CN113479897A - Method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof - Google Patents

Method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof Download PDF

Info

Publication number
CN113479897A
CN113479897A CN202110806007.2A CN202110806007A CN113479897A CN 113479897 A CN113479897 A CN 113479897A CN 202110806007 A CN202110806007 A CN 202110806007A CN 113479897 A CN113479897 A CN 113479897A
Authority
CN
China
Prior art keywords
attapulgite
preparing
silicate
acid solution
hydrochloric acid
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.)
Granted
Application number
CN202110806007.2A
Other languages
Chinese (zh)
Other versions
CN113479897B (en
Inventor
李霞章
仲明辉
石安琪
左士祥
姚超
李忠玉
吴凤芹
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.)
Changzhou University
Original Assignee
Changzhou University
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 Changzhou University filed Critical Changzhou University
Priority to CN202110806007.2A priority Critical patent/CN113479897B/en
Publication of CN113479897A publication Critical patent/CN113479897A/en
Application granted granted Critical
Publication of CN113479897B publication Critical patent/CN113479897B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/23—
    • B01J35/39—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of new chemical materials, and particularly relates to a method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof, wherein the preparation process comprises the following steps: firstly, the attapulgite powder is subjected to dispersion and dissociation of one-dimensional crystal beams and is uniformly dispersed in an acid solution, and precipitates are washed and dried to obtain a white precursor. Dispersing the white precursor in water to form suspension, ultrasonically dispersing, and dripping NH4NO3And then transferring the turbid liquid into a polytetrafluoroethylene reaction kettle for microwave hydrothermal reaction, centrifugally separating out solids after the reaction is finished, washing, drying, and grinding into powder to obtain the two-dimensional silicate, wherein the two-dimensional silicate is applied to preparing methanol from photocatalytic carbon dioxide. Compared with the traditional noble metal catalyst, the photocatalyst for preparing methanol from carbon dioxide has the advantages of low cost of raw materials, simple and convenient synthesis method and the like, and is beneficial to large-scale popularization.

Description

Method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof
Technical Field
The invention belongs to the technical field of new chemical materials, and particularly relates to a method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof.
Background
In recent years, in order to achieve the national strategic goals of "carbon peak reaching" and "carbon neutralization", resource utilization of carbon dioxide has become a hot direction of research. Modern social development relies heavily on a stable and reliable supply of energy, forcing people to tighten the development of sustainable and renewable energy sources to alleviate the dependence on fossil fuels. The carbon dioxide photocatalytic reduction is always a great research direction for solar energy utilization and storage, and the path can directly hydrogenate carbon dioxide and convert the carbon dioxide into hydrocarbon fuel which can be utilized by people. Methanol is the simplest saturated alcohol, is widely used in industries such as organic synthesis, medicine, pesticides, coatings, dyes, automobiles, national defense and the like, and is also an important chemical industry basic raw material and a clean liquid fuel. At present, methods such as noble metal deposition or rare earth ion doping are mostly adopted for the photocatalyst to improve the effect of reducing carbon dioxide, and the cost is higher. In addition, some catalysts such as indium zinc sulfide have a serious influence on their photocatalytic performance due to their flower-like spheres being too large and easily collapsing. Therefore, researchers have turned their eyes to natural minerals with abundant reserves, low prices, and nanometer sizes, and have sought to develop a novel catalyst that can overcome the above disadvantages.
Attapulgite is used as a natural mineral clay material, has abundant reserves in China, good dispersibility, larger specific surface area and unique one-dimensional nano rod-shaped structure, and is mostly used as a catalyst carrier. From the physicochemical property, the modification of the attapulgite can comprise acidification, alkalization, surface functionalization, ion exchange and the like. From the structure, the attapulgite is a hexacyclic silicate mineral crystal, the special chain layer structure of the attapulgite consists of hexacyclic silicon-oxygen tetrahedrons, the vertexes of the hexacyclic silicon-oxygen tetrahedrons in the attapulgite are alternately turned up and down and form a chain structure, the geological condition formed by the ore presents the chain layer structure due to the existence of metal magnesium atoms as a support, the coordination number of cations between layers is usually 6, and the space distribution is remodeled and transversely spread under the condition of removing the original cation octahedron. The transition element in attapulgite is often Fe2+,Fe3+But the content thereof is low, so that the absorptivity thereof to light is low.
Disclosure of Invention
The invention aims to provide preparation and application of a photocatalytic carbon dioxide reduction material which is low in price, easily available in raw materials and high in photoproduction electron hole separation efficiency, and particularly relates to a method for preparing a two-dimensional nanosheet silicate by using attapulgite and application thereof. The preparation method is simple, the synthesis condition is mild, complex and expensive equipment is not needed, and the method is favorable for large-scale popularization.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
the two-dimensional nano-sheet silicate material provided by the invention has a general formula: MSiO3Wherein M is any one of Fe, Co, Cu and Ni.
The method for preparing the two-dimensional nanosheet silicate by using the attapulgite comprises the following steps:
(1) immersing the attapulgite powder into 3-7 mol/L hydrochloric acid solution, mixing and stirring for pretreatment for 0.5-4 h, wherein the solid-to-liquid ratio of the attapulgite powder to the hydrochloric acid solution is preferably 1: 1. Too high a concentration of hydrochloric acid and too long a pretreatment time may result in dissociation of the hexacyclic silicon oxide tetrahedron, and too low a concentration of hydrochloric acid and too short a pretreatment time may result in incomplete removal of the metal cations and limit dispersion of the hexacyclic silicon oxide tetrahedron. Then washing and drying to obtain pretreated attapulgite powder;
(2) dispersing the attapulgite powder pretreated in the step (1) into an acid solution (the acid solution can be one of hydrochloric acid, nitric acid or sulfuric acid) of less than 5mol/L, carrying out hydrothermal stirring for 4-16 h, separating out solids, washing, and drying to obtain the hexacyclic silica tetrahedron white precursor. The solid-to-liquid ratio of the pretreated attapulgite powder to the hydrochloric acid solution in the step is preferably 1:10, and the concentration of the hydrochloric acid solution is 2 mol/L. The time control of the step is critical, the long time can cause the dissociation of the six-ring-shaped silicon-oxygen tetrahedral unit to influence the appearance of the synthesized silicate, and the short time can cause incomplete removal of metal ions, influence the purity of the subsequent silicate and influence the appearance of the silicate structure.
(3) Dispersing the precursor prepared in the step (2) in water to form a suspension, ultrasonically dispersing the suspension, adjusting the pH to 6-10 during stirring (preferably dropwise adding a sodium hydroxide solution or a dilute hydrochloric acid solution to adjust the pH), dissolving transition metal nitrate in the suspension, and then dissolving NH4NO3Adding the mixture into the turbid liquid, dropwise adding ammonia water into the turbid liquid, and stirring the mixture until the mixture is uniform to obtain a uniform turbid liquid, wherein the molar ratio of silicon to transition metal elements to ammonium ions is 1-2: 1-4: 1-12, and the transition metal nitrate is any one of Fe, Co, Cu and Ni nitrates;
(4) and (4) transferring the uniform suspension obtained in the step (3) into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out microwave reaction for 30-120 min at 120-220 ℃, then naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying to obtain the two-dimensional nanosheet silicate.
Preferably, the concentration of the hydrochloric acid solution in the step (1) is 5mol/L, and the pretreatment time is 2 h. The purpose of pretreating the attapulgite powder and the hydrochloric acid in the step (1) is to strip and remove a large amount of metal cations in the attapulgite body and impurities in pore canals of a chain layer, and if the concentration of the hydrochloric acid is lower than 3mol/L, incomplete cation removal and uneven dispersion of a hexacyclic silicon-oxygen tetrahedral unit can be caused, so that the appearance of subsequent silicate is influenced.
In order to ensure that cations which are not completely removed are sufficiently cleaned, and simultaneously, the dissociation of hexacyclic-ring-shaped silicon-oxygen tetrahedral units is avoided, and amorphous agglomerated silicon dioxide is formed, the hydrochloric acid concentration in the step (2) is not higher than 5mol/L, preferably, the hydrochloric acid concentration is 2mol/L, the hydrothermal temperature is 80 ℃, and the hydrothermal stirring time is 6 hours. The use of 2mol/L hydrochloric acid in step (2) is used to wash the incompletely removed cations and to avoid the dissociation of the hexacyclic silicon oxygen tetrahedral unit to form amorphous agglomerated silica.
Preferably, the ultrasonic dispersion time in step (3) is 30 min.
Preferably, the concentration of the sodium hydroxide solution in the step (3) is 0.5mol/L, and the concentration of the dilute hydrochloric acid solution is 0.1 mol/L.
Preferably, the mass concentration of the ammonia water in the step (3) is 28%, and the stirring time is 10 min.
Preferably, the vacuum drying temperature in the step (4) is 60 ℃, and the vacuum drying time is 2 h.
The two-dimensional nanosheet silicate prepared by the method is used for photocatalytic carbon dioxide reduction.
The specific method comprises the following steps: dispersing the two-dimensional nano-sheet silicate in deionized water, then adding the deionized water into a photocatalytic reaction device, and then adding CO2And introducing the mixture into a reaction device at a set flow rate, and then irradiating to catalyze carbon dioxide for reduction to prepare the methanol.
SiO of six-ring based silicon-oxygen tetrahedron structure2Plays an important role in the present application if the SiO of the hexacyclic type siloxatetrahedral structure is not added2Then the transition metal nitrate is easily converted to the transition metal nitrate in the hydrothermal environmentTransition metal oxide nanoparticles are more likely to agglomerate into spheres under the microwave hydrothermal condition, so that the obtained composite catalyst cannot achieve the ideal carbon dioxide reduction effect. The two-dimensional nano-sheet silicate generated by the invention can well overcome the problem, and meanwhile, the reaction can be effectively promoted due to abundant active sites on the surface of the two-dimensional nano-sheet silicate and excellent photo-generated electron hole separation efficiency.
The invention adopts a microwave hydrothermal method, under a high-frequency energy field, the molecular motion is changed from the original disordered state into ordered high-frequency vibration, so that the heating is more uniform, under the condition, smaller structural units forming a six-ring-based silicon-oxygen tetrahedron structure can be self-assembled, and a new nano-layer sheet structure is formed under the participation of a complex formed by ammonium ions and transition metal cations.
The invention has the advantages that: selecting natural attapulgite clay minerals abundant in nature as raw materials, introducing metal elements Fe, Co, Cu or Ni, and substituting Mg occupying the central position of cation octahedron2+,Al3+The novel silicate photocatalyst which has a stable two-dimensional lamellar structure and is high in photo-generated electron hole separation efficiency and good in photocatalytic carbon dioxide reduction effect is synthesized by means of microwave hydrothermal reaction, and a silicon-oxygen tetrahedron in the transition metal silicate is easy to distort and polarize, so that the migration rate of photo-generated carriers is enhanced; meanwhile, the method has the advantages of rich raw material sources, low cost, environmental friendliness, simple preparation process and contribution to large-scale popularization.
Drawings
Figure 1 is an XRD pattern of two-dimensional nanosheet silicate prepared in examples 1 to 4;
FIG. 2 is a CuSiO solid prepared in example 13TEM image of the sample at 50nm scale range;
FIG. 3 is a summary of methanol yields for examples 1-5 and comparative examples 1-2;
fig. 4 shows XRD patterns of comparative example 1 and comparative example 2 (upper curve in the figure corresponds to comparative example 1, and lower curve corresponds to comparative example 2).
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
examples the optimum formulation and the process are preferred as examples, and the summary of the invention is further elaborated, in which the specific conditions are not indicated, and are carried out according to the conventional conditions. The raw materials, reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 6h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.3g of the prepared precursor in water to form a suspension and ultrasonically dispersing for 30min, then, adding 0.5mol/L sodium hydroxide solution dropwise while stirring, adjusting the pH to 10, and then, adding 10mmol of Cu (NO)3)2·3H2O and 20mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 60min at the temperature of 220 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain two-dimensional nanosheets CuSiO3。
For the two-dimensional nanosheet CuSiO prepared in this example3Performing X-ray powder diffraction experiment, and transmittingThe appearance and structure of the film are observed under an electron microscope.
The XRD pattern is shown in figure 1 by comparing CuSiO3The PDF card of (1) can know that CuSiO appears at angles of 21.64 °, 30.70 °, 36.19 °, 62.26 °, and the like3The specific diffraction characteristic peak is combined with a TEM picture 2, and the two-dimensional nanosheet CuSiO can be proved3The successful synthesis of the compound.
The TEM photograph is shown in FIG. 2, in which the upper lamellar growth is uniform and the band-shaped edge CuSiO is observed3The film tends to grow into a sheet shape, and the film has uniform thickness and good dispersion.
The two-dimensional nanosheet CuSiO3The method is used for photocatalytic carbon dioxide reduction and comprises the following application methods: weighing prepared two-dimensional nanosheet CuSiO30.05g of the solution is dispersed in 100mL of deionized water and then added into a photocatalytic reaction device, and CO is added2Introducing into a reaction device at a flow rate of 30mL/min, introducing CO2After 60min, a 300W xenon lamp is used as a simulated light source for irradiation, 5mL of samples are collected every 60min, and after centrifugation, the samples are quantitatively analyzed by using a gas chromatography external standard method.
The methanol concentration reached 8.16. mu. mol. L after 6h, as determined by the method described above-1。
Example 2
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 6h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.6g of the prepared precursor in water to form a suspension and ultrasonically dispersing for 30min, then, adding 0.5mol/L sodium hydroxide solution dropwise while stirring, adjusting pH to 9, and then adding 10mmol of Ni (NO)3)2·3H2O and 40mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) Transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, 2Microwave reacting at 00 deg.C for 120min, naturally cooling to room temperature, centrifuging to separate solid, washing, and vacuum drying at 60 deg.C for 2 hr. Obtaining two-dimensional nano sheet Ni2SiO4。
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the result shows that the methanol concentration reaches 3.68 mu mol.L after 6h-1。
Example 3
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 6h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.6g of the prepared precursor in water to form a suspension and ultrasonically dispersing for 30min, then, adding 0.5mol/L sodium hydroxide solution dropwise while stirring, adjusting pH to 8, and then, adding 20mmol of Co (NO)3)2·3H2O and 30mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 170 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃. Obtaining two-dimensional nanosheet Co2SiO4。
The subsequent detection method for photocatalytic carbon dioxide reduction was as in example 1, and the result showed that the methanol concentration reached 2.74. mu. mol. L after 6 hours-1。
Example 4
(1) Mixing attapulgite powder and 5mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 2h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 6h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.9g of the prepared precursor in water to form a suspension and carrying out ultrasonic separationDispersing for 30min, stirring, adding 0.5mol/L sodium hydroxide solution and 0.1mol/L diluted hydrochloric acid solution, adjusting pH to 7, and adding 30mmol Fe (NO)3)2·6H2O and 60mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 60min at the temperature of 150 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃. Obtaining two-dimensional nano-sheet FeSiO3。
The subsequent detection method for photocatalytic carbon dioxide reduction was as in example 1, and the result showed that the methanol concentration reached 1.76. mu. mol. L after 6 hours-1。
Example 5
(1) Mixing attapulgite powder and 3mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 4h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 4h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.6g of the prepared precursor in water to form a suspension and ultrasonically dispersing for 30min, then, dropwise adding 0.1mol/L diluted hydrochloric acid solution while stirring, adjusting the pH to 6, and then, adding 20mmol of Cu (NO)3)2·3H2O and 60mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 90min at the temperature of 120 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃. Obtaining two-dimensional nanosheet CuSiO3。
The subsequent detection method for photocatalytic carbon dioxide reduction was as in example 1, and the result showed that the methanol concentration reached 1.62. mu. mol. L after 6 hours-1。
Example 6
(1) Mixing attapulgite powder and 7mol/L hydrochloric acid solution at a solid-to-liquid ratio of 1:1, stirring for 0.5h, washing, and oven drying. Dispersing the obtained solid into 2mol/L hydrochloric acid solution according to the solid-liquid ratio of 1:10, carrying out hydrothermal stirring at 80 ℃ for 16h, separating out the solid, washing, and drying to obtain the white precursor of the hexacyclic group silicon-oxygen tetrahedron.
(2) Dispersing 0.3g of the prepared precursor in water to form a suspension and ultrasonically dispersing for 30min, then, adding 0.5mol/L sodium hydroxide solution dropwise while stirring, adjusting the pH to 10, and then, adding 10mmol of Cu (NO)3)2·3H2O and 20mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 200 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃. Obtaining two-dimensional CuSiO3Nanosheets.
The subsequent detection method for photocatalytic carbon dioxide reduction was as in example 1, and the result showed that the methanol concentration reached 1.38. mu. mol. L after 6 hours-1。
Comparative example 1
(1) 0.3g of commercial SiO2Dispersing in water to obtain suspension, ultrasonically dispersing for 30min, adding 0.5mol/L sodium hydroxide solution while stirring, adjusting pH to 10, and adding 10mmol Cu (NO)3)2·3H2O and 20mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 220 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain a solid-1.
The XRD patterns are shown in FIG. 4 by comparing CuO and SiO2The PDF card of (1) shows that diffraction characteristic peaks peculiar to CuO appear at angles of 35.45 °, 28.73 °, 48.76 °, 61.57 °, and CuSiO is not obtained3A large amount of micron-sized spherical copper oxide was observed from the TEM image.
The subsequent detection method for photocatalytic carbon dioxide reduction is as in example 1, and the result shows that the methanol concentration only reaches 0.24 mu mol.L after 6h-1。
Comparative example 2
(1) Adding 10mmol of Na2SiO4·9H2Dispersing O in water to obtain suspension, ultrasonically dispersing for 30min, adding 0.5mol/L sodium hydroxide solution while stirring, adjusting pH to 10, and adding 10mmol Cu (NO)3)3·3H2O and 20mmol NH4NO3And preparing an aqueous solution, adding the aqueous solution into the suspension, dropwise adding 1mL of 28% ammonia water into the suspension, and stirring for 10 min.
(3) And transferring the obtained suspension into a polytetrafluoroethylene hydrothermal reaction kettle with the capacity of 100mL, carrying out microwave reaction for 120min at the temperature of 220 ℃, naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain a solid-2.
The XRD pattern is shown in FIG. 4, and CuSiO is not obtained3Sample, amorphous.
The subsequent detection method for photocatalytic carbon dioxide reduction was as in example 1, and the results showed that the methanol concentration reached only 0.27. mu. mol. L after 6 hours-1。
In combination with the above examples, it can be seen that SiO is obtained by the process of the invention2Still retains the structure of six-ring-base type silicon-oxygen tetrahedron, while the SiO is commercially available2The shape of the microsphere is mostly smooth surface microsphere, and the microsphere does not have a six-ring-based silicon-oxygen tetrahedron structure, and the purpose of converting the attapulgite into SiO in the invention cannot be achieved in application2The effect of (1).
In addition, although the SiO2 crystal prepared by a precipitation method (silicate is acidified to obtain loose, finely dispersed SiO2 crystal precipitated in a flocculent structure) in the prior art also exists in the form of silicon-oxygen tetrahedron, the SiO2 crystal is scattered without any sign, does not have a unit of 'hexacyclic-ring-based silicon-oxygen tetrahedron' in attapulgite, and does not have structural advantages in the process of synthesizing lamellar silicic acid.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (10)

1. A method for preparing two-dimensional nanosheet silicate from attapulgite comprises the following steps: MSiO3Wherein M is any one of Fe, Co, Cu and Ni, and is characterized in that: the method comprises the following steps:
(1) immersing the attapulgite powder into 3-7 mol/L hydrochloric acid solution, mixing, stirring and pretreating for 0.5-4 h, then washing and drying to obtain pretreated attapulgite powder;
(2) dispersing the attapulgite powder pretreated in the step (1) into an acid solution with the concentration of less than 5mol/L, carrying out hydrothermal stirring for 4-16 h, separating out solids, washing, and drying to obtain a hexacyclic silica tetrahedron white precursor;
(3) dispersing the precursor prepared in the step (2) in water to form a suspension, ultrasonically dispersing the suspension, adjusting the pH to 6-10 during stirring, dissolving transition metal nitrate in the suspension, and then dissolving NH4NO3Adding the mixture into the turbid liquid, dropwise adding ammonia water into the turbid liquid, and stirring the mixture until the mixture is uniform to obtain a uniform turbid liquid, wherein the molar ratio of silicon to transition metal elements to ammonium ions is 1-2: 1-4: 1-12, and the transition metal nitrate is any one of Fe, Co, Cu and Ni nitrates;
(4) and (4) transferring the uniform suspension obtained in the step (3) into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out microwave reaction for 30-120 min at 120-220 ℃, then naturally cooling to room temperature, centrifugally separating out solids, washing, and carrying out vacuum drying to obtain the two-dimensional nanosheet silicate.
2. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: in the step (1), the solid-to-liquid ratio of the attapulgite powder to the hydrochloric acid solution is 1:1, the concentration of the hydrochloric acid solution is 5mol/L, and the pretreatment time is 2 hours.
3. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: the solid-to-liquid ratio of the pretreated attapulgite powder to the hydrochloric acid solution in the step (2) is 1:10, the concentration of the hydrochloric acid solution is 2mol/L, the hydrothermal temperature is 80 ℃, and the hydrothermal stirring time is 6 hours.
4. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: in the step (3), 0.5mol/L sodium hydroxide solution or 0.1mol/L hydrochloric acid solution is dripped to adjust the pH.
5. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: and (4) the ultrasonic dispersion time in the step (3) is 30 min.
6. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: the mass concentration of ammonia water in the step (3) is 28%, and the stirring time is 10 min.
7. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: in the step (4), the vacuum drying temperature is 60 ℃, and the vacuum drying time is 2 hours.
8. The method for preparing two-dimensional nanosheet silicate with attapulgite according to claim 1, wherein: the acid solution in the step (2) is one of hydrochloric acid, sulfuric acid or nitric acid.
9. Use of a two-dimensional nanosheet silicate produced by the process of any one of claims 1 to 8, wherein: the method is used for preparing methanol by photocatalytic carbon dioxide reduction.
10. Use of a two-dimensional nanosheet silicate as defined in claim 9, wherein: dispersing the two-dimensional nano-sheet silicate in deionized water, then adding the deionized water into a photocatalytic reaction device, and then adding CO2And introducing the mixture into a reaction device at a set flow rate, and then irradiating to catalyze carbon dioxide for reduction to prepare the methanol.
CN202110806007.2A 2021-07-16 2021-07-16 Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof Active CN113479897B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110806007.2A CN113479897B (en) 2021-07-16 2021-07-16 Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110806007.2A CN113479897B (en) 2021-07-16 2021-07-16 Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof

Publications (2)

Publication Number Publication Date
CN113479897A true CN113479897A (en) 2021-10-08
CN113479897B CN113479897B (en) 2023-10-24

Family

ID=77939829

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110806007.2A Active CN113479897B (en) 2021-07-16 2021-07-16 Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof

Country Status (1)

Country Link
CN (1) CN113479897B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116618048A (en) * 2023-04-24 2023-08-22 陕西科技大学 Preparation method and application of single-wall copper silicate nano Guan Guangfen ton catalyst

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1359367A (en) * 1970-08-31 1974-07-10 Exxon Research Engineering Co Layered complex metal silicate composition their preparation and use in hydrocarbon conversion reactions
NL7613957A (en) * 1976-12-16 1978-06-20 Shell Int Research CRYSTALLINE SILICATES.
JPH05245A (en) * 1991-06-24 1993-01-08 Kiyohisa Ota Conversion of carbon dioxide, carbonic ion or hydrocarbonic ion to high value added substance by photocatalytic action
AU8324698A (en) * 1997-07-15 1999-02-10 University Of Queensland, The Catalytic conversion of gases via cation-exchangeable alumino-silicate materials
JP2005145800A (en) * 2003-11-19 2005-06-09 National Institute Of Advanced Industrial & Technology Method of manufacturing layered silicate compound
US20080253953A1 (en) * 2005-10-12 2008-10-16 Basf Se Silicate Producing Method
WO2011156971A1 (en) * 2010-06-18 2011-12-22 海洋王照明科技股份有限公司 Halosilicate luminescent materials and preparation methods and uses thereof
CN102666387A (en) * 2009-12-22 2012-09-12 东曹株式会社 Novel metallosilicate, production method thereof, nitrogen oxide purification catalyst, production method thereof, and nitrogen oxide purification method making use thereof
CN105802282A (en) * 2016-02-29 2016-07-27 中国科学院兰州化学物理研究所 Method for preparing red hybridized pigment from red attapulgite clay
WO2016123711A1 (en) * 2015-02-04 2016-08-11 Pc-Cups Ltd. Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks
CN107804854A (en) * 2017-11-27 2018-03-16 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 The method that cupric silicate nanotube is prepared using low-grade attapulgite clay
CN108238605A (en) * 2018-04-08 2018-07-03 吉林大学 A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof
CN108479777A (en) * 2018-03-28 2018-09-04 常州大学 A kind of preparation method and applications of attapulgite composite photo-catalyst
KR101920897B1 (en) * 2017-06-09 2018-11-21 골든비엔씨 (주) Method of manufacturing for silica composite using coal ash
JP2018202411A (en) * 2017-05-31 2018-12-27 古河電気工業株式会社 Carbon dioxide reduction catalyst structure and method for producing the same, and carbon dioxide reduction device having the carbon dioxide reduction catalyst structure
CN109569580A (en) * 2018-11-29 2019-04-05 南昌航空大学 A kind of composite photocatalyst and its preparation method and application
CN109911908A (en) * 2019-03-26 2019-06-21 中国科学院兰州化学物理研究所 The method for preparing various structures nano material using the low-grade clay mineral of rich iron
US20190275474A1 (en) * 2018-03-07 2019-09-12 Hitachi Zosen Corporation Cha-type titanosilicate separation membrane and production method therefor and gas separation method
CN110603097A (en) * 2017-04-04 2019-12-20 沙特基础工业全球技术公司 Nano zeolite catalyst with high silicon-aluminium ratio
CN111437809A (en) * 2020-04-29 2020-07-24 江苏纳欧新材料有限公司 Preparation method and application of rare earth element doped bismuth silicate photocatalyst
CN111450814A (en) * 2020-04-29 2020-07-28 江苏纳欧新材料有限公司 Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1359367A (en) * 1970-08-31 1974-07-10 Exxon Research Engineering Co Layered complex metal silicate composition their preparation and use in hydrocarbon conversion reactions
NL7613957A (en) * 1976-12-16 1978-06-20 Shell Int Research CRYSTALLINE SILICATES.
JPH05245A (en) * 1991-06-24 1993-01-08 Kiyohisa Ota Conversion of carbon dioxide, carbonic ion or hydrocarbonic ion to high value added substance by photocatalytic action
AU8324698A (en) * 1997-07-15 1999-02-10 University Of Queensland, The Catalytic conversion of gases via cation-exchangeable alumino-silicate materials
JP2005145800A (en) * 2003-11-19 2005-06-09 National Institute Of Advanced Industrial & Technology Method of manufacturing layered silicate compound
US20080253953A1 (en) * 2005-10-12 2008-10-16 Basf Se Silicate Producing Method
CN102666387A (en) * 2009-12-22 2012-09-12 东曹株式会社 Novel metallosilicate, production method thereof, nitrogen oxide purification catalyst, production method thereof, and nitrogen oxide purification method making use thereof
WO2011156971A1 (en) * 2010-06-18 2011-12-22 海洋王照明科技股份有限公司 Halosilicate luminescent materials and preparation methods and uses thereof
CA3147965A1 (en) * 2015-02-04 2016-08-11 Pc-Cups Ltd. Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks
WO2016123711A1 (en) * 2015-02-04 2016-08-11 Pc-Cups Ltd. Metallo-silicate catalyst (msc) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks
CN105802282A (en) * 2016-02-29 2016-07-27 中国科学院兰州化学物理研究所 Method for preparing red hybridized pigment from red attapulgite clay
CN110603097A (en) * 2017-04-04 2019-12-20 沙特基础工业全球技术公司 Nano zeolite catalyst with high silicon-aluminium ratio
JP2018202411A (en) * 2017-05-31 2018-12-27 古河電気工業株式会社 Carbon dioxide reduction catalyst structure and method for producing the same, and carbon dioxide reduction device having the carbon dioxide reduction catalyst structure
KR101920897B1 (en) * 2017-06-09 2018-11-21 골든비엔씨 (주) Method of manufacturing for silica composite using coal ash
CN107804854A (en) * 2017-11-27 2018-03-16 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 The method that cupric silicate nanotube is prepared using low-grade attapulgite clay
US20190275474A1 (en) * 2018-03-07 2019-09-12 Hitachi Zosen Corporation Cha-type titanosilicate separation membrane and production method therefor and gas separation method
CN108479777A (en) * 2018-03-28 2018-09-04 常州大学 A kind of preparation method and applications of attapulgite composite photo-catalyst
CN108238605A (en) * 2018-04-08 2018-07-03 吉林大学 A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof
CN109569580A (en) * 2018-11-29 2019-04-05 南昌航空大学 A kind of composite photocatalyst and its preparation method and application
CN109911908A (en) * 2019-03-26 2019-06-21 中国科学院兰州化学物理研究所 The method for preparing various structures nano material using the low-grade clay mineral of rich iron
CN111437809A (en) * 2020-04-29 2020-07-24 江苏纳欧新材料有限公司 Preparation method and application of rare earth element doped bismuth silicate photocatalyst
CN111450814A (en) * 2020-04-29 2020-07-28 江苏纳欧新材料有限公司 Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
F. GONZALEZ, 等: "Thermal investigation of acid-activated attapulgites: influence of isomorphic substitution in the octahedral sheet", THERMOCHIMICA ACTA, pages 239 - 246 *
IMANE GHIAT，等: "Efficient hydrogen generation over a novel Ni phyllosilicate photocatalyst", JOURNAL OF PHOTOCHEMISTRY & PHOTOBIOLOGY A: CHEMISTRY, pages 111952 *
LAN WANG，等: "Two-Dimensional Layered Zinc Silicate Nanosheets with Excellent Photocatalytic Performance for Organic Pollutant Degradation and CO2 Conversion", ANGEW. CHEM., pages 8187 *
LIN LIAO,等: "Robust nickel silicate catalysts with high Ni loading for CO2 methanation", CHEM ASIAN J., pages 678 *
WENBO WANG，等: "Mesoporous hybrid Zn-silicate derived from red palygorskite clay as a high-efficient adsorbent for antibiotics", MICROPOROUS AND MESOPOROUS MATERIALS, pages 317 - 325 *
乔峥: "硅酸盐纳米材料的制备及光催化性能探索", 中国优秀硕士论文全文数据库 *
李红玑;王发良;李享;杨靖;宋经华;李波;: "活化凹凸棒石对多级孔分子筛合成种类和孔道结构的影响", 材料工程, no. 04 *
鲁冰倩;张长明;朱天瑜;陈艳;周文伟;黄晨峰;张小超;: "光催化还原CO_2材料的研究进展", 化工新型材料, no. 06 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116618048A (en) * 2023-04-24 2023-08-22 陕西科技大学 Preparation method and application of single-wall copper silicate nano Guan Guangfen ton catalyst
CN116618048B (en) * 2023-04-24 2024-01-12 陕西科技大学 Preparation method and application of single-wall copper silicate nano Guan Guangfen ton catalyst

Also Published As

Publication number Publication date
CN113479897B (en) 2023-10-24

Similar Documents

Publication Publication Date Title
CN106563481B (en) A kind of ultra-thin graphite phase carbon nitride photochemical catalyst of ammonification and preparation method thereof
CN102101693A (en) Preparation method and application of double-function micro-nano hierarchical structural zinc oxide power
CN109395749B (en) Bismuth oxyhalide nano material, preparation method and application thereof
CN105585043B (en) Preparation method of flowerlike cerium oxide nano-material
CN108996557B (en) Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof
CN103111254A (en) Preparation method of hollow microspheres with hierarchical structure
CN102649590A (en) Method for preparing mesoporous material NiAl2O4 without specific surface active agent
CN107814408B (en) SnS rich in S vacancy2Preparation method of ultrathin nanosheet
CN109336161A (en) A kind of preparation method of CeO2 nanotube, CeO2 nanotube and application
CN111450814A (en) Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof
CN113479897B (en) Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof
CN101693552A (en) Method for preparing tin dioxide nanostructure material with floriform appearance by hydrothermal synthesis
CN109928406A (en) A kind of analcime and its synthetic method
CN107803170A (en) A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball
CN114392734A (en) Tungsten oxide composite material and preparation method and application thereof
CN116371433A (en) Flower ball-shaped TiO 2 Heterojunction material with/BiOBr core-shell structure and preparation method and application thereof
CN110563036A (en) bismuth oxide nano material rich in oxygen vacancy and preparation method thereof
CN112456556A (en) Method for preparing tantalum oxide nanospheres
CN110227517B (en) CuBi2O4/BiPO4P-n type heterojunction photocatalyst, preparation method and application thereof
WO2021238083A1 (en) Method for preparing silicate/carbon composite by using attapulgite, and application of material
CN114014316B (en) Composite photo-thermal material based on titanium carbide and preparation method thereof
CN113877556B (en) Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof
CN113415821B (en) Hollow Zn x Cd 1-x Preparation method and application of S solid solution nanosphere
CN113845397A (en) Porous hollow structure thermite and preparation method thereof
CN103232043A (en) Crystallized mesoporous zinc silicate/silicon oxide composite powder 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
GR01 Patent grant
GR01 Patent grant