CN108554433B - Preparation method of sulfur-doped boron nitride nanosheet - Google Patents

Preparation method of sulfur-doped boron nitride nanosheet Download PDF

Info

Publication number
CN108554433B
CN108554433B CN201810319049.1A CN201810319049A CN108554433B CN 108554433 B CN108554433 B CN 108554433B CN 201810319049 A CN201810319049 A CN 201810319049A CN 108554433 B CN108554433 B CN 108554433B
Authority
CN
China
Prior art keywords
boron nitride
sulfur
preparation
preparing
bnns
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
CN201810319049.1A
Other languages
Chinese (zh)
Other versions
CN108554433A (en
Inventor
赵刚
战泽宇
徐锡金
程艳玲
赵宏
董晓晶
赵爽
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.)
University of Jinan
Original Assignee
University of Jinan
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 University of Jinan filed Critical University of Jinan
Priority to CN201810319049.1A priority Critical patent/CN108554433B/en
Publication of CN108554433A publication Critical patent/CN108554433A/en
Application granted granted Critical
Publication of CN108554433B publication Critical patent/CN108554433B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/583Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of photocatalysis, and provides a preparation method of a sulfur-doped boron nitride nanosheet. The method is simple and effective, and the prepared photocatalyst has the advantages of outstanding effect, no toxicity to the environment, high adsorption quantity and good photodegradation effect.

Description

Preparation method of sulfur-doped boron nitride nanosheet
Technical Field
The invention relates to the field of nanosheet preparation, and in particular relates to a preparation method of sulfur-doped boron nitride nanosheets.
Background
With the rapid development of economy, the urbanization trend is continuously strengthened, more and more domestic garbage are flushed into the water environment, and the water source is seriously polluted. The search for a nontoxic, cheap and efficient photocatalyst for photocatalytic water purification is a research hotspot in the field of photocatalysis. Cadmium sulfide, bismuth oxide and transition metal oxides have been found to exhibit good photodegradation properties under visible light long ago. (see references a.ye, w.fan, q.zhang, w.deng, y.wang, cat.sci.technol.2012, 2,969.g.zhao, s.w.liu, q.f.lu and l.j.song, ind.eng.chem.res.2012,51,10307.) however, most photocatalysts contain heavy metalsAnd toxic elements, causing irreversible pollution to the water body. Subsequently, titanium dioxide (TiO)2) Has been discovered and studied as a non-toxic photocatalyst. Compared with noble metal catalysts (Pt, Au), the catalyst has lower price, but is not metal catalysts (g-C)3N4S) phase ratio, TiO2The price of (a) is relatively high. Furthermore, TiO2The photoresponse under visible light is small, for example, photocatalytic degradation of organic pollutants under visible light is inefficient. Also, for pure non-metallic catalysts (g-C)3N4S), the photo-oxidative corrosion effect affects the photostability of the catalyst under visible light. (see reference A.Vitetadini, A.Selloni, F.P.Rotzinger, M.
Figure BDA0001624731990000011
Phys.rev.lett.1998,81,2954.c.w.peng, t.y.ke, l.brohan, m.r.plouet, j.c.huang, e.puzenat, h.t.chu and c.y.lee, chem.mater.2008,20,2426.x.q.gong, a.selloni, m.batzll, u.diebold, nat.mater.2006,5,665.x.c.wang, k.maeda, a.thomas, k.takanabe, g.xin, j.m.carlsson, k.domen, and m.antonieti, Nature mater.2009,8,76.g.liu, p.niu, l.c.yin h.m.m.90j.am.m.9070, amalga, non-toxic catalysts, anti-oxidative metals, nociceptive catalysts, sorla, etc. catalysts are sought.
Two-dimensional nanomaterials, e.g. graphene, MoS2(molybdenum disulfide) nanosheets, h-BN (hexagonal boron nitride) nanosheets, WS2The (tungsten disulfide) nanosheets and the like have excellent physical and chemical properties and have wide application prospects in the aspects of energy storage, laser modulation, fluorescence, catalysis, machinery and the like, so the nanosheets and the like become research hotspots in the material field in recent years. Among these materials, two-dimensional non-metallic hexagonal boron nitride nanosheets (h-BNNS) are attracting attention for their excellent adsorption and oxidation resistance. From the results of the present study, H-BNNS has very good adsorption of contaminants. (see references W.Lei, D.Portehault, D.Liu, S.Qin, Y.Chen, nat. Commun.20134,1777.) then, we designed and prepared a novel two-dimensional non-metal photocatalyst, namely sulfur-doped boron nitride nanosheet (S-BNNS), which is non-toxic, high in adsorption capacity and high in photodegradation effect, and researches show thatThe invention has excellent application prospect of purifying water source by photodegradation pollutants, therefore, the invention has good practical value.
Disclosure of Invention
Aiming at the problems of the existing two-dimensional non-metal photocatalyst in preparation and catalysis, the invention provides a method for simply and directly preparing a photocatalyst, namely a sulfur-doped boron nitride nanosheet (S-BNNS), which has the advantages of high adsorption capacity, high photodegradation efficiency, no toxicity to the environment, ultra-stable catalytic performance and the like when being used as the photocatalyst.
A preparation method of sulfur-doped boron nitride nanosheets comprises the following steps:
(1) preparing an activated boron nitride nanosheet:
preparing hexagonal boron nitride nanosheets in batches by a rotary ultrasonic stripping preparation method, and obtaining active boron nitride nanosheets through hydroxylation;
(2) preparing sulfur-doped boron nitride nanosheets:
adopting a double-heat-source vacuum tube furnace, and under the protective atmosphere, mixing sulfur powder with the HO-BNNS obtained in the step (1) according to the mass ratio of 1: 1-100:1, respectively arranged in a front heating zone and a rear heating zone of the tubular furnace, wherein the temperature of the front heating zone is set to 200-.
The protective atmosphere is one of argon, nitrogen or ammonia.
The method is used for the boron nitride ceramic artware, so that the boron nitride ceramic artware has a photocatalysis function.
The invention has the following beneficial effects:
(1) the invention discloses a method for preparing a two-dimensional non-metal photocatalyst S-BNNS by using a chemical vapor deposition method, which realizes the adjustment of the band gap of an h-BNNS nanosheet through the doping of sulfur atoms, so that the h-BNNS with originally non-photocatalytic performance is changed into the S-BNNS photocatalyst with visible light degradation performance.
(2) The method is simple and effective, and the prepared photocatalyst has the advantages of outstanding effect, no toxicity to the environment, high adsorption quantity and good photodegradation effect.
(3) The method can be used for boron nitride ceramic artware to enable the boron nitride ceramic artware to have a photocatalytic function.
Drawings
FIG. 1 field emission and transmission electron microscopy scans of HO-BNNS obtained in example 1, step (1).
FIG. 2 is a schematic flow diagram of the present invention.
FIG. 3 is a field emission electron microscope scan and an EDX scan of the two-dimensional non-metallic photocatalyst S-BNNS obtained in example 1 (panel b corresponds to sulfur element; panel c corresponds to boron element; panel d corresponds to nitrogen element).
FIG. 4 shows the photodegradability of the two-dimensional non-metal photocatalyst S-BNNS obtained in example 1 to rhodamine B.
FIG. 5 is a comparison of the photo-degradation performance of the two-dimensional non-metal photocatalyst S-BNNS obtained in example 1 and rhodamine B by using several commonly used photocatalysts.
Detailed Description
Example 1
In this example, a two-dimensional nonmetal sulfur-doped hexagonal boron nitride nanosheet (S-BNNS) photocatalyst is prepared as follows:
(1) preparing H-BNNS nanosheets by batch stripping with a rotary ultrasonic stripping method, and obtaining H0-BNNS through hydroxylation.
(2) 0.1 g of HO-BNNS is placed in a post-heating zone of a CVD tube furnace, and 1g of sulfur powder is used as a sulfur source and is placed in a pre-heating zone.
(3) Heating to 300 ℃ in a preposed heating zone to obtain sublimed sulfur.
(4) In the post-reaction zone, the sulfur rising and HO-BNNS react at the high temperature of 600 ℃ in the protective atmosphere of argon for 0.5 h.
(5) And finally, characterizing the product by means of a scanning electron microscope, a Fourier transform infrared spectrum and the like.
Example 2
The present group of examples includes 9 embodiments, and differs from example 1 in that the dosage of HO-BNNS in step (2) is changed to 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, 0.8g, 0.9g, 1g, respectively, and the dosage ratio of HO-BNNS to S is ensured to be 1: 10.
Example 3
This example is different from example 1 in that the temperature of the preheating zone in step (3) was changed from 300 ℃ to 200 ℃.
Example 4
This example is different from example 1 in that the temperature of the preheating zone in step (3) was changed from 300 ℃ to 400 ℃.
Example 5
This example is different from example 1 in that in step (4), the post-reaction temperature was changed to 700 ℃.
Example 6
This example is different from example 1 in that in step (4), the post-reaction temperature was changed to 800 ℃.
Example 7
The difference between this example and example 1 is that in step (4), the protective atmosphere was changed from argon to nitrogen or ammonia.
Example 8
This example differs from example 1 in that the reaction time of the sulfur uptake and HO-BNNS in step (4) is 1 h.
Example 9
This example differs from example 1 in that the reaction time of the sulphur hydride with HO-BNNS in step (4) is 1.5 h.

Claims (3)

1. A preparation method of sulfur-doped boron nitride nanosheets comprises the following steps:
(1) preparing an activated boron nitride nanosheet:
preparing hexagonal boron nitride nanosheets in batches by a rotary ultrasonic stripping preparation method, and obtaining active boron nitride nanosheets through hydroxylation;
(2) preparing sulfur-doped boron nitride nanosheets:
adopting a double-heat-source vacuum tube furnace, and under the protective atmosphere, mixing sulfur powder with the HO-BNNS obtained in the step (1) according to the mass ratio of 1: 1-100:1, respectively arranged in a front heating zone and a rear heating zone of the tubular furnace, wherein the temperature of the front heating zone is set to 200-.
2. The method of producing sulfur-doped boron nitride nanosheets of claim 1, wherein the protective atmosphere is one of argon, nitrogen or ammonia.
3. The method for preparing sulfur-doped boron nitride nanosheets of claim 1, wherein the method is used in boron nitride ceramic artwork, such that it has a photocatalytic function.
CN201810319049.1A 2018-04-11 2018-04-11 Preparation method of sulfur-doped boron nitride nanosheet Active CN108554433B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810319049.1A CN108554433B (en) 2018-04-11 2018-04-11 Preparation method of sulfur-doped boron nitride nanosheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810319049.1A CN108554433B (en) 2018-04-11 2018-04-11 Preparation method of sulfur-doped boron nitride nanosheet

Publications (2)

Publication Number Publication Date
CN108554433A CN108554433A (en) 2018-09-21
CN108554433B true CN108554433B (en) 2021-02-02

Family

ID=63534469

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810319049.1A Active CN108554433B (en) 2018-04-11 2018-04-11 Preparation method of sulfur-doped boron nitride nanosheet

Country Status (1)

Country Link
CN (1) CN108554433B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110201628A (en) * 2019-05-29 2019-09-06 沈阳航空航天大学 A kind of doping boron nitride and preparation method thereof removing heavy metal in high-temperature flue gas
CN112240898B (en) * 2019-07-17 2021-08-27 湖南大学 Photoelectrochemical aptamer sensor and preparation method and application thereof
CN113184899B (en) * 2021-04-29 2022-08-30 山东大学 Sulfur-doped K 2 Ti 6 O 13 Nanowire, preparation method and application thereof
CN113198513B (en) * 2021-05-18 2022-02-25 中南大学 Catalyst for preparing olefin by dehydrogenating alkane, preparation method and dehydrogenation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103910345A (en) * 2014-03-24 2014-07-09 中国科学院深圳先进技术研究院 Preparation method of boron nitride composite material
CN104591181A (en) * 2015-02-13 2015-05-06 山东大学 Method for preparing two-dimensional composite material by utilizing nanosheet layer peeling

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103910345A (en) * 2014-03-24 2014-07-09 中国科学院深圳先进技术研究院 Preparation method of boron nitride composite material
CN104591181A (en) * 2015-02-13 2015-05-06 山东大学 Method for preparing two-dimensional composite material by utilizing nanosheet layer peeling

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Enhanced visible-light response of metal-free doped bulk h-BN as potential efficient photocatalyst: a computational study;Fang Wang等;《J Mol Model》;20170107;第1-9页 *
Large-quantity and continuous preparation of two-dimensional nanosheets;Gang Zhao等;《Nanoscale》;20160208;第1-5页 *

Also Published As

Publication number Publication date
CN108554433A (en) 2018-09-21

Similar Documents

Publication Publication Date Title
CN108554433B (en) Preparation method of sulfur-doped boron nitride nanosheet
Jo et al. N-doped C dot/CoAl-layered double hydroxide/g-C3N4 hybrid composites for efficient and selective solar-driven conversion of CO2 into CH4
Zhou et al. The preparation, and applications of gC 3 N 4/TiO 2 heterojunction catalysts—a review
Gao et al. Reversing Free‐Electron Transfer of MoS2+ x Cocatalyst for Optimizing Antibonding‐Orbital Occupancy Enables High Photocatalytic H2 Evolution
Faisal et al. Novel mesoporous NiO/TiO2 nanocomposites with enhanced photocatalytic activity under visible light illumination
Weng et al. One-dimensional nanostructure based materials for versatile photocatalytic applications
Mahmoud et al. Influence of Mn, Cu, and Cd–doping for titanium oxide nanotubes on the photocatalytic activity toward water splitting under visible light irradiation
Liu et al. Facile fabrication of multi-walled carbon nanotubes (MWCNTs)/α-Bi 2 O 3 nanosheets composite with enhanced photocatalytic activity for doxycycline degradation under visible light irradiation
CN104399510B (en) A kind of preparation method of the optic catalytic composite material of graphite oxide and carbonitride
Koutavarapu et al. A novel one-pot approach of ZnWO 4 nanorods decorated onto gC 3 N 4 nanosheets: 1D/2D heterojunction for enhanced solar-light-driven photocatalytic activity
CN103601162B (en) Preparation method of graphite type carbon nitride nanotubes
CN102580736B (en) Grapheme / silver vanadium oxide nanometer composite visible light catalyst and preparation method thereof
Ortiz et al. Silver oxidation state effect on the photocatalytic properties of Ag doped TiO2 for hydrogen production under visible light
Iqbal et al. Molybdenum impregnated g-C3N4 nanotubes as potentially active photocatalyst for renewable energy applications
Yang et al. Insights into the surface/interface modifications of Bi2MoO6: Feasible strategies and photocatalytic applications
US20160107149A1 (en) Composition for enhanced life time of charge carriers for solar hydrogen production from water splitting
Tao et al. Photocatalyst Co3O4/red phosphorus for efficient degradation of malachite green under visible light irradiation
Chen et al. Highly efficient photocatalytic performance of graphene oxide/TiO 2–Bi 2 O 3 hybrid coating for organic dyes and NO gas
Li et al. Carbon black-doped anatase TiO2 nanorods for solar light-induced photocatalytic degradation of methylene blue
Guan et al. Solvothermal synthesis of p-type Cu 2 ZnSnS 4-based nanocrystals and photocatalytic properties for degradation of methylene blue
Hao et al. Utilizing new metal phase nanocomposites deep photocatalytic conversion of CO2 to C2H4
Barakat et al. N-doped Ni/C/TiO2 nanocomposite as effective photocatalyst for water splitting
Zhao et al. Polyoxometalates-doped TiO 2/Ag hybrid heterojunction: removal of multiple pollutants and mechanism investigation
Ahmed et al. Quantum-confinement induced enhancement in photocatalytic properties of iron oxide nanoparticles prepared by Ionic liquid
Kheradmand et al. Cobalt oxide on mesoporous carbon nitride for improved photocatalytic hydrogen production under visible light irradiation

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