CN114685808B - Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof - Google Patents

Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof Download PDF

Info

Publication number
CN114685808B
CN114685808B CN202210426732.1A CN202210426732A CN114685808B CN 114685808 B CN114685808 B CN 114685808B CN 202210426732 A CN202210426732 A CN 202210426732A CN 114685808 B CN114685808 B CN 114685808B
Authority
CN
China
Prior art keywords
dimensional
carbon
ligand
titanium
complex
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
Application number
CN202210426732.1A
Other languages
Chinese (zh)
Other versions
CN114685808A (en
Inventor
沈意
姚彦池
许俊杰
朱超
吴佳鑫
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.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
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 Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202210426732.1A priority Critical patent/CN114685808B/en
Publication of CN114685808A publication Critical patent/CN114685808A/en
Application granted granted Critical
Publication of CN114685808B publication Critical patent/CN114685808B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/022—Preparation from organic compounds
    • C01B15/026—Preparation from organic compounds from alcohols
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a pseudo three-dimensional titanium-carbon-based micron complex associated with a hydrogen bond with one-dimensional pores opened, and a preparation method and application thereof. Dissolving tetraisopropyl titanate as a metal precursor in acetonitrile; 2, 5-dihydroxy terephthalic acid is taken as a main ligand, benzene-1, 4-di-hydroxamic acid is taken as an auxiliary ligand, the two are mixed and placed in isopropanol, and ultrasonic dispersion is carried out; pouring the mixed ligand suspension into the metal precursor acetonitrile solution under stirring, and fully stirring; obtaining a multi-element ligand titanium carbon-based micron complex material through solvothermal reaction; and (3) carrying out heat treatment on the material obtained after washing and drying under the protection of inert gas, and controlling the decomposition rate of the unstable ligand by changing the treatment temperature and the duration time, so as to construct the pseudo three-dimensional titanium-carbon-based micron complex associated with the hydrogen bond with one-dimensional pores. The synthesis method is simple and controllable, and the material has the advantages of large specific surface area, strong absorption capacity in a visible light range, small forbidden bandwidth, and stability and high efficiency in reducing oxygen to generate hydrogen peroxide.

Description

Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof
Technical Field
The invention belongs to the field of material preparation, and relates to a hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and a preparation method and application thereof.
Background
Finding a convenient way to convert solar energy into chemical energy is a key step in realizing large-scale utilization of solar energy. Hydrogen peroxide is an environmentally friendly oxidant, has a high oxidation potential, and can oxidize various organic and inorganic substrates by simple liquid phase or gas phase reactions. In particular H 2 O 2 As by ultraviolet irradiation and catalysis (e.g. Fe) 2+ And Cu 2+ ) The precursor which generates OH is activated and can be used for advanced oxidation process in wastewater treatment. These unique properties allow for H 2 O 2 Plays an important role in a wide range of industrial and commercial applications such as chemical production, medical practice and environmental remediation. Conventional H 2 O 2 Production methodMethods such as anthraquinone method and electrochemical synthesis have the problems of huge energy consumption, potential explosion risk, high-toxicity byproduct generation and the like, and the method for producing hydrogen peroxide by selectively reducing oxygen driven by sunlight is a promising option and has the advantages of environmental friendliness, renewable energy drive, simple and safe raw materials and the like. There are many catalysts for photocatalytic production of hydrogen peroxide, such as carbon dioxide, graphitic carbon nitride, zinc oxide, carbon-based nanomaterials, and the like. The metal-containing carbon-based complex composed of metal nodes and organic ligands is a new functional porous material, and has attracted wide attention of scientists due to the advantages of easy adjustment of structural functions, huge specific surface area and the like. The titanium-oxygen metal node in the titanium-carbon-based complex endows the titanium-oxygen metal node with excellent photocatalysis potential, however, the titanium-carbon-based complex, particularly the pseudo-three-dimensional titanium-carbon-based complex, has poor reactant interception and adsorption capacity due to single aperture direction and small specific surface area, and the adsorption and photocatalysis capacity is limited by the titanium-oxygen metal node. In addition, the stability of titanium-carbon based complex catalysts is susceptible to various factors, including environmental solvents, PH, processing time, cations and anions, etc., especially in applications for producing hydrogen peroxide, and because of the harsh low PH requirements of the processing procedure, the titanium-carbon based complex is challenging to apply in this regard and is not favored by those skilled in the relevant research fields.
The dilemma of titanium carbon-based complex materials with photocatalysis potential in the production and application of hydrogen peroxide forces to think again, how to artificially construct a titanium carbon-based complex, increase the contact chance of the surface of the catalyst and reactants, improve the capability of intercepting the reactants, maintain the self-stability of the catalyst in a reaction system for producing the hydrogen peroxide by photocatalysis, realize high-efficiency production and widen the application field range of the catalyst.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex with one-dimensional pores opened, and a preparation method and application thereof. The pseudo three-dimensional titanium-carbon-based micro complex catalyst material which is associated with the hydrogen bonds and opens the one-dimensional pores has the advantages of low synthesis cost, wide photoresponse range, increased photon-generated carrier migration rate, larger particle size, good catalyst settling property, convenience for subsequent recovery and capability of realizing efficient and stable production of hydrogen peroxide under the drive of visible light.
NTU-9 and MUV-11 are taken as typical titanium carbon-based micro-complexes, the synthetic metal precursor is also tetraisopropyl titanate, a single titanium atom in NTU-9 is coordinated with six oxygen atoms of three 2, 5-dihydroxy terephthalic acid, and the layers are associated and stacked by hydrogen bonds to form the titanium carbon-based complex with pseudo three-dimensional structure one-dimensional pores. The single titanium atom of MUV-11 coordinates with the six oxygen atoms of the three benzene-1, 4-bishydroxamic acids, which are similarly stacked between layers to form a one-dimensional pore. The extremely similar topological structure and macroscopic hexagonal crystal form create objective conditions for successfully constructing the multi-ligand titanium carbon-based micro complex.
The invention innovatively modifies the idea and provides a two-step method of 'multi-ligand titanium carbon-based micron complex-inert gas protected heat treatment' for opening one-dimensional pores in the hydrogen bond associated pseudo three-dimensional titanium carbon-based micron complex, the method endows a larger specific surface area and exposes more active sites, so that the single diffusion direction of a reactant in the one-dimensional pores is changed into the multi-element diffusion direction, and the adsorption of the reactant on the surface of a catalyst and the reactant retaining capacity of a catalyst pore channel are enhanced. Firstly, synthesizing a multi-ligand titanium carbon-based micro complex by using a mixed ligand method, then controlling the decomposition rate of an auxiliary ligand by using the complex as a mother set through regulating and controlling the heat treatment temperature protected by inert gas, protecting a main ligand from being removed, and successfully opening one-dimensional pores in a hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex by introducing vacancy nodes. The hydrogen bond associated pseudo three-dimensional titanium carbon based micron complex with one-dimensional pores is characterized in that channels formed by the one-dimensional pores are communicated with each other in an original hexagonal crystal due to the existence of vacancy nodes, the original macroscopic skeleton appearance can be maintained within the condition range of certain temperature and time, the cross section size is larger than 20 microns, the side surface size is larger than 10 microns, the vacancy nodes are uniformly distributed, the electronic structure is optimized, and the oxygen contact area and photocatalytic activity sites in the pores are increased by the opened vacancy nodes.
A pseudo three-dimensional titanium carbon-based micro complex associated with a hydrogen bond with one-dimensional pores opened is provided, the complex has a pseudo three-dimensional sepia hexagonal structure, the layers are connected by the hydrogen bond, and partial connectors are removed to open the one-dimensional pores; the vacant nodes connecting the different one-dimensional pores appear as local fractures of the edges on the outside of the interior of the crystal.
A preparation method of a hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened comprises the following steps:
1) The main ligand and the auxiliary ligand are mixed in the solvent A and are dispersed in an ultrasonic manner for 6-10 min, so that the two ligands are uniformly dispersed in isopropanol, the agglomeration state is destroyed, the repeated contact and assembly with a metal precursor are facilitated to form a topological structure, the subsequent two functionalized ligands are uniformly and discretely distributed in a multi-ligand titanium-carbon-based micron complex framework, and conditions are created for keeping the original macroscopic three-dimensional framework during the heat treatment under the protection of inert gas;
2) Adding the solution after ultrasonic dispersion into the metal precursor solution which is continuously magnetically stirred, and continuously magnetically stirring;
3) After stirring, carrying out heat treatment on the obtained mixture, after the thermal reaction is finished, washing and drying to obtain a multi-ligand titanium-carbon-based micron complex;
4) Grinding the complex obtained in the step 3) into powder, sending the powder into a tubular furnace for heat treatment under the protection of inert gas, controlling the decomposition rate of the unstable ligand by changing the treatment temperature and the duration, constructing a vacancy node which opens up the one-dimensional pore, and naturally cooling after the heat treatment is finished to obtain the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micron complex which opens up the one-dimensional pore.
The dynamic stirring state is always kept in the whole process of the middle and later periods before and after the metal precursor and the mixed ligand are mixed, and the operation mode is similar to that of a fully mixed aeration tank in the field of water pollution control.
Further, the ligand mixture after ultrasonic treatment is timely and uniformly mixed with the metal precursor solution in continuous stirring, and the mixture is continuously stirred for 0.8 to 1.2 hours, so that the uniform multi-ligand titanium carbon-based micron complex with two dispersed functional ligands is formed, and the synthesis failure caused by overhigh concentration of local ligands is prevented.
Further, the main ligand is 2, 5-dihydroxyterephthalic acid, the auxiliary ligand is benzene-1, 4-di-hydroxamic acid, and the molar ratio of the two is 18-20: 1.
further, the metal precursor solution is a mixture of tetraisopropyl titanate and acetonitrile, the concentration of tetraisopropyl titanate is 58-68 mmol/L, the molar ratio of 2, 5-dihydroxyterephthalic acid, benzene-1, 4-bishydroxamic acid and tetraisopropyl titanate is 18-20: 1:3 to 5.
Further, the solvent A in the step 1) is isopropanol, and the volume ratio of the acetonitrile to the isopropanol is controlled to be 0.8-1.2: 1.
further, the mixture in the step 3) is transferred into a reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, the reaction temperature is controlled to be 110-130 ℃, the duration is controlled to be 46-50 h, an organic solvent is adopted for washing, the organic solvent is one or more of methanol, ethanol, acetonitrile, isopropanol and acetone, the boiling point is low, the mixture is volatile, and the mixture can be desorbed from the surface of the titanium-carbon-based micron complex to a greater extent after vacuum drying; drying under vacuum condition, controlling the drying temperature at 58-62 ℃; the drying time is controlled to be 10-15 h.
Further, the reaction conditions of the inert gas protected heat treatment process are as follows: stabilizing for 20-40 min, preferably 30min under the continuous introduction of inert gas, starting to heat up after the external environment and the internal pore structure of the material are fully exposed to the inert gas, and controlling the programmed heating rate at 4-6 ℃/min, preferably 5min; the temperature is controlled between 190 and 230 ℃, and preferably 210 ℃; after the temperature rise is finished, the duration is controlled to be 50-70 min, preferably 60min, and the inert gas is preferably argon or nitrogen.
Before the temperature rise is started, the material should be completely stabilized in the inert gas for a long enough time, and the flow rate of the inert gas is controlled to be 50-80 ml.min -1 The main purpose of the inert gas for the whole-process protection of the material is to prevent the material from being oxidized or carbonized due to contact with oxygen or other reactive gases in the air, and the removal of hydroxyl atoms causes the change of the overall properties of the material.
The temperature for the initial decomposition of the main ligand is more than 250 ℃, the initial decomposition temperature of the auxiliary ligand is about 190 ℃, the target effect can be achieved only within the range of 190-230 ℃ in order to protect the main ligand from being coordinated with the metal node due to the fact that the auxiliary ligand is slowly and mildly removed, the activity of the defect material in the photocatalytic production of hydrogen peroxide can be obviously reduced when the temperature exceeds the temperature range, and the possible reason is that the photocatalytic activity is reduced due to the damage of an original frame.
The auxiliary ligand benzene-1, 4-di-hydroxamic acid is prepared by a water bath method, and the specific method comprises the following steps: mixing hydroxylamine hydrochloride with sodium hydroxide in deionized water, then adding the solution to a methanol suspension of dimethyl terephthalate, stirring the resulting mixture at 30-50 ℃ for 60-84 h, preferably 40 ℃ for 72h, cooling the crude material to room temperature, and then acidifying with a 4-6% hydrochloric acid solution to a pH = 5-6, preferably pH =5.5; the white solid obtained was as ionic water (60 mL), saturated NaHCO 3 The solution (3X 30 mL) and deionized water (2X 30 mL) were filtered and washed in that order; finally vacuum drying overnight, wherein the concentration of hydroxylamine hydrochloride is controlled to be 1.6-2.0 mol/L, preferably 1.8mol/L; the concentration of the sodium hydroxide is controlled to be 3.4-3.8 mol/L, and preferably 3.6mol/L; the concentration of the dimethyl terephthalate is controlled between 550 and 650mmol/L.
An application of a pseudo three-dimensional titanium carbon-based micro complex associated with a hydrogen bond with one-dimensional pores opened in photocatalytic production of hydrogen peroxide.
The method for opening one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex has the following advantages in implementation and use:
1) The synthesis method of the hydrogen bond associated pseudo three-dimensional titanium carbon-based micron complex with one-dimensional pores is simple, the heat treatment temperature and time protected by inert gas are reasonably regulated, the modification and modification of the material are completed, the complete macro structure is kept, the micron-sized crystal has good settling property, the micron-sized crystal is convenient to recover after use, and the recovery cost is reduced.
2) The removal rate of the auxiliary ligand can be effectively regulated and controlled by setting different treatment temperatures and durations of the heat treatment under the protection of inert gas, and the macroscopic angle influences the number and size of vacancy nodes formed by the heat treatment to change, so that the open rate of one-dimensional pores can be effectively regulated and controlled.
3) The original one-dimensional pores are opened by the method provided by the invention, so that the specific surface area of the catalyst is increased, the adsorption capacity to gas is improved, and the reaction active sites are increased. Research shows that the hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex with one-dimensional pores opened has ultrahigh activity in hydrogen peroxide preparation under the drive of visible light.
Drawings
FIG. 1 is a scanning electron micrograph of a hydrogen bond associated pseudo-three dimensional titanium carbon based micro-complex with one dimensional pores opened as prepared in example 1;
FIG. 2 is a transmission electron microscope image of the hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex with one-dimensional pores opened prepared in example 1;
FIG. 3 is a scanning electron micrograph of a hydrogen-bonded pseudo three-dimensional titanium-carbon based micro-complex with one-dimensional pores opened prepared in example 3;
FIG. 4 is a TEM image of the hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex with one-dimensional pores opened as prepared in example 3;
FIG. 5 is a TEM image of the hydrogen bond associated pseudo three-dimensional titanium carbon-based micro-complex with one-dimensional pores opened as prepared in example 5;
FIG. 6 is a scanning electron micrograph of a hydrogen-bonded pseudo three-dimensional titanium-carbon based micro-complex with one-dimensional pores opened prepared in example 5;
Detailed Description
The present invention is further described with reference to the accompanying drawings and the detailed description so that those skilled in the art can more fully understand the implementation and details of the present invention. Reagents and raw materials used in the experiment are purchased from commercial sources without special description, and further purification is not needed.
Preparing a multi-ligand titanium-carbon-based micro complex: the preparation method of the multi-ligand titanium-carbon-based micro complex has a plurality of possible ways, the mixed ligand method provided by the invention is only a preferred mode, and the respective proportion parameters and mode methods can be adjusted according to actual conditions.
In the heat treatment step under the protection of inert gas, the invention achieves the purpose of regulating and controlling the decomposition rate of the auxiliary ligand and changing the opening rate of one-dimensional pores by changing the treatment temperature and the duration. The specific embodiment is as follows: example 1
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-di-hydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol, and subjected to ultrasonic dispersion for 8min;
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuing to magnetically stir for 1h;
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, wherein the reaction temperature is set at 120 ℃, and the reaction time is set at 48 hours;
(4) After the solvothermal reaction is finished, washing the mixture by using methanol, and drying the mixture in a vacuum drying oven at the temperature of 60 ℃ for 12 hours;
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micro complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micro complex into powder, placing the powder into an open transparent quartz boat, sending the powder into a tube furnace, stabilizing for 30min under the continuous introduction of argon, setting the flow rate of the argon to be 50-80 ml/min, starting a temperature rise program, setting the temperature rise rate to be 5 ℃/min, setting the processing temperature to be 190 ℃, setting the duration to be 60min, keeping the flow rate of the argon unchanged, and after the program is finished, naturally cooling to obtain the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex material with one-dimensional pores.
As shown in figures 1 and 2, the obtained hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex material with one-dimensional pores has complete and smooth edges, no obvious fragmentation or pore structure in the material, a tan hexagonal crystal structure, hydrogen bonds between layers and a cross section size of more than 20 microns. The heat treatment temperature set in the embodiment is low, the decomposition rate of the auxiliary ligand is low, so that the number of decomposed unstable ligands is small, vacancy nodes among one-dimensional pores are mainly distributed in a discrete mode, no adjacent metal nodes fall off, the one-dimensional pores of the pseudo three-dimensional titanium carbon-based micron complex are mainly communicated through the vacancy of a single ligand, and a related local vacancy node structure cannot be observed in a transmission electron microscope.
Example 2
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-di-hydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol, and subjected to ultrasonic dispersion for 8min;
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuing to magnetically stir for 1h;
(3) And transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, wherein the reaction temperature is set at 120 ℃, and the reaction time is set at 48h.
(4) After the solvothermal reaction was complete, the mixture was washed clean with methanol and dried in a vacuum oven at 60 ℃ for 12h.
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder in an open transparent quartz boat, sending the powder into a tube furnace, stabilizing for 30min under the continuous introduction of argon, setting the flow rate of the argon to be 50-80 ml/min, starting a temperature rise program, setting the temperature rise rate to be 5 ℃/min, setting the treatment temperature to be 200 ℃, setting the duration to be 60min, and keeping the flow rate of the argon unchanged. And after the heat treatment procedure is finished, naturally cooling to obtain the pseudo three-dimensional titanium-carbon-based micron complex material associated with the hydrogen bonds with the one-dimensional pores.
Example 3
In this embodiment, the method for opening the one-dimensional pores in the hydrogen bond associated pseudo-three-dimensional titanium carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid serving as a main ligand and 50mg of benzene-1, 4-di-hydroxamic acid serving as an auxiliary ligand are preliminarily blended into 20ml of isopropanol and ultrasonically dispersed for 8min;
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuing to magnetically stir for 1h;
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, wherein the reaction temperature is set at 120 ℃, and the reaction time is set at 48 hours;
(4) After the solvothermal reaction is finished, washing the mixture by using methanol, and drying the mixture in a vacuum drying oven at the temperature of 60 ℃ for 12 hours;
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder in an open transparent quartz boat, sending the powder into a tube furnace, stabilizing the powder for 30min under the continuous introduction of argon, setting the argon flow rate to be 50-80 ml/min, starting a temperature raising program, setting the temperature raising rate to be 5 ℃/min, setting the treatment temperature to be 210 ℃, setting the duration to be 60min, keeping the argon flow rate unchanged, and after the heat treatment program is finished, naturally cooling the powder to obtain the pseudo three-dimensional titanium-carbon-based micron complex material in which the hydrogen bonds associated with the one-dimensional pores are opened.
As shown in figures 3 and 4, the macro morphology of the obtained hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex material with one-dimensional pores opened is represented by a hexagonal crystal structure, the layers are connected by hydrogen bonds, the cross section size is larger than 20 micrometers, however, the structural integrity is damaged to a certain degree, and the fracture surface is in a layered structure. In electron microscope results, the vacancy nodes connecting different one-dimensional pores appear as local fractures of the edge on the outer side inside the crystal. The heat treatment temperature and time in the embodiment enable the decomposition rate of unstable ligands distributed in the multi-ligand titanium-carbon-based micron complex to be moderate, and open the vacancy nodes of one-dimensional pores, so that the macro structure of the original titanium-carbon-based micron complex is reserved, and the adsorption and the interception of reactants are facilitated.
Example 4
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-di-hydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol, and subjected to ultrasonic dispersion for 8min;
(2) Then, adding the isopropanol solution of the mixed ligand into 20ml of acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuously magnetically stirring for 1h;
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, wherein the reaction temperature is set at 120 ℃, and the reaction time is set at 48 hours;
(4) After the solvothermal reaction is finished, washing the mixture with methanol, and drying the mixture in a vacuum drying oven at the temperature of 60 ℃ for 12 hours;
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder in an open transparent quartz boat, sending the powder into a tube furnace, stabilizing the powder for 30min under the continuous introduction of argon, setting the flow rate of the argon to be 50-80 ml/min, starting a temperature raising program, setting the temperature raising rate to be 5 ℃/min, setting the processing temperature to be 220 ℃, setting the duration to be 60min, keeping the flow rate of the argon unchanged, and obtaining the pseudo three-dimensional titanium-carbon-based micron complex material associated with the hydrogen bonds with the one-dimensional pores after the heat treatment program is finished and naturally cooling the pseudo three-dimensional titanium-carbon-based micron complex material.
Example 5
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-di-hydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol, and subjected to ultrasonic dispersion for 8min;
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuing to magnetically stir for 1h;
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvothermal treatment, wherein the reaction temperature is set to 120 ℃, and the reaction time is set to 48 hours;
(4) After the solvothermal reaction is finished, washing the mixture with methanol, and drying the mixture in a vacuum drying oven at the temperature of 60 ℃ for 12 hours;
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder into an open transparent quartz boat, sending the powder into a tube furnace, stabilizing the powder for 30min under the continuous introduction of argon, setting the flow rate of the argon to be 50-80 ml/min, starting a temperature rise program, setting the temperature rise rate to be 5 ℃/min, setting the treatment temperature to be 230 ℃, setting the duration to be 60min, and keeping the flow rate of the argon unchanged; and after the heat treatment procedure is finished, naturally cooling to obtain the pseudo three-dimensional titanium-carbon-based micron complex material associated with the hydrogen bonds with the one-dimensional pores.
As shown in figures 5 and 6, the morphology of the obtained hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex material with one-dimensional pores is thoroughly changed, the original hexagonal crystal morphology structure with the section size larger than 20 mu m is converted into a prismatic crystal form with a smaller section size, and the fracture surface presents a layered structure. The heat treatment temperature in this example is higher and the removal rate of the auxiliary ligand is faster, so that the labile ligands distributed in the multi-ligand titanium carbon-based micro-complex are almost completely removed, and the one-dimensional pores are opened by countless vacancy nodes generated. Because the number of vacancy nodes is large, the continuously distributed vacancies lead the hexagonal crystal structure to be fractured along different directions, and the collapse of the whole framework is caused.
Example 6
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-bishydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol and ultrasonically dispersed for 8min,
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, continuously magnetically stirring for 1h,
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, setting the reaction temperature at 120 ℃ and the reaction time at 48h,
(4) After the solvothermal reaction is finished, the mixture is washed clean by methanol and dried in a vacuum drying oven at 60 ℃ for 12 hours,
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder in an open transparent quartz boat, sending the powder into a tube furnace, stabilizing the powder for 30min under the continuous introduction of argon, setting the flow of the argon to be 50-80 ml/min, starting a temperature rise program, setting the temperature rise rate to be 5 ℃/min, setting the treatment temperature to be 210 ℃, setting the duration to be 50min, and keeping the flow rate of the argon unchanged. And after the heat treatment procedure is finished, naturally cooling to obtain the pseudo three-dimensional titanium-carbon-based micron complex material associated with the hydrogen bonds with the one-dimensional pores.
Example 7
In this embodiment, the method for opening the one-dimensional pores on the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex specifically comprises the following steps:
(1) 950mg of 2, 5-dihydroxyterephthalic acid as a main ligand and 50mg of benzene-1, 4-bishydroxamic acid as an auxiliary ligand were preliminarily blended in 20ml of isopropanol and subjected to ultrasonic dispersion for 8min,
(2) Then adding the isopropanol solution of the mixed ligand into 20ml acetonitrile solution containing 375 mu L of tetraisopropyl titanate which is continuously magnetically stirred in time, and continuing to magnetically stir for 1h,
(3) Transferring the mixture obtained after stirring into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, setting the reaction temperature at 120 ℃ and the reaction time at 48h,
(4) After the solvothermal reaction is finished, the mixture is washed clean by methanol and dried for 12 hours in a vacuum drying oven at the temperature of 60 ℃,
(5) Accurately weighing 100mg of the multi-element ligand titanium-carbon-based micron complex obtained in the step (4), grinding the multi-element ligand titanium-carbon-based micron complex into powder, placing the powder in an open transparent quartz boat, sending the powder into a tube furnace, stabilizing the powder for 30min under the continuous introduction of argon, setting the flow rate of the argon to be 50-80 ml/min, starting a temperature raising program, setting the temperature raising rate to be 5 ℃/min, setting the treatment temperature to be 210 ℃, setting the duration to be 70min, and keeping the flow rate of the argon unchanged. And after the heat treatment procedure is finished, naturally cooling to obtain the hydrogen bond associated pseudo three-dimensional titanium-carbon-based micron complex material with one-dimensional pores.
Example 8
A method for preparing hydrogen peroxide under the drive of visible light of a pseudo three-dimensional titanium carbon-based micro complex associated with a hydrogen bond with a one-dimensional pore, which comprises the following specific steps:
(1) Respectively weighing 20mg of the photocatalyst prepared in all the above examples, adding the photocatalyst into a glass jacket beaker containing 20ml of triethanolamine serving as a cavity sacrificial agent and 80ml of acetonitrile serving as a reaction solvent, and controlling the total liquid phase volume to be 100ml;
(2) Before starting illumination, blowing pure oxygen into the obtained mixed solution in a dark place, controlling the time to be 20min, keeping a magnetic stirring state during the period, setting the oxygen flow to be 40ml/min, and controlling the reaction temperature to be 25 ℃;
(3) Under the condition of magnetic stirring, the suspension is placed under a metal halide lamp for irradiation, and the incident light intensity is controlled to be 100mW/cm 2 Measuring by an optical power meter, using a cut-off filter with the wavelength of 400nm, and continuously performing oxygen compensation in the irradiation process, wherein the flow is 40ml/min;
(4) The hydrogen peroxide concentration is measured by adopting a titanium potassium oxalate method, 0.05mol/L of titanium potassium oxalate solution is used as a color developing agent, pH is adjusted by 3mol/L of sulfuric acid solution, 2ml of reaction system solution is taken at the sampling time, 2ml of titanium potassium oxalate solution and 1ml of sulfuric acid solution are respectively added, the solution is diluted to 10ml, the absorbance is measured by taking a reagent blank as a reference under the wavelength of 400nm, and finally the hydrogen peroxide concentration is calculated by referring to a standard curve.
The results of the above experiments were processed to obtain the yield results of the reaction for preparing hydrogen peroxide under the drive of visible light for 3 hours as shown in table 1, and the pseudo-three-dimensional hydrogen bond-associated reaction prepared under the conditions of different heat treatment temperatures and durations under the protection of argon gas and opening one-dimensional poresThe titanium carbon-based micro complex can efficiently and stably produce hydrogen peroxide under the drive of visible light, wherein the heat treatment temperature in example 3 is 210 ℃, and when the heat treatment duration is 60min, the synthesized pseudo three-dimensional titanium carbon-based micro complex which is associated by the hydrogen bond and opens the one-dimensional pore has the highest efficiency on the production of the hydrogen peroxide under the visible light, and the yield of the hydrogen peroxide after 3h of light radiation is 3625 mu mol.h -1 ·g -1 The method explains that the vacancy nodes with proper concentration are distributed discretely, so that the one-dimensional pores of the pseudo-three-dimensional titanium carbon-based micron complex are communicated to a certain extent, the macroscopic morphology of the material is maintained, and the catalytic activity of the material on the visible light-driven preparation of hydrogen peroxide is improved to a great extent. The heat treatment temperature range of the argon protection is 190-230 ℃, the duration is 60min, the activity of the prepared catalyst for photocatalytic production of hydrogen peroxide is firstly improved and then reduced along with the increase of the treatment temperature, and the optimum temperature is reached when the temperature is 210 ℃. Similarly, when the heat treatment temperature under the protection of argon is equal to 210 ℃ and the duration is 50-70 min, the activity of the prepared catalyst for photocatalytic production of hydrogen peroxide is firstly improved and then reduced along with the increase of the treatment time, and the optimal activity is achieved when the duration is 60 min.
TABLE 1 yield of hydrogen peroxide (μmol. H) after 3h irradiation of hydrogen bond associated pseudo three-dimensional titanium carbon-based micro-complexes with one-dimensional pores opened prepared in different examples -1 ·g -1 )
Examples Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Yield of hydrogen peroxide 2875 3385 3625 2654 1885 2687 1934
The method for opening one-dimensional pores on the hydrogen bond associated pseudo-three-dimensional titanium carbon-based micro complex and the method for preparing hydrogen peroxide under the drive of visible light provided by the invention are elaborated by the description of the specific examples, and are intended to help researchers and technicians in the related field to understand the specific processes and core ideas of the invention.
In this example, only argon is used as the protective gas, but the same effect as that of the present invention can be obtained by using a protective gas which can protect the material from oxidation or carbonization during the heat treatment. In this example, only methanol, ethanol, acetonitrile, isopropanol, acetone are listed as crystal washing solvents, but as long as the crystal washing solvents have low boiling point characteristics, the solvents which can be effectively removed under vacuum drying conditions can achieve the same effect as the present patent. In this example, only acetonitrile and isopropanol are listed as contact media for mixing the ligand and the metal precursor, but any solvent that can achieve the purpose of dispersing the ligand and dissolving the metal precursor can achieve the same effect as the patent. It is therefore expressly intended that all such modifications and variations as may occur to those skilled in the art to which the invention relates be deemed to lie within the scope and range of equivalents of the claims.

Claims (8)

1. A preparation method of a hydrogen bond associated pseudo three-dimensional titanium carbon-based micro complex with one-dimensional pores opened is characterized by comprising the following steps:
1) Mixing a main ligand and an auxiliary ligand in a solvent A, and dispersing for 6 to 10min by ultrasound to obtain a ligand mixture A;
2) Adding the ligand mixture A subjected to ultrasonic dispersion into a mixture of tetraisopropyl titanate and acetonitrile which is continuously magnetically stirred, and continuously magnetically stirring;
3) Carrying out solvent heat treatment on the mixture obtained after stirring, washing and drying after the reaction is finished to obtain the multi-ligand titanium-carbon-based micron complex;
4) Grinding the multi-element ligand titanium-carbon-based micro complex obtained in the step 3) into powder, sending the powder into a tube furnace for heat treatment under the protection of inert gas, controlling the decomposition rate of an unstable ligand by changing the treatment temperature and the duration time, constructing a vacancy node which breaks through one-dimensional pores, and naturally cooling after the heat treatment is finished to obtain a pseudo three-dimensional titanium-carbon-based micro complex which breaks through hydrogen bond association of the one-dimensional pores;
the reaction conditions of the inert gas blanketed heat treatment process are as follows: controlling the temperature programming rate to be 4-6 ℃/min; controlling the temperature to be 190-230 ℃; after the temperature rise is finished, controlling the duration time to be 50-70 min;
the main ligand is 2, 5-dihydroxyterephthalic acid, the auxiliary ligand is benzene-1, 4-di-hydroxamic acid, and the molar ratio of the two is 18 to 20:1.
2. the process according to claim 1, wherein the concentration of tetraisopropyl titanate in acetonitrile is from 58 to 68mmol/L, and the molar ratio of 2, 5-dihydroxyterephthalic acid, benzene-1, 4-bishydroxamic acid and tetraisopropyl titanate is from 18 to 20:1:3 to 5.
3. The preparation method according to claim 1, wherein the solvent A in the step 1) is isopropanol, and the volume ratio of acetonitrile to isopropanol is controlled to be 0.8 to 1.2:1.
4. the preparation method according to claim 1, wherein the ligand mixture after the ultrasonic treatment is mixed with the metal precursor solution in time and under continuous stirring uniformly, and the mixture is continuously stirred for 0.8 to 1.2h.
5. The preparation method according to claim 1, wherein in the step 3), the mixture is transferred to a reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, the reaction temperature is controlled to be 110 to 130 ℃, the duration is controlled to be 46 to 50h, and an organic solvent is used for washing, wherein the organic solvent is one or more of methanol, ethanol, acetonitrile, isopropanol and acetone; drying under a vacuum condition, wherein the drying temperature is controlled to be 55 to 65 ℃; the drying time is controlled to be 10 to 15h.
6. The pseudo three-dimensional titanium-carbon-based micro complex associated with the hydrogen bond and provided with the one-dimensional pores opened, which is prepared by the preparation method of claim 1, is characterized in that the complex has a pseudo three-dimensional sepia hexagonal structure, the cross section size is larger than 20 microns, the layers are connected by the hydrogen bond, and the one-dimensional pores are opened by removing part of connectors.
7. The pseudo-three-dimensional titanium carbon-based micro-complex associated with hydrogen bonding opened with one-dimensional pores according to claim 6, wherein the vacancy nodes connecting different one-dimensional pores show local fragmentation of the edge at the outer side of the crystal interior.
8. Use of the hydrogen-bond associated pseudo-three-dimensional titanium-carbon based micro-complex with one-dimensional pores opened according to claim 7 in the photocatalytic production of hydrogen peroxide.
CN202210426732.1A 2022-04-22 2022-04-22 Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof Active CN114685808B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210426732.1A CN114685808B (en) 2022-04-22 2022-04-22 Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210426732.1A CN114685808B (en) 2022-04-22 2022-04-22 Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114685808A CN114685808A (en) 2022-07-01
CN114685808B true CN114685808B (en) 2023-02-28

Family

ID=82145767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210426732.1A Active CN114685808B (en) 2022-04-22 2022-04-22 Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114685808B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5976486A (en) * 1998-03-27 1999-11-02 University Of Southern California Method for catalytic production of hydrogen peroxide and catalyst therefor
CN106179314B (en) * 2016-07-06 2018-08-07 南京工业大学 Multi-component composite photocatalyst and preparation method and application thereof
EP3424594A1 (en) * 2017-07-06 2019-01-09 Ecole Polytechnique Federale De Lausanne (Epfl) Photocatalytic system comprising a titanium-based mof
CN109647540B (en) * 2019-01-04 2021-10-12 浙江理工大学 Porous titanium metal-organic framework material for hydrogen production by visible light photocatalysis and preparation method thereof
CN110721815B (en) * 2019-11-12 2021-07-27 中南大学 Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof
CN111871465B (en) * 2020-08-18 2023-03-21 苏州荣格君新材料有限公司 Double-ligand metal organic framework photocatalyst and preparation method thereof
CN112316982A (en) * 2020-09-30 2021-02-05 宁波大学科学技术学院 Method for preparing titanium-based metal organic framework homologous heterojunction photocatalyst

Also Published As

Publication number Publication date
CN114685808A (en) 2022-07-01

Similar Documents

Publication Publication Date Title
CN106732524B (en) Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof
CN108993550B (en) Surface oxygen vacancy modified bismuth oxybromide photocatalyst and preparation method thereof
CN113663693B (en) Preparation method of indium zinc sulfide-titanium dioxide composite material and application of indium zinc sulfide-titanium dioxide composite material in production of hydrogen peroxide for wastewater treatment
CN102674451A (en) Preparation method of {001} face exposed titanium dioxide nanocrystals
CN112958061B (en) Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof
CN113289647A (en) Biochar-doped BiOBrxCl1-xPhotocatalyst, preparation method and application
CN112774718A (en) Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof
CN111250146A (en) Preparation method of oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material
CN111185152A (en) Multifunctional coupled PAC/Bi2O3/TiO2Method for preparing composite material
CN107008337B (en) Non-stoichiometric copper bismuthate nano material and preparation method and application thereof
CN113694946A (en) Bi with core-shell structure2O2CO3@ rGO photocatalyst, and preparation method and application thereof
CN114685808B (en) Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof
CN106000370A (en) Preparation method of photoinduced Ti<3+> self-doped TiO2 photocatalyst
CN111604067B (en) Halogen silicon bismuth oxide material and preparation method and application thereof
CN109794289B (en) Handwheel type titanyl oxalate photocatalyst and preparation method thereof
CN111686767A (en) Microspherical Bi3O4Preparation and application of Cl/BiOI compound
CN111266114A (en) Metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst and preparation method and application thereof
CN115608367A (en) Zn1-xCuxO/TiO with core-shell structure 2 Preparation method and application of photocatalytic composite material
CN113304742B (en) Activated carbon supported Ti 3+ Self-doping TiO 2 Preparation method of photocatalytic material
CN110116014A (en) A kind of N-TiO with hollow structure2Photochemical catalyst preparation method
CN111974428B (en) Bi (Bi) 2 O 2 CO 3 -Bi 2 WO 6 Preparation method of composite photocatalyst
CN112403505A (en) CoP-g-C3N4Electronic current collector photocatalyst and preparation method and application thereof
CN112871174A (en) Preparation method and application of hexagonal flaky nano nickel oxide catalyst
CN111468098A (en) Porous sphere-like photocatalytic material and preparation method and application thereof
CN115744973B (en) Supported gray mesoporous TiO 2 Laser preparation method of (2)

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