improve the adsorption performance of the composite material on palladium ions.
The invention provides a preparation method of a hydrated carbon/amorphous molybdenum selenide composite material in the technical scheme, which comprises the following steps:
(1) mixing a carbon-containing material with water, and carrying out hydrothermal carbonization reaction to obtain hydrated carbon;
(2) mixing selenium and hydrazine hydrate solution, and carrying out oxidation-reduction reaction to obtain selenium anion solution;
(3) mixing the hydrated carbon, the selenium anion solution, ammonium molybdate and an organic solvent, and carrying out a solvothermal reaction to obtain a hydrated carbon/amorphous molybdenum selenide composite material; the temperature of the solvothermal reaction is not lower than 140 ℃;
the step (1) and the step (2) have no chronological order.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, the carbon-containing material and water are mixed for hydrothermal carbonization reaction to obtain the hydrated carbon.
In the present invention, the carbonaceous material preferably comprises one or more of waste cigarette butts, pasture, straw and rice hulls. In the present invention, the carbonaceous material is preferably pulverized before use, and the pulverization method of the present invention is not particularly limited, and a pulverization method known to those skilled in the art may be used. In the invention, the size of the crushed carbonaceous material is 0.15-0.27 mm. The invention takes the waste cigarette butts, the pasture, the straws and the rice hulls as preparation raw materials, has wide raw material sources and low cost, realizes waste utilization, and lightens the pollution of the waste cigarette butts, the pasture, the straws and the rice hulls to the environment.
In the present invention, the ratio of the mass of the carbonaceous material to the volume of water is preferably 1 g: (10-20) mL, more preferably 1 g: (12-18) mL, most preferably 1 g: (15-26) mL.
In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the invention, the temperature of the hydrothermal carbonization reaction is preferably 180-220 ℃, more preferably 190-210 ℃, and most preferably 200 ℃; the time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and most preferably 4 hours. In the present invention, during the hydrothermal carbonization reaction, the carbonaceous material is carbonized to obtain hydrated carbon containing oxygen-containing functional groups (carboxyl groups, hydroxyl groups).
After the hydrothermal carbonization reaction, the method preferably further comprises the steps of carrying out solid-liquid separation on a system of the hydrothermal carbonization reaction, washing the obtained solid component with water, and drying to obtain the hydrated carbon. The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode well known by a person skilled in the art can be adopted; in an embodiment of the present invention, the solid-liquid separation is preferably centrifugal separation; the rotating speed of the centrifugal separation is preferably 8000-10000 r/min, more preferably 8500-9500 r/min, and most preferably 9000 r/min; the time for centrifugal separation is preferably 5-10 min, more preferably 6-9 min, and most preferably 7-8 min. The number of times of washing with water is not particularly limited, and the washing with water is carried out until the washing solution is transparent. In the invention, the drying temperature is preferably 60-110 ℃, more preferably 70-100 ℃, and most preferably 80-90 ℃; the time is preferably 6 to 12 hours, more preferably 7 to 11 hours, and most preferably 8 to 10 hours.
Selenium and hydrazine hydrate solution are mixed and subjected to oxidation-reduction reaction to obtain selenium anion solution.
In the invention, the selenium is preferably selenium powder, and the granularity of the selenium powder is preferably 37-74 μm, and more preferably 45-58 μm.
In the present invention, the mass ratio of the selenium to the hydrazine hydrate in the hydrazine hydrate solution is preferably 1: (0.12-0.13). In the invention, the concentration of the hydrazine hydrate solution is preferably 20 to 80 wt%, more preferably 30 to 70 wt%, and most preferably 40 to 50 wt%. In the present invention, the ratio of the mass of selenium to the volume of hydrazine hydrate solution is preferably 1 g: (60-70) mL, more preferably 1 g: (62-68) mL, most preferably 1 g: (64-65) mL.
In the invention, the mixing mode is preferably stirring mixing, and the stirring mixing speed is preferably 300-600 r/min, more preferably 350-550 r/min, and most preferably 400-500 r/min; the stirring and mixing time is not particularly limited, and the raw materials can be uniformly mixed.
In the present invention, the temperature of the redox reaction is preferably room temperature; the time is preferably 6 to 12 hours, more preferably 7 to 11 hours, and most preferably 8 to 10 hours. In the present invention, hydrazine hydrate having strong reducibility reduces selenium to Se during the redox reaction4-。
After the hydrated carbon and the selenium anion solution are obtained, the hydrated carbon, the selenium anion solution, ammonium molybdate and an organic solvent are mixed for solvothermal reaction to obtain the hydrated carbon/amorphous molybdenum selenide composite material.
In the invention, the dosage of the selenium anion solution is calculated by the mass of selenium, and the mass ratio of the hydrated carbon, the selenium and the ammonium molybdate is preferably 1: (4-8): (5-10), more preferably 1: (5-7): (6 to 8), most preferably 1 (6.2 to 6.5) to (6.6 to 7).
In the present invention, the organic solvent preferably includes methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, or acetone. The dosage of the organic solvent is not specially limited, and the hydrated carbon, the selenium anion solution and the ammonium molybdate can be uniformly dispersed. In the embodiment of the present invention, the ratio of the mass of ammonium molybdate to the volume of the organic solvent is preferably 0.33 g: 20 mL.
In the present invention, the sequence of mixing the hydrated carbon, the selenium anion solution, the ammonium molybdate and the organic solvent is preferably that the ammonium molybdate and the organic solvent are firstly mixed, the hydrated carbon is added for second mixing, and then the selenium anion solution is dropwise added for third mixing. The first mixing mode and the second mixing mode are not particularly limited, and the raw materials can be uniformly mixed, specifically, stirring mixing or ultrasonic mixing. The invention adopts the mixing sequence, which is beneficial to the uniform distribution of the molybdenum selenide on the surface of the hydrated carbon. In the present invention, the third mixing is preferably ultrasonic mixing, the ultrasonic power of the ultrasonic mixing is not particularly limited in the present invention, and the ultrasonic power well known to those skilled in the art may be used, and the time of the third mixing is preferably 30 to 60min, and more preferably 40 to 50 min. The dropping speed is not specially limited, and the selenium anion solution is added dropwise at a constant speed, so that the molybdenum selenide is uniformly distributed on the surface of the hydrated carbon.
In the invention, the temperature of the solvothermal reaction is not lower than 140 ℃, preferably 140-210 ℃, more preferably 150-200 ℃, and most preferably 160-180 ℃; the time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours. The container for the solvent thermal reaction in the present invention is not particularly limited, and a container for the solvent thermal reaction known to those skilled in the art may be used, specifically, a reaction vessel.
After the solvothermal reaction, the method preferably further comprises cooling a solvothermal reaction system to room temperature, performing solid-liquid separation, and sequentially performing alcohol washing, water washing, drying and crushing on the obtained solid component to obtain the hydrated carbon/amorphous molybdenum selenide composite material. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used. The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically centrifugal separation; the rotating speed of the centrifugal separation is preferably 8000-10000 r/min, more preferably 8500-9500 r/min, and most preferably 9000 r/min; the time for centrifugal separation is preferably 5-10 min, more preferably 6-9 min, and most preferably 7-8 min.
In the present invention, the alcohol used for the alcohol washing preferably includes ethanol or methanol; the number of times of alcohol washing is preferably 3-10 times, and more preferably 5-8 times; the purpose of the water wash is to remove organic impurities. In the invention, the washing time is preferably 3-10 times, and more preferably 5-8 times; the purpose of the water washing is to remove water-soluble impurities. In the invention, the drying temperature is preferably 50-70 ℃, more preferably 55-65 ℃, and most preferably 60 ℃; the time is preferably 6 to 24 hours, more preferably 10 to 20 hours, and most preferably 12 to 15 hours. The pulverization method of the present invention is not particularly limited, and pulverization methods known to those skilled in the art may be used. In the invention, the particle size of the hydrated carbon/amorphous molybdenum selenide composite material is preferably 10-80 μm, and more preferably 30-60 μm.
The invention also provides the application of the hydrated carbon/amorphous molybdenum selenide composite material or the hydrated carbon/amorphous molybdenum selenide composite material prepared by the preparation method in the technical scheme in palladium recovery.
In the present invention, the recovered palladium is preferably adsorbed pd (II) ions in the palladium (II) -ion-containing water body. In the invention, the pH value of the water body containing palladium (II) ions is preferably 1-6, and when the pH value of the water body containing palladium (II) ions does not meet the requirements, the pH value of the water body containing palladium (II) ions is preferably adjusted to 1-6. The acid or base used for adjusting the pH value in the present invention is not particularly limited, and any acid or base known to those skilled in the art may be used, specifically, sodium hydroxide or hydrochloric acid.
In the present invention, the method of application preferably comprises the steps of: mixing the hydrated carbon/amorphous molybdenum selenide composite material with a palladium (II) -containing ionic water body for palladium adsorption. In the invention, the concentration of palladium in the palladium-containing wastewater is preferably 2.5-300 mg/L, more preferably 10-250 mg/L, and most preferably 50-200 mg/L. In the invention, the mass ratio of the hydrated carbon/amorphous molybdenum selenide composite material to palladium in the palladium-containing wastewater is preferably 1: (0.025 to 3), more preferably 1: (0.1 to 2.5), most preferably 1: (1-2). In the present invention, the mixing is preferably shaking mixing or stirring mixing; the mixing speed is preferably 100-300 r/min, more preferably 150-250 r/min, and most preferably 200 r/min; the time for the oscillating and mixing is preferably 1-24 hours, more preferably 5-20 hours, and most preferably 10-15 hours.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Crushing 1g of waste cigarette butts to the size of 0.15-0.27 mm, mixing the crushed waste cigarette butts with 15mL of water, performing hydrothermal carbonization reaction for 4h at 220 ℃, then centrifuging the mixture for 10min at the speed of 10000r/min, washing the obtained solid component with water, and drying the solid component for 15h at the temperature of 110 ℃ to obtain the hydrated carbon.
Under the stirring condition of 360r/min at room temperature, 0.31g of selenium powder with the particle size of 45-58 mu m and 20mL of hydrazine hydrate solution (80 wt%) are mixed and then subjected to oxidation reaction for 12 hours to obtain the selenium anion solution.
Adding 0.33g of ammonium molybdate tetrahydrate into 20mL of ethanol, adding 50mg of hydrated carbon, uniformly mixing, dropwise adding the selenium anion solution, ultrasonically mixing for 60min, transferring the solution into a reaction kettle, carrying out solvothermal reaction for 12h at 140 ℃, cooling to room temperature, centrifuging for 10min at the speed of 10000r/min, washing the obtained solid component with ethanol for 3 times and water for 3 times, drying for 12h at 60 ℃, and crushing to obtain the hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe) with the granularity of 30-60 mu m to obtain the hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe)x/hydrochar-140)。
Example 2
A hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe) was prepared according to the method of example 1, except that the temperature of the solvothermal reaction was 160 ℃ to obtain a hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe)x/hydrochar-160)。
Example 3
A hydrated carbon/amorphous molybdenum selenide composite was prepared as in example 1The difference from example 1 is that the temperature of the solvothermal reaction is 180 ℃ to obtain a hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe)x/hydrochar-180)。
Example 4
A hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe) was prepared according to the method of example 1, except that the temperature of the solvothermal reaction was 200 ℃ to obtain a hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe)x/hydrochar-200)。
Comparative example 1
A hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe) was prepared according to the method of example 1, except that the temperature of the solvothermal reaction was 120 ℃ to obtain a hydrated carbon/amorphous molybdenum selenide composite material (abbreviated as MoSe)x/hydrochar-120)。
Comparative example 2
And under the stirring condition of 360r/min at room temperature, 0.31g of selenium powder with the particle size of 45-58 mu m and 20mL of hydrazine hydrate solution (80 wt%) are mixed and then subjected to oxidation reaction for 12 hours to obtain a selenium anion solution.
Adding 0.33g of ammonium molybdate tetrahydrate into 20mL of ethanol, dropwise adding the selenium anion solution, ultrasonically mixing for 60min, transferring the solution into a reaction kettle, carrying out solvothermal reaction for 12h at 140 ℃, cooling to room temperature, centrifuging for 10min at the speed of 10000r/min, washing the obtained solid component with ethanol for 3 times and water for 3 times, drying for 12h at 60 ℃, and crushing to obtain amorphous molybdenum selenide (abbreviated as MoSe) with the particle size of 30-60 mu m to obtain the amorphous molybdenum selenide (abbreviated as MoSe)x-140)。
Comparative example 3
200mg of MoSe prepared in example 4xPlacing the/hydrochar-200 in a corundum crucible, placing the corundum crucible in a horizontal alumina tube furnace, heating to 550 ℃ at the speed of 5 ℃/min under the argon atmosphere, and calcining for 2h to obtain crystalline molybdenum selenide (MoSe for short)2)。
Comparative example 4
And under the stirring condition of 360r/min at room temperature, 0.31g of selenium powder with the particle size of 45-58 mu m and 20mL of hydrazine hydrate solution (80 wt%) are mixed and then subjected to oxidation reaction for 12 hours to obtain a selenium anion solution.
Adding 0.33g of ammonium molybdate tetrahydrate into 20mL of ethanol, adding 50mg of activated carbon, uniformly mixing, dropwise adding the selenium anion solution, ultrasonically mixing for 60min, transferring the solution into a reaction kettle, carrying out solvothermal reaction for 12h at 180 ℃, cooling to room temperature, centrifuging for 10min at the speed of 10000r/min, washing the obtained solid component with ethanol for 3 times and water for 3 times, drying for 12h at 60 ℃, and crushing to the particle size of 30-60 mu m to obtain the amorphous molybdenum selenide/activated carbon composite material (abbreviated as MoSe)x/AC-180)。
Comparative example 5
And under the stirring condition of 360r/min at room temperature, 0.31g of selenium powder with the particle size of 45-58 mu m and 20mL of hydrazine hydrate solution (80 wt%) are mixed and then subjected to oxidation reaction for 12 hours to obtain a selenium anion solution.
Adding 0.33g of ammonium molybdate tetrahydrate into 20mL of ethanol, adding 50mg of carbon nano tube, uniformly mixing, dropwise adding the selenium anion solution, ultrasonically mixing for 60min, transferring the solution into a reaction kettle, carrying out solvothermal reaction for 12h at 140 ℃, cooling to room temperature, centrifuging for 10min at the speed of 10000r/min, washing the obtained solid component with ethanol for 3 times and water for 3 times, drying for 12h at 60 ℃, crushing to the particle size of 30-60 mu m, and obtaining the amorphous molybdenum selenide/carbon nano tube composite material (abbreviated as MoSe)x/CNTs-140)。
Hydrated carbon prepared in example 1, MoSe prepared in comparative example 2x-140 and MoSe prepared in examples 1-4xThe scanning electron micrograph of/hydrochar is shown in FIG. 1, wherein a is hydrated carbon, and b is MoSex-140, c is MoSex(hydrogen-140, d is MoSe)x(hydrogen-160) e is MoSex(hydrogen-180, f is MoSe)xHydrogen-200. As can be seen from a in FIG. 1, the hydrated carbon has an irregular spherical shape and a smoother surface; as can be seen from b in fig. 1, the amorphous molybdenum selenide is granular and shaped like a nanoflower; the shape and particle size of the composite material c-e in figure 1 are similar to those of the amorphous molybdenum selenide in b, and the smooth spherical particles are hydrated carbon. The invention successfully prepares the molybdenum selenide/hydrated carbon composite material.
MoSe prepared in example 1x/Hydrogen-140 MoSe prepared in comparative example 2x-140 and MoSe prepared in comparative example 32The X-ray diffraction pattern of (a) is shown in fig. 2. As can be seen from FIG. 2, MoSe2Six strong peaks in the map correspond to MoSe respectively2The (002), (100), (103), (105), (106) and (110) crystal planes of (A) and (B), and MoSe2The peak patterns of (A) and (B) are highly consistent with PDF #29-0914, which shows that the crystalline MoSe prepared in comparative example 32(ii) a The two materials of MoSex/hydrogen-140 and MoSex-140 have two broad peaks at the positions of 33 degrees and 56 degrees, and no other material has MoSe2The appearance of characteristic peaks corresponding to the peak patterns shows that the molybdenum selenides of the two materials are in an amorphous state, the peak patterns of the two materials are basically consistent, and the composition of the amorphous molybdenum selenide and the hydrated carbon does not obviously change the crystalline structure of the amorphous molybdenum selenide.
The infrared spectrum of the hydrated carbon prepared in example 1 is shown in fig. 3. As can be seen from FIG. 3, 1703cm-1At 2923cm, where is C ═ O peak-1The peak is O-H.
MoSe prepared in example 1xMoSe prepared by/hydrogen-140 and comparative example 2xEDSMapping results for-140 are shown in FIG. 4 and Table 1, where a is MoSex(hydrogen-140, b is MoSe)x-140。
TABLE 1MoSexHydrogen-140 and MoSex-140 mass and molar ratios of the elements
In Table 1, K and L are electron shell numbers.
As can be seen from FIG. 4 and Table 1, MoSexHydrogen-140 and MoSexThe Se/Mo molar ratio in 140 is 2.52 and 2.33 respectively, the Se/Mo ratio is greater than that of crystalline molybdenum selenide, the increase of the ratio indicates that the crystal form of the molybdenum selenide is deteriorated, after the hydrated carbon is added, the molar ratio of the molybdenum selenide is further improved compared with that without the hydrated carbon, and the selenium content in unit mole is higher after the hydrated carbon is compounded, so that the palladium ions can be captured efficiently; and the hydration produced by the present inventionThe carbon has oxygen-containing functional groups.
Application example 1
5mg of the hydrated carbon/amorphous molybdenum selenide composite materials prepared in examples 1 to 4 and comparative example 1 were added to 50mL of a water body containing palladium (II) ions and having a concentration of 100mg/L, pH ═ 3, the flask was shaken at 25 ℃ and 180r/min for 12 hours, and then the supernatant was aspirated by a syringe, and the filtrate was filtered through a 0.45 μm inorganic filter membrane, and the concentration of pd (II) in the filtrate was measured by flame atomic absorption, and the adsorption capacity for pd (II) is shown in table 2.
TABLE 2 adsorption capacities for Pd (II) of the composites prepared in examples 1-4 and comparative example 1
| Element(s) | Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 |
| Adsorption capacity | 694mg/g | 873mg/g | 836mg/g | 776mg/g | 730mg/g |
As can be seen from table 2, as the solvothermal reaction temperature decreased, the adsorption capacity of the composite gradually increased, which indicates that the lower the temperature, the worse the crystalline form of molybdenum selenide, the more effective adsorption sites were exposed, and when the solvothermal reaction temperature was below 140 ℃, the adsorption capacity of the amorphous molybdenum selenide/hydrated carbon composite decreased again, because the temperature was too low to synthesize molybdenum selenide.
Application example 2
5mg of MoSe prepared in example 1 were added to the solutionx/Hydrogen-140 MoSe prepared in comparative example 2x-140 and MoSe prepared in comparative example 32Adding the adsorbent into a conical flask containing 50mL of a series of palladium (II) -containing ionic water with the concentration of 2.5-300 mg/L, pH-3, wherein the concentration of the adsorbent in the palladium (II) -containing ionic water is 0.1g/L, adjusting the pH value to 3, shaking the conical flask at 25 ℃ and 180r/min for 2h, sucking the supernatant by using a syringe, passing the supernatant through a 0.45-micron inorganic filter membrane, measuring the concentration of Pd (II) in the supernatant by using a flame atomic absorption method, and the adsorption capacity for Pd (II) is shown in figure 5.
As can be seen from FIG. 5, the initial low concentration (C) of Pd (II)e) Then, MoSe2And MoSexAdsorption Capacity (Q) of/Hydrogen-140 to Pd (II)e) Rapidly increases, the adsorption capacity of the adsorbent to Pd (II) is gradually increased along with the gradual increase of the initial concentration of Pd (II), and finally, the equilibrium is reached, wherein MoSe2The maximum adsorption capacity for Pd (II) is 141mg/g, MoSexThe maximum adsorption capacity of/hydrochar-140 for Pd (II) is 856mg/g, due to the crystalline MoSe2The layer spacing is small and the exposed Se sites are very limited, while the MoSe prepared by the embodiment of the inventionxThe surface area of the/hydrogen-140 is larger, the effective Se sites are more, and the mass transfer and the adsorption of adsorbates on the surface of an adsorbent are facilitated, so that MoSexThe/hydrogen-140 has specific crystalline MoSe2Higher adsorption capacity.
To further explore the adsorption of palladium ions and the adsorbent in solution and the maximum adsorption capacity of the adsorbent, the adsorption data were analyzed using Langmuir and Freundlich isothermal adsorption models, and the fitting data of the Langmuir isothermal adsorption model (fig. 6 and formula 1) and the Freundlich isothermal adsorption model (fig. 7 and formula 2) are shown in table 3:
in formulae 1 and 2, Qm(in mg/g) is the theoretical maximum adsorption capacity of the adsorbent;
qe (in mg/g) is the adsorption capacity of the adsorbent at equilibrium;
Ce(unit mg/L) is the concentration of Pd (II) in the adsorption solution at adsorption equilibrium;
KL(unit L/g) is the Langumir constant;
KF(unit mg)1-(1/n)L1/ng-1) And n is the Freundlich constant, which represents the magnitude of the adsorption strength and the adsorption capacity, respectively.
TABLE 3 data fitting of Langmuir and Freundlich isothermal adsorption models
As can be seen from Table 3, the correlation coefficient (R) of the Langmuir isothermal adsorption model (FIG. 6)2) Very close to 1, the Langmuir isothermal adsorption model (fig. 6) is better suited to describe the entire adsorption process than the Freundlich adsorption isotherm model (fig. 7), indicating that the adsorption sites on the adsorbent surface are uniformly distributed. Further, MoSe2And MoSexTheoretical maximum adsorption capacity Q obtained by calculation of/hydrogen-140m139mg/g and 833mg/g, respectively, with MoSe2And MoSexThe actual adsorption amount of/hydrocar-140 is very close, which shows that the Langmuir isothermal adsorption model is more suitable for describing the whole adsorption behavior.
Application example 3
To inhibit PdCl4 2-At a concentration of 200mg/L,Adding NaCl into palladium (II) -containing ionic water with the pH value of 3, wherein the concentration of the NaCl in the palladium (II) -containing ionic water is 0.025mol/L, adjusting the pH value of 50mL of palladium (II) -containing ionic water to 1, 2, 3, 4, 5 and 6 by using 0.1mol/L NaOH solution and 0.1mol/L hydrochloric acid solution respectively, and adding 5mg of MoSe prepared in example 1xThe supernatant was aspirated by a syringe after shaking at 25 ℃ and 180r/min for 2 hours/hydrocar-140, and the concentration of Pd (II) in the supernatant was measured by flame atomic absorption through a 0.45 μm inorganic filter, and the adsorption capacity for Pd (II) is shown in Table 4 and FIG. 8.
TABLE 4 MoSexHydrogen-140 for Pd (II) in water containing palladium (II) ions with different pH values
Adsorption capacity
| |
1 | 2 | 3 | 4 | 5 | 6 |
| Adsorption capacity (mg/g) | 167 | 242 | 586 | 708 | 695 | 848 |
As can be seen from Table 4 and FIG. 8, MoSe gradually increased with increasing pHxThe adsorption capacity of the/hydrogen-140 to palladium ions is gradually increased and reaches 848mg/g at the pH value of 6.
Application example 4
5mg of each of the composite materials prepared in example 3 and comparative example 4 was put into a conical flask containing 50mL of a water body containing palladium (II) ions at a concentration of 100mg/L, pH ═ 3, the conical flask was shaken at 25 ℃ and 180r/min for 1min, 5min, 15min, 30min and 60min, then the supernatant was aspirated by a syringe, the supernatant was filtered through a 0.45 μm inorganic filter, the concentration of Pd (II) in the filtrate of the supernatant at various times was measured by flame atomic absorption, and the adsorption capacity for Pd (II) was as shown in Table 5 and FIG. 9.
TABLE 5 adsorption capacities for Pd (II) for the composites prepared in example 3 and comparative example 4
| Adsorption time | 1min | 5min | 15min | 30min | 60min |
| MoSex/AC-180 | 178mg/g | 205mg/g | 218mg/g | 230mg/g | 255mg/g |
| MoSex/hydrochar-180 | 265mg/g | 303mg/g | 320mg/g | 325mg/g | 361mg/g |
As can be seen from Table 5 and FIG. 9, MoSex/AC-180 and MoSexThe adsorption capacity of the/hydrogen-180 to Pd (II) is increased along with the increase of the adsorption time, the balance is basically achieved within 5min, and the MoSe is achieved at 60minx/AC-180 and MoSexThe adsorption capacity of the/hydrogen-180 to Pd (II) is 255mg/g and 361mg/g respectively. Compared with activated carbon, the method has the advantages that the hydrated carbon is used as a carrier, so that the adsorption performance of the composite material on Pd (II) can be improved, and the hydrated carbon prepared by the method has more oxygen-containing functional groups (such as-OH and-COOH) on the surface compared with the activated carbon, and the effect of the molybdenum selenide loaded on the hydrated carbon rich in the oxygen-containing functional groups is obviously better than that of the activated carbon, so that the adsorption performance on Pd (II) is better.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A hydrated carbon/amorphous molybdenum selenide composite material, which comprises hydrated carbon and amorphous molybdenum selenide dispersed on the surface of the hydrated carbon;
the surface of the hydrated carbon has oxygen-containing functional groups;
the molar ratio of selenium to molybdenum in the amorphous molybdenum selenide is (2.3-2.6): 1;
the preparation method of the hydrated carbon/amorphous molybdenum selenide composite material comprises the following steps:
(1) mixing a carbon-containing material with water, and carrying out hydrothermal carbonization reaction to obtain hydrated carbon; the carbon-containing material comprises one or more of waste cigarette butts, pasture, straws and rice hulls;
(2) mixing selenium and hydrazine hydrate solution, and carrying out oxidation-reduction reaction to obtain selenium anion solution;
(3) mixing the hydrated carbon, the selenium anion solution, ammonium molybdate and an organic solvent, and carrying out a solvothermal reaction to obtain a hydrated carbon/amorphous molybdenum selenide composite material; the temperature of the solvothermal reaction is not lower than 140 ℃;
the step (1) and the step (2) have no chronological order.
2. The hydrated carbon/amorphous molybdenum selenide composite material according to claim 1, wherein the loading amount of the amorphous molybdenum selenide is 45-65 wt%.
3. The hydrated carbon/amorphous molybdenum selenide composite material according to claim 1 or 2, wherein the amorphous molybdenum selenide has a particle size of 20 to 50 nm.
4. A method for preparing a hydrated carbon/amorphous molybdenum selenide composite material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing a carbon-containing material with water, and carrying out hydrothermal carbonization reaction to obtain hydrated carbon; the carbon-containing material comprises one or more of waste cigarette butts, pasture, straws and rice hulls;
(2) mixing selenium and hydrazine hydrate solution, and carrying out oxidation-reduction reaction to obtain selenium anion solution;
(3) mixing the hydrated carbon, the selenium anion solution, ammonium molybdate and an organic solvent, and carrying out a solvothermal reaction to obtain a hydrated carbon/amorphous molybdenum selenide composite material; the temperature of the solvothermal reaction is not lower than 140 ℃;
the step (1) and the step (2) have no chronological order.
5. The preparation method according to claim 4, wherein the temperature of the hydrothermal carbonization reaction is 180-220 ℃ and the time is 2-6 h.
6. The method according to claim 4, wherein the mass ratio of the selenium to the hydrazine hydrate in the hydrazine hydrate solution is 1: (0.12-0.13).
7. The preparation method according to claim 4, wherein the selenium anion solution is used in an amount calculated by the mass of selenium in the raw materials for preparation, and the mass ratio of the hydrated carbon to the selenium to the ammonium molybdate is 1: (4-8): (5-10).
8. The method according to claim 4, wherein the organic solvent comprises methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, or acetone.
9. The preparation method according to claim 4, 7 or 8, wherein the temperature of the solvothermal reaction is 140-210 ℃ and the time is 10-15 h.
10. Use of the hydrated carbon/amorphous molybdenum selenide composite material according to any one of claims 1 to 3 or the hydrated carbon/amorphous molybdenum selenide composite material prepared by the preparation method according to any one of claims 4 to 9 in recovery of palladium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010667500.6A CN111777056B (en) | 2020-07-13 | 2020-07-13 | Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010667500.6A CN111777056B (en) | 2020-07-13 | 2020-07-13 | Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111777056A CN111777056A (en) | 2020-10-16 |
| CN111777056B true CN111777056B (en) | 2022-02-01 |
Family
ID=72768142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010667500.6A Active CN111777056B (en) | 2020-07-13 | 2020-07-13 | Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111777056B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880316B (en) * | 2021-11-17 | 2022-05-27 | 青岛延晖环保科技有限公司 | Method for desalting seawater by using biological membrane |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132941A (en) * | 2015-09-10 | 2015-12-09 | 北京航空航天大学 | Molybdenum diselenide/carbon black composite hydrogen evolution electro-catalysis material and preparation method thereof |
| CN107275609A (en) * | 2017-06-16 | 2017-10-20 | 南京理工大学 | A kind of selenizing molybdenum/carbonization bacteria cellulose lithium ion battery negative material and preparation method thereof |
| CN105932252B (en) * | 2016-06-03 | 2018-10-02 | 东华大学 | A kind of sulphur selenizing molybdenum/carbon nano tube compound material and its preparation and application |
| CN109225276A (en) * | 2018-08-22 | 2019-01-18 | 江苏大学 | The flower-shaped two selenizings molybdenum/carbon nano tube compound material of one kind and synthetic method and application |
| CN110237812A (en) * | 2019-06-05 | 2019-09-17 | 镇江市高等专科学校 | A kind of biomass carbon modification selenizing molybdenum nano material, preparation method and its application |
| CN110890224A (en) * | 2019-11-05 | 2020-03-17 | 西北大学 | Molybdenum diselenide/carbon nanotube array composite electrode, preparation method and application |
-
2020
- 2020-07-13 CN CN202010667500.6A patent/CN111777056B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132941A (en) * | 2015-09-10 | 2015-12-09 | 北京航空航天大学 | Molybdenum diselenide/carbon black composite hydrogen evolution electro-catalysis material and preparation method thereof |
| CN105932252B (en) * | 2016-06-03 | 2018-10-02 | 东华大学 | A kind of sulphur selenizing molybdenum/carbon nano tube compound material and its preparation and application |
| CN107275609A (en) * | 2017-06-16 | 2017-10-20 | 南京理工大学 | A kind of selenizing molybdenum/carbonization bacteria cellulose lithium ion battery negative material and preparation method thereof |
| CN109225276A (en) * | 2018-08-22 | 2019-01-18 | 江苏大学 | The flower-shaped two selenizings molybdenum/carbon nano tube compound material of one kind and synthetic method and application |
| CN110237812A (en) * | 2019-06-05 | 2019-09-17 | 镇江市高等专科学校 | A kind of biomass carbon modification selenizing molybdenum nano material, preparation method and its application |
| CN110890224A (en) * | 2019-11-05 | 2020-03-17 | 西北大学 | Molybdenum diselenide/carbon nanotube array composite electrode, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Cotton Wool Derived Carbon Fiber Aerogel Supported Few-Layered;Youfang Zhang等;《Applied Materials & Interfaces》;20160229;第8卷;第7077-7085页 * |
| 活性炭硒化钼近红外光催化降解氨氮的研究;顾勤勤等;《苏州科技大学学报》;20190615;第36卷(第2期);第47-54页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111777056A (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Facile low-temperature one-step synthesis of pomelo peel biochar under air atmosphere and its adsorption behaviors for Ag (I) and Pb (II) | |
| Zhu et al. | In situ carbothermal reduction synthesis of Fe nanocrystals embedded into N-doped carbon nanospheres for highly efficient U (VI) adsorption and reduction | |
| CN108722356B (en) | Preparation method of nano zero-valent iron-loaded hydrophilic porous biochar composite material | |
| CN103663450B (en) | A kind of high-specific surface area carbosphere and preparation method thereof | |
| JP2020510527A (en) | Production method of composite modified straw granular activated carbon adsorption material and its use in phosphorus adsorption | |
| CN108483444B (en) | Preparation method of alpha-FeOOH nanorod-loaded porous biochar composite material | |
| CN109126893B (en) | Titanium oxycarbide-metal organic framework composite material, and preparation method and application thereof | |
| Li et al. | Performance of lead ion removal by the three-dimensional carbon foam supported nanoscale zero-valent iron composite | |
| CN101973620A (en) | Method for removing heavy metal ions in water by using graphene oxide sheet | |
| CN114177891B (en) | Preparation method of biochar composite metal organic framework adsorbing material | |
| CN105536660B (en) | A kind of preparation method of nano-silver loaded oil-tea camellia husks pyrolysis carbosphere | |
| González et al. | Synthesis and applications of MOF-derived nanohybrids: A review | |
| CN113713816A (en) | Preparation and application of copper-cobalt/carbon catalyst derived from metal organic framework material | |
| CN108855108A (en) | Starch-based bio activated carbon loaded nano catalysis material and preparation method thereof | |
| CN111777056B (en) | Hydrated carbon/amorphous molybdenum selenide composite material and preparation method and application thereof | |
| Zhang et al. | Biological self-assembled hyphae/starch porous carbon composites for removal of organic pollutants from water | |
| Liu et al. | Metal-organic frameworks derived TiO2/carbon nitride heterojunction photocatalyst with efficient catalytic performance under visible light | |
| Zheng et al. | Metal organic frameworks derived nano materials for energy storage application | |
| CN112934177A (en) | Manganese sulfide-phosphoric acid modified biochar composite material and preparation method and application thereof | |
| CN105597779A (en) | Composite material with nano-nickel particles and nano-palladium particles on graphene and preparation method of composite material | |
| CN113856630A (en) | Straw carbon magnesium lanthanum LDH nano-phosphorus adsorption material and preparation method and application thereof | |
| Jiang et al. | Synthesis of flower-like Cu3SnS4 microspheres and Cu3SnS4/reduced graphene oxide composite with high photocatalytic activity | |
| CN109338466B (en) | Preparation of single crystal Fe2O3Method for self-assembling nano-particle into elliptical micro-nano structure | |
| Fan et al. | Hollow Co@ HCN derived from ZIF-67 as a highly efficient catalyst for hydrogenation of o-cresol to o-methyl cyclohexanol | |
| CN115025783B (en) | Synthetic method and application of multi-niobium oxygen cluster/ZIF-67 derivative composite material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |