CN110217819A - A kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material - Google Patents

A kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material Download PDF

Info

Publication number
CN110217819A
CN110217819A CN201910583397.4A CN201910583397A CN110217819A CN 110217819 A CN110217819 A CN 110217819A CN 201910583397 A CN201910583397 A CN 201910583397A CN 110217819 A CN110217819 A CN 110217819A
Authority
CN
China
Prior art keywords
nano material
hollow mesoporous
sio
step synthesis
mixed solution
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
CN201910583397.4A
Other languages
Chinese (zh)
Other versions
CN110217819B (en
Inventor
郑子良
张瑞平
贾卓
赵振祥
谢鲜梅
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.)
Shanxi Medical University
Original Assignee
Shanxi Medical 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 Shanxi Medical University filed Critical Shanxi Medical University
Priority to CN201910583397.4A priority Critical patent/CN110217819B/en
Publication of CN110217819A publication Critical patent/CN110217819A/en
Application granted granted Critical
Publication of CN110217819B publication Critical patent/CN110217819B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00Compounds of bismuth
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • C01P2004/34Spheres hollow
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter
    • C01P2006/17Pore diameter distribution
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

The present invention relates to hollow Nano biomaterial preparation technical fields, more specifically, are related to a kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material.Using ethyl orthosilicate, surfactant, albumin, inorganic bismuth source, dust technology, sodium hydroxide, ammonium nitrate, dehydrated alcohol as raw material, is rejected by thermostatic crystallization, template, centrifuge separation, hollow mesoporous Bi is made2S3/SiO2Nano material material, to increase substantially Bi2S3/SiO2The purity of nano material expands Bi2S3/SiO2Applications to nanostructures range.This technical process is a kind of quick, hollow mesoporous Bi of controlledly synthesis2S3/SiO2The technique of nano material can be realized by the additive amount of surfactant, ethyl orthosilicate and albumin in change synthetic system to hollow mesoporous Bi2S3/SiO2The controllable adjustment of the microspherulite diameter of nano material, voided layer thickness.Hollow mesoporous Bi made from the method for the present invention2S3/SiO2Nano material property is as follows: partial size 80~150nm, hollow 10~20nm of outer layer thickness, and product purity reaches 99.9%.

Description

A kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material
Technical field
The present invention relates to hollow Nano biomaterial preparation technical fields, more specifically, are related to a kind of spherical hollow Jie Hole bismuth sulfide/silica nano material one-step synthesis.
Background technique
Cancer is one of the major disease that precisely medical treatment is mainly captured at present, is carried out using molecular image technology to tumour early Phase diagnosis and boundary refine, and construct personalized treatment, it is expected under the influence of low side effect, realize to the efficient accurate of cancer Diagnosis and treatment.As nanotechnology is risen, using nano material characteristic, the application field of molecular image technology is expanded, realizes nanometer material Expect the application in terms of disease treatment, be not only of great significance to molecular image technology, but also is exploitation novel cancer Means provide new era.
Currently, there are many nano-probes to realize clinical conversion, due to tumor tissues medium vessels are abundant, vascular wall gap compared with Width, poor structural integrity, nano material can be enriched in tumor locus by Thief zone and long retention effect (EPR).Researcher's hair Existing, size has good passive target effect in the nano particle of 50-100nm, and circulation time is relatively long in vivo, can Enter lesions position by the gap that blood vessel dynamic aperture " intermittence eruption " generates, subsequent gap is gradually closed, and promotes large scale Nano particle is detained in inside, reduces clearance rate, nano particle is substantially improved in the deposition of lesions position.
Hollow structure mesopore silicon oxide (HMSN) has biggish specific surface area and hollow structure inside, and medicine can be substantially improved Object useful load, meanwhile, outer shell density is lower, is conducive to degrade rapidly in vivo, be metabolized, internal accumulation is effectively reduced Toxicity.Silica is regarded as " GenerallyRecognizedAsSafe " (GRAS) by U.S. FDA, is widely used in taking orally The drugs such as reagent, HMSN provide a kind of new approaches as a kind of preferred material, for nano material biomedicine research and development application.So And construct hollow mesoporous monox nanometer particle at present and mostly use substep synthesis mode, preparation process is complicated, variable factor compared with It is more, it is not easy large-scale production, strongly limits its further investigation and clinical conversion.
Summary of the invention
In the presence of overcoming the shortcomings of the prior art, the present invention provides that a kind of synthesis step is simple, product structure is easy Control, the spherical hollow mesoporous Bi that product purity can be substantially improved2S3/SiO2One-step synthesis.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows:
A kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material, comprising the following steps:
S1, by deionized water: surfactant: albumin is according to 277.778~555.556:0.082~0.329: 2.257·10-3~6.02010-3Molar ratio at mixed solution, 5~15min is stirred at 30 DEG C;
S2, inorganic bismuth source is dissolved in the dust technology that concentration is 2mol/L, is added dropwise in S1 and mixes after sufficiently dissolving dispersion It closes in solution, 10~20min of high-speed stirred;Inorganic bismuth source and dust technology molar ratio are 0.024~0.198:1.6~2.4
S3, into S2, the sodium hydroxide solution that concentration is 2mol/L is added dropwise in mixed solution, and adjustment pH value is permanent at 12,37 DEG C 10~30h of temperature stirring;
S4, into S3, ethyl orthosilicate is slowly added dropwise in mixed solution, sealing, and constant temperature stirs 20~40h at 37 DEG C;It is described just Silester and surfactant molar ratio are 1.307~6.533:0.082~0.329;
S5, mixed solution in S4 is washed, centrifugation, freeze-drying through deionized water, is not gone the hollow of template agent removing Mesoporous Bi2S3/SiO2Nano material;
S6, according to the hollow mesoporous Bi for not removing template agent removing2S3/SiO2: ammonium nitrate: dehydrated alcohol=0.5~1:5~25: Ammonium nitrate is added to absolute ethanol to be added after forming mixed solution and does not go the hollow of template agent removing by 1000~2000 mass ratio Mesoporous Bi2S3/SiO2, sufficiently after dissolution dispersion, 2~6h is stirred at 60 DEG C, mixture is made;
S7, mixture in S6 is successively separated by solid-liquid separation, deionized water washing, drying, repeats above step three times, obtains To hollow mesoporous Bi2S3/SiO2Nano material.
Preferably, the surfactant is cetyl trimethylammonium bromide.
Preferably, the albumin is bovine serum albumin(BSA).
Preferably, the inorganic bismuth source is five nitric hydrate bismuths.
Preferably, S2 high speed stirring uses ultrasonic disperse instrument, frequency 59KHz.
Preferably, dissolution dispersion uses ultrasonic disperse instrument, frequency 59KHz, jitter time 5min in S6.
Compared with prior art, the advantageous effect of present invention is that:
The present invention provides a kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material, with white Albumen and surfactant are as template, by adding to surfactant, ethyl orthosilicate and albumin in synthetic system Amount carries out modulation and compensates for conventional method to reach the structure optimization to hollow Nano particle and prepare hollow meso-porous titanium dioxide The cumbersome defect with the more difficult regulation of grain structure of the preparation process multistep of silicon, synthetic method is simple and easy, is greatly improved Bi2S3/SiO2The purity of nano material expands Bi2S3/SiO2Applications to nanostructures range, be a very ideal step quickly, The hollow mesoporous Bi of controllable preparation2S3/SiO2The method of nano material.
Detailed description of the invention
Fig. 1 is hollow mesoporous Bi2S synthesized by the embodiment of the present invention 13/SiO2The XRD spectra of nano material.
Fig. 2 is hollow mesoporous Bi2S synthesized by the embodiment of the present invention 13/SiO2The TEM of nano material schemes.
Fig. 3 is hollow mesoporous Bi2S synthesized by the embodiment of the present invention 13/SiO2The nitrogen adsorption of nano material-desorption spectrum Figure.
Fig. 4 is hollow mesoporous Bi2S synthesized by the embodiment of the present invention 13/SiO2The graph of pore diameter distribution of nano material.
Fig. 5 is hollow mesoporous Bi2S synthesized by the embodiment of the present invention 13/SiO2The XPS spectrum figure of nano material.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved into volumetric flask In, it is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 120mL, bovine serum albumin(BSA) 3.750g are removed, cetyl trimethylammonium bromide 1.05g is added together In beaker, 30 DEG C of stirring 10min form clear solution;Five nitric hydrate bismuth 0.36g are taken to be dissolved in the nitric acid solution of 15mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 15h, solution is by transparent Become brownish black;
Ethyl orthosilicate 15mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 30h;Product Through deionized water washing, centrifugation, freeze-drying, the hollow mesoporous Bi of template agent removing is not removed2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 1.0g, ammonium nitrate 25g, with Ethyl alcohol 2.5L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min.It is heated to 60 DEG C of constant temperature stirring 3h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Fig. 1 is hollow mesoporous Bi2S synthesized by the present embodiment3/SiO2The nano material of the XRD spectra synthesis of nano material Show its distinctive characteristic diffraction peak.
Fig. 2 is hollow mesoporous Bi2S synthesized by the present embodiment3/SiO2The TEM of nano material schemes, and a is 100nm mark in figure TEM under ruler schemes, and b is the TEM figure under 50nm scale in figure.Synthesized nano material is evenly distributed as seen from the figure, during pattern is It is empty spherical.
Fig. 3 is hollow mesoporous Bi2S synthesized by the present embodiment3/SiO2The nitrogen adsorption of nano material-desorption spectrogram.It inhales Attached-desorption isotherm shows as IV type curve, in the lower section (P/P of relative partial pressure0=0.08~0.21) it is solidifying that there are capillarys Poly- phenomenon, it was demonstrated that material has uniform duct.
Fig. 4 is hollow mesoporous Bi2S synthesized by the present embodiment3/SiO2The graph of pore diameter distribution of nano material.In desorption branch The pore-size distribution being calculated using BJH model is relatively narrow, and average pore size is about 3.1nm.
Fig. 5 is hollow mesoporous Bi2S synthesized by the present embodiment3/SiO2The XPS spectrum figure of nano material.As seen from the figure, exist The peak XPS corresponds to Bi at 159.0 and 164.1eV2S3The peak Bi4F7/2 and 4F5/2 of nano particle, 2p peak of the S at 163.5eV by BSA stable Bi2S3Bi and S, which is combined, in nanoparticle generates.
Embodiment 2
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved in volumetric flask, It is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 75mL, bovine serum albumin(BSA) 2.250g are removed, cetyl trimethylammonium bromide 0.45g is added together In beaker, 30 DEG C of stirring 5min form clear solution;Five nitric hydrate bismuth 0.18g are taken to be dissolved in the nitric acid solution of 12mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 10h, solution is by transparent Become brownish black;
Ethyl orthosilicate 4.5mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 20h;It produces Object is washed through deionized water, centrifugation, is freeze-dried, and is not removed the hollow mesoporous Bi of template agent removing2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 0.5g, ammonium nitrate 6g, with second Alcohol 1.5L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min. It is heated to 60 DEG C of constant temperature stirring 2h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Embodiment 3
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved into volumetric flask In, it is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 150mL, bovine serum albumin(BSA) 6.000g are removed, cetyl trimethylammonium bromide 1.80g is added together In beaker, 30 DEG C of stirring 15min form clear solution;Five nitric hydrate bismuth 1.44g are taken to be dissolved in the nitric acid solution of 18mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 30h, solution is by transparent Become brownish black;
Ethyl orthosilicate 22.5mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 40h;It produces Object is washed through deionized water, centrifugation, is freeze-dried, and is not removed the hollow mesoporous Bi of template agent removing2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 1.5g, ammonium nitrate 40g, with Ethyl alcohol 4.0L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min.It is heated to 60 DEG C of constant temperature stirring 6h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Embodiment 4
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved into volumetric flask In, it is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 120mL, bovine serum albumin(BSA) 3.750g are removed, cetyl trimethylammonium bromide 1.05g is added together In beaker, 30 DEG C of stirring 10min form clear solution;Five nitric hydrate bismuth 0.36g are taken to be dissolved in the nitric acid solution of 15mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 15h, solution is by transparent Become brownish black;
Ethyl orthosilicate 18mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 30h;Product Through deionized water washing, centrifugation, freeze-drying, the hollow mesoporous Bi of template agent removing is not removed2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 1.2g, ammonium nitrate 35g, with Ethyl alcohol 3.1L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min.It is heated to 60 DEG C of constant temperature stirring 3h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Embodiment 5
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved into volumetric flask In, it is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 120mL, bovine serum albumin(BSA) 3.750g are removed, cetyl trimethylammonium bromide 0.6g is added together In beaker, 30 DEG C of stirring 10min form clear solution;Five nitric hydrate bismuth 0.36g are taken to be dissolved in the nitric acid solution of 15mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 15h, solution is by transparent Become brownish black;
Ethyl orthosilicate 15mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 30h;Product Through deionized water washing, centrifugation, freeze-drying, the hollow mesoporous Bi of template agent removing is not removed2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 0.8g, ammonium nitrate 20g, with Ethyl alcohol 2L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min. It is heated to 60 DEG C of constant temperature stirring 3h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Embodiment 6
Taking concentration is 65% nitric acid 138.6mL, deionized water 806mL, and beaker is added together and is sufficiently mixed, by mixed liquor It moves in volumetric flask, it is spare to be made into the nitric acid solution that concentration is 2moL/L;
Sodium hydroxide 83.33g, deionized water 1L are taken, beaker is added together and is sufficiently mixed, mixed liquor is moved into volumetric flask In, it is spare to be made into the sodium hydroxide solution that concentration is 2moL/L;
Ionized water 120mL, bovine serum albumin(BSA) 4.500g are removed, cetyl trimethylammonium bromide 1.2g is added together In beaker, 30 DEG C of stirring 10min form clear solution;Five nitric hydrate bismuth 0.36g are taken to be dissolved in the nitric acid solution of 15mL2moL/L Afterwards, it is added in mixed solution, is placed in ultrasonic wave separating apparatus and carries out dissolution dispersion, frequency 59KHz, jitter time 10min;It utilizes The pH of mixed solution is adjusted to 12 by the sodium hydroxide solution prepared in advance, is heated to 37 DEG C of constant temperature stirring 15h, solution is by transparent Become brownish black;
Ethyl orthosilicate 10mL is taken, is slowly added dropwise into brownish black mixed solution, is sealed, 37 DEG C of constant temperature stir 30h;Product Through deionized water washing, centrifugation, freeze-drying, the hollow mesoporous Bi of template agent removing is not removed2S3/SiO2Nano material.
The hollow mesoporous Bi for not removing template agent removing after weighing drying2S3/SiO2Nano material 1.0g, ammonium nitrate 20g, with Ethyl alcohol 2.2L is added in beaker together, is placed in ultrasonic wave separating apparatus and is carried out dissolution dispersion, frequency 59KHz, jitter time 5min.It is heated to 60 DEG C of constant temperature stirring 3h later, obtains hollow mesoporous Bi2S3/SiO2Nano material.
Hollow mesoporous Bi made from the method for the present invention2S3/SiO2Nano material property is as follows: partial size 80~150nm, hollow 10~20nm of outer layer thickness, product purity reach 99.9%.
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment, Within the knowledge of a person skilled in the art, it can also make without departing from the purpose of the present invention each Kind variation, various change should all be included in the protection scope of the present invention.

Claims (6)

1. a kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material, which is characterized in that including following Step:
S1, by deionized water: surfactant: albumin is according to 277.778~555.556:0.082~0.329:2.257 10-3~6.02010-3Molar ratio at mixed solution, 5~15min is stirred at 30 DEG C;
It S2, according to inorganic bismuth source and nitric acid molar ratio is 0.024~0.198:1.6~2.4, inorganic bismuth source, which is dissolved in concentration, is In the dust technology of 2mol/L, to be added dropwise in S1 in mixed solution after completely dissolution, 10~20min of high-speed stirred;
S3, into S2, the sodium hydroxide solution that concentration is 2mol/L is added dropwise in mixed solution, and adjustment mixed solution pH value is 12,37 DEG C Lower constant temperature stirs 10~30h;
S4, according to ethyl orthosilicate and surfactant molar ratio it is 1.307~6.533:0.082~0.329, is mixed into S3 Ethyl orthosilicate is slowly added dropwise in solution, sealing, and constant temperature stirs 20~40h at 37 DEG C;
S5, mixed solution in S4 is washed, centrifugation, freeze-drying through deionized water, is not gone the hollow mesoporous of template agent removing Bi2S3/SiO2Nano material;
S6, according to the hollow mesoporous Bi2S for not removing template agent removing3/SiO2: ammonium nitrate: dehydrated alcohol=0.5~1:5~25:1000 Ammonium nitrate is added to absolute ethanol to be added after forming mixed solution and does not go the hollow mesoporous of template agent removing by~2000 mass ratio Bi2S3/SiO2, sufficiently after dissolution dispersion, 2~6h is stirred at 60 DEG C, mixture is made;
S7, mixture in S6 is successively separated by solid-liquid separation, deionized water washing, drying, repeats above step three times, obtains sky The mesoporous Bi of the heart2S3/SiO2Nano material.
2. the one-step synthesis of the spherical hollow mesoporous bismuth sulfide/silica nano material of one kind according to claim 1, It is characterized by: the surfactant is cetyl trimethylammonium bromide.
3. the one-step synthesis of the spherical hollow mesoporous bismuth sulfide/silica nano material of one kind according to claim 1, It is characterized by: the albumin is bovine serum albumin(BSA).
4. the one-step synthesis of the spherical hollow mesoporous bismuth sulfide/silica nano material of one kind according to claim 1, It is characterized by: the inorganic bismuth source is five nitric hydrate bismuths.
5. the one-step synthesis of the spherical hollow mesoporous bismuth sulfide/silica nano material of one kind according to claim 1, It is characterized by: the S2 high speed stirring uses ultrasonic disperse instrument, frequency 59KHz.
6. the one-step synthesis of the spherical hollow mesoporous bismuth sulfide/silica nano material of one kind according to claim 1, It is characterized by: dissolution dispersion uses ultrasonic disperse instrument, frequency 59KHz, jitter time 5min in the S6.
CN201910583397.4A 2019-07-01 2019-07-01 One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material Active CN110217819B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910583397.4A CN110217819B (en) 2019-07-01 2019-07-01 One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910583397.4A CN110217819B (en) 2019-07-01 2019-07-01 One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material

Publications (2)

Publication Number Publication Date
CN110217819A true CN110217819A (en) 2019-09-10
CN110217819B CN110217819B (en) 2022-02-08

Family

ID=67815609

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910583397.4A Active CN110217819B (en) 2019-07-01 2019-07-01 One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material

Country Status (1)

Country Link
CN (1) CN110217819B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408404A (en) * 2020-11-26 2021-02-26 山西医科大学 One-step synthesis method of degradable rod-like mesoporous silica nano material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446595A (en) * 2013-08-01 2013-12-18 华中科技大学 Multifunctional probe for CT (Computed Tomography) and dual-mode fluorescent imaging based on nanometer bismuth sulfide
CN106252661A (en) * 2016-10-14 2016-12-21 成都理工大学 Bismuth sulfide/carbon nano tube compound material and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446595A (en) * 2013-08-01 2013-12-18 华中科技大学 Multifunctional probe for CT (Computed Tomography) and dual-mode fluorescent imaging based on nanometer bismuth sulfide
CN106252661A (en) * 2016-10-14 2016-12-21 成都理工大学 Bismuth sulfide/carbon nano tube compound material and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU YAO ET AL.: ""Enhancing Osteosacoma Killing and CT Imaging Using Ultrahigh Drug Loading and NIR-Responsive Bismuth", 《ADVANCED HEALTHCARE MATERIALS》 *
YONG WANG ET AL.: ""BSA-Mediated Synthesis of Bismuth Sulfide Nanotheranostic Agents for Tumor Multimodal Imaging and Thermoradiotherapy"", 《ADVANCED FUNCTIONAL MATERIALS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408404A (en) * 2020-11-26 2021-02-26 山西医科大学 One-step synthesis method of degradable rod-like mesoporous silica nano material

Also Published As

Publication number Publication date
CN110217819B (en) 2022-02-08

Similar Documents

Publication Publication Date Title
Rao et al. Novel approaches for preparation of nanoparticles
Xiao et al. Core–shell structured 5-FU@ ZIF-90@ ZnO as a biodegradable nanoplatform for synergistic cancer therapy
CN104925845B (en) A kind of multi-layer core-shell structure CeO2The no template synthesis method of nano-hollow ball
CN107596391A (en) Preparation method of metal organic frame base nanometer diagnosis and treatment probe and products thereof and application
CN104607231B (en) There is carbon nitride photocatalyst of three-dimensional ordered macroporous structure and preparation method thereof
KR20050107428A (en) Ferric organic compounds, uses thereof and methods of making same
Xue et al. Synthesis of nanosized ZSM-5 zeolite with intracrystalline mesopores
CN104497032A (en) Nanoscale aluminium-based metal-organic framework structure material and preparation method thereof
CN110217819A (en) A kind of one-step synthesis of spherical hollow mesoporous bismuth sulfide/silica nano material
Dong et al. A general strategy for facile synthesis of ultrathin transition metal hydroxide nanosheets
Wu et al. Template route to chemically engineering cavities at nanoscale: a case study of Zn (OH) 2 template
CN104591105B (en) Cobalt selenide nano material and application thereof
Wang et al. Solvothermal synthesis of Bi 2 WO 6 hollow microspheres via Ostwald ripening with their enhanced photocatalytic activity
Liu et al. Synthesis of hollow mesoporous HAp-Au/MTX and its application in drug delivery
Sun et al. Monodispersed large-mesopore mesoporous silica nanoparticles enabled by sulfuric acid assisted hydrothermal process
CN111217372B (en) Chiral mesoporous core-shell structure silica nanoparticle and preparation method and application thereof
CN111569072B (en) Gadolinium chelated tungsten oxide spindle-shaped nanocomposite and preparation method and application thereof
Dougherty et al. Facile solvothermal synthesis and functionalization of polyethylene glycol-coated paramagnetic Gd2 (CO3) 3 particles and corresponding Gd2O3 nanoparticles for use as MRI contrast agents
Wang et al. Nonspherical hollow α-Fe 2 O 3 structures synthesized by stepwise effect of fluoride and phosphate anions
CN104250020A (en) Vaterite type calcium carbonate micro-nano hierarchical structure and additive-free preparation method thereof
CN115043420B (en) Porous hollow calcium carbonate nanosphere and preparation method and application thereof
CN105948086B (en) Citric acid pillared hydrotalcite supramolecular materials and its intercalation assemble method
CN109529035B (en) Preparation method of near-infrared light-enriched cysteine-modified bismuth sulfide hollow sphere and application of bismuth sulfide hollow sphere in photothermal therapy and drug controlled release
Huang et al. Solution inheritance of CoC2O4· 2H2O rods to nanoparticle-assembled Co3O4 rods
CN101172617A (en) Method for synthesizing nano type A molecular sieve

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