CN112619636A - Preparation method and application of quantum-size bismuth vanadate nanoparticles - Google Patents

Preparation method and application of quantum-size bismuth vanadate nanoparticles Download PDF

Info

Publication number
CN112619636A
CN112619636A CN202011361401.1A CN202011361401A CN112619636A CN 112619636 A CN112619636 A CN 112619636A CN 202011361401 A CN202011361401 A CN 202011361401A CN 112619636 A CN112619636 A CN 112619636A
Authority
CN
China
Prior art keywords
bivo
quantum
silica gel
quantum size
method comprises
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011361401.1A
Other languages
Chinese (zh)
Inventor
牛利
韩冬雪
范英英
朱祥连
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.)
Guangzhou University
Original Assignee
Guangzhou 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 Guangzhou University filed Critical Guangzhou University
Priority to CN202011361401.1A priority Critical patent/CN112619636A/en
Publication of CN112619636A publication Critical patent/CN112619636A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • 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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of photocatalysts, and particularly discloses a preparation method and application of quantum-sized bismuth vanadate nanoparticles. The method specifically comprises the following steps: respectively dissolving bismuth nitrate and ammonium metavanadate in nitric acid to obtain two precursor solutions, then adding a template, drying and calcining to obtain BiVO4-a silica composite; then removing the template from the composite material by a hydrothermal method to obtain the quantum-sized BiVO4And (3) nanoparticles. Measurement of the inventionSub-sized BiVO4The band structure is optimized, namely the conduction band is more negative and the valence band is more positive, so that the generation of more OH can be promoted, and high-efficiency CH is satisfied4And (4) activating. No organic phase is added in the synthesis process, so that the subsequent CH is avoided4Carbon source contamination is present in the oxidation reaction.

Description

Preparation method and application of quantum-size bismuth vanadate nanoparticles
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a preparation method and application of quantum-sized bismuth vanadate nanoparticles.
Background
Methane (CH)4) Is the main component (70-90%) of natural gas, and is not easy to decompose due to the structural stability, so that the natural gas exists in large quantity on the surface of the earth or underground. CH (CH)4Belongs to one kind of greenhouse gas, and has 25 times of greenhouse effect compared with the same amount of carbon dioxide. If an efficient way can be found to assign CH4Conversion to commercial chemicals, or liquid fuels, would be a valuable task. Can realize CH in a large range4There are two ways of conversion into liquid hydrocarbons: conversion to gasoline and fischer-tropsch synthesis. Both of which are indirect conversions, first of all by high energy consumption steam reforming techniques (reaction temperatures up to 1100K) to produce synthesis gas (hydrogen and carbon monoxide) and then to convert them into the products of interest. The conventional CH4The indirect conversion method has two problems to be solved, namely multi-step reaction process and high energy consumption.
The photocatalytic reaction can replace heat energy with light energy, reduce the temperature required by the reaction and realize CH at normal temperature4Direct transformation of (2). Current photocatalytic CH4Transformation efforts are relatively minor but have begun to attract attention from researchers. Materials such as tungsten trioxide semiconductor and silicalite which can generate hydroxyl radical (. OH) by light energy to capture CH4H atom in (1), and further CH4And (4) oxidation conversion. Wherein the activated cleavage of the C-H bond is in CH4Plays a role in determining the speed in the oxidation process, and OH is the key to realizing C-H bond breakage.
Bismuth vanadate (BiVO)4) The photocatalyst has attracted extensive attention from researchers in the decomposition of organic dyes and the oxidation of water to produce oxygen, and has a valence band with a sufficiently high oxidation potential and a conduction band with a sufficiently strong reduction potential, which can be independently dependent on H2Direct oxidation of O molecule and O2Reduction of the molecule produces the OH radical. What is needed isWith BiVO4Is considered to be photocatalytic CH4Conversion-selective preparation of methanol (CH)3OH) as a potential catalyst. To date, two references have been made to BiVO4Photocatalytic selective oxidation of CH4Preparation of CH3OH research is reported. The reaction mechanism utilized is as follows:
Figure BDA0002804074820000021
h++H2O→H++·OH (2)
CH4+·OH→·CH3+H2O (3)
·CH3+H2O→CH3OH+1/2H2 (4)
according to this reaction mechanism, two reports utilize short wave ultraviolet UVC (165-275 nm) to irradiate Bi-and V-modified zeolite beta catalysts or BiVO4Catalyst, reaction temperature is controlled at 70 ℃, and the maximum yield of liquid-phase product obtained by anaerobic oxidation is 11.3 mu mol h-1g-1Proves that BiVO is utilized4Realization of CH as photocatalyst4The possibility of transformation. But based on the BiVOs4CH (A) of4The conversion reaction also has a short plate with short excitation wavelength and high reaction temperature. These short plates are present because of the too small number of OH groups and CH4The activation step is inefficient.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention provides a method for preparing quantum-sized bismuth vanadate nanoparticles.
The invention also aims to provide the quantum-size bismuth vanadate nano-particles prepared by the method.
The invention further aims to provide the quantum-sized bismuth vanadate nano-particles for catalyzing and converting CH4The use of (1).
The purpose of the invention is realized by the following scheme:
a preparation method of quantum size bismuth vanadate nanoparticles comprises the following steps:
(1)BiVO4-preparation of silica composite: adding bismuth nitrate (Bi (NO)3)3·5H2O) and ammonium metavanadate (NH)4VO3) Respectively dissolved in nitric acid (HNO)3) Obtaining two precursor solutions; mixing the two precursor solutions, and adding silica gel as a template; after rotary evaporation and drying, calcining to obtain BiVO4-a silica composite;
(2) quantum size BiVO4Preparing nano particles: for BiVO4Carrying out hydrothermal reaction on the silicon dioxide composite material to remove the template and obtain the quantum size BiVO4And (3) nanoparticles.
In the step (1), the mass-to-volume ratio of bismuth nitrate to nitric acid is 0.2-0.6 g:10mL, preferably 0.48g:10 mL; the mass volume of the ammonium metavanadate and the nitric acid is 0.06-0.2 g: 15mL, preferably in a ratio of 0.12 g: 15 mL.
The concentration of the nitric acid in the step (1) is 0.1-10M, and 1M is preferred.
The volume ratio of the precursor solution containing bismuth nitrate to the precursor solution containing ammonium metavanadate in the step (1) is 1: 1-4, preferably 2:3
In the step (1), the silica gel is preferably added in the form of a silica gel aqueous solution, the mass fraction of the silica gel aqueous solution is 1-70%, and the volume ratio of the silica gel aqueous solution to the precursor solution is 0.1-20 mL: 100 mL; preferably 10-20 mL: 100mL, more preferably 10 mL: 100 mL. The diameter of the silica gel is 10-25nm, preferably 12 nm.
In the step (1), the calcination is carried out at 380-700 ℃ for 1-8 h; preferably, the calcination is carried out for 3-8 h at 400-700 ℃.
In the step (2), the hydrothermal reaction is carried out for 12-36 h at 160-200 ℃; preferably at 180 ℃ for 24 h.
The quantum size bismuth vanadate nano-particles are prepared by the method.
Catalytic conversion of CH by the quantum-sized bismuth vanadate nanoparticles4In (1)。
Compared with the prior art, the invention has the following advantages and beneficial effects:
BiVO-based that has been published at present4Photocatalytic CH of4Mainly utilizes the BiVO with submicron or dozens of nanometers4Particles whose conduction band and valence band are only sufficient for low OH production, activate CH4The efficiency is low. In contrast, BiVO of the present invention has a quantum size4The band structure is optimized, namely the conduction band is more negative and the valence band is more positive, so that the generation of more OH can be promoted, and high-efficiency CH is satisfied4And (4) activating.
Quantum-sized BiVO in the invention4The synthesis method is initiated, no organic phase is added in the synthesis process, and the subsequent CH is avoided4Carbon source contamination is present in the oxidation reaction.
Drawings
FIG. 1 shows BiVO obtained in example 14TEM images of silica composites.
FIG. 2 shows the quantum size BiVO obtained in example 14A topographic size map of the nanoparticles, wherein (a) (b) (d) are TEM images at different magnifications; (c) the particle size distribution diagram is shown.
FIG. 3 shows the quantum size BiVO obtained in example 14Xrd (a) and hrtem (b) patterns of nanoparticles.
FIG. 4 shows the results of example 313CH4Gas chromatography-mass spectrometry spectrum (a) and nuclear magnetism of1And (b) an H spectrum.
FIG. 5 shows the quantum size BiVO in example 44Ultraviolet visible UV-Vis diffuse reflectance spectrum (a) of the nano-particles, transformed Kubelka-Micke theory Kubelka-Munk function (b) and model Schottky Mott-Schottky curve (c) and quantum size BiVO4Energy belt structure (d)
FIG. 6 is BiVO in example 44Fluorescence spectra of the photocatalyst in the absence of oxygen (a) and in the presence of oxygen (b).
FIG. 7 shows CH in example 43Gas chromatography-mass spectrometry of OH.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1)BiVO4-preparation of silica composite: adding bismuth nitrate (Bi (NO)3)3·5H2O,0.48g) dissolved in 10mL of 1M nitric acid (HNO)3) Simultaneously adding ammonium metavanadate (NH)4VO30.12g) was added another 15mL of 1M HNO3In the solution, two precursor solutions with the concentration of 1mM are respectively obtained. The two precursor solutions were mixed under vigorous stirring, and 2.5mL of aqueous silica gel (12 nm diameter, 40% by mass) was added as template. After rotary evaporation and drying, calcining the prepared powder for 3 hours at 400 ℃ to obtain BiVO4-a silica composite.
(2) Quantum size BiVO4Preparing nano particles: in the aspect of template removal, the composite material is subjected to hydrothermal reaction treatment at 180 ℃ for 24h to obtain quantum-size BiVO4And (3) nanoparticles.
The sample was analyzed by TEM to obtain a projection electron micrograph thereof. As shown in FIG. 2, the TEM image showed a dotted quantum size BiVO4Constituting spherical aggregates (a, b), quantum-sized BiVO4The average particle size is about 4.5nm (c). BiVO is known4Has a Bohr radius of about 2nm, so that the quantum size BiVO4Has a radius size close to the Bohr radius (2.25 nm). Thus, quantum size BiVO4A stronger quantum size effect can be exhibited.
As shown in fig. 3, XRD showed that the synthesized quantum size BiVO was4Is monoclinic white tungsten structure and does not contain any impurity crystal phase (a). Both the clear lattice fringes and the SAED mode (b) in HRTEM confirmed the quantum size BiVO4High crystallinity.
Example 2
(1)BiVO4-preparation of silica composite: adding bismuth nitrate (Bi (NO)3)35g) nitric acid (HNO) dissolved in 100mL5M3) In, will bias simultaneouslyAmmonium vanadate (NH)4VO32g) another 100mL of 3M HNO was added3In the solution, two precursor solutions with the concentration of 3mM are respectively obtained. The two precursor solutions were mixed with vigorous stirring, and 20mL of aqueous silica gel (diameter 24nm, mass fraction 70%) were added as template. After rotary evaporation and drying, calcining the prepared powder at 700 ℃ for 8h to obtain BiVO4-a silica composite.
(2) Quantum size BiVO4Preparing nano particles: in the aspect of template removal, the composite material is subjected to hydrothermal reaction treatment at 200 ℃ for 24h to obtain quantum-size BiVO4And (3) nanoparticles.
The sample was analyzed by TEM to obtain a projection electron micrograph thereof. TME similar to example 1, TEM image showed dotted quantum size BiVO4Constituting spherical aggregates (a, b), quantum-sized BiVO4The average particle size is about 4.5nm (c). BiVO is known4Has a Bohr radius of about 2nm, so that the quantum size BiVO4Has a radius size close to the Bohr radius (2.25 nm). Thus, quantum size BiVO4A stronger quantum size effect can be exhibited. The XRD pattern was similar to that of example 1.
Example 3 photocatalytic oxidation of CH4
Photocatalytic oxidation of CH4The reaction apparatus of (a) is a standard stainless steel pressure vessel with a high light transmittance top plate quartz glass window. 10mL of H2O and 10mg of Quantum-size BiVO prepared in example 14Photocatalyst mixing, CH4And O2The total pressure of the mixed gas was fixed at 20 bar.
Items 1 to 4 in Table 1 show O2To CH3Influence of OH yield. CH in 3h of reaction time with increasing partial pressure of oxygen from 6 to 10bar3The amount of OH and HCHO increased from 780 to 2326. mu. mol g, respectively–1And increased from 1468 to 1895. mu. mol g-1. Further increase of O2Partial pressure of over 10bar, CH3The amount of OH decreased and HCHO continued to increase (Table 4). Therefore, when CH4And O2In a ratio of 1:1, CH3OH gave the maximum yield. Time of dayThe Yield (STY) has been considered to evaluate CH4An important benchmark for oxidation yield. As can be seen from entries 3,5-7 of Table 1, CH occurs when the reaction time exceeds 3h3The amount of OH was reduced, and the STY value after 7 hours was 68% less than that at 3 hours. Reaction times of more than 3h lead to the formation of CH3OH continues to oxidize, presenting a net depletion trend. In contrast, the yield of HCHO after 7h of reaction reaches 4070 mu mol g-1Approximately 2 times 3 h.
TABLE 1 different O2q-BiVO under quantity and reaction time4To CH4The conversion performance of (a).
Figure BDA0002804074820000061
Sequence numbers 1-4: different O2Comparison of catalytic performance under quantity.
#Sequence No. 3, 5-7: comparison of catalytic performance at different reaction times.
To more fully demonstrate the liquid phase oxidation product CH3OH and HCHO being from CH4Is converted by oxidation to form13CH4Instead of the former12CH4To carry out the reaction. Isotopic labelling13CH4Gas chromatography-mass spectrometry (GC-MS) of (1) shows that, CH4Is CH3Carbon source of OH product, appearing at m/z 3313CH3OH peak (fig. 4 a).1H NMR 13CH3The satellite peaks at δ -3.12 ppm and 3.40ppm in OH indicate CH3Carbon 100% source of OH from CH4(FIG. 4 b).
Example 4 Quantum size BiVO4Generating·Capacity of OH
(1) In order to explore the quantum size BiVO4Generating·The OH capacity, the band structure, was studied.
Determination of UV-Vis Diffuse reflectance Spectroscopy: adding 40mg of barium sulfate into 200mL of deionized water, performing ultrasonic treatment for 30min, performing suction filtration on the solution by using a suction filtration device, forming a thin layer of barium sulfate on a filter membrane, namely a blank sample, and performing sealing, storage and drying by using tinfoil. Will be provided with40mg of barium sulfate was added to 200mL of deionized water and sonicated for 30min while 5mg of the quantum-sized BiVO prepared in example 1 was added4Adding a sample into 25mL of deionized water, carrying out ultrasonic treatment for 30min, carrying out suction filtration on 200mL of barium sulfate solution by using a suction filtration device, carrying out suction filtration on 25mL of sample solution, forming a thin-layer sample on a filter membrane and combining barium sulfate, namely the sample, and carrying out sealing, storage and drying by using tinfoil. Mott-Schottky curve test: it is in the range of 0.5mol L-1Na2SO4The potential ranges from-0.1 to 1V using 500Hz,700Hz and 900Hz frequencies, maintaining an AC amplitude of 10mV at different potentials.
FIG. 5 shows an ultraviolet visible UV-Vis diffuse reflection spectrum (a), a transformed Kubelka-Micke theory Kubelka-Munk function (b) and a model Schottky Mott-Schottky curve (c), which are used for accurately calculating the quantum size BiVO4The band structure (d). BiVO according to quantum size4In the energy band diagram (d), conduction band electrons are easily reduced to O2Generating·OH，(O2/·OH:0.695eV vs. RHE), while the valence band hole (2.555eV vs. RHE) readily oxidizes H2O production·OH，(·OH/H2O:2.380eV vs.RHE)。
(2)·And (5) detecting OH. Detecting by monitoring the formation of 7-OH-coumarin with coumarin as probe·Generation of OH.
In general, 8mg of photocatalyst was dispersed in 15mL of 1mM coumarin aqueous solution and stirred, followed by injection of argon to create an anaerobic environment or bubbling under closed conditions to create saturated O2. After 1h of irradiation, a certain amount of reaction solution was taken out and centrifuged to detect the fluorescence spectrum. As can be seen from FIG. 6, in the absence of O2In the case of (a), the quantum-sized BiVO prepared in example 1 was used4Or submicron BiVO4The photocatalyst can obtain an enhanced fluorescence signal, which indicates that holes in the semiconductor successfully convert H2Oxidation of O to·And (5) OH. In addition, the quantum size BiVO4The reason why the fluorescence intensity of (A) is larger than that of the submicron BiVO4In contrast, the quantum size BiVO4Has larger valence band potential and larger specific surface area. When the solution is coated with O2After saturation (b)Quantum size BiVO4Has a fluorescence intensity ratio of O2Increased by 2.3 times, confirming O2To pair·The formation of OH also contributes significantly. Similarly, the quantum size BiVO4At O2Specific submicron BiVO under saturation condition4Shows better yield·The OH capacity. Apparently, the quantum size BiVO4Can pass through H2O oxidation and O2Reduction to form·OH。
(3) Oxygen isotope18O2And H2 18And (4) testing: GC-MS analysis (FIG. 7) shows that18O2And H2 16When O is, CH3 18OH fragment strength of 100%, and use16O2And H2 18When O is, CH3 16The OH fragment intensity was 100%. From this it can be deduced that CH3The oxygen source of OH is derived from O2，H2O elements in O do not participate in all CH3OH is generated.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A method for preparing quantum size bismuth vanadate nano-particles is characterized by comprising the following steps:
(1)BiVO4-preparation of silica composite: respectively dissolving bismuth nitrate and ammonium metavanadate in nitric acid to obtain two precursor solutions; mixing the two precursor solutions, and adding silica gel as a template; after rotary evaporation and drying, calcining to obtain BiVO4-a silica composite;
(2) quantum size BiVO4Preparing nano particles: for BiVO4Carrying out hydrothermal reaction treatment on the-silicon dioxide composite material to remove the template and obtain the quantum size BiVO4And (3) nanoparticles.
2. The method of claim 1, wherein the method comprises: in the step (2), the hydrothermal reaction is carried out for 12-36 hours at 160-200 ℃.
3. The method of claim 1, wherein the method comprises: the hydrothermal reaction in the step (2) is carried out for 24 hours at 180 ℃.
4. The method of claim 1, wherein the method comprises: in the step (1), the mass-to-volume ratio of bismuth nitrate to nitric acid is 0.2-0.6 g:10 mL; the mass volume of the ammonium metavanadate and the nitric acid is 0.06-0.2 g: 15 mL.
5. The method of claim 1, wherein the method comprises: the volume ratio of the precursor solution containing bismuth nitrate to the precursor solution containing ammonium metavanadate in the step (1) is 1: 1-4.
6. The method of claim 1, wherein the method comprises: the volume ratio of the precursor solution containing bismuth nitrate to the precursor solution containing ammonium metavanadate in the step (1) is 2: 3.
7. The method of claim 1, wherein the method comprises: in the step (1), the silica gel is added in the form of a silica gel aqueous solution, the mass fraction of the silica gel aqueous solution is 1-70%, and the volume ratio of the silica gel aqueous solution to the precursor solution is 0.1-20 mL: 100 mL; the diameter of the silica gel is 10-25 nm.
8. The method of claim 1, wherein the method comprises: in the step (1), the calcination is carried out at 380-700 ℃ for 1-8 h.
9. A quantum size bismuth vanadate nanoparticle prepared by the method according to any one of claims 1 to 8.
10. The quantum size bismuth vanadate nanoparticles according to claim 9 for catalytically converting CH4The use of (1).
CN202011361401.1A 2020-11-27 2020-11-27 Preparation method and application of quantum-size bismuth vanadate nanoparticles Pending CN112619636A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011361401.1A CN112619636A (en) 2020-11-27 2020-11-27 Preparation method and application of quantum-size bismuth vanadate nanoparticles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011361401.1A CN112619636A (en) 2020-11-27 2020-11-27 Preparation method and application of quantum-size bismuth vanadate nanoparticles

Publications (1)

Publication Number Publication Date
CN112619636A true CN112619636A (en) 2021-04-09

Family

ID=75306532

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011361401.1A Pending CN112619636A (en) 2020-11-27 2020-11-27 Preparation method and application of quantum-size bismuth vanadate nanoparticles

Country Status (1)

Country Link
CN (1) CN112619636A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992402A (en) * 2012-10-31 2013-03-27 同济大学 Method for synthesizing monoclinic phase mesoporous bismuth vanadate through template method
CN105688889A (en) * 2016-03-21 2016-06-22 江苏大学 Preparation method for bismuth vanadate hollow microspheres
CN106012018A (en) * 2016-06-12 2016-10-12 华东理工大学 Preparation method for bismuth vanadate mesoporous single crystal
CN109133169A (en) * 2018-09-17 2019-01-04 南京景铄新材料科技有限公司 A kind of pucherite and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992402A (en) * 2012-10-31 2013-03-27 同济大学 Method for synthesizing monoclinic phase mesoporous bismuth vanadate through template method
CN105688889A (en) * 2016-03-21 2016-06-22 江苏大学 Preparation method for bismuth vanadate hollow microspheres
CN106012018A (en) * 2016-06-12 2016-10-12 华东理工大学 Preparation method for bismuth vanadate mesoporous single crystal
CN109133169A (en) * 2018-09-17 2019-01-04 南京景铄新材料科技有限公司 A kind of pucherite and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YINGYING FAN, ET AL: "Photocatalytic selective oxidation of methane by quantum sized bismuth vanadate", 《RESEARCH SQUARE》 *

Similar Documents

Publication Publication Date Title
Bafaqeer et al. Well-designed ZnV2O6/g-C3N4 2D/2D nanosheets heterojunction with faster charges separation via pCN as mediator towards enhanced photocatalytic reduction of CO2 to fuels
Han et al. Narrowing band gap energy of CeO2 in (Ni/CeO2)@ SiO2 catalyst for photothermal methane dry reforming
Xiong et al. Selective photocatalytic CO2 reduction over Zn-based layered double hydroxides containing tri or tetravalent metals
Zhang et al. Photocatalytic ammonia synthesis: Recent progress and future
Liu et al. Photocatalytic reduction of carbon dioxide using sol–gel derived titania-supported CoPc catalysts
Dosado et al. Novel Au/TiO2 photocatalysts for hydrogen production in alcohol–water mixtures based on hydrogen titanate nanotube precursors
Li et al. Exploring the photocatalytic conversion mechanism of gaseous formaldehyde degradation on TiO2–x-OV surface
Zhao et al. Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction
Chen et al. Effect of alcohol sacrificial agent on the performance of Cu/TiO2 photocatalysts for UV-driven hydrogen production
Huang et al. Promotion effect of ultraviolet light on NO+ CO reaction over Pt/TiO2 and Pt/CeO2–TiO2 catalysts
Clarizia et al. In situ photodeposited nanoCu on TiO2 as a catalyst for hydrogen production under UV/visible radiation
Wang et al. Ammonia from photothermal N2 hydrogenation over Ni/TiO2 catalysts under mild conditions
Li et al. Enhanced activity of AgMgOTiO2 catalyst for photocatalytic conversion of CO2 and H2O into CH4
Jiang et al. Insight into the Ag-CeO2 interface and mechanism of catalytic oxidation of formaldehyde
Wang et al. The mechanism of photodriven oxidation of CO over anatase and rutile TiO2 investigated from the hydrogen adsorption behavior
Zhang et al. Titania-morphology-dependent Pt–TiO2 interfacial catalysis in water-gas shift reaction
Mohamed et al. Innovative approach for the production of carbon nanotubes (CNTs) and carbon nanosheets through highly efficient photocatalytic water splitting into hydrogen using metal organic framework (MOF)-nano TiO 2 matrices as novel catalysts
Azam et al. In-situ synthesis of TiO2/La2O2CO3/rGO composite under acidic/basic treatment with La3+/Ti3+ as mediators for boosting photocatalytic H2 evolution
He et al. Preparation, characterization and activity evaluation of V2O5–LaVO4 composites under visible light irradiation
Liu et al. Visible-light-driven photocatalysis over nano-TiO2 with different morphologies: From morphology through active site to photocatalytic performance
Xu et al. Mesoporous (101)-TiO 2 nanocrystals with tailored Ti 3+ and surface oxygen vacancies for boosting photocatalytic hydrogenation of nitrobenzenes
Bardey et al. Plasmonic photocatalysis applied to solar fuels
Garay-Rodríguez et al. Photocatalytic CO 2 reduction over A 2 Ti 6 O 13 (A= Na and K) titanates synthesized by different pH-catalyzed sol–gel
Mousavi-Salehi et al. Gold supported on graphene oxide/silica photocatalyst for hydrogen generation from formic acid
Feng et al. Phase-dependent photocatalytic selective oxidation of cyclohexane over copper vanadates

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210409